A series of CeO2‐MnOx‐Al2O3 mixed oxide catalysts (Ce:Mn:Al mole ratio=6:4:x, x=0.25, 0.5, 1, 2) were prepared by a simple one‐step inverse co‐precipitation method to investigate the influence of the incorpo...A series of CeO2‐MnOx‐Al2O3 mixed oxide catalysts (Ce:Mn:Al mole ratio=6:4:x, x=0.25, 0.5, 1, 2) were prepared by a simple one‐step inverse co‐precipitation method to investigate the influence of the incorporation of Al3+ into CeO2‐MnOx mixed oxides. CeO2‐MnOx, CeO2‐Al2O3, and MnOx‐Al2O3 mixed oxides, and CeO2 were prepared by the same method for comparison. The samples were characterized by XRD, Raman, N2 physisorption, H2‐TPR, XPS, and in situ DRIFTS. The catalytic re‐duction of NO by CO was chosen as a model reaction to evaluate the catalytic performance. The incorporation of a small amount of Al3+into CeO2‐MnOx mixed oxides resulted in a decrease of crys‐tallite size, with the increase of the BET specific surface area and pore volume, as well as the in‐crease of Ce3+and Mn4+. The former benefits good contact between catalyst and reactants, and the latter promotes the adsorption of CO and the desorption, conversion and dissociation of adsorbed NO. All these enhanced the catalytic performance for the NO+CO model reaction. A reaction mecha‐nism was proposed to explain the excellent catalytic performance of CeO2‐MnOx‐Al2O3 catalysts for NO reduction by CO.展开更多
First-row transition metal compounds have been widely explored as oxygen evolution reaction(OER)electrocatalysts due to their impressive performance in this application.However,the activity trends of these electrocata...First-row transition metal compounds have been widely explored as oxygen evolution reaction(OER)electrocatalysts due to their impressive performance in this application.However,the activity trends of these electrocatalysts remain elusive due to the effect of inevitable iron impurities in alkaline electrolytes on the OER;the inhomogeneous structure of iron-based(oxy)hydroxides further complicates this situation.Bimetallic metal-organic frameworks(MOFs)have the advantages of well-defined and uniform atomic structures and the tunable coordination environments,allowing the structure-activity relationships of bimetallic sites to be precisely explored.Therefore,we prepared a series of iron-based bimetallic MOFs(denoted as Fe_(2)M-MIL-88B,M=Mn,Co,or Ni)and systematically compared their electrocatalytic performance in the OER in this work.All the bimetallic MOFs exhibited higher OER activity than their monometallic iron-based counterpart,with their activity following the order FeNi>FeCo>FeMn.In an alkaline electrolyte,Fe2Ni-MIL-88B showed the lowest overpotential to achieve a current density of 10 mA cm^(–2)(307 mV)and the smallest Tafel slope(38 mV dec^(–1)).The experimental and calculated results demonstrated that iron and nickel exhibited the strongest coupling effect in the series,leading to modification of the electronic structure,which is crucial for tuning the electrocatalytic activity.展开更多
The SnO2-polyaniline(SnO2-PAn) composite was prepared by microemulsion polymerization method using aniline,ammonium peroxodisulfate and SnO2 as starting materials.The SnO2-PAn composite was characterized by X-ray diff...The SnO2-polyaniline(SnO2-PAn) composite was prepared by microemulsion polymerization method using aniline,ammonium peroxodisulfate and SnO2 as starting materials.The SnO2-PAn composite was characterized by X-ray diffractometer,scanning electron microscope and electrochemical techniques.The results show that PAn in the composites is amorphous.PAn formed in the reaction is deposited preferentially on the SnO2 particles,giving a SnO2-PAn composite,in which SnO2 is coated with PAn.SnO2-PAn composite shows a reversible capacity of 657.6 mA·h/g and the capacity loss per cycle is only 0.092% after 80 cycles,suggesting that SnO2-PAn composite is a promising anode material for lithium ion batteries.展开更多
Both activated carbon and magnetite have been reported to promote the syntrophic growth of Geobacter metallireducens and Geobacter sulfurreducens co-cultures, the first model to show direct interspecies electron trans...Both activated carbon and magnetite have been reported to promote the syntrophic growth of Geobacter metallireducens and Geobacter sulfurreducens co-cultures, the first model to show direct interspecies electron transfer (DIET); however, differential transcriptomics of the promotion on co-cultures with these two conductive materials are unknown. Here, the comparative transcriptomic analysis of G. metallireducens and G. sulfurreducens co-cultures with granular activated carbon (GAC) and magnetite was reported. More than 2.6-fold reduced transcript abundances were determined for the uptake hydrogenase genes of G. sulfurreducens as well as other hydrogenases in those co-cultures to