Removal of Hazardous Organic Dyes from Liquid Wastes Using Advanced Nanomaterials

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Removal of Hazardous Organic Dyes from Liquid Wastes Using Advanced Nanomaterials

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A peer-reviewed article of this preprint also exists.

Francisco Jose Alguacil^*

Manuel Alonso

Francisco Jose Alguacil^*

Manuel Alonso

This version is not peer-reviewed

Submitted:

16 May 2024

Posted:

17 May 2024

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Abstract

The presence of organic dyes in aqueous environments is of extreme hazardousness against life due to the toxicity of these compounds. Thus, its removal from these various aquatic media is of the utmost importance and several technologies are constantly proven to match this goal. Among these technologies, various types of degradation and adsorption are the most widely used, and of the various types of materials used within these technologies, nanomaterials are constantly developed and investigated, probably due to the various properties that these nanomaterials presented. This work reviewed recent developments (2023 year) about the use of these nanomaterials on the treatment of solutions contaminated with these toxic organic dyes.

Keywords:

Subject: Environmental and Earth Sciences - Pollution

1. Introduction

Organic dyes are commonly used chemicals in textile industry to give colour to the various products manufactured in it. As consequence of this use, the effluents produced within this industry contained variable concentrations of these harmful dyes, thus its removal from these effluents is of the utmost necessity to avoid environmental issues.

To remove these dyes, many type of materials are using, and among them, nanomaterials are gaining a considerable importance due to its inherent properties. The importance of the removal of these dyes and the use of nanomaterials on this removal it reflects in the number or recent reviews about this matter. Table 1 summarized the different classes of nanomaterials recently reviewed (2023 year), as it can be seen there is an amply subclasses of this type of materials, and the way in which they remove organic dyes from the effluents is mainly by two type of processes: adsorption and/or (photo)catalysis.

The present work reviewed the most recent literature (papers published in 2023 year) about this field of interest as the use of nanomaterials in the removal or organic dyes is; this review classified the investigation considering the type of dyes involved in the literature: anionic, cationic and nanomaterials used for the treatment of both anionic and cationic dyes.

2. Nanomaterials and Anionic Organic Dyes

2.1. Adsorption of Anionic Dyes on Nanomaterials

Computational investigation was used to study the performance of TiO₂ in the uptake of Acid Yellow 36 and Acid Orange 6 dyes on (1 1 0) surface of the oxide [49] . The results of these simulations indicated that Acid Yellow 36 was more reactive and had a greater adsorption uptake than Acid Orange 6.

Gelatin-bearing semi-IPN hydrogels containing different concentrations of itaconic acid-based protic ionic liquids (PILs) were prepared to remove Reactive Red 21 and Reactive Blue 19 from water [50]. When the hydrogels contained zero or low PILs concentrations, the adsorption uptake was maximum, being the best-performing hydrogel composition (GelITA1) tested in real wastewater (cotton samples were dyed with both dyes and the resulted wastewater was used in the experimentation) with an average 75% removal efficiency of the dyes. Maximum dye uptakes were 106 mg/g and 147 mg/g for Reactive Red 21 and Reactive Blue 19, respectively.

ZnO/C nanocomposites were fabricated at temperatures in the 500-700º C range. Among all the composites, ZnO/C-700 sample was the nanomaterial with better adsorption characteristics for the removal of Congo Red from solutions [51]. The maximum ye load was near 47 mg/g

Sol-gel procedure was used to form MgO nanoparticles which were used to adsorb Reactive Red 21 [52], with a maxium adsorption loading of 385 mg/g at a pH range of 5–9, and 20 min of contact time. Dye-bearing MgO nanoparticles was regenerated at 500° C during two hours and reused with a reasonable efficiency (pink colour appeared in the solution after the sixth cycle, increasing in colour within the seventh cycle). These MgO nanoparticles presented a 98% dye removal from a real textile wastewater (formed as in [50]).

CuFe-LDH/g-C₃N₄ (CFL/CN) nanocomposites were prepared and investigate to remove Alizarin Red S, and the results were compared with the derived from the use of CFL/CN nanoadsorbent [53]. Sono-CFL/CN nanoadsorbent was more effective (near 96%) on the removal of the dye in comparison to hydro-CFL/CN nanomaterial (53%). Maximum dye uptake was in the 65-75 mg/g range, which was dependent on the technology used to remove the dye. Sono-CFL/CN lost its initial adsorption capacity under continuous use (Table 2).

A nanostructured composite based on superparamagnetic iron oxide nanoparticles (SPIONs), coated with hydroxyapatite (HAp), was show to be a good adsorbent against the presence of Congo Red in aqueous solutions [54]. Amongst the various formulations, the composite containing 35 wt.% of SPION was selected to adsorb the organic dye. Results concluded that the best efficiency on the removal of the dye were achieved when 0.10 g of SPION/HAp treated 50 mL of a solution containing 50 mg/L of the dye at pH 0 and a contact time of four hours. The maximum Congo Red adsorption uptake using the SPION/HAp adsorbent was determined to be 158.98 mg/g. The composite can be separated from the solution using magnets.

Ion gelation procedure was used to fabricate chitosan nanoparticles which were used on the removal on the removal of anionic dyes (Reactive Yellow 145, Reactive Blue 19, and Reactive Red 195) from solutions [55]. The utilization of polyaluminium chloride (PAC) (80 mg/L) and chitosan nanoparticles (150 mL/L) at pH= 6.6 produced the maximum (92%) color removal efficiency. Thus, with the use of chitosan nanoparticles, the amount of PAC needed to increase the color removal efficiency was reduced. Furthermore, the effect of chitosan nanoparticles on the adsorption of the dyes revealed that the Langmuir type II isotherm equation was followed, with a maximum adsorption capacity of 1100 mg/g.

This reference [56], investigated the production of amorphous biochar from breadfruit leaves, product which was utilized to remove Congo Red from solutions. The average size of the char was of 190 nm, however, after the adsorption of the dye the average size increased to 460 nm. The adsorption of Congo Red was studied under different dye concentrations (5-50 mg/L), reaction time (30 min-four hours), pH (6-9), and char dosages (0.5-2 g/100 mL). RSM-BBD design results showed maximum removal efficiency (99.96%) at pH 6.37, dye concentration of 45 mg/L, time 105 min, and biochar dosage of 1.92 g. Adsorption data fitted well to the Langmuir Type-II isotherm with maximum upload of almost 18 mg/g.

A nanobiosorbent was fabricated via microwave crosslinking of nanosilica gel with banana peels nanobiochar (BPNB) and chitosan hydrogel (Chit Hgel) to produce BPNB-NSiO₂-Chit Hgel nanobiosorbent (22.48–26.23 nm) [57]. The influence of nanobiosorbent dosage (1–50 mg), pH (2–12), reaction time (1–45 min), dye concentration (5–100 mg/L), temperature (15-60^o C), and interfering salts on the adsorption of Congo Red was investigated. Maximum dye uptake were about 58 mg/g. Removal of the dye (92.8–95.0 %) from tap, sea, and wastewater can be reached.

Zinc ferrite (ZnFe₂O₄, BET surface area 85.88 m2/g) and copper ferrite (CuFe₂O₄, BET surface area 41.81 m2/g) nanoparticles were formed, and used as adsorbents, in the removal of Alizarin Yellow R, Thiazole Yellow G, Congo Red, and Methyl Orange from industrial wastewater [58]. The use of acidic pH values favoured the removal of the dyes, being the maximum monolayer adsorption capacities higher using zinc ferrite than copper ferrite (Table 3).

In this work [59], multifunctional Fe₃O₄@N-C (nitrogen-doped carbon) nanocomposites with hollow porous core-shell structure were formed by different procedures. These included, i) hydrothermal method, ii) polymer coating, iii) thermal annealing process in nitrogen and iv) etching step in HCl medium. Fe₃O₄@N-C nanocomposites etched by HCl for different lengths of time, especially Fe₃O₄@N-C-3 (30 min of etching time) nanocomposites, also adsorbed Methyl Orange (98.7 % after 100 min).

Sodium alginate/gellan gum and polyethyleneimine were utilized to fabricate a material with 3D hierarchical porous architecture and used in the removal of Congo Red from waters [60]. The aerogel showed an adsorption uptake of 3 g/g, selectively separate Congo Red in the presence of other dyes from binary systems: Congo Red plus Amaranth (anionic dye), or Safranine T (cationic dye), or Methyl Orange (anionic dye) or Rhodamine B (cationic dye). From single dye solutions, the affinity of the aerogel from the dyes followed the order: Congo Red> Rhodamine B> Methyl Orange> Amaranth> Safranine T. After three cycles, the adsorption capacity decreased by 14.8%, maintaining an adsorption capacity of near 0.5 g/g (0.65 g/g in the first cyle).

Congo Red was removed, from solution, using green pea peels biochar (GPBC), and zinc oxide green pea peels biochar nanocomposite (ZnO/GPBC, particle size 14.58 nm) [61]. The experimental conditions used in the investigation were: dye concentration (50–250 mg/L), GPBC and ZnO/GPBC dosage (50-250 mg/100 mL), pH (2−12), temperature (20–60o C) and time (0–90 min). The results showed that ZnO/GPBC was more effective to remove the dye than GPPBC (98% versus 90%, respectively) under the optimized conditions. The monolayer adsorption capacities were 114.94 mg/g and 62.11 mg/g for ZnO/GPBC and GPBC, also respectively. In both cases, there was a decrease in the dye removal capacity with the number of cycles: ZnO/GPBC (98.4% in the first cycle against 88.8% in the fifth cycle), GPBC (90.4% first cycle versus 76.2% fifth cycle).

The removal of Congo Red, from mimic wastewater, was used to evaluate the properties of different composition ratios of CMC-nZVI (nano zero-valent iron coated with carboxymethyl cellulose) [62]. At an initial dye concentration of 500 mg/L, the increase of CMC contents favoured the decolorization process. The removal efficiency were of near 100%, at the CMC:Fe²⁺ ratio of 0.004 within 10 seconds after the addition of CMC-nZVI to the dye solution, whereas the optimal decolorization rate (90%, with an uptake capacity of near 8 g/g) was observed when the iron concentration was of 1 g/L. The above results were attributable to the break of the chromophore groups (-N[dbnd]N-), responsibles of the color of the dye, to N–H bonds.

F-Ln (Ln= Ce, Pr and Nd) nanosheets, provided of surface acetates groups, were prepared through a hydrothermal synthetic methodology at room temperature and pressure, and used in the adsorption of Congo Red and Coomassie Brilliant Blue G-250 anionic dyes [63]. The maximum Langmuir adsorption capacities for the respective two dyes were 4334 mg/g and 2827 mg/g. Both dyes, loaded onto the adsorbent via its exchange with the surface acetates groups of the F–Ce nanosheets. Furthermore, these nanosheets presented a salt-tolerance in saturated NaCl medium or elevated concentrations of Na₂SO₄, K₂CO₃ and NaNO₃ in the solutions.

2.2. Photo)-Catalytic Degradation of Anionic Dyes Using Nanomaterials

By means of Moringa stenopetala seed extract, copper oxide nanoparticles (average particle size 6.6 nm) were formed and used to degrade Congo Red and Alizarin Red S [64]. After two hours of exposure to irradiation and varying experimental conditions, Congo Red degraded near 98%, whereas the degradation of Alizarin Red S reached 95%. The continuous use of the catalyst for five cycles also was investigated, and in both cases, the adsorbent lost its effectiveness after each cycle.

Under a chemical precipitation procedure, zinc oxide (ZnO), copper ferrite (CuFe₂O₄) and the zinc oxide-copper ferrite binary composite were prepared, following by the formation of a ternary composite (ZnO-CuFe₂O₄-CNTs) [65]. These compounds were used to search the photocatalytic degradation of Congo Red under sunlight exposure, reaching 82% dye degradation in two hours. ZnO-CuFe₂O₄-CNT nanocomposite had better degradation efficiency than the pure oxides and their binary composite.

