The adsorption capacity of biochar was greatly improved by heating activation of biochar with concentrated hydrochloric acid. There are hydroxyl, phenolic hydroxyl, cyclolide peroxide and other oxygen-containing groups in the modified biochar. The existence of these groups leads to different surface hydrophilicity and surface acidity of biochar, resulting in different surface charges. The surface negative charge of biochar modified by concentrated hydrochloric acid is greatly reduced, and the positive charge is increased, which enhances the adsorption of negatively charged nitrate ions. At the same time, in the process of heating activation, a large amount of cellulose decomposes, the surface sediment is reduced, and micro-pores are formed on the surface of biochar. In the process of high temperature activation, the surface area of biochar increased, the surface adsorption point of biochar increased, and the adsorption of nitrate by biochar increased[
52]. Substrate modification and bacterial modification were applied to the vertical flow constructed wetland (VFCW) to treat NH
4+-N, NO
3--N, TN, TP and COD. At the same time, the adsorption capacity of the matrix was greatly improved after the improved VFCW[
53]. The humic acid (HA) doped into activated carbon of biomass waste and modified biochar by phosphoric acid activation also had a good removal effect on heavy metals in water[
54]. The surface function and adsorption capacity of activated carbon can be improved by using phosphoric acid to activate biochar and in-situ modification[
19]. The coupled CW by chemical reduction and denitrification of biochar and iron microorganisms has a good effect on nitrate removal. When biochar was added to CW, the quantity and activity of microorganisms were further increased[
21]. During the modification process, iron will react with the surface of biochar to form a large number of particles, resulting in a rough surface of biochar and improved exchange capacity. At the same time, iron may block the pore structure of biochar and affect the adhesion of microorganisms, but large particles will form a thin layer of iron oxide on the surface of biochar, strengthening the adsorption and fixation of anions[
55]. Hydrochloric acid can reduce the negative charge on the surface of biochar, increase the positive charge, and improve the adsorption of anionic nitrate by enhancing the electrostatic attraction[
50]. The results show that when the ferric chloride modified biochar (Fe-B) is added to CW, when the hydraulic retention time (HRT) is 96h, the treatment effect of the wastewater with C/N less than 3 is particularly obvious. Biochar has a high adsorption capacity for NH
4+-N, and the iron-modified biochar also has a strong capacity for nitrification of NH
4+-N and microorganisms. At the same time, due to its physical and chemical properties, Fe-B can trap nitrite nitrogen well and improve its processing capacity[
21]. However, the iron ions produced by the modified biochar prepared by pyrolysis of ferric chloride will affect the water environment, and the excessive iron content will lead to the proliferation of iron bacteria, resulting in pipeline blockage[
52]. Modified biochar can also improve the quality of soil in CWs, promote the absorption of pollutants by CWs plants, and promote the growth of wetland organisms[
56]. The DOM released from porous biochar provides a good living environment and carbon source for microorganisms[
57]. Substrate adsorption and microbial degradation are the main mechanisms for pollutant removal in CWs, and the removal effect of TN in CWs is better through matrix modification by using biochar in aerobic zone and microbial modification by using denitrifying bacteria in saturated zone[
58]. The addition of amorphous Fe(OH)
3 to biochar modified system can provide stronger performance than wood chip system, reduce SO
42- production and increase the removal rate of nitrate nitrogen[
59].
Figure 2 shows the correlation mechanism of iron-modified biochar on CWs.