Ultrahigh Performance H2 O2 Generation by Single-Atom Fe Catalysts with N/O Bidentate Ligand via Oxalic Acid and Oxygen Molecules Activation.

Single-atom catalysts (SACs) for photocatalytic hydrogen peroxide (H2 O2 ) generation are researched but it is still challenging to obtain high H2 O2 yields. Herein, graphite carbon nitride (FeSA /CN) confined single Fe atoms with N/O coordination is prepared, and FeSA /CN shows high H2 O2 production via oxalic acid and O2 activation. Under visible light illumination, the concentration of H2 O2 generated by FeSA /CN can achieve 40.19 mM g-1 h-1 , which is 10.44 times higher than that of g-C3 N4 . The enhanced H2 O2 generation can be attributed to the formation of metal-organic complexes and rapid electron transfer. Moreover, the O2 activation of photocatalysts is revealed by 3,3',5,5'-tetramethylbenzidine oxidation. The results display that the O2 activation capacity of FeSA /CN is higher than that of g-C3 N4 , which facilitates the formation of H2 O2 . Finally, density functional theory calculation demonstrates that O2 is chemically adsorbed on Fe atomic sites. The adsorption energy of O2 is enhanced from -0.555 to -1.497 eV, and the bond length of OO is extended from 1.235 to 1.292 Å. These results exhibit that the confinement of single Fe atoms can promote O2 adsorption and activation. Finally, the photocatalytic mechanism is elaborated, which provides a deep understanding for SACs-catalyzed H2 O2 generation.

Peroxymonosulfate and peroxydisulfate activation by fish scales biochar for antibiotics removal: Synergism of N, P-codoped biochar.

Social development is accompanied by technological progress, which commonly leads to the expansion of pollution As an essential resource of modern medical treatment, antibiotics have become a hot topic in the aspect of environmental pollution. In this study, we first used fish scales to synthesize N, P-codoped biochar catalyst (FS-BC) as peroxymonosulfate (PMS) and peroxydisulfate (PDS) activator to degrade tetracycline hydrochloride (TC). At the same time, peanut shell biochar (PS-BC) and coffee ground biochar (CG-BC) were prepared as reference materials. Among them, FS-BC exhibited the best catalytic performance due to the excellent defect structure (ID/IG = 1.225) and the synergism of N, P heteroatoms. PS-BC, FS-BC and CG-BC achieved degradation efficiencies of 86.26%, 99.71% and 84.41% for TC during PMS activation and 56.79%, 93.99% and 49.12% during PDS, respectively. In both FS-BC/PMS and FS-BC/PDS systems, non-free radical pathways involved singlet oxygen (1O2), surface-bound radicals mechanism and direct electron transfer mechanism. Structural defects, graphitic N and pyridinic N, P-C groups and positively charged sp2 hybridized C adjacent to graphitic N were all critical active sites. FS-BC has the potential for practical applications and development because of its robust adaptation to pH and anions and stable re-usability. This study not only provides a reference for biochar selection, but also suggests a superior strategy for TC degradation in the environment.

Effects of oxytetracycline and zinc ion on nutrient removal and biomass production via microalgal culturing in anaerobic digester effluent.

Removal of nutrients from swine wastewater digester effluent (SWDE) by microalgae Coelastrella sp. and production of Coelastrella sp. were investigated at the presence of oxytetracycline (OTC) and Zn(II). Mechanisms of stress of OTC and Zn(II) on microalgae were discussed via analyzing the removal performance of SWDE and biochemical characteristics of microalgae. Results showed that removal efficiency of ammonia nitrogen and biomass yield of microalgae at the presence of 5000 µg/L of OTC decreased by 13.1% - 50.1% and 28.2% -71.5%, respectively, when Zn concentration was increased from 0.50 mg/L to 5.0 mg/L. The presence of 5.0 mg/L Zn(II) promoted the accumulation of lipids in microalgae, and the presence of 50 µg/L OTC increased unsaturation of fatty acid methyl ester. Content of glutathione and activity of both glutamine synthetase and superoxide dismutase decreased with the increase of OTC concentration, while content of adenosine triphosphatase increased when Zn(II) concentration was also increased.

Sonochemical synthesis of ZnS nanolayers on the surface of microbial cells and their application in the removal of heavy metals.