Bi₂O₃-NiO heterojunction was formed from the respective Ni(II) and Bi(III) nitrates and used to degrade Methyl Orange under visible-light exposure [66]. The photocatalytic degradation of the dye reached rates of 46% (nickel oxide), 67% (bismuth oxide) and 100% (mixed nickel-bismuth oxide). Transfer of positive holes and electrons and the separation being the responsible for the better activity of the mixed oxides heterojunction, which apparently can be recycled several times, as written in the published Abstract, however these data did not appear in the publication.

Bi₂WO₆ nanomaterials, containing a chelating agent (EDTA), were used to degrade Methyl Orange and Congo Red in the presence of NaBH₄, being the catalytic efficiency of Bi₂WO₆ surpassed by that of the EDTA-Bi₂WO₆. This catalyst could be recycled up to five times without undergoing a significant loss in activity [67].

Carbohydrate conjugated Ag, Au and Ag-Au alloy biocompatible nanoparticles (14.5, 11.7 and 16.3 nm respective average particle size) had been fabricated through bio-reduction of the metal salts in the presence of Lobaria retigera (high altitude lichen) [68]. These nanoparticles acted as catalysts for the degradation of Methyl Orange.

In order to control its characteristics, β-cyclodextrin and honey were used, as surfactants, during the synthesis of ZnO nanoparticles, which were coupled with silver to form ZnO-xAg, ZnO-C-xAg and ZnO-H-xAg binary structures with typical crystalline sizes of 9.38 nm [69]. The photodegradation of Bromophenol Blue showed increased photoactivity upon modification with cyclodextrin, honey, and silver nanoparticles. Dye photodegradation was near 100% by the use of ZnO-H-3Ag (3 wt% silver).

Ti₃C₂ MXene and its nitrogen-doped derivative (N-Ti₃C₂ MXene) were used in the removal of Methyl Orange from waters [70]. The results indicated that the catalytic efficiency of N-Ti₃C₂ MXene increased near ten times in comparison with the corresponding of the Ti₃C₂ MXene nanomaterial. N-Ti₃C₂ 1:8 MXene composition performed best, since the degradation of a 20 mg/L dye solution reached more than 98% after twenty minutes of UV lamp irradiation. The effectiveness of this material was attributable to the presence of more abundant surface functional groups, improving the charge transfer efficiency and enhance the electrical conductivity of the catalyst.

Ag/Mn–ZnO nanomaterial (4-5 nm) was used to remove Methyl Orange and Alizarin Red S from solutions, both dyes degraded near 70% after 100 min of reaction time [71]. However, and in the case of Alizarin Red S, the nanomaterial did not maintain intact its degradation efficiency until continuous use (five cycles).

2D borate anions B₄O₅(OH)₄^2- intercalated layered double hydroxide (ZnGa-BLDH) nanosheets (5–6 nm) were investigated in the photodegradation removal of Congo Red from aqueous environment [72].

The aqueous extract of Ulva lactuca and ZnO nanopowders were used to fabricate ZnO@C nanocomposites, material which was investigated to degrade Congo Red under UV and visible light exposure [73]. This nanocomposite degraded better the dye than the pristine zinc oxide nanopowder.

Undoped TiO₂ and Fe-doped TiO₂ materials, prepared via sol-gel and precipitation procedure, were used as photocatalysts to remove Methyl Orange under UV-A and visible-light irradiations [74]. The photocatalytic experiments revealed an increase of the photocatalytic activity of 0.5%wt Fe-doped TiO₂ composition, and only under UV-A light, compared to the rest of the prepared nanomaterials. This increase was due to the efficient charge separation of electrons and holes.

Iron oxide nanoparticles (IONPs, composed of amorphous FeOOH and FeII/III-polyphenol complexes)) with extracts of the plant Camellia sinensis, were used to remove Methyl Orange from solutions [75]. The nanoparticles were used as heterogeneous-Fenton catalysts for the removal of the dye. Best results were obtained at pH values around 3.

Graphene oxide nanosheets-yttrium oxide (Y₂O₃)–silicon oxide (SiO₂) ternary nanostructures were fabricated to investigate its photo-degradation activity against the presence (20 ppm) of Methyl Orange in aqueous solutions [76]. The photo-degradation of the dye improved from 1.17% for Y₂O₃/SiO₂ nanostructures to 52% when the concentration of the graphene oxide nanosheets reached 15 wt% and 45 min of reaction time.

Pristine Fe₂O₃, 1 wt% metal (Ag, Co, and Cu) doped Fe₂O₃ nanoparticles (NPs) were fabricated using a hydrothermal and wet impregnation method [77]. The nanoparticles were employed as photosensitizers for the degradation of Reactive Red and Orange II dyes under sunlight irradiation. The synthesized 1 wt% Ag–Fe₂O₃ (AgF) NPs had the best catalytic properties, compared with pristine Fe₂O₃ and CoF and CuF, to degrade (98.32%) both dyes within 120 min of reaction time.

The photocatalytic properties of polymeric g-C₃N₄ layers coated with various dosages of erbium oxide nanoparticles were investigated on the oxidation of Orange G under visible-light exposure. The nanoparticles maintained its activity above 95% up to three cycles of reusability [78].

ZnO-ZnS-CdO-CdS quaternary core-shell nanocomposites (NCs) were fabricated using Ricinus communis as stabilizing agent and hydrazine hydrate as reducing agent [79]. The nanocatalysts were used in the degradation of Congo Red and Methyl Red dyes, being active both in the degradation of single or a mixture of the dyes.

The removal of Congo Red, under UV light in the presence of H₂O₂, and the photocatalytic activity of copper oxide nanoparticles (CuONPs, 25-90 nm size) were investigated [80]. The UV light decomposed H₂O₂ with formation of ·OH radicals, which improved the degradation of the dye. This degradation occurred by reaction of the dye with the radicals, though other reactions of the dye with i.e. a positive hole (h⁺_vb), contribute to the elimination of this harmful compound.

A one-step laser technology was used to fabricate boron, doped and boron and nitrogen co-doped highly reduced graphene oxide and multiwall carbon nanotubes/Ni oxide and Ni hydroxide nanohybrid layers [81]. These materials were employed to investigate its properties on the photocatalytic removal of Methyl Orange. The best photocatalytic activities resulted for boron and nitrogen co-doped materials formed by the use of H₃BO₃ and urea as boron and nitrogen precursors, respectively; however, the degradation efficiency failed after continuous use: 80% in the 1^st cycle and 3% in the third cycle.

Direct thermal polymerization procedure was utilized in the fabrication of 1D/2D g-C₃N₅/g-C₃N₄ heterojunction (1D/2D-N₅/N₄) used in the removal of Methyl Orange from wastewater [82]. 1D/2D-N₅/N₄ had one-dimensional g-C₃N₅ nanorods and two-dimensional g-C₃N₄ nanosheets. The photocatalytic degradation of the dye reached a rate of 99.6 %, maintaining a 92.20 % after five cycles.

Attapulgite (ATP) mineral nanomaterials grafted with magnetic Fe₃O₄ nanoparticles, with a further modification with polyethyleneimine (PEI), served to the fabrication of functionalized magnetic attapulgite composites (ATP-Fe₃O₄-PEI), which was utilized for the removal of Congo Red from wastewater [83]. The removal of the dye by means of the nanocomposite was attributed to a catalytic degradation process. However, without photoirradiation and the presence of oxidants in the solution, the system formed H₂O₂ and hydroxyl radicals (·OH) to catalytically degraded dye molecules. Moreover, the removal of the dye was further increased by adsorption on the composite material through electrostatic attraction, hydrogen bonds, and π-π interaction. Under two removal tests, the removal rate of the dye exceeded 95%, corresponding to a removal capacity of 943.77 mg/g, at pH 3 and 25° C. This composite presented removal effectiveness and uptake capacity exceeding 82% and 799 mg/g, respectively, after four cycles.

The efficiency of Mn-20wt%Ni and Mn-30wt%Ni particle powders in relation to the degradation of Reactive Black 5 as function of different experimental variables was investigated [84]. Mn-20wt%Ni particles presented better degradation efficiency and faster rate of reaction than Mn-30wt%Ni material.

The metal assisted chemical etching (MACE) technique was used to produce SiNWs-NiNPs/NiONPs [85], these nanoparticles were used to the photocatalystic assisted degradation of Methyl Orange from an aqueous solution. The degradation of 20 ppm of the dye had an efficiency of 66.5% after three hours and under UV exposure.

Manganese oxide (MnO₂)/silicon carbide (SiC) nanostructures doped polystyrene (PS)–polycarbonate (PC) blend was used to investigate its properties to degrade Methyl Orange [86]. Results indicated that the use of PS–PC/MnO₂–SiC nanocomposites, under UV-exposure, removed the dye colour with an efficiency of near 54% within 90 min, and using the 5.2 wt% MnO₂/SiC NPs formulation.

Carbon dots with diameters of 4.9±1.5 nm and 4.1±1.2nm were fabricated from nitric and sulphuric acids, respectively, and Ilex paraguariensis as raw material [87]. These dots were used to fabricate magnetite-containing nanocomposites, being these nanocomposites utilized to investigate the photocatalytic degradation of Methyl Orange. At pH 6.2, 8.5 ppm dye concentration and 100 ppm nanomaterials doses, all the above nanocompounds presented catalytic activity allowing the removal of up to 98% dye under visible irradiation (400 nm) and seven hours of reaction.

Cetyltrimethylammonium bromide surfactant assisted hierarchical TiO₂ heterojunction was doped with europium to form a nanostructure with crystallyte sizes in the 4-10 nm range [88]. Further, Congo Red dye was photocatalytic degraded within the above materials in the presence of UV ligh, increasing the degradation rate with the reaction time. After 75 min, the efficiency in the dye degradation reached 97%; it was also concluded that the degradation is dependant on the dispersion of the nanomaterials.

Multifunctional surface-modified CuO nanomaterials were used for the degradation of AR88 dye. At pH 11, the nanomaterial degraded near 95% of the dye under UV exposure, and utilizing 1 g/L nanomaterial dose [89].

Zinc oxide/copper oxide nanocomposites (ZnO/CuO NCs) presenting various proportions of binary oxides were investigated for the degradation of Congo Red [90]. Experiments carried out on dye-bearing water and real textile wastewater, under visible light irradiation by 0.5 M ZnO:0.5 M CuO nanocomposite, showed both acting as catalysts by tuning doping concentration of copper oxide in ZnO.

Polymethyl methacrylate (PMMA)-polycarbonate (PC)/antimony oxide (Sb₂O₃)-graphene oxide (GO) nanocomposites films were fabricated [91]. These nanomaterials were used in the photodegradation of a 20 ppm Methyl Orange solution. This degradation was due to a rise in electron–hole pairs and a reduction in fix replication.

This reference investigated a ceramic-based nanomaterial catalyst (a reduced graphene oxide-ZnS, rGO-ZnS) for the oxidative photocatalytic degradation of Naphtol Blue Black dye solution under exposure to sunlight [92]. The dye was degraded (93.7%) under exposure to direct solar light.

SiO₂/g-C₃N₄ photocatalyst was fabricated, fixing the amount of SiO₂, and varying the concentration of graphitic carbon nitride in the ratio (1:x, where x= 1, 2, 3); these nanocomposites were used to investigate their photocatalytic properties to degrade Auramine O and Xylenol Orange dyes [93]. The results showed that SCN₂ (x= 2) nanocomposite improved the photocatalytic activity, under visible light exposure, with degradation efficiencies of 70% and 84.6% for the respective above dyes, being these results attributable to the large surface area and the electron–hole separation rate that the nanocomposites presented.

