Edible fungus slag derived nitrogen-doped hierarchical porous carbon as a high-performance adsorbent for rapid removal of organic pollutants from water.

In this work, agricultural waste edible fungus slag derived nitrogen-doped hierarchical porous carbon (EFS-NPC) was prepared by a simple carbonization and activation process. Owing to the biodegradation and infiltrability of hyphae, this EFS-NPC possessed an ultra-high specific surface area (3342 m2/g), large pore volume (1.84 cm3/g) and abundant micropores and mesopores. The obtained EFS-NPC could effectively adsorb bisphenol A (BPA) with the maximal adsorption capacity of 1249 mg/g and the removal process reached 89.9% of the equilibrium uptake in the first 0.5 h. Besides, the EFS-NPC showed much better removal performance towards 2,4-dichlorophenol (2,4-DCP) and methylene blue (MB) than commercial activated carbons (Norit RO 0.8 and DARCO granular activated carbon). Furthermore, adsorption isotherms, thermodynamics and kinetics researches indicated that the adsorption process of BPA was monolayer, exothermic and spontaneous. This research has given evidence that the low-cost EFS-NPC can serve as a high-efficient adsorbent for removing organic contaminants from water.

[Oxidation Process of Dissolvable Sulfide by Manganite and Its Influencing Factors].

As one of the manganese oxides, which are easily generated and widely distributed in supergene environment, manganite participates in the oxidation of dissolvable sulfide (S²â»), and affects the migration, transformation, and the fate of sulfides. In the present work, the redox mechanism was studied by determining the intermediates, and the influence of initial pH and oxygen atmosphere on the processes were studied. The chemical composition, crystal structures and micromorphologies were characterized by XRD, FTIR and TEM. The concentration of S²â» and its oxidation products were analyzed using spectrophotometer, high performance liquid chromatograph and ion chromatograph. The results indicated that elemental sulfur was formed as the major oxidation product of S²â» oxidation, and decreased pH could accelerate the oxidation rate of S²â» in the initial stage, however, there was no significant influence on final products. Elemental S could be further oxidized to S2O3²â» when the reaction system was bubbled with oxygen, and manganite exhibited excellent catalytic performance and chemical stability during the oxidation of dissolvable sulfide by oxygen. After reaction of more than 10 h, the crystal structure of manganite remained stable.

[Lead adsorption and arsenite oxidation by cobalt doped birnessite].

In order to study the effects of transition metal ions on the physic-chemical properties of manganese dioxides as environmental friendly materials, three-dimensional nano-microsphere cobalt-doped birnessite was synthesized by reduction of potassium permanganate by mixtures of concentrated hydrochloride and cobalt (II) chloride. Powder X-ray diffraction, chemical analysis, N2 physical adsorption, field emission scanning electron microscopy (FE-SEM) and X-ray photoelectron spectra (XPS) were used to characterize the crystal structure, chemical composition and micro-morphologies of products. In the range of molar ratios from 0.05 to 0.20, birnessite was fabricated exclusively. It was observed that cobalt incorporated into the layers of birnessite and had little effect on the crystal structure and micromorpholgy, but crystallinity decreased after cobalt doping. Both chemical analysis and XPS results showed that manganese average oxidation state decreased after cobalt doping, and the percentage of Mn3+ increased. Co(III) OOH existed mainly in the structure. With the increase of cobalt, hydroxide oxygen percentage in molar increased from 12.79% for undoped birnessite to 13.05%, 17.69% and 17.79% for doped samples respectively. Adsorption capacity for lead and oxidation of arsenite of birnessite were enhanced by cobalt doping. The maximum capacity of Pb2+ adsorption increased in the order HB (2 538 mmol/kg) < CoB5 (2798 mmol/kg) < CoB10 (2932 mmol/kg) < CoB20 (3 146 mmol/kg). Oxidation percentage of arsenite in simulated waste water by undoped birnessite was 76.5%, those of doped ones increased by 2.0%, 12.8% and 18.9% respectively. Partial of Co3+ substitution for Mn4+ results in the increase of negative charge of the layer and the content of hydroxyl group, which could account for the improved adsorption capacity of Pb2+. After substitution of manganese by cobalt, oxidation capacity of arsenite by birnessite increases likely due to the higher standard redox potential of Co3+/Co2+ than those of Mn4+/Mn3+/Mn2+. Therefore, Co-doped birnessite is more applicable for the remediation of water polluted with heavy metal ions, implying new methods of modification of manganese dioxides in practice.

[Adsorption of heavy metals on the surface of birnessite relationship with its Mn average oxidation state and adsorption sites].

