1. Introduction
Usually in the field of inorganic pigments metal oxides are closely attached to the subject, may it be by researching to synthetize new pigments by combination of chromo-phore, usually metals, with diverse support structures, example metal oxides, new syn-thetic routes, or optimization of already know pigments properties [
1,
2].
Recently the compound MgO have attracted great attention of scientists for his properties of diverse nanostructures, high surface area and nontoxicity [
3]. Thus, a vast number of applications are being explored on different fields such as catalysis [
4], superconductor [
5], biological activities [
6,
7,
8], treatment of wastewater [
9], pigments [
3] and others more. One of the common ways of obtaining MgO is related to Mg(OH)
2 calcination [
10]. It is related on literature that MgO and Mg(OH)
2 are interchangeable depending on the procedure of hydration or dehydration [
11].
According to by Wang
et al. [
12] organic-inorganic pigments utilizing Mg(OH)
2 pigment for modifying polymer silane and afterward grafting on cellulose fiber were explored. The study also comments on the Mg(OH)
2 characteristics as flame retardant, low toxicity and cost, and smoke suppressing ability. In the work at Primo
et al. [
13] reported the search for new eco-friendly routes to synthetize zinc oxides as being related with the use of natural additives for their capabilities in reducing calcination temperature and complexing gelling. A natural additive utilized on the route was cassava starch, a biodegradable polysaccharide from renewable raw material sources, consisting of amylose and amylopectin molecules that are composed of D-glucose units [
14].
Green is usually associated with nickel on octahedral sites as explained by Hajjajji
et al. [
15] when studying the synthesis of green olivine pigment (NiSiO
4) utilizing industry waste. Lately, the inorganic pigment academia field are researching NIR reflective pigments for their cooling abilities, and applications focus on roof paint [
16,
17]. Zou
et al. [
18] explain the influence of high nickel concentration may result in to increase of absorbance at NIR, which is not favorable for cooling action, nevertheless, nickel is a low-cost metal used as chromophore. Thus, doping BaTi
5O
11 with <10% concentration of nickel and the results obtained displayed high NIR reflection.
Hence, nickel is a metal chromophore utilized on the production of diverse inorganic pigments, and MgO properties form a promisor supporting structure, and up to this date no NiMg(OH)2 applications as a pigment were found on literature. Therefore, the objective of the paper is to synthesize NiMg(OH)2 green pigments and characterize these compounds evaluating the influence of precursor salt anion.
4. Discussion
A simple route for the synthesis of green pigments from nickel and magnesium oxide based on solution-base hydroxide formation. As presented by the XRD,
Figure 2, the structural crystalline phase identified was the brucite of Mg(OH)
2. Furthermore, β-Ni(OH)
2 is isostructural to Mg(OH)
2 [
6,
27]. The FTIR spectra (
Figure 5), demonstrates that the compounds are a solid solution of Ni
xMg
1-x(OH)
2 because the band 3691 cm-1 is correlating to the metal-O less covalency interaction, compared to β-Ni(OH)2, in which directly influences the O-H bond, in way it becomes less polarized with more concentration of Mg in the lattice, shifting the ν(OH) band to higher wavenumbers [
27]. Hence, the difference on electronegativity of Mg [
1,
2] and Ni [
1,
8] possibilities the exchange of Mg for Ni in the crystalline structure [
27].
Brucite is the mineral form of magnesium hydroxide [Mg(OH)
2]. It is associated as a product of modification of the periclase phase found in marble [
14]. Synthetic brucite is mainly used as a precursor to magnesia (MgO), an important refractory insulator [
36]. It can be used as a flame retardant because it decomposes thermally and releases water in a similar way to aluminum hydroxide and mixtures of Huntite and Hydromagnesite.