Bismuth oxychloride (BiOCl) nanoplatelets and lignin-based biochar were used as precursors to fabricate composites formed by bismuth oxyhalide nanoparticles, being investigated the simultaneous photocatalytic and adsorptive efficiency of the Biochar–BiOCl (%BC-BiOCl) composites on the removal of Methyl Orange [94]. The maximum dye removal and degradation (100%) was reached under the next experimental conditions: composite dose of 1.39 g/L, initial dye concentration of 41.8 mg/L, pH of 3.15, and one hour of reaction under light exposure. Similarly to other nanomaterials, there was an efficiency lost after various cycles; in this case the efficiency dropped from 99% in the 1st cycle to 63% in the fifth cycle (1 g/L of 15BCPC dosage, 30 mg/L initial dye concentration at pH 5).

1-hexyl-3-methyl-2-(2-oxo-ethyl)-3H-imidazol-1-ium bromide (HMIB) ionic liquid embedded on CdO-TiO₂ (HMIB-CT) hybrid nanomaterial was used in the removal of Tripan Blue dye from solutions [95]. Complete dye removal under natural sun beam irradiation, required for the photocatalytic activity, was accomplished at pH 7 and one hour of reaction time.

After the formation of the magnetic photocatalyst Scendesmus sp./Fe₃O₄/TiO₂, its sonophotocatalytic properties with respect to the degradation of the Red195 dye were investigated [96]. At pH of 5, photocatalyst dosage of 100 mg, initial dye concentration of 100 mg/L, ultrasound power of 38W, and an exposure time of 20 min, the maximum Red195 removal efficiency (100%) resulted. After five cycles of recycling, the degradation efficiency remained above 95%. Experiments on scavenging indicated that electrons (h+) and OH^- groups were necessary to act as decomposition reagents.

2.3. Remarks to the Use of Nanomaterials in the Removal of Anionic Dyes from Solutions

Whereas subsections 2.1. and 2.2. show that two approaches are using by scientists to remove anionic dyes from solutions: adsorption or (photo)-catalysis, Table 4 summarized the various anionic dyes object of these investigations. For the number of references, it is clear that (photo)-catalytic degradation of organic dyes is the methodology of preference against the use of adsorption-elution to fit this environmental task. In any case, it is difficult to compare results due to the various experimental conditions used in each reference. Using (photo)-catalysis, the degradation of the dye occurs at the few minutes or hours (see Table 5), whereas in the case of adsorption procedures, dye uptakes vary from a few mg/g to the g/g order (see text and also Table 10).

From the above, just one reference, [58], utilized a real industrial wastewater in the investigation, also, his Table shows that Congo Red and Methyl Orange are the most investigated anionic dyes, .

3. Nanomaterials and Cationic Dyes

3.1. Adsorption of Cationic Dyes on Nanomaterials

Two different processes (Calix-MNPs and Calix-Si-MNPs) were used to modify magnetite nanoparticles with p-sulfonatocalix[6]arene and were used for the removal of Crystal Violet from aqueous solution [97]. Calix-Si-MNPs showed a better adsorption capacity than Calix-MNPs, attributable to the modification on the surface of magnetite nanoparticles through a spacer. The nanoadsorbent can be recovered using a magnet, however, there was a considerable lost of capacity up to four cycles of adsorption (pH 7)-desorption (water plus acetone).

In this work [98], amorphous and crystalline products based on Zr, Mg, and Mn were fabricated through the Pechini sol–gel procedure and used to remove Basic Fuchsin dye from solutions. Samples fabricated before calcination was amorphous, whereas the samples calcined at 500° C or 700° C presented mean diameters of 45.16 nm and 76.28 nm, respectively. Figure 1 showed that increasing the temperature of calcination the dye uptake onto the nanomaterials decreased. Maximum dye uptake varies in the 93-240 mg/g concentrations range.

Succinic anhydride modifying the surface of native cellulose nanocrystals was used to adsorb Golden Yellow and Methylene Blue. No data about the desorption step were given in the work [99].

Bionanocomposites formed of chitosan grafted by various monomers, such as acrylamide, acrylic acid, 4-styrene sulfonic acid, and hybrid nanoparticles of graphene oxide/titanium dioxide nanoparticles (GO@TiO₂-NPs) were fabricated and used in the adsorption of Basic-Red 46 [100]. The removal of the dye from the aqueous solution followed the pseudo second-order kinetics and Langmuir isotherm models, with maximum upload in the 43-79 mg/g range..

Food industry waste hazelnut shells were used as precursors to prepare, via impregnation with ZnCl₂ followed by chemical activation with KOH, porous carbon materials to be used as adsorbents of a Methylene Blue-wastewater [101]. The Fusso effect, which can reduce the size of the dye molecules, increased the adsorption properties of the carbon. The material showed a dye uptake of 694.03 mg/g, which can be increased to 882.46 mg/g in 0.1 M NaCl medium.

Calcium silicate nanopowders were fabricated from marble sawing dust and silica fume using microwave irradiation-assisted route. These nanomaterials were investigated in the removal of Malachite Green from solutions in the pH 2-12 range, with best results yielded (near 100% removal) at the pH of 12. Adsorption data fitted well with the linear form of the Freundlich isotherm. Dye-desorption was investigated by the use of acetone; after continuous adsorption-desorption cycles, it was shown that after six cycles the adsorption efficiency decreased from 100% (first cycle) to 78% (sixth cycle). This decrease attributable to the decrease in the number of the surface-active sites after continuous use [102].

Under the polyol process, FePt nanoparticles with a size less than 2 nm, were uniformly distributed over the surface of hexagonal boron nitride nanosheets. These materials were used in the adsorption of Methylene Blue, Methylene Violet and Brilliant Green [103]. The removal of the dyes from the solution depended on the composition of the nanomaterial used in the experimentation and the annealing temperature (Figure 2). However, no data about the desorption step were provided in the published manuscript.

A nanomanufacturing process which included the treatment of α-chitin nanocrystals (ChNCs) by electron-beam irradiation, EBI-induced ChNCs, with nano-sized and rod-like morphology with tunable lengths averaging 259-608 nm and uniform widths of 12-16 nm, were formed [104]. The anionic groups presented in the nanomaterials reacted with Toluidine Blue O dye via electrostatic attraction, forming hydrogels, which were self-supporting after centrifugation. No desorption data were included in the manuscript.

Nano-sized polylactic acid was decorated on the surface of graphene oxide to investigate it performance on the removal of Methylene Blue from an aqueous solution [105]. Optimum adsorption parameters were: adsorbent dosage of 0.5 g/L, pH 4, reaction time of two hours, and 45º C. Data fitted with the Langmuir isotherm with maximum uptakes in the 104-224 mg/g range. Experimental results showed that the loading capacity of the polylactic acid-graphene oxide nanoadsorbent increased near 70% in comparison with that of sulphur oxide. The nanoadsorbent presented a loss of near 27% adsorption efficiency after five cycles.

Using the co-precipitation method, superparamagnetic iron oxide nanoparticles (SPIONs) with size of 13.6±1.9 nm were synthesized [106]. Further, the surface of SPIONs was modified by polyvinyl alcohol, chitosan, and graphene oxide, and the modified nanomaterials were used to adsorb Methylene Blue. Removal efficiency at pH 7 reached near 87% after 13 days, and the highest dye loading capacity was 3.6 mg/g, while the highest loading amount achieved was 36.4 mg/g. The cumulative desorption capacity of the adsorbent at pH 3.8 was at its maximum at almost 9.0% after 30 days.

Tin oxide nanorods and SnO₂/MoO₃ nanocomposite were fabricated, via the use of the leaf extract of Magnifera indica, the presence of polyphenols in the extract facilitated the reduction of the precursor metal salt to the corresponding oxide [107]. The catalytic properties of the above materials were investigated on the degradation of Methylene blue. The photocatalytic efficiency of the mixture of oxides improved to 73% as compared to that of SnO₂ (69.0%).

In this reference [108], Zn-modified biochar obtained from zinc carbonate and Jerusalem artichokes straw was used to explore its effect on the adsorption of Methylene Blue. Compared with the original biochar, the specific surface area (1037.17 m²/g) of the Zn-modified biochar by pyrolysis at 800° C (Zn-BC 800) increased approximately 22 times. The adsorption of Methylene Blue with Zn-BC 800 followed the pseudo-second-order kinetic model. At 45° C, Zn-BC 800 had a maximum adsorption loading of 477.13 mg/g. Hydrogen bond and π-π interaction were the main responsible for the dye adsorption onto Zn-BC 800. The adsorbent lost its initial dye uptake of near 420 mg/g until 350 mg/g in the fifth cycle, in these series of experiments, anhydrous ethanol and distilled water were used as eluent.

Yellow phosphorus slag was used to develop a SiO₂ matrix material, which was loaded with MgO, and then the formed composite was investigated as adsorbent of Malachite Green dye [109]. These investigations demonstrated that when using this composite, a maximum dye adsorption rate of 97.72 % was reached, with a dye uptake of 115.64 mg/g, experimental data responded well to the Freundlich isotherm. In this case, 0.1 M sodium chloride medium was utilized to desorb the loaded dye, after four cycles of continuous use there was a slight decrease in the adsorption efficiency.

3.2. Nanomaterials–Forming Membranes for the Removal of Cationic Dyes

A ZIF-67/SA@PVDF (ZSA3@PVDF) mixed matrix membrane had been produced by incorporating silicon aerogel (SA) and zeolitic imidazolate framework material 67 (ZIF-67) nanoparticles in a polyvinylidene fluoride (PVDF) membrane [110]. By the use of this membrane, Methylene Blue removal rate exceeded 99% when filtrating 100 mL of a 5 mg/L dye solution. The continuous use of the membrane showed that its removal efficiency was maintained above 98% after three cycles of the dynamic adsorption process.

3.3.(. Photo)-Catalytic Degradation of Cationic Dyes Using Nanomaterials

Pure Fe₂O₃ (FO with 46 nm particle size) and a series of 5%, 10% and 15% Ni doped Fe₂O₃ (5-NFO, 10-NFO and 15-NFO) nanoparticles (19 nm particle size) were synthesized to investigate the effect of nickel concentration on the photocatalytic activity on Methylene Blue degradation [111]. The highest dye degradation was yielded using 10-NFO nanoparticles and 100 min of reaction time. The optimal concentration of 10-NFO accelerated the photoreduction of the dye due to the photocatalyst characteristics to trap electrons.

Pristine Fe₂O₃ hematite and Nb-doped Fe₂O₃ nanostructures with different doping concentrations of 5%, 10%, and 15% of niobium, were used to investigate the degradation of Methylene Blue [112]. After 100 min of exposure to visible light, the highest level of dye degradation was attained by 10%-NFO composition. The photocatalytic properties of doped Fe₂O₃ was attributed to a decrease in band gap energy.

Mn₄(P₂O₇)₃ nanoflakes were synthesized and used to remove Methylene Blue from water [113]. The electrostatic interaction between the negatively charged group of the nanoflakes and dye cationic molecules ruled the adsorption process; further, the dye was degraded via a heterogeneous catalytic process performed at basic pH in the presence of H₂O₂ and reactive oxygen species production. After 30 min and using an initial dye concentration of 40 mg/L, the degradation rate reached 99.2%.

Rhodamine B was degraded by a photocatalytic process, under direct sunlight, by the use of sol-immobilization synthesized monometallic (Pd and Au) and bimetallic (Pd-Au) hybrid nanomaterials supported on reduced graphene oxide (rGO) [114]. Bimetallic Au-Pd-rGO composites had better catalytic efficiencies than mono-metals-rGO nanomaterials. Under the best formulation (Au0.75-Pd0.25/rGO), the degradation efficiency reached 98%, whereas the nanocomposite can be used for five cycles maintaining 89% of its activity.

The degradation of Methylene blue and Rhodamine B had been investigated using cadmium sulfide nanoparticles (CdSNPs, average size less than 20 nm) encapsulated by natural extract [115]. These nanoparticles were synthesized via green chemical reduction route that uses natural stabilizers such as rice water, papaya fruit extracts and precursors such as cadmium chloride, cadmium nitrate, and cadmium sulphur.