In order to improve the adsorption performance of microorganisms, we synthesized a novel material - phanerochaete chrysosporium cells covered with a layer of ZnS nanoparticles (ZnS-cells). The preparation of the ZnS-cells is based on the Sonochemical method to synthesize the ZnS nanoparticle layer on the surface of the microbial cells. The ZnS-cells were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR). Characterization results showed that wurtzite ZnS was coated on the cell surface in the form of nanoclusters by sonochemical reaction, and the formation of ZnS was related to the carboxyl group on the cell surface. Batch experiments showed that the ZnS-cells exhibited high adsorption efficiency for Pb2+and Cd2+, the removal rate of Pb2+ and Cd2+ by ZnS-cells was 140 % and 160 % higher than that of pure P. chrysosporium, respectively. Studies on the adsorption mechanism showed that the removal of heavy metals by ZnS-cells mainly depended on the complexation of surface functional groups on the surface of the cells and the ion exchange of ZnS nanofilms.

Fungal cell with artificial metal container for heavy metals biosorption: Equilibrium, kinetics study and mechanisms analysis.

White-rot fungi show low-cost superiority as a promising biosorbent in heavy metal removal, but limited by its poor biosorption capacity. Herein, a novel biosorbent, functionalized Phanerochaete chrysosporium with intracellular mineral scaffold, was prepared for the biosorption of heavy metal ions. The functionalized fungi cells with intracellular mineral scaffold that serve as internal metal container exhibiting high biosorption efficiency for Pb(II) and Cd(II) ions. Adsorption isotherm models were employed to investigate the biosorption isotherm and determine the biosorption equilibrium. The Freundlich model shows better fit with the experimental data of both metal ions (R2 = 0.9866 and 0.9897 for Pb(II) and Cd(II) respectively). Three kinetic models, pseudo-first-order, pseudo-second-order and intra-particle diffusion models, were used to determine the biosorption kinetics. The pseudo-second-order model shows the better fit with the experimental data, and we suggests the rate-limiting step of the biosorption could be a chemisorption step which involves sharing or exchanging of electrons between adsorbent and adsorbate. Intra-particle diffusion model study result shows the biosorption process could be divided into three steps: a fast surface adsorption stage, a slow transfer stage from external to internal, and a stage of andante reaching equilibrium. The biosorption mechanism was carefully analyzed by various characterization methods.

The improved methods of heavy metals removal by biosorbents: A review.

For decades, a vast array of innovative biosorbents have been found out and used in the removal of heavy metals, including bacteria, algae and fungi, etc. Although extensive biological species have been tried as a biosorbent for heavy metals removal, for removal efficiency or economy efficiency limited, it has failed to make a substantial breakthrough in practical application. Thus, many improved methods based on biosorbents emerged. In this review, based on the literature and our research results, we highlight three types of novel methods for biosorbents removal of heavy metals: chemical modification of biosorbents; biomass and chemical materials combination; multiple biomass complex systems. We mainly focus on their configuration, biosorption performance, their creation method, regeneration/reuse, their application and development in the future. Through the comparative analysis of various methods, we think that intracellular autogenous nanomaterials may open up another window in biosorption of heavy metals area. At the same time, the combination of various treatment methods will be the development tendency of heavy metal pollution treatment in the future.

Highly efficient extraction of lead ions from smelting wastewater, slag and contaminated soil by two-dimensional montmorillonite-based surface ion imprinted polymer absorbent.

The rapid, efficient and selective extraction of heavy metal ions is significant for wastewater pretreatment and metal ion recycle. Using montmorillonite as the template substrate and Pb2+ as template ions, a novel two-dimensional montmorillonite-based surface ion imprinted polymer (IIP-MMT) adsorbent is successfully synthesized via activators generated by electron transfer for atom transfer radical polymerization (AGET-ATRP). Batch adsorption experiments are performed to assess the properties of the imprinted polymer sorbent, along with its selectivity and reusability in practical extraction of Pb2+. It is interesting that the crosslinking density of the imprinted polymer has impact on the sorption property, where suitable density is coupled with the highest adsorption capacity and the best selectivity. Benefiting from the surface-imprinting technique and AGET-ATRP, IIP2-MMT is proved to own a highly effective Pb2+ adsorption capacity to reach 158.68 mg/g within 30 min, where the corresponding maximum adsorption capacity is 201.84 mg/g. Moreover, this material exhibits satisfactory stability and reusability that the high adsorptive capability of IIP-MMT retains more than 95% after six cycles. Thus, it is expected to reduce the wastewater disposal expenses. Besides, owing to the characteristics of PHEMA brushes and SHA chelating ligand, IIP-MMT has strong anti-interference and anti-blockage abilities to extract Pb2+ from smelting wastewater, slag and contaminated soil. Considering the low cost, excellent stability, high extraction efficiency, environmental friendliness, it is expected that the proposed material is very promising for treatment of heavy metals-contaminated wastewaters and soil, or ion recycle.

Difunctional chitosan-stabilized Fe/Cu bimetallic nanoparticles for removal of hexavalent chromium wastewater.