Adsorption characteristics of mineral surface for heavy metal ions are largely determined by the type and amount of surface adsorption sites. However, the effects of substructure variance in manganese oxide on the adsorption sites and adsorption characteristics remain unclear. Adsorption experiments and powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) were combined to examine the adsorption characteristics of Pb2+, Cu2+, Zn2+ and Cd2+ sequestration by birnessites with different Mn average oxidation state (AOS), and the Mn AOS dependent adsorption sites and adsorption characteristics. The results show that the maximum adsorption capacity of Pb2+, Cu2+, Zn2+ and Cd2+ increased with increasing birnessite Mn AOS. The adsorption capacity followed the order of Pb2+ > Cu2+ > Zn2+ > Cd2+. The observations suggest that there exist two sites on the surface of birnessite, i. e., high-binding-energy site (HBE site) and low-binding-energy site (LBE site). With the increase of Mn AOS for birnessites, the amount of HBE sites for heavy metal ions adsorption remarkably increased. On the other hand, variation in the amount of LBE sites was insignificant. The amount of LBE sites is much more than those of HBE sites on the surface of birnessite with low Mn AOS. Nevertheless, both amounts on the surface of birnessite with high Mn AOS are very close to each other. Therefore, the heavy metal ions adsorption capacity on birnessite is largely determined by the amount of HBE sites. On birnessite surface, adsorption of Cu2+, Zn2+, and Cd2+ mostly occurred at HBE sites. In comparison with Zn2+ and Cd2+, more Cu2+ adsorbed on the LBW sites. Pb2+ adsorption maybe occupy at both LBE sites and HBE sites simultaneously.

[Investigation on the oxidation behaviors and kinetics of sulfide by cryptomelane].

As one of the common manganese oxide minerals in supergene environment, cryptomelane affects the migration, transformation and environmental fate of sulfur in soil. In this work, oxidation process of sodium sulfide solution by cryptomelane was investigated without oxygen gas. The species and concentration of oxidation products of sulfide in solution were determined by spectrophotometry and ion chromatography, and the crystal structures and micro-morphologies of solid oxidation products of sulfide were characterized by XRD and SEM. The influence of solution temperature, pH value of solution, manganese average oxidation state (AOS) and the amount of added cryptomelane on the initial oxidation rate of S2- was studied. It was observed that the oxidation products of sulfide were S2O3(2-), SO3(2-), SO4(2-) and S, and S was the main one for that the total transformation rate of S2- to S2O3(2-), SO3(2-) and SO4(2-) was below 13.4%. The initial oxidation rate of S2- follows a pseudo-first-order law. Oxidation rate increased with elevating reaction temperature, decreasing pH value of solution and the increase of the amount of added mineral. The oxidation capacity of cryptomelane increased with the increase of Mn(III) content, and the initial oxidation rate constants (K(obs)) of S2- were 0.220 3 min(-1) and 0.1729 min(-1) when cryptomelane was applied with AOS about 3.81 and 3.98, respectively. During the redox process, cryptomelane was reduced to Mn(OH)2, which could be oxidized into Mn3O4, by O2 in air, and Mn3O4 was further transformed into MnOOH likely due to the reaction of surface-adsorbed water on manganese oxide and O2 and Mn3O4.

[Effects of Mn(III) on oxidation of Cr(III) with birnessites].

Cr(III) could be oxidized only by manganese oxide minerals as natural inorganic oxidants in nature, and so the rate and mechanism of interaction between manganese oxide minerals and Cr(III) were widely concerned. The effects of Mn(III) in birnessites, the most common Mn oxide mineral in the environment, on the rate of Cr(III) oxidation with birnessites and the kinetic characteristics were investigated through batch kinetic technique. The results show that Cr(III) oxidation rate follows a pseudo-first-order reaction, and the apparent rate constant K(obs), is 0.031 3 min(-1) when the average oxidation state (AOS) of Mn is about 3.50 in birnessite. When the birnessite is pretreated with Na4P2O7 solution, and the Mn(III) can be complexed out from the solid oxides. Therefore the content of Mn(III) in the birnessites decreases and the AOS of manganese increases. The AOSs of Mn for the pretreated birnessites increase from 3.50 to 3.63, 3.73 and 3.78 when the concentrations of Na4P2O7 are about 10, 20 and 50 mmol/L respectively. The Mn(III) content does not affect the initial oxidation rate of Cr(III) markedly, although oxidation amount of Cr(III) increases with the AOS of Mn. The apparent rate constants for the corresponding pretreated birnessites are 0.035 1, 0.032 5 and 0.0309 min(-1) respectively. The oxidation rate of Cr( III) is markedly influenced by the amount of Mn(III) produced in the transformation process of Mn(VN) --> Mn(III). The newly formed Mn(III) is complexed by Na4P2O7 and the oxidation rate decreases to 45%-88%. The lower content of Mn(III) in birnessites, the more Mn(III) newly formed from the transformation of Mn(IV) is complexed out from the minerals, and the greater amplitude in the decrease of Cr(III) oxidation rate. Thus the newly formed Mn(III) is highly active and possesses fast rate of electron transfer, however the rate of electron transfer in the transformation process of Mn(IV) --> Mn(III) is relatively slow. It could be deduced that the controlling step of initial oxidation rate of Cr(III) with birnessites may be the electron transfer process of Mn(IV) --> Mn(III).