Cerium doped cobalt-magnesium ferrites Co_0.7Mg_0.3Ce_xFe_2xO₄ were prepared and used to investigate its potential as degrading agent against Methylene Blue [116]. The nanocomposite with x= 0.1 presented a degradation efficiency of near 95.5% in one hour, with free radicals O₂^·-and OH^. acting as the active species to promote dye degradation, which produced CO₂ and water as final products. This material presented a near constant recyclability efficiency after five cycles (95.5%-94.8%).

The next investigation used ZnO–NPs from milky sap of Calotropis procera parts to degrade Malachite Green and Methylene Blue under UV-light exposure [117]. The degradation efficiency reached 85.3% (Malachite Green) and 86.3% (Methylene Blue), being, in both cases, increased the efficiency from pH 4 to pH 10.

A soft nanocomposite hydrogel, comprising a pyrene-based chiral amphipath having an amino acid (l-phenylalanine) core with pendant oligo-oxyethylene hydrophilic chains and sulphur oxide, was used in the degradation of Methylene Blue and Rhodamine B [118]. Experimental results indicated that the removal efficiency was better in the case of Methylene Blue than Rhodamine B.

Montmorillonite K30 nanosheets were decorated with Carrisa edulis fruit extract capped spherical shape Co₃O₄ nanoparticles (size of 11.25 nm) to degrade methylthioninium chloride (Methylene Blue) [119]. Attributable to the generation of OH and O₂ radicals, the 20% loaded Co₃O₄ on MK30 nanocomposites had the best photocatalytic performance (near 98%) on exposing to visible light.

0.2CoFe₂O₄/0.8TiO₂-5%La nanocomposite was prepared, by a co-precipitation and hydrothermal process, to be used as a high activity photocatalyst for degradation of Methylene Blue under visible light irradiation [120]. This dye was degraded by 99% after 50 min of exposure time to the light.

Pure phased rare earth doped ZnO nanoparticles were fabricated for the degradation of Malachite Green and Crystal Violet [121]. For these dyes, the maximum degradation efficiency was near 98% when dysprosium doped ZnO nanoparticles were used to degrade the dyes. A tailored band gap and the presence of defects, which helped in the creation of a reactive species were the main responsible for dyes degradation.

Ionic mesoporous organosilica (IMOS) forming a polyethylene glycol (PEG)-linked bis-imidazolium chloride framework was prepared for the selective recovery of tungstate ions from wastewater and its further use as a photocatalyst against the presence of Rhodamine B in waters [122]. Under column experiments, a maximum recovery of tungstate ions (123 mg/g) was reached using a bed height of 3 cm and a flow rate of 3 mL/min. The use of this W(VI)-immobilized IMOS (W-IMOS), oxidized Rhodamine B through successive adsorption (30%) in the dark and photocatalytic degradation (66%) under UV-vis light irradiation.

Nanomaterials containing the SrMoO₄/g-C₃N₄ heterostructure were synthesized in a single step by the sonochemical method at controlled temperatures, further, these nanomaterials were used to degrade some cationic dyes [123]. The results of the photocatalytic investigations showed that the insertion of CN promoted photocatalytic degradation of Methylene Blue (99.58%), Rhodamine B (100%) and Crystal Violet (98.65%).

Two nanocomposites were prepared with varying compositions of ZnO and acid-activated kaolinite for use as photocatalysts to degrade Methylene Blue [124]. The ZK-30 nanocomposite (30 wt% ZnO) removed 98% of the dye from an aqueous solution of pH 10. The recyclability experiments about the continuous use of the nanocomposites showed 80–99 % dye removal for up to three consecutive photocatalytic cycles.

N/p-type nanomaterials loaded on the surface of cellulose nanoparticles had been used to fabricate hybrid nanomaterials to be used in the photocatalytic degradation of Methylene Blue and Rhodamine B dyes [125]. In single dye solutions, the degradation efficiency reached 95% for Methylene Blue and 47.4% in the case of Rhodamine B dye, whereas in a mixed dye solution the degradation reached 53% and 89.8% for Rhodamine B and Methylene Blue, respectively.

Titanium dioxide nanoparticles were prepared by a sol-gel process and calcined for 2 h at temperatures in the 300° C- 600° C range [126]. The increase of the calcination temperature produced an increase in the size of the nanoparticles. The photodegradation performance of these nanoparticles was investigated in the removal of 10 ppm Methylene Blue from water, showing the nanomaterial calcined at 400° C the best efficiency (near 95%) over the other nanoparticles examined in this work.

The tannic acid coating method was utilized to synthesize Ag nanoparticles-loaded ultralong hydroxyapatite (HAP). The nanowires were employed as building blocks together with chitosan (CS) to fabricate highly porous flow-through reactors (Ag@HAP/CS) for continuous catalytic reduction of Methylene Blue [127]. These nanomaterials presented efficiencies of near 99% at high fluxes, i.e. 2000 L/m²·h, and using a very low concentration of NaBH₄ i.e. dye:NaBH₄ of 1.

Pseudobrookite (Fe₂TiO₅) was fabricated and used in the photocatalytic degradation of Rhodamine B [128]. The degradation process was associated with the adsorption of protons and the formation of an electron-hole pair. The nanomaterial thermally treated under nitrogen atmosphere presented better catalytic activity than those fabricated in air.

This reference [129], described the use of natural cotton substrates and the in situ mineralization of β-FeOOH nanorods as precursors in the synthesis of an inorganic–organic compound semiconductor nanomaterials (Cot-FeOOH). These materials had photocatalytic activity (98%) for Rhodamine B dye under visible light irradiation and in the presence of hydrogen peroxide.

Fe₃O₄ nanoparticles with a size of (350±50 nm) were synthesized by solvothermal method. Then, the nanoparticles were coated with a shell made of 3-aminophenol-formaldehyde (APF) resin to prevent agglomeration, and further, core–shell Fe₃O₄@APF nanospheres were produced by polycondensation within 10 min [130]. The magnetic Fe₃O₄@APF@Ag nanomaterials catalyzed the reduction, via the use of sodium borohydride, of Rhodamine B and Methylene Blue dyes, with conversion of these chemicals above 90% within 3 min of reaction time and a slight decrease in the reduction efficiency after seven cycles.

Ag₂O nanoparticles, with cubic structure and crystalline diameter of 18.5 nm, were prepared and used in the photocatalytic degradation of Rhodamine B [131]. The exposure of an aqueous solution containing the dye to UV-visible light during one hour produced a 76 % reduction of the compound. The main responsible in the degradation process were the reactions with super oxide radical (O₂^•) and the hydroxyl radical (^•OH).

Nanoparticles (average size of 1.87 nm) composed of Fe₃O₄/Mn₃O₄/CuO were used as nanocatalyst in the degradation of Methylene Blue under ultrasonic conditions [132]. The degradation of the dye was investigated under various experimental conditions, being the best of these conditions: temperature of 28^o C, 0.03 g/L of initial dye concentration, 1.0 g/L of nanoparticles dosage, 5 mM of H₂O₂, and 60 kHz. A maximum of 95.04% dye degradation using these nanoparticles was reached after 150 min.

Using attapulgite (ATP) as carrier, Fe₃O₄ and g-C₃N₄ were grafted onto ATP, and the surface was then modified with polyethyleneimine (PEI) to produce photocatalyst ATP-Fe₃O₄-g-C₃N₄-PEI, which was used in the treatment of a Malachite Green-bearing wastewater [133]. Electron paramagnetic resonance analysis confirmed that the nanocomposite generated hydroxyl radicals (·OH) and superoxide radicals (·O₂^-) which degraded the dye. Under the action of H⁺, ·O₂^-, and ·OH, a removal rate of 98% was reached at pH 3. Recyclability experiments showed that there was a continuous degradation of the photocatalyst from the first (98% dye removal efficiency) to the fourth (65% dye removal efficiency) cycle.

The controlled synthesis of bismuth with various morphologies: nanoparticles (20-50 nm), nanorods (diameter of 20 nm and length 1 µm) nanocubes (150-200 nm) and micro-spheres (10 µm) has been investigated [134]. The degradation efficiency, after 90 minutes of exposure to visible-light irradiation, against the presence of Rhodamine B in solutions were 99.9%, 98.9%, 97% and 68.3% for the above morphologies, respectively. The catalytic activity of the same morphologies increased with the decrease of pH value, maintaining a removal rate of 73.5% after forty cycles. Remarkably, this is a work which investigates the reusability of these adsorbents for a number of cycles as high as 40, when the ordinary number rarely exceeded five cycles.

Superparamagnetic Fe₃O₄ nanoparticles synthesized via an electrochemical procedure were used as a catalyst for the oxidation of Rhodamine B in a photo-Fenton-like process [135]. The rate of color removal was 85% after 12 minutes at dye concentration of 2 mg/L, H₂O₂ concentration of 0.18 mM, and Fe₃O₄ concentration of 0.2 g/L. In addition, electrochemically synthesized superparamagnetic Fe₃O₄ nanoparticles showed that the catalyst activity decreased from 85% in the first cycle to 78% in the fifth cycle.

Silver chromate/reduced graphene oxide nanocomposites (Ag₂CrO₄/rGO NCs) with a narrow dissemination size were used for the removal of Methylene Blue [136]. The photodegradation of the dye was carried out under solar light irradiation. Experimental results indicated removal efficiencies of near 92% after one hour of irradiation, result which compared well with the results reached by pure Ag₂CrO₄ (46%) and rGO (30%) nanomaterials. The nanocomposites maintained their efficiency to degrade for up to five cycles.

The spherical shaped monoclinic structures, ZnO (24.9 nm) and CuO (17.0 nm) nanoparticles and ZnO/CuO (22.6 nm) nanocomposites were synthesized using extract of Musa acuminate fruit peel as the stabilizing and capping agent [137]. Degradation investigations on Methylene Blue had been carried out using these nanomaterials under a visible light source. ZnO, CuO, and ZnO/CuO showed degradation efficiencies of 57%, 50%, and 90%, respectively.

Polypyrrole (Ppy)-In₂O₃ nanoparticles hybrids were fabricated to leverage its superoxide radical decomposition for Methylene Blue degradation [138].

The nanoemulsion procedure was utilized to synthesize Bi_xSn_6−2xS_y (0.33≤x≤ 2.95) photocatalysts with morphological structures that changed from nanowhiskers to quantum dots [139]. Particularly, BiSn₄S_4.5 formulation, photodegraded Methylene Blue in the shortest time under UV-visible light (Table 6).

Copper oxide (CuO) was used to dope tin oxide (SnO₂) in order to yield a heterostructured photocatalyst, which were used in the degradation of Methylene Blue [140]. The oxides mixture degraded the dye with 90% efficiency in three hours, which improved the results derived with the use of SnO₂.

Black titanium dioxide (BTO) nanoparticles were formed, using pulsed laser irradiation in liquids, from de-ionized water, isopropyl alcohol, and 1:1 mixtures of water and alcohol [141]. Photocatalytic degradation of Methylene Blue was improved at neutral pH values of the solution. This degradation occurred via reaction of the dye with ·OH, O₂^·-and ·OOH radicals to produce CO₂ and water. The efficiency decay, for every adsorbent, approximately 10% after continuous use (three cycles), though for the four adsorbents tested, only BTOWA degraded the dye at 54% in the first cycle.

Ag-manganese oxide, with plasmon-enhanced photocatalytic activity, the photodegradation of Crystal Violet dye was formed. Manganese oxide was prepared by an acidic precipitation method using potassium permanganate, manganese acetate, and nitric acid as precursors. Silver nanoparticles were deposited on the manganese oxide using leaf extracts of Calotropis gigantean [142]. The deposition of silver increased the photocatalytic activity of the manganese oxide from 68 to 95%. By the use of 10% Ag-OMS, near 100, 95, and 75% efficiencies in the photodegradation of 50, 100, and 150 mg/L dye concentrations was observed in 90, 120, and 120 min, respectively. After three cycles of activity, the efficiency to degrade the dye was maintained above 90%.