Bimetallic Fe/Cu nanoparticles were successfully stabilized by chitosan used for remediating hexavatlent chromium contaminated wasterwater. However, the over-loaded chitosan on the surface of Fe/Cu particles limited the Cr(VI) reduction due to the occupation of the surface reactive sites. Weighing the colloid stability and the reduction reactivity, the optimal dosage of chitosan is 2.0 wt% and the optimal Cu doping dosage is 3.0 wt%. SEM and TEM images showed that the chitosan-stabilized Fe/Cu bimetallic nanoparticles (CS-Fe/Cu nanoparticles) were uniformly dispersed, which had loose and porous surface. FTIR characterization showed that the binding sites of nZVI and chitosan. XRD demonstrated that the presence of copper and chitosan did not change the existence form of zero-valent iron. Most importantly, the contribution of chitosan and Cu in the removal mechanism was studied by the reduction experiments and the XPS analysis. On the one hand, chitosan could effectively combine with Cr(VI) due to chelation, on the other hand, Cu played an important role in the precipitation and coprecipitation phenomena. These findings indicate that CS-Fe/Cu has the potential to be a promising material for wastewater treatment.

Organic matters removal from landfill leachate by immobilized Phanerochaete chrysosporium loaded with graphitic carbon nitride under visible light irradiation.

This study investigated the technical applicability of a combination of Phanerochaete chrysosporium (P. chrysosporium) with photocatalyst graphitic carbon nitride (g-C3N4) for organic matters removal from landfill leachate under visible light irradiation. Photocatalyst g-C3N4 was well immobilized on the hyphae surface of P. chrysosporium by calcium alginate. The typical absorption edge in visible light region for g-C3N4 was at about 460 nm, and the optical absorption bandgap of g-C3N4 was estimated to be 2.70 eV, demonstrating the great photoresponsive ability of g-C3N4. An optimized g-C3N4 content of 0.10 g in immobilized P. chrysosporium and an optimized immobilized P. chrysosporium dosage of 1.0 g were suitable for organic matters removal. The removal efficiency of total organic carbon (TOC) reached 74.99% in 72 h with the initial TOC concentration of 100 mg L-1. In addition, the gas chromatography coupled with mass spectrometry (GC-MS) measurements showed that immobilized P. chrysosporium presented an outstanding removal performance for almost all organic compounds in landfill leachate, especially for the volatile fatty acids and long-chain hydrocarbons. The overall results indicate that the combination P. chrysosporium with photocatalyst g-C3N4 for organic matters removal from landfill leachate may provide a more comprehensive potential for the landfill leachate treatment.

Study on biodegradation process of lignin by FTIR and DSC.

The biodegradation process of lignin by Penicillium simplicissimum was studied to reveal the lignin biodegradation mechanisms. The biodegradation products of lignin were detected using Fourier transform infrared spectroscopy (FTIR), UV-Vis spectrophotometer, different scanning calorimeter (DSC), and stereoscopic microscope. The analysis of FTIR spectrum showed the cleavage of various ether linkages (1,365 and 1,110 cm(-1)), oxidation, and demethylation (2,847 cm(-1)) by comparing the different peak values in the corresponding curve of each sample. Moreover, the differences (Tm and ΔHm values) between the DSC curves indirectly verified the FTIR analysis of biodegradation process. In addition, the effects of adding hydrogen peroxide (H2O2) to lignin biodegradation process were analyzed, which indicated that H2O2 could accelerate the secretion of the MnP and LiP and improve the enzymes activity. What is more, lignin peroxidase and manganese peroxidase catalyzed the lignin degradation effectively only when H2O2 was presented.

[Biodegradation of lignocellulose by Penicillium simplicissimum and characters of lignocellulolytic enzymes].

Penicillium simplicissimum(Oudem.) Thomrn BGA can secrete lignocellulolytic enzymes, among these enzymes the highest activities of hemicellulase, cellulase, lignin peroxidase (Lip), manganese peroxidase (Mnp) and laccase are 146.82 Iu.g-1, 2.78 U.g-1, 47.97 U.g-1, 34.56 U.g-1 and 17.94 U.g-1 respectively. According to the results and the statistical analysis of SPSS, the ability of secreting lignocellulolytic enzymes by Penicillium simplicissimum significantly correlated with the structure of lignocellulose, and the biodegradation of lignocellulose was probably a kind of synergistic effect of several lignocellulolytic enzymes. In the solid-state fermentation of 30 days, the hemicellulose content has a significantly negative correlation with the fermentation days(r = -0.946, P < 0.01), there was also a significantly negative correlation between the cellulose-biodegradation and the lignin-biodegradation (r = -0.818, P<0.05). As unselected enzymes, Lip and Mnp can degrade hemicellulose and cellulose corporately when biodegrades lignin. The significant correlation is showed between Lip, Mnp and cellulose (correlation parameters are r = 0. 922, P <0.01; r = 0.807, P<0.05 respectively). In addition, the biosorption is found to have a very important effect in the removal of liquid alkali lignin by Penicillium simplicissimum. Key words:Penicillium simplicissimum; lignocellulolytic enzymes; biodegradation; biosorption; synergistic effect

Use of potassium dihydrogen phosphate and sawdust as adsorbents of ammoniacal nitrogen in aerobic composting process.

