In this work,the gold nanoparticles（Au-NPs）were in-situ generated on the surface of MnO2nanosheets to form MnO2/Au-NPs nanocomposite in a simple and cost-effective way.Multiple experiments were carried out to optimi...In this work,the gold nanoparticles（Au-NPs）were in-situ generated on the surface of MnO2nanosheets to form MnO2/Au-NPs nanocomposite in a simple and cost-effective way.Multiple experiments were carried out to optimize the oxidation of basic dye（Methylene Blue（MB））,including the molar ratio of MnO2to chloroauric acid（HAu Cl4）,the p H of the solution and the effect of initial material.Under the optimal condition,the highest degradation efficiency for MB achieved to 98.9%within 60 min,which was obviously better than commercial MnO2powders（4.3%）and MnO2nanosheets（74.2%）.The enhanced oxidative degradation might attribute to the in-situ generation of ultra-small and highly-dispersed Au-NPs which enlarged the synergistic effect and/or interfacial effect between MnO2nanosheets and Au-NPs and facilitated the uptake of electrons by MnO2from MB during the oxidation,thus validating the application of MnO2/Au-NPs nanocomposite for direct removal of organic dyes from wastewater in a simple and convenient fashion.展开更多
The sorption of AuCL4- ,AuCl2- and Au(S2O3)23- on δ-MnO2 was investigated at pH2-11.6, 0.01 mol/L and 0.1 mol/L NaNO3 solutions. At pH 4 in two electrolyte strength solutions, Au sorption densities on δ-MnO2 are 0. ...The sorption of AuCL4- ,AuCl2- and Au(S2O3)23- on δ-MnO2 was investigated at pH2-11.6, 0.01 mol/L and 0.1 mol/L NaNO3 solutions. At pH 4 in two electrolyte strength solutions, Au sorption densities on δ-MnO2 are 0. 18-0.21 and 0.28 μmoL/m2 for AuCl4 and Au(S2O3)23- , respectively, and the Au surface coverage is approximate to or lower than 1 % . This adsorption of the two Au complexes decreases as the solution pH increases, which conforms to the sorption regularity of the anion on δ-MnO2. The Au sorption decreases in the sequence of Au(S2O3)23- >AuCl4- > AuCl2- . The intrinsic equilibrium constants (logKint) of the three Au complexes are 1.17-2.7, much higher than those of Cu and Cd. The hydrolysis products of AuCLi are preferentially adsorbed by δ-MnO2 and the inner-sphere Au-surface complexes are formed on the surface.展开更多
MnO2 microspheres with various surface structures were prepared using the hydrothermal method, and Au/MnO2 catalysts were synthesized using the sol-gel method. We obtained three MnO2 microspheres and Au/MnO2 samp...MnO2 microspheres with various surface structures were prepared using the hydrothermal method, and Au/MnO2 catalysts were synthesized using the sol-gel method. We obtained three MnO2 microspheres and Au/MnO2 samples： coherent solid spheres covered with wire-like nanostructures, solid spheres with nanosheets, and hierarchical hollow microspheres with nanoplatelets and nanorods. We investigated the properties and catalytic activities of formaldehyde oxidation at room temperature. Crystalline structures of MnO2 are the main factor affecting the catalytic activities of these samples, and γ- MnO2 shows high catalytic performance. The excellent redox properties are responsible for the catalytic ability of γ-MnO2. The gold-supported interaction can change the redox properties of catalysts and accelerate surface oxygen species transition, which can account for the catalytic activity enhancement of Au/MnO2. We also studied intermediate species. The dioxymethylene （DOM） and formate species formed on the catalyst surface were considered intermediates, and were ultimately transformed into hydrocarbonate and carbonate and then decomposed into CO2. A proposed mechanism of formaldehyde oxidation over Au/MnO2 catalysts was also obtained.展开更多
基金supported by the National Natural Science Foundation of China (Nos. 21277048 and 21505046)the China Postdoctoral Science Foundation (No. 2016 M590336)+1 种基金the "Chenguang Program" funded by Shanghai Education Development FoundationShanghai Municipal Education Commission (No. 15CG21)
文摘In this work,the gold nanoparticles（Au-NPs）were in-situ generated on the surface of MnO2nanosheets to form MnO2/Au-NPs nanocomposite in a simple and cost-effective way.Multiple experiments were carried out to optimize the oxidation of basic dye（Methylene Blue（MB））,including the molar ratio of MnO2to chloroauric acid（HAu Cl4）,the p H of the solution and the effect of initial material.Under the optimal condition,the highest degradation efficiency for MB achieved to 98.9%within 60 min,which was obviously better than commercial MnO2powders（4.3%）and MnO2nanosheets（74.2%）.The enhanced oxidative degradation might attribute to the in-situ generation of ultra-small and highly-dispersed Au-NPs which enlarged the synergistic effect and/or interfacial effect between MnO2nanosheets and Au-NPs and facilitated the uptake of electrons by MnO2from MB during the oxidation,thus validating the application of MnO2/Au-NPs nanocomposite for direct removal of organic dyes from wastewater in a simple and convenient fashion.
基金Project supported by the National Studying-abroad Foundation, the National Natural Science Foundation of China (Grant No. 49573200) and the Australian Mining Industry.
文摘The sorption of AuCL4- ,AuCl2- and Au(S2O3)23- on δ-MnO2 was investigated at pH2-11.6, 0.01 mol/L and 0.1 mol/L NaNO3 solutions. At pH 4 in two electrolyte strength solutions, Au sorption densities on δ-MnO2 are 0. 18-0.21 and 0.28 μmoL/m2 for AuCl4 and Au(S2O3)23- , respectively, and the Au surface coverage is approximate to or lower than 1 % . This adsorption of the two Au complexes decreases as the solution pH increases, which conforms to the sorption regularity of the anion on δ-MnO2. The Au sorption decreases in the sequence of Au(S2O3)23- >AuCl4- > AuCl2- . The intrinsic equilibrium constants (logKint) of the three Au complexes are 1.17-2.7, much higher than those of Cu and Cd. The hydrolysis products of AuCLi are preferentially adsorbed by δ-MnO2 and the inner-sphere Au-surface complexes are formed on the surface.
基金This work is financially supported by the National Natural Science Foundation of China （Grant Nos. 21107124 and 21337003）, Dean＇s Award Startup Funds of the Chinese Academy of Sciences, the National High Technology Research and Development Program of China （No. 2012AA063101）, and Science Promotion Program of Research Center for Eco-Environmcntal Sciences, CAS （YSW2013B05）.
文摘MnO2 microspheres with various surface structures were prepared using the hydrothermal method, and Au/MnO2 catalysts were synthesized using the sol-gel method. We obtained three MnO2 microspheres and Au/MnO2 samples： coherent solid spheres covered with wire-like nanostructures, solid spheres with nanosheets, and hierarchical hollow microspheres with nanoplatelets and nanorods. We investigated the properties and catalytic activities of formaldehyde oxidation at room temperature. Crystalline structures of MnO2 are the main factor affecting the catalytic activities of these samples, and γ- MnO2 shows high catalytic performance. The excellent redox properties are responsible for the catalytic ability of γ-MnO2. The gold-supported interaction can change the redox properties of catalysts and accelerate surface oxygen species transition, which can account for the catalytic activity enhancement of Au/MnO2. We also studied intermediate species. The dioxymethylene （DOM） and formate species formed on the catalyst surface were considered intermediates, and were ultimately transformed into hydrocarbonate and carbonate and then decomposed into CO2. A proposed mechanism of formaldehyde oxidation over Au/MnO2 catalysts was also obtained.