Pristine and carboxylic acid (CXA)-modified MIL-53 (Al) nanostructures were used to investigate its performance on the adsorption of Rhodamine B and Methylene Blue from solutions [143]. The incorporation of the acidic function to MIL-53 (Al) produced an increase of the adsorption capacity, though Rhodamine B was adsorbed better than Methylene Blue due to its higher adsorption energy.

Cellulose acetate/polycaprolactone (CA/PCL)-based nanocomposites with manganese tungstate (MnWO₄) nanoparticles were formed, and used on the Crystal Violet photocatalytic degradation under UV light source [144]. The photocatalytic efficacy of the CA/PCL/MnWO₄ nanocomposites was higher to that of the individual components.

2D layered molybdenum disulphide/boron nitrate/reduced graphene oxide (MoS₂by/BN/rGO) ternary nanocomposites was formed by sonication assisted hydrothermal procedure, and its potential to treat water contaminated with Methylene Blue was investigated [145]. The nanocomposite ability to degrade the dye reached 98% after 45 min, with a ten percent loss of effectiveness, with respect to the first cycle, in the seventh cycle. The presence of superoxide radicals (·O₂^-) and hydroxyl radicals (·OH^-) were responsible for the degradation process.

TiO₂ nanotubes were annealed in the 400-900° C temperatures range to yield different nanomaterials and marked as TiO₂ ST-NT, moreover, part of these nanopowders were decorated with Fe₃O₄ nanoparticles to form TiO₂ ST-NT@Fe₃O₄NPs [146]. These nanocompounds were investigated for the photocatalytic decomposition of Methylene Blue under UV light. The best photocatalytic activity of TiO₂ ST-NT and TiO₂ ST-NT@Fe₃O₄NPs were yielded at annealing temperatures of 600 and 700° C, respectively.

Graphitic carbon nitride (g-C₃N₄) photocatalysts were prepared using mixtures of urea and thiourea, as precursors, by varying calcination temperatures ranging from 500 to 650° C for three hours in air medium, and used to remove Rhodamine B from liquid solutions [147]. The results showed that Rhodamine B removal by g-C₃N₄ formed at 600 °C was near 95% within three hours of visible LED light irradiation

NiMn₂O₄ nanoparticles had been prepared through PEG assisted hydrothermal method. This Ni4 nanosphere was used as a visible light photocatalyst for the degradation of Methylene Blue and Rhodamine B dyes [148]. Under optimized conditions and 210 min, the degradation rates of the two dyes were 68 and 80.7 %, respectively, whereas under five cycles of continuous use, the efficiency was maintained above 95% for both dyes.

Zinc oxide nanoparticles with spherical (40-100 nm) and rod (200 nm) shapes were fabricated using the extract from Scallion peel, and used to remove Methylene Blue presented in a mimic wastewater [149]. UV and visible light irradiation were used to degrade the dye. Experimental results showed that UV light was more effective (10 min) than visible light (30 min) to eliminate the dye from the solution.

Z-scheme V₂O₅/g-C₃N₄ photocatalytic composites were synthesized and used to degrade Methylene Blue [150]. This investigation showed that the optimum composite formulation had a 90% efficiency in the degradation of the dye, result which was near 6.18-fold higher than that of pristine GCN catalyst. After five cycles of continuous use, the GVO2 heterostructure showed a decrease in its degradation efficiency (from 90% in the first cycle to 80% in the fifth cycle).

Zn, and Fe co-doped TiO₂ photocatalyst were fabricated by the sol-gel method at room temperature, presenting the tetragonal anatase phase of TiO₂ in all synthesized nanoparticles [151]. Also, it was shown the presence of spherical nanoparticles in ZFT_2.5 photocatalyst with a diameter ranging from 8 to 20 nm. The photocatalyst ZFT_2.5 was investigated for the photocatalytic degradation of a mixture of three cationic dyes (Rhodamine B, Malachite Green and Methylene Blue) under exposure to visible light. Experimental results indicated that the above dyes degraded with 90.57%, 91.54% and 88.39%, respectively.

Graphite oxide and carbon quantum dots (CQDs) were added to polyacrylonitrile nanofibers to investigate its performance, under visible light irradiation, on the photocatalytic degradation of Methylene Blue. Quantitative degradation efficiency for the dye was found after 25 min, showing the nanocomposite better efficiency than the pristine precursors [152].

A green procedure was used to create MgO NPs using Manilkara zapota as a bio source, further, activated carbon/magnesium oxide (AC/MgO) photocatalyst was blended through a solution evaporation procedure [153]. This photocatalyst was used for photodegradation of Rhodamine B using an UV–visible spectrophotometer. The dye can be degraded (99%) under simulated solar irradiation.

Cadmium doped ZnO nanocomposites was prepared to investigate its performance on the photocatalytic degradation of Methylene Blue [154]. Cadmium doping in ZnO nanostructure acted as an electron scavenger, stopping electron-hole (e^-/h⁺) pairs from recombination on the surface of ZnO and increasing charge transfer.

Pure and TiO₂ doped MnO₂ spherical nanoparticles were made using a sol-gel technique. These nanoparticles were investigated in the photocatalytic degradation, under visible light exposure, of Methylene Blue [155]. However, the use of the titanium-bearing nanomaterial only produced, after 120 min, a little improvement over the use of MnO₂. The utilization of both nanomaterials under continuous cycles indicated that there was a continuous loss of the activity after five cycles, being more displayed in the case of MnO₂ than in the TiO₂-MnO₂ material.

Titanium dioxide nanoparticles (spherical shape) were formed, using leaf extracts of a sausage tree (Kigelia Africana), and evaluated for the photocatalytic degradation of Toluidine Blue [156]. This nanomaterial removed the dye with a 99.6 % efficiency within one hour and under an UV–visible source.

A MoS₂/FeMoO₄ composite was formed by introducing MoS₂ (which actuate as inorganic promoter) into MIL-53(Fe)-derived PMS-activator [157]. The prepared MoS2/FeMoO₄ activated peroxymonosulfate (PMS) to reach 99.7% of Rhodamine B degradation after 20 min. Both Fe(II) and sulfur vacancies were responsibles as the main active sites on catalyst surface, where sulfur vacancies can promote adsorption and electron migration between PMS and MoS₂/FeMoO₄ to boost peroxide bond activation.

Rough copper oxide with a nanostructural morphology and located on the surface of a copper sheet was formed by an electrochemical anodic oxidation procedure; these nanostructures were used in the degradation of Rhodamine 6G under the irradiation of visible light [158].

Silver-doped borophene and the corresponding zero-dimensional boron were constructed [159]. They were used to investigate its performance on the photocatalytic degradation, under UV-visible irradiation, of Rhodamine B. The dye completely degraded after 120 min, though a small but continuous decrease in the efficiency after the 2nd and 3rd cycles was shown.

The same dye (Rhodamine B), than in the previous reference, was photocatalytic degraded by the action of Bi₂O₃@Zn-MOF hybrid nanomaterials, which were synthesized by supporting Zn-based metal-organic framework (Zn-MOF) through a hydrothermal process [160]. A catalytic efficiency of 97% was reached after 90 min of exposure to visible light irradiation. Generation of free radicals (·O₂^- and ·OH) was responsible for the decomposition of the dye into CO₂ and water. The nanocomposite can be reused three times, though the degradation efficiency decreased to 78 %.

MnS₂/MnO₂-CC heterostructure dual-functional catalysts formed of ultrathin nanosheets were prepared by a two-step electrodeposition method for used in the degradation of Methylene Blue [161]. The dye removal efficiency of the heterostructural catalyst with a better kinetic rate (0.0226) can reach 97.76%, which is much higher than that of the MnO_x-CC catalyst (72.10%).

Based on the biopolymer pomelo peels (PP) and metal-oxide catalyst manganese oxide (MnO_x), an adsorption-enhanced catalyst (MnO_x-PP) was constructed for catalytic Methylene Blue oxidative-degradation [162]. The dye was adsorbed onto the biopolymer and then the continuous generation of active substances (O₂^· and OH^·) degraded via an oxidative process the adsorbed dye molecules. Methylene Blue was degraded at a 99.5% rate at 25º C and one hour, with a slight (5%) but continuous dynamic degradation efficiency during 72 h based on the self-built continuous single-pass dye purification device.

3.4. Remarks to the Use of Nanomaterials in the Removal of Cationic Dyes from Solutions

In the case of cationic dyes, the use of (photo)-catalysis methodology surpass the utilization of adsorption-elution processes to remove these harmful dyes. A new approach, as being the formulation of nanomaterials-bearing mixed matrix membranes has been developed for the removal of cationic dyes (Methylene Blue) from a simulated wastewater. Similarly to the case of anionic dyes, it is extremely subjective, independently of the used methodology, to compare one nanomaterial from another due to the various experimental conditions used in the works. In the case of (photo)-catalytic approaches, times to degrade the very same dye varies from 10 min to 3 hours (Methylene Blue) or 12 min to 3 hours (Rhodamine B), whereas in the case of adsorption processing the dye uptakes also show a variety of numbers. Table 7 showed a list of dyes used in the various investigations. In the case of cationic dyes, Methylene Blue is the dye most investigated using any removal methodology. Table 8 summarized some results about efficiencies found in the removal of Methylene Blue or Rhodamine B using the (photo)-catalytic approach, it can be seen that efficiencies in the removal of these dyes ranged from a few minutes to hours. It is also worth to notice here that despite the good removal characteristics of the different nanomaterials, very few show significant stability under continuous use. Also, no one of these investigations used real wastewaters.

4. Nanomaterials for the Removal of Anionic and Cationic Dyes

To mark some difference with the previous Sections in which nanomaterials were developed to remove anionic or cationic dyes, some scientists developed nanomaterials to be applied on the removal of both anionic and cationic dyes from solutions. This Section reviewed the performance of such nanomaterials with double use.

4.1. Adsorption of Anionic and Cationic Dyes on Nanomaterials

Black Liquors-based aerogels with Carbon Nanostructures (BL-CN), performance against dyes uptake, was compared with that of Carbon Nanostructures aerogels (CN) without the presence of Black Liquors [163]. Experimental results concluded that BL-CN aerogels presented better adsorption loadings of Methylene Blue and Brilliant Blue than those produced by CN-based aerogels: 256 mg/g (CN) versus 307 mg/g (BL-CN) for Methylene Blue, and 7 mg/g (CN) to 61 mg/g (BL-CN) for Brilliant Blue. BL-CN materials from pulping of RS with alkaline reagents (NaOH and KOH–NH₄OH) were the basis for the best Methylene Blue adsorbents, whereas best Brilliant Blue uptakes were obtained with BL-CN adsorbents from sulfite reagent.

Next reference [164], investigated the performance of biological graphene hydrogel (BGH) formed by Shewanella putrefaciens CN32 on the removal of Methyl Orange and Methylene Blue. Using BGHs and 24 hours of reaction time, removal efficiencies reached near 93% and 91%, for the respective anionic and cationic dye, increasing the efficiency with respect to the use of non-graphene materials. No data about the recyclability of the nanomaterial.

Carbon dots/silica nanoaggregates for dye adsorption were synthesized via a hydrothermal reaction of N-doped carbon dots with (3-aminopropyl)triethoxysilane. With experimental data fitted to the Langmuir isotherm model, these nanoaggregates presented adsorption uptakes of 1327 mg/g for Alizarina Red S and 4091 mg/g for Malachite Green [165].

The next reference [166], presented a machine learning investigation about the adsorption of organic dyes onto nanozeolites and to conclude which variables influenced their adsorption uptake from wastewater. Four ML algorithms (Random Forest, Light Gradient Boosting, eXtreme Gradient Boosting, and Artificial Neutral Network) were tested as regression models, with XGB presenting the best usefulness in terms of prediction of the adsorption uptake of nanozeolite from a relatively small dataset. The data concluded that cationic dyes (Crystal Violet and Acridrine Orange) uptake (about 12 mg/g) are much better than that of anionic dyes (less than 0.5 mg/g) on these nanoadsorbents.