The impact of the precursor salts on the characterization of the compounds were analyzes. The acetate anion influences the crystalline lattice, producing a more amorphous compound [
26] as is document in literature for the β-Ni(OH)
2 , and shown on the diffractogram
Figure 2a, this being the resulting intercalation of the anion to the hexagonal structure [
5,
26]. Also is notable the appearance of the shoulder on peak at 2θ = 18° attributed to the shift on the (001) plane from the acetate intercalation [
5,
31]. Relating to the XRD data the FTIR bands,
Figure 5a, at 1568 cm
-1 and 1391 cm
-1 identifying ν(COO
-) symmetric and asymmetric vibration modes [
30,
31], reinforcing the evidence of intercalation of the acetate anion on the structure. Synthesis utilizing nitrate nickel salt interfered as well on the crystallinity of the material, with the appearance of a shoulder on the 2θ = 18° peak,
Figure 2c being this related to the presence of NO
3-, agreeing with the FTIR spectrum band of 1384 cm
-1,
Figure 5c, that are typical of Dh3 symmetry of free NO
3- on the interlayer of the lamellar structure [
31]. The chloride precursor produced the more crystalline compound when comparing the 100% peak at 2θ = 37° intensity and shape with the other precursors salts, Figure (b).
A morphological analysis,
Figure 3, of the Ni
xMg
1-x(OH)
2 compounds exhibit the granular arrangement of Mg(OH)
2 [
28]. Worth noting, the needle shape morphologies highlighted on
Figure 4, for chloride precursor compound, can correlate to formation of 1D-like structure from the hexagonal configuration already discussed in literature [
9,
37] . Hao
et al. [
37] explains that the mechanism for formation of nanotubes follows the pathway of ionization of Mg to Mg
+2, and the results of utilizing NaCl as electrolyte offered more efficiency in the formation for said morphology when comparing to NaAc. Therefore, the exchange of Ni for Mg on the lattice of the structure allied with the anion chloride maybe the responsible for this morphology appearance.
After examining the electronic spectra, Figure X, we can now again relate to the structure of the pigments, as explained by Qi
et al. [
33] the brucite β-Ni(OH)
2 the optical properties are based on the metal d-d orbitals of nickel, considering that it is surrounded by six O in a typical octahedral configuration, endorsing the Ni exchange with Mg at the structure.
The color of the pigments was characterized utilizing the Cie L*a*b*. Subsequently, MgO is a white powder [
38], the explanation is the Mg having no free electron to excite to 3s orbital after losing the two 3s electrons to form Mg-O bond, and the pigments present negative a*, at Cie L*a*b* color space this relates to intensity of green, thus confirming the Ni as the chromophore.
Regarding the application, some works, such as Balaba
et al. (2023) [
6], show that MgO has antimicrobial activity at a concentration of 400 μg.mL
-1 for
S. aureus, E. coli and
C. albicans; in comparison with this work, Ni
xMg
1-x(OH)
2(Cl) stands out, which had an inhibition at a concentration of 0.312 μg.μL
-1, showing a better bacteriostatic action for Gram-negative bacteria. This is considered a good result because the inhibition of Gram-negative bacteria is more complex.
Studies such as Murtaza et al. (2023) [
39] and Liao et al. (2023) [
34] show that MgO has better efficiency when combined with other compounds and still has a wide range of applications, such as an alternative therapeutic approach or for the treatment of plants with bacterial infections. In the work of Nguyen et al. (2018) [
41] on the study of the activity of the MgO compost, the inhibition activity was 1.0 mg.mL-1 for E. coli, 0.7 mg.mL-1 for S. aureus and 1.2 mg.mL-1 for C. albicans, respectively. When these values are compared with the data obtained in this work, it is observed that the MIC values were lower and that there is no need for such a high concentration to inhibit microbial growth, mainly considering that the doping with Ni and the anion of the compost interfere in the microbial inhibition activity, improving cytotoxic activity. For NPs (nanoparticles) of Ni(OH)2, the inhibition reaches 5 mg.ml-1, shown in the work of Chaudhari et al. (2022) [
42].