Three kinds of adsorbents-potassium dihydrogen phosphate, sawdust and mixture of potassium dihydrogen phosphate and sawdust were added respectively into composting to investigate their adsorption effect on ammonia. The experimental results showed that all the adsorbents could restrain ammonia volatilizing, with the sorption of potassium dihydrogen phosphate adsorbents being the best of all, the sorption of mixture adsorbent with potassium dihydrogen phosphate and sawdust being the second and the sorption of sawdust adsorbent being the last. Therefore, the total nitrogen loss ratios respectively reduced from 38% to 13%, 15% and 21% after adding these three kinds of adsorbents into composting. However, potassium dihydrogen phosphate produced negative influence on composting properties as its supplemented amount exceeded a quantity basis equivalent to 18% of total nitrogen in the composting, for example: pH value had been lessened, microorganism activity reduced, which finally resulted in the reduction of biodegradation ratio of organic matter. But it did not result in these problems when using the mixture of potassium dihydrogen phosphate and sawdust as adsorbent, in which the amount of potassium dihydrogen phosphate was under a quantity basis equivalent to 6% of total nitrogen in the composting. Moreover, the mixture adsorbent produced better adsorption effect on ammonia, and raised biodegradation ratio of organic matter from 26% to 33%.

Composting of lead-contaminated solid waste with inocula of white-rot fungus.

The treatment of the simulated lead-contaminated solid waste by composting with white-rot fungus was studied at laboratory scale. The composting system without the inocula of white-rot fungus was prepared as control, and the composting of the uncontaminated solid waste with the inocula of white-rot fungus was carried out as the other control. The results indicated that the solid waste inoculated with white-rot fungus could be successfully processed. The final compost was mature with 70.5% of lead (Pb) in residual fraction and none in exchangeable fraction. Germination index reached 120%. All the results indicated that the bioavailability of Pb in compost was reduced and the potential harm of Pb in compost was alleviated by composting with the inocula of white-rot fungus.

[Application of white-rot fungi in composting lead-contaminated waste].

Simulative lead polluted wastes which containing unpolluted soil, household waste, straw, bran and lead nitrate were prepared. Inoculation of white-rot fungi and uninoculation in composting of lead-contaminated waste were studied. Change of chemical factor, biological parameter and biological toxicity analyses with time during the composting process were determined to study effect of heavy metal on composting process and probability of application of white-rot fungi in composting of metal-contaminated waste. The results show the composting of lead-contaminated waste inoculated white-rot fungi could be successfully processed, which lead to the reduction of the bioavailability of Pb in compost and alleviate the potential harm from heavy metal. Under this composting process, for the final compost, pH, water-soluble organic carbon/nitrogen, volatile solid, lignin and coarse fibre remained reached 7.9, 4.01, 36.1%, 22.4g, 30.1g, respectively. In addition, 63.38% of Pb in residual fraction and 0% of Pb in soluble-exchangeable fraction were found in final compost, and the germination index of final compost reached 121%.

[Influence of different sorbents on adsorption effect of ammonia and compost property in aerobic composting].

The three kinds of sorbents of 0.18% KH2PO4, 0.06% KH2PO4 + 15% sawdust mixture and 30% sawdust are added separately into composting to investigate their adsorption effect on ammonia. The experiment results exhibite that all the sorbents can restrain ammonia volatilizing. But sorption of 0.18% KH2PO4 sorbnet was best of all, one of 0.06% KH2PO4 + 15% sawdust mixture sorbent was secondly, one of 30% sawdust sorbent was thirdly. The total nitrogen loss ratios were separately reduced 25%, 23% and 17% after adding the three kinds of sorbents into composting. However, excessive KH2PO4 would produce negative influence on compost property, such as pH value being lessened, microorganism activity being reduced, and finally resulting in the reduction of biodegradation ratio of organic matter also. Comparing with it, there were not these problems as 0.06% KH2PO4 + 15% sawdust mixture being sorbent. The mixture sorbent not only produced finer adsorption effect on ammonia, but also made biodegradation ratio of organic matter to be promoted 7%.