Cellulose was obtained, from coconut husk fiber, via an alkali-acid hydrolysis procedure with formation of nano-crystalline cellulose (NCC), presenting spherical shape with diameters below 40 nm [167]. NCC was investigated for its adsorption capacity against various dyes, being the removal efficiencies near 91% for Methylene Blue and 90% for Congo Red at all the pH values, with the adsorption of Crystal Violet reaching a maximum at pH 9, and the corresponding to Methyl Red at pH 5.

Spirulina-mediated titanium oxide nanoparticles (STONPs) were fabricated and used to investigate its performance on the adsorption of Methyl Orange and Malachite Green [168], and whereas Methyl Orange was best remove from the solution at pH 4, the pH value for the maximum Malachite Green removal was 12. The maximum uptake using the Langmuir isotherm model was 272.5 mg/g and 209.6 mg/g for the respective above dyes. There was a continuous and important lost of removal efficiency after five cycles.

4.2. Nanomaterials–Forming Membranes for the Removal of Anionic and Cationic Dyes

An MXene nanocomposite functionalized with a zwitterion (Z-MXene) was fabricated to be used as nanofiller in the development of self-cleaning permeable membranes [169]. The presence of functional groups and negative charge on the nanocomposite surface improved the separation of Congo Red and Methylene Blue by near 275 and 400%, respectively; at the same time, a high water flux was maintained. The composite membrane is chemically stable in the presence of corrosive (2 M HCl) and oxidative (NaOCl) media.

A polyacrylonitrile (PAN) electrospun membrane was build as scaffold to incorporate nanomaterial adsorbents in a layer-by-layer hierarchical structure [170]. Two different nanomaterials were incorporated: a positively charged metal organic framework as MIL-101(Cr), and negatively charged functionalized multi-walled carbon nanotubes; these were used to remove anionic (Methyl Orange and Rose Bengal) and cationic (Methylene Blue) dyes. Operating at 0.04 bar, removal efficiencies of the membrane incorporating MIL-101(Cr) were 5% (Methyl Orange) and 99% (Rose Bengal) from an iso-propylic alcohol medium. MWCNT-based membrane showed 90% removal of Methylene Blue also in the same alcoholic medium, and operating at 0.07 bar.

Graphene oxide–copper oxide (GO–CuO) nanomaterial had been incorporated into cellulose-acetate (CA) and poly-ether sulfone (PES) blend polymer by using phase inversion process to fabricate thin film nanocomposite (TFN) membranes, which were used on the removal of Methylene Blue, Rhodamine B, Methyl Orange and Congo Red [171]. In equilibrium conditions, the composite membrane removed 92%, 89%, 59% and 68% of the above respective dyes; thus, the TFN membrane seemed to be more effective to remove cationic dyes than anionic ones. The membrane was also used on the purification of a textile industry effluent sample (with no mention of the dyes contained in it), an all physio-chemical properties of the sample showed a decrease in their values when compared to the respective ones of the laboratory synthetic effluent.

Heterojunctions formed by UiO-66-NH2 and carbon quantum dots (CQDs) to investigate their synergetic advantages as nanofillers in thin-film nanocomposite (TFN) membranes for dye removal were utilized [172]. Comparing to the pristine thin-film composite membranes, the optimal TFN membranes embedded with 0.2 wt% UiO-66-NH₂/CQD improved pure water permeance by 89.7% and higher rejection of dyes of different charges and molecular weights (Methylene Blue, Methyl Blue, Methyl Orange and Direct Red 23). Moreover, the decrease of water flux caused by dye adsorption during the long-term filtration process can be recovered by 92–99% via photocatalytic degradation of the embebbed dyes within 10 min.

4.3.(Photo)-Catalytic Degradation of Anionic and Cationic Dyes Using Nanomaterials

A mesoporous rod-shaped ZnO/CuO/CeO₂ n-p-n heterojunction via a two-step co-precipitation technique was formed, to investigate its use on the degradation of Crystal Violet and Methyl Orange [173]. Under sunlight, the degradation efficiencies were 96% (Crystal Violet) and 88% (Methyl Orange), after 90 min of irradiation. The ultimate oxidizing species that degraded the dyes were O₂^- and •OH over photocatalyst under sunlight illumination. Also, the recycling experiments showed that the nanomaterial maintained its activity after three cycles.

Lanthanum and neodymium substituted cobalt–strontium (Co–Sr) spinel ferrite (Co_0.5Sr_0.5RE_xFe_2-xO₄, x= 0.00 and 0.06) catalysts were synthesized and used to degrade Congo Red and Rhodamine B dyes from an aqueous solution mixture [174]. It was determined that the energy bandgap ranged from 2.91 to 2.52 eV. The formulation in which x= 0.06 presented the greatest degradation rates for both dyes, being the ferrite containing Nd³⁺ the species presenting the highest rates of all (Table 9).

α-Fe₂O₃ was built at the nanometer (nanofibers) level via the electrospinning procedure to yield a nanomaterial with advanced characteristics to be used as photocatalysts to degrade Rhodamine B and Methyl Orange dyes [175]. The nanofibers fabricated from FeCl₃·6H₂O presented the best photocatalytic degradation, under visible-light irradiation, against the presence of both dyes in solution. The iron source is the key to yield a photocatalyst with the best degradation properties.

A solvothermal method was used to form mesoporous TiO₂, and (1-3 wt%) Cu-doped mesoporous TiO₂ membrane. Using artificial light source exposures, the effectiveness of the above materials on the degradation of Congo Red and Methylene Blue was investigated [176]. Cu-doping shifted the light absorption of mesoporous TiO₂ from the ultraviolet to the visible region. 3wt% Cu-doped mesoporousTiO₂ photocatalyst showed lower band gap energy (2.6eV) than TiO₂ (3.2 eV), thus, allowing the use of solar energy, and the exposure was shifted towards the visible region. Congo Red was degraded a 61% using mesoporous TiO₂ material, whereas the degradation reached 99% under the use of 3 wt% Cu-doped mesoporous TiO₂ material and pH of 5, in both cases the light exposure time was of 50 min. In the case of Methylene Blue, maximum degradation (95%) occurred at a pH value of 9.

It was investigated [177], the usage of Au/WO₃ composite as a photocatalyst for the degradation of dyes under solar light irradiation. Au/WO₃ nanocomposites (nanoplatelets and pseudospheres) were synthesized using an acid precipitation method followed by an impregnation/reduction at room temperature. The derived composites were formed with gold nanoparticles of 7 nm in size, whereas W(VI) was reduced to the W(V) oxidation state, and favouring the presence of oxygen vacancies and the presence of a surface plasmon resonance effect at 540 nm. At pH 5, the degradation produced with these Au/WO₃ photocatalysts was highly efficient on cationic dyes (Methylene Blue and Rhodamine B) rather than in Methyl Orange (anionic dye). Au/WO₃ forming pseudospheres, was the most efficient degrading material towards cationic dyes (near quantitative degradation at 60 min and 90 min for Rhodamine B and Methylene Blue, respectively). In the case of Methyl Orange, the gold-tungsten oxide was totally useless, at alkaline pH values, to degrade the dye, but at acidic pH values the degradation of the dye reached 80%.

Chitosan capped silver nanoparticles (Ag NPs-CS) adsorbents to remediate dye pollution had been photochemically formed under direct sunlight [178]. An aqueous Ag NPs-CS (100 μg/mL) degraded more than 95% of a mixed dye solution (25 mg/mL) containing equal volumes of Rhodamine B, Methylene Blue and Methyl Orange.

ZnO and Ag/ZnO nanocomposites were fabricated from Basella alba aqueous leaf extract. The Ag/ZnO nanocomposite showed degradation properties against the presence of Rhodamine B, Methylene Blue, and Methyl Orange, being the degradation efficiencies of 88%, 90%, and 92% for the respective dyes [179].

Copper-based organic@inorganic hybrid nanoflowers (Cu-hNFs) were obtained from Tornabea scutellifera lichen extract as the organic component [180]. Catalytic activity was show against Methylene Blue (maximum degradation effectiveness at pH 7.4) and Brillant Blue (best removed at pH 5). Both dyes degraded via a Fenton-like process.

α-MoO₃ nanoparticles synthesized by chemical co-precipitation were used as photocatalysts on the degradation of Methyl Orange and Methylene Blue under visible light exposure. Maximum degradation efficiencies reached 73% (anionic dye) and 95% (cationic dye) after 90 min [181].

Three commercially available ZnO powders were used for the tribocatalytic degradation of Rhodamine B, Methyl Violet, Methyl Blue and Methyl Orange dyes [182]. The removal of Rhodamine B reached near 99% efficiency after two hours, whereas after five hours of reaction time, the catalytic efficiencies in the removal of the separate dyes, followed the next order: Methyl Violet (99%)>Methyl Orange (85%)>Methyl Blue (55%). In the process, h+, ·O₂^- and ·OH were generated, these radicals being responsible for the degradation of the respective dyes.

Bimetallic oxides were formed after the calcination of nanomaterials derived from metal-organic frameworks. When, Mn(M)-BTC nanomaterials was doped with Cu²⁺, Fe²⁺, Ce³⁺ or trimesic acid (H₃BTC), several derivatives were formed, being the material containing Cu²⁺, the nanomaterial which presented the best degradation efficiency of several dyes: Methylene Blue, Rhodamine 6G, Eosin Y and Gentian Violet, in all these cases, the degradation efficiency was above 95% [183].

Semiconductor heterojunction systems of C-modified Zn-doped TiO₂ composite nanomaterials with nanofiber structures (150-200 nm diameter) were synthesized by electrospinning and hydrothermal methods [184]. Against the presence of Methylene Blue, Methyl Orange, Rhodamine B and Malachite Green, the composite nanofiber film had photocatalytic activity for all dyes attributable to the large specific surface area, small size effect and synergistic effects of multiple heterojunctions and dopant atom. The removal efficiency followed the Malachite Green>Methylene Blue>Methyl Orange>Rhodamine B order, being Methyl Orange efficiently removed with just 15 minutes.

Hybrid multifunctional nanoplexes composed of ZnS semiconductor quantum dots (ZnS QDs) chemically biofunctionalized with ε-poly-L-lysine (ɛPL), and coupled with magnetic iron oxide nanoparticles (MION, Fe₃O₄) stabilized by carboxymethylcellulose (CMC) were fabricated [185]. These nanoplexes were used to investigate its photocatalytic activity in the presence of Methylene Blue, Methyl Orange, Congo Red, and Rhodamine dyes. Degradation occurred via oxidation of the dyes by ·O₂^-and ·OH radicals, and also by oxidation of dyes by holes:

Z n S Q D {(h}_{V B}^{+}) + d y e \to d e g r a d a t i o n b y - p r o d u c t s

(1)

In this investigation [186], ZnO nanoparticles (average size 15-30 nm) were synthesized by biosynthesis using dried Peumus boldus leaves. The photocatalytic activity of these nanomaterials indicated that it is possible the quantitative degradation of Methylene Blue in three hours, 92% in the case of Methyl Orange also in the same time, and 100% degradation of Rhodamine B in 30 minutes.

A n-type semiconductor as ZnO were coupled to a p-type one as CuO to form a p-n heterojunction. Further, the active surface of the heterojunction was increasedby addition of SiO₂-Aerogel [187]. By application of ultrasound, aerogel particles were better distributed, which the number of active sites were increased. CuO-ZnO/SA(P= 200) formulation (1 g/L) photocatalytically degraded 20 mg/L of each dye at pH 8: 95.4% in the case of Methylene Blue, whereas Methyl Orange degraded 56.1% and Congo Red until 71.3%. In the case of Methylene Blue, there was a continuous loss of efficiency after four cycles: 90.6% in the first cycle versus 78% in the fourth one.

Several materials such as, graphene oxide, magnetite-(FeO·Fe₂O₃), and hematite-(α-Fe₂O₃) decorated graphene oxide were investigated as Integrated Photocatalyst Adsorbents (IPCAs) in the oxidation of Methylene Blue, Crystal Violet and Tartrazine Yellow [188]. The cationic dyes showed maximum degradation, whereas the anionic dye presented acceptable removal rates when iron-decorated nanomaterials were used. In these cases, the efficiency order was: graphene oxide-αFe₂O₃>graphene oxide-Fe₃O₄>graphene oxide. All the nanomaterials maintained their photocatalytic activity for five cycles with dyes removal in the 86%-95% range.

Zinc selenide nanomaterials, produced from waste peels of orange and potato using the hydrothermal method, were utilized as photocatalysts to degrade Methylene Blue and Congo Red using sunlight [189]. Citrate in orange peel–mediated synthesis helped to form particle size of 1.85 nm and a surface area of 17.078 m²/g, resulting in an increase of surface-active sites. These nanomaterials had a degradation efficiency of 97.16% and 93.61% for Methylene Blue and Congo Red, respectively.

Magnetic SiO₂ (MagSiO₂@PDA@MnO₂) were synthesized using magnetic, monodisperse-porous SiO₂ (MagSiO₂₎ as the starting material [190]. MagSiO₂@PDA@MnO₂ material was used to remove Rhodamine B, Methyl Orange and Methylene Blue, being the removal of the dyes attributable both, to physical adsorption and degradation via peroxymonosulfate activation. Removal efficiency followed ethylene Blue>Rhodamine B>Methyl Orange sequence, whereas the dyes removal rate showed that the degradation occurred viaphysical adsorption and peroxymonosulfate oxidation. After five cycles, there was a small decrease in the dyes removal efficiencies probably due a decrease in the manganese content of the material.

Silver nanoparticles (AgNPs) were synthesized from Echinophora platyloba plant extract, which acted as both reducing agent and capping agent in the synthesis of the nanoparticles [191]. It was found that pH played a key role in determining particle sizes, which can be tuned from 15 nm to 53 nm when the pH decreased from 10 to 7. AgNPs (15 nm) showed remarkable catalytic performance in degradation of different individual azo dyes (i.e. Methylene Blue (90.1%), Congo Red (80.1%), Rhodamine B (87.2%), Methyl Red (80.3%), Bromocresol Blue (92.5%) and Imido Black (79.8%)), as well as their mixture. It was found, that 79.2% of the mixture of dyes were decomposed in eleven minutes, following a pseudo-first order kinetic model.

Sunlight-active n–n heterojunction of TiO₂-coupled-CdS (TiO₂-CdS) was prepareded by using seed extract of Sapindus mukorossi and investigated in the removal of Rhodamine B and Congo Red [192]. The nanocomposite presented degradations of 93% and 95% for the above respective dyes, under the next experimental conditions: 25 mg/L dyes concentration, 15 mg of nanocomposite dosage, neutal pH and five hours of reaction time. Under continuous use (eight cycles of dye uptake and degradation), there was a continuous but slight efficiency lost in the treatment of both dyes, better displayed in the case of Rhodamine B than in Congo Red.

A solvothermal procedure converted electrical furnace slag into a steel slag nanocomposite (average particle size 34.8 nm), which were supported by H₂O₂ for Fenton and photo-Fenton-like degradation of various dyes in both suspension and spin-coated modes [193]. Using Methylene Blue and based on the optimum dye removal conditions (30 mg/L dye concentracion, pH 11, 1.59 mL/L H₂O₂ concentration, 58.1 mg/L nanocomposite dosage, and one hour) five cycles were carried out for suspension and spin-coated modes. In the fifth cycle, resulting data showed that 92.89% of dye degraded for suspension mode and 88.21% for spin-coated mode. At pH 7 and 30 mg/L of each dye, the photodegradation efficiency of Methylene Blue, Methyl Red, Rhodamine B, Congo Red, Acid Blue 25, and Methyl Orange depended largely on the type of dye, with cationic dyes removed more efficiently than anionic ones (Table 10).

Different heterogeneous photocatalysts composed of highly reduced graphene oxide (HRG) and vanadium oxide (VO_x)-based nanocomposites (HRG-VOx) were formed (nanorods, nanosheets and urchins), and their photocatalytic activities to photodegrade Methylene Blue and Methyl Orange were investigated [194]. Among all the morphologies, nanocomposite consisting of urchin-shaped VO_x nanoparticles (HRG-VO_x-U) demonstrated superior photocatalytic properties towards the degradation of the dyes (99.1% for Methylene Blue after 45 minutes, and 97.2% for Methyl Orange after 35 minutes). After three cycles and under UV-light irradiation, there was a continuous lost in the efficiency of Methylene Blue degradation.

A supramolecular material (3-4 nm average particle diameter) formed by the hybridization of hydrophilic hydrazide-pillar[5]arene, as surface-modifier, and silver nanoparticles was used in the reduction of Methylene Blue, Rhodamine B, Rhodamine 6G, and Methyl Orange [195]. After five cycles of continuous use, the degradation efficiency was maintained almost constant in the case of Rhodamine B and Methyl Orange dyes, but suffered a continuous lost in the case of Rhodamine 6G (most notably) and Methylene blue.

ZnO nanoparticles (10 nm), as photocatalyst material, were used to degrade Remazol Brilliant Blue R and Brilliant Green [196]. Zinc acetate, sodium hydroxide, polyvinylpyrrolidone and ethylene glycol at 197° C formed the nanoparticles. After 90 min of reaction time, 500 ppm of ZnO degraded 73% and 51% of the respective above dyes.

MgO–ZnO (MZ) nanocomposite (nanoplates with 35-100 nm of thickness) was prepared by a co-precipitacion procedure with enhanced photodegradation properties under natural sunlight exposure [197]. Both cationic and anionic dyes were used in the degradation experiments, and it was found that both types of dyes completely degraded after 20 min of sunlight exposure. After five cycles of use, Rhodamine B, Methyl Orange, and Methylene Blue presented variations in their degradation efficiency: 96-91%, 91–85% and 98–92%, respectively.

Another nanomaterial, with photodegradation properties under sunlight exposure, to degrade cationic and anionic dyes, was used in the next investigation [198]. In this case, the material was a ZnO/CuO nanocomposite, with ZnO and CuO nanoparticles, and the cationic dyes were Methylene Blue and Rhodamine B, whereas Methyl Orange was the anionic dye used in the investigation. ZnO and CuO nanoparticles had been synthesized by a biosynthesis procedure using Ficus benghalensis leaf extract, whereas the nanocomposite was fabricated by the mortar pestle crushing/milling method. As it was somewhat expected, the efficiency of the nanocomposite to degrade the three dyes was higher than that yielded by the use of the single oxides. Using the nanocomposite during three hours and sunlight exposure, Methylene Blue degrades about 99%, against 80% of Rhodamine B and 67% of Methyl Orange.

Potato-on-rod-like Z-scheme plasmon Ag₂CrO₄–Ag₂Mo₂O₇ heterojunction nano-photocatalyst was synthesized by precipitation method to photodegrade different organic dyes under artificial sunlight [199]. Under the best experimental conditions of 0.1 g dose of (3:1) nanophotocatalyst, 10 mg/L dyes concentration and 90 minutes of exposure to light, the above nanophotocatalyst formulation exhibited the greatest efficiency in the photodegradation of 2-Naphthol Orange (97.8%), Rhodamine B (99.7%), Crystal Violet (98.9%), and Methyl Orange (56.1%). In the case of 2-Naphtol Orange, the 3:1 catalyst formulation showed an acceptable reusability since the dye adsorption ran from 97.8% (1st cycle) to 95.7% in the fourth cycle.

One-step hydrothermal procedure were used to form Bi₂O_2.33//Bi₂O₃@ECNF (electrospun carbon nanofibers), which combines both adsorption and photocatalytic performance. The nanocomposite removed 95% of Methyl Orange and 83% of Rhodamine B after 2 and 3 hours, respectively. Both h⁺ and ·OH were the main active species in the photocatalytic process under light exposure [200].

4.4. Remarks to the Use of Nanomaterials in the Removal of Anionic and Cationic Dyes from Solutions

At a first instance, the uses of these nanomaterials have the advantage, over the utilization of nanomaterials with a single use, that they are triggered with a broad scope since they are useful to remove anionic as well as cationic dyes from solutions. However, they present somewhat the same negative characteristics than the others, especially to that refereed to their stability under continuous cycle, when this data are shown in the published manuscript, because in many of the reviewed references, authors did not mention this issue about their respective investigated nanomaterial. As in previous cases, comparison between the different nanomaterials is subjective due to the different experimental conditions, and in this case another variable must be considered: the different mixtures of dyes used in the investigations. As it is previously done, Table 11 summarized the methodologies used to remove the mixture of anionic and cationic dyes.

As an example of what it is mentioned above, using the same mixture (Methylene Blue, Rhodamine B and Methyl Orange) of dyes, results indicated that in [197] complete degradation of the dyes occurred after 20 min, against efficiencies of 99% (Methylene Blue), 80% (Rhodamine B) or 67% (Methyl Orange) in 3 hours declared in [198]. These last results hardly compared with data from [186], in which is demonstrated that Rhodamine B is completely eliminated after 30 min. Another mixture of dyes (Methylene Blue and Methyl Orange) show the same disparity in results, since 90 min are needed to remove 95% and 75% of the respective cationic and anionic dye [181], and 45 min (99% Methylene Blue) or 35 min ( 97% Methyl Orange) as concluded in [194].

Conclusions

This review emphasized the importance that the removal or organic dyes from solutions have on the scientific community; in this removal, two approaches are followed: adsorption or catalytic-photocatalytic degradation of the dye, whereas the use of nanomaterials is of widespread use.

In the case of adsorption methodology, all the references reviewed but two fitted its experimental data to the Langmuir isotherm model, the two exceptions are references [102] and [109] which fitted its data to the Freundlich isotherm. However, these nanomaterials performed quite different in the removal of both cationic and anionic dyes, and within the very same dye, as results in Table 12 demonstrated in the case of the adsorption of Congo Red and Methylene Blue. In the case of the anionic dye, maximum loadings vary from a few mg/g to the g/g magnitude order, whereas in the case of Methylene Blue the tendency is the same. These variations can be generalized to other dyes.

With these results, it is amazing that some authors expressed their data as 8300 mg/g instead of the more logical 8.3 g/g form.

In the utilization of (photo)-catalytic methodology the results have the same tendency as those showed in Table 12 and commented in subsection 2.3. (Table 5), subsection 3.4. (Table 8) and text on subsection 4.4. The efficient in the removal of a given anionic or cationic dye is reached after minutes or several hours depending of the nanomaterial used. In the opinion of the present authors, other considerations (see below) may be taking into account prior to select one or another nanomaterial for each specific use or the methodology used to carry out this removal.

A point to consider is the tendency that some authors provided data with little scientific sense, as it is exemplified with the values of the thermodynamic data calculated from selected references (Table 13).

As it is seen, values are given within three-four decimals which does not correspond with the accuracy of the methodology used to calculate such numbers, also the responsibility to publish such values is not only of the authors but also of the respective reviewers (and Editors) allowing to do this.

Since the removal of dyes from solutions is of the utmost interest, future trends may be focused in: i) the development of more stable nanomaterials to be used in cycles (a general rule observed in this review is that there is a loss of efficiency with continuous cycles), ii) investigations of the use of nanomaterials on real dye-bearing wastes (in this review just only two, [58] and [171], references use industrial wastewaters in the investigation, iii) the use of dynamic conditions (columns) in the removal of dyes, and iv) a reliable knowledge about the easiness and costs to fabricate the nanomaterials in a greater scales than laboratory one. All the above will be key-points to understand the performance of the nanomaterials in the selected technology under long-term use.

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Figure 1. Influence of the calcination temperature on Basic Fuchsin uptake. From [98].

Figure 2. Efficiency in the removal of Methylene Blue (MB), Methylene Violet (MV) and Brilliant Green (BG), after 24 hours, with different FePt/h-BN heteromaterials. BN: boron nitride. FPB: as-synthesized. FPB500: annealed at 500º C. FPB700: annealed at 700º C. From [103].

Table 1. Some recent reviews about the use of nanomaterials on the removal of organic dyes from solutions.

Nanomaterial	Reference
Heteropolyacids-supported on nanocatalysts Nanomaterials Bi-based nanocompounds Graphitic carbon nitride Sr-based nanomaterials Nano-metal oxides-activated carbon TiO₂-based nanomaterials Nanoparticle-hybridized polyaniline Metal ferrites-based nanomaterials Metal sulphides-based nanostructures Polymeric nanocomposite membranes Metals and metals oxides in pure form Graphene-based nanomaterials Cellulose-based nanocompounds Biomass-metallic nanoparticles Nanozymes 2D MXene-based adsorbents Ba-TiO₃ nanomaterials Gum-based nanomaterials Chitosan-based nanomaterials Carbon-based nanomaterials	[1] [2,3,4,5,6,7,8] [9,10,11] [12,13] [14] [15] [16,17,18,19] [20] [21] [22,23] [24,25] [26,27,28,29,30] [31,32] [33,34,35] [36] [37,38,39,40] [41,42,43] [44] [45] [46] [47,48]

Nanomaterial

Reference

Heteropolyacids-supported on nanocatalysts
Nanomaterials
Bi-based nanocompounds
Graphitic carbon nitride
Sr-based nanomaterials
Nano-metal oxides-activated carbon
TiO₂-based nanomaterials
Nanoparticle-hybridized polyaniline
Metal ferrites-based nanomaterials
Metal sulphides-based nanostructures
Polymeric nanocomposite membranes
Metals and metals oxides in pure form
Graphene-based nanomaterials
Cellulose-based nanocompounds
Biomass-metallic nanoparticles
Nanozymes
2D MXene-based adsorbents
Ba-TiO₃ nanomaterials
Gum-based nanomaterials
Chitosan-based nanomaterials
Carbon-based nanomaterials

[1]
[2,3,4,5,6,7,8]
[9,10,11]
[12,13]
[14]
[15]
[16,17,18,19]
[20]
[21]
[22,23]
[24,25]
[26,27,28,29,30]
[31,32]
[33,34,35]
[36]
[37,38,39,40]
[41,42,43]
[44]
[45]
[46]
[47,48]

Table 2. Percentage of reusability of SONO-CFL/CN nanomaterial.

Cycle	Adsorption	Sono-sorption
1st 2nd 3rd 4th	78.4 60.4 59.9 57.4	96.2 87.6 76.5 74.7

1. Experimental conditions: 0.02 g adsorbent/50 mL solution. Time: 30 min. Temperature: 25º C. Initial dye concentration: 20 mg/L. pH: 2.0±0-5. From [53].

Table 3. Dyes uptake (mg/g) using zinc or copper ferrites in nanoparticulated form.

Nanoparticle	Alizarin Red S	Thiazol Yellog G		Congo Red	Methyl Orange
ZnFe₂O₄ CuFe₂O₄	54.6 46.4	37.0 30.1	29.8 21.9		26.8 20.8

From [58].

Table 4. Summary of the use of nanomaterials in the removal of anionic dyes.

Methodology	Anionic dye	Reference
Adsorption	Acid Yellow 36, Acid Orange 6 Reactive Red 21, Reactive Blue 19 Congo Red Alizarin Red S Reactive Yellow 145, Reactive Red 195 ^aVarious (industrial wastewater) Methyl Orange Congo Red, Brilliant Blue G-250	[49] [50,52,55] [51,54,56,57,60,61,62,63] [53] [55] [58] [59] [63]
-	Congo Red, Alizarin Red S Methyl Orange Brilliant Blue Reactive Red, Orange II Orange G Congo Red,Methyl Red Reactive Black 5 AR88 Napthol Blue Black Auramine O, Xylenol Orange Tripan Blue Red 195	[64,65,67,71,72,73,79,80,83,88,90] [66,67,68,70,71,74,75,76,81,82,85,86,87,91], [94] [69] [77] [78] [79] [84] [89] [92] [93] [95] [96]

^a Alizarin Yellow R, Thiazole Yellow G, Congo Red, and Methyl Orange.

Table 5. Some efficiencies in the removal of anionic dyes using (photo)-catalysis.

Dye	Nanomaterial		Efficiency-time	Reference
Congo Red Methyl Orange Reactive Red Orange II Tripan Blue		Cu oxide nanoparticles ZnO-CuFe₂O₄-CNTs Eu-TiO₂ N-Ti₃C₂MXene Y₂O₃-SiO₂ Various nanomaterials Carbon dots Biochar-BiOCl Ag-Fe₂O₃ Ag-Fe₂O₃ Cd,Ti oxides-Ionic liquid	93%-2 hours 82%-2 hours 97%-75 min 98%-20 min 52%-45 min 67%-3 hours 98%-7 hours 100%-1 hour 98%-2 hours 98%-2 hours 100%-1 hour	[64] [65] [88] [70] [76] [84] [87] [94] [77] [77] [95]

Table 6. Percentage of degradation, under UV-visible light, of Methylene Blue using various Bi_xSn_6-2xS_y formulations.

Material	0 hours	10 min	0.25 hours	1 hour	3 hours
SnS Bi_0.3Sn_5.34S_5.8 BiSn₄S_5.5	0 0 0	no data no data 100	68 43 100	86 50 100	93 82 100

From [139].

Table 7. Summary of methodologies and cationic dyes used in the investigations.

Methodology	Cationic dye	Reference
Adsorption	Crystal Violet Basic Fuchsin Golden Yellow, Methylene Blue Basic Red 114 Malachite Green Methylene Blue, Methylene Violet, Brilliant Green Toluidine Blue O Rhodamine B	[97] [98] [99,101,103,105,106,107,108] [100] [102,109] [103] [104] [107]
Membranes	Methylene Blue	[110]
(Photo)-catalysis	Methylene Blue Rhodamine B Malachite Green Crystal Violet Toluidine B Rhodamine 6G	[111,112,113,115,116,117,118,119,120,123,124,125,126,127,130,132,136,137,138,139,140,141,143,145,146,149,150,151,152,153,154,155,161,162] [114,115,118,122,123,128,129,130,131,134,135,147,148,151,154,157,159,160] [117,121,133,151] [121,123,142,144] [156] [159]

Table 8. (Photo)-catalytic removal of Methylene Blue and Rhodamine B.

Dye	Nanomaterial	Efficiency-time	Reference
Methylene Blue Rhodamine B	Mn₄(P₂O₇) Ce-Co,Fe ferrites La-Co,Fe,Ti composite Fe₃O₄@APF@Ag Mixed Fe,Mn,Cu oxides AgCrO₄-rGO CuO-SnO₂ NiMn₂O₄ CO-CQ dots Fe₃O₄@APF@Ag AgO nanoparticles Fe₃O₄ nanoparticles g-C₃N₄ NiMn₂O₄ Mo,Fe-sulphur-oxide	99%-30 min 95%-1 hour 99%-50 min 90%-3 min 95%-2.5 hours 92%-1 hour 90%-3 hours 68%-3.5 hours 100%-25 min 90%-3 min 76%-1 hour 85%-12 min 95%-3 hours 81%-3.5 hours 99.7%-20 min	[113] [116] [120] [130] [132] [136] [140] [148] [152] [130] [131] [135] [147] [148] [157]

Table 9. Percentages of dyes degradation using various Co_0.5Sr_0.5RE_xFe_2-xO₄ formulations.

Nanomaterial	Congo Red	Rhodamine B
Co_0.5Sr_0.5Fe₂O₄ Co_0.5Sr_0.5La_0.06Fe_1.94O₄ Co_0.5Sr_0.5Nd_0.06Fe_1.94O₄	73 81 90	45 67 85

Time: One hour. From [174].

Table 10. Efficiency in the removal of dyes with the steel slag nanocomposite.

Dye	% Efficiency
Methylene Blue Methyl Red Rhodamine B Congo Red Acid Blue 25 Methyl Orange	85.8 74.5 70.5 58.7 45.2 40.4

Time: one hour. Neutral pH. From [193].

Table 11. Summary of methodologies and anionic and cationic dyes used in the investigations.

Methodology	Dyes	Reference
Adsorption	Methylene Blue, Brilliant Blue Methyl Orange, Methylene Blue Alizarin Red S, Malachite Green Crystal Violet, Acridine Orange MB.CR,CV,MR Methyl Orange, Malachite Green	[163] [164] ` [165] [166] [167] [168]
Membranes	Congo Red, Methylene Blue MO,RB,MB MB,RhB,MO,CR MB,MeB,MO	[169] [170] [171] [172]
(Photo)-catalysis	Crystal Violet, Methyl Orange Congo Red, Rhodamine B Rhodamine B, Methyl Orange Congo Red, Methylene Blue MB,RhB,MO Methylene Blue, Methyl Orange Methylene Blue, Brilliant Blue RhB,MV,MeB,MO MB,RhB,EY,GV MB,MO,RhB,MG MB,MO,CR,RhB MB,MO,CR MB,CV,TY MB,CR,RhB,MeR MB,MeR,RhB,CR,AB25,MO MB,RhB,Rh6G,MO RBBR,BG NO,RhB,CV,MO Methyl Orange, Rhodamine B	[173] [174,192] [175] [176,189] [177,178,186,190,197,198] [179,181,194] [180] [182] [183] [184] [185] [187] [188] [191] [193] [195] [196] [199] [200]

AB25: Acid Blue 25. BG: Brilliant Green. CR: Congo Red. CV: Crystal Violet. EY: Eosin Y. GV: Gentian Violet. MB: Methylene Blue. MeB: Methyl Blue. MeR: Methyl Red. MG: Malachite Green. MO: Methyl Orange MR: Methyl Red. MV. Methyl Violet. NO: Napthol Orange. RBBR: Ramazol Brillian Blue R. RhB: Rhodamine B. Rh6G: Rhodamine 6G. RS: Rose Bengal. TY: Tartarzine yellow.

Table 12. Some maximum capacities of dyes on nanomaterials. .

Congo Red, mg/g	Reference	Methylene Blue, mg/g	Reference
17.8 47.4 57.8 3017 4334 8300	[56] [51] [57] [60] [63] [62]	5.78 36.4 332 477 736	[118] [166] [105] [108] [101]

Table 13. Some strange thermodynamic values taken from the literature.

ΔH◦, kJ/mol	ΔS◦	Reference
-3.1689 54.996 3.568 7.09731	-0.0112 J/K·mol 0.283 kJ/K·mol 0.0278 kJ/K·mol 40.4502 J/K·mol	[101] [105] [108] [168]

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Removal of Hazardous Organic Dyes from Liquid Wastes Using Advanced Nanomaterials

Abstract

1. Introduction

2. Nanomaterials and Anionic Organic Dyes

2.1. Adsorption of Anionic Dyes on Nanomaterials

2.2. Photo)-Catalytic Degradation of Anionic Dyes Using Nanomaterials

2.3. Remarks to the Use of Nanomaterials in the Removal of Anionic Dyes from Solutions

3. Nanomaterials and Cationic Dyes

3.1. Adsorption of Cationic Dyes on Nanomaterials

3.2. Nanomaterials–Forming Membranes for the Removal of Cationic Dyes

3.3.(. Photo)-Catalytic Degradation of Cationic Dyes Using Nanomaterials

3.4. Remarks to the Use of Nanomaterials in the Removal of Cationic Dyes from Solutions

4. Nanomaterials for the Removal of Anionic and Cationic Dyes

4.1. Adsorption of Anionic and Cationic Dyes on Nanomaterials

4.2. Nanomaterials–Forming Membranes for the Removal of Anionic and Cationic Dyes

4.4. Remarks to the Use of Nanomaterials in the Removal of Anionic and Cationic Dyes from Solutions

References

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