which conductive materials had been added. This is consistent with electron transfer in G. metallireducens-G. sulfurreducens co-cultures as evinced by direct interspecies electron transfer (DIET). Transcript abundance for the structural component of electrically conductive pili (e-pili), PilA, was 2.2-fold higher in G. metallireducens, and, in contrast, was 14.9-fold lower in G. sulfurreducens in co-cultures with GAC than in Geobacters co-cultures without GAC. However, it was 9.3-fold higher in G. sulfurreducens in co-cultures with magnetite than in Geobacters co-cultures. Mutation results showed that GAC can be substituted for the e-pili of both strains but magnetite can only compensate for that of G. sulfurreducens, indicating that the e-pili is a more important electron acceptor for the electron donor strain of G. metallireducens than for G. sulfurreducens. Transcript abundance for G. metallireducens c-type cytochrome gene GMET_RS14535, a homologue to c-type cytochrome gene omcE of G. sulfurreducens was 9.8-fold lower in co-cultures with GAC addition, while that for OmcS of G. sulfurreducens was 25.1-fold higher in co-cultures with magnetite, than in that without magnetite. Gene deletion studies showed that neither GAC nor magnetite can completely substitute the cytochrome (OmcE homologous) of G. metallireducens but compensate for the cytochrome (OmcS) of G. sulfurreducens. Moreover, some genes associated with central metabolism were up-regulated in the presence of both GAC and magnetite; however, tricarboxylic acid cycle gene transcripts in G. sulfurreducens were not highly-expressed in each of these amended co-cultures, suggesting that there was considerable redundancy in the pathways utilised by G. sulfurreducens for electron transfer to reduce fumarate with the amendment of GAC or magnetite. These results support the DIET model of G. metallireducens and G. sulfurreducens and suggest that e-pili and cytochromes of the electron donor strain are more important than that of the electron acceptor strain, indicating that comparative transcriptomics may be a promising route by which to reveal different responses of electron donor and acceptor during DIET in co-cultures.展开更多
This paper presents the complete energy matrix of the 3d2system containing the electron-electron interaction, the ligand-fieldinteraction, the spin-orbit coupling interaction, and the Zeeman interaction, in which the ...This paper presents the complete energy matrix of the 3d2system containing the electron-electron interaction, the ligand-fieldinteraction, the spin-orbit coupling interaction, and the Zeeman interaction, in which the optical spectra and g-factor of V3+andTi2+ions in the series of tetrahedral AIIBVI(AII=Zn, Cd, BVI=S, Se, Te) semiconductor materials are determined. In the inves-tigation of the optical and magnetic properties of these transition-metal ions in the tetrahedral coordination complexes, wecompared the data obtained from the transition-metal ions in the tetrahedral coordination complexes with those obtained fromthe corresponding ions in the octahedral ones, and found that the tetrahedral complexes have weaker crystal-field strength, in-verse energy level ordering and stronger covalence effect.展开更多
基金supported by the National Natural Science Foundation of China (21507130)the Open Project Program of Chongqing Key Laboratory of Environmental Materials and Remediation Technology from Chongqing University of Arts and Sciences (CEK1405)+3 种基金the Open Project Program of Beijing National Laboratory for Molecular Sciences (20140142)the Open Project Program of Jiangsu Key Laboratory of Vehicle Emissions Control (OVEC001)the Open Project Program of Chongqing Key Laboratory of Catalysis and Functional Organic Molecules from Chongqing Technology and Business University (1456029)the Chongqing Science & Technology Commission (cstc2014pt-gc20002)~~
文摘A series of CeO2‐MnOx‐Al2O3 mixed oxide catalysts (Ce:Mn:Al mole ratio=6:4:x, x=0.25, 0.5, 1, 2) were prepared by a simple one‐step inverse co‐precipitation method to investigate the influence of the incorporation of Al3+ into CeO2‐MnOx mixed oxides. CeO2‐MnOx, CeO2‐Al2O3, and MnOx‐Al2O3 mixed oxides, and CeO2 were prepared by the same method for comparison. The samples were characterized by XRD, Raman, N2 physisorption, H2‐TPR, XPS, and in situ DRIFTS. The catalytic re‐duction of NO by CO was chosen as a model reaction to evaluate the catalytic performance. The incorporation of a small amount of Al3+into CeO2‐MnOx mixed oxides resulted in a decrease of crys‐tallite size, with the increase of the BET specific surface area and pore volume, as well as the in‐crease of Ce3+and Mn4+. The former benefits good contact between catalyst and reactants, and the latter promotes the adsorption of CO and the desorption, conversion and dissociation of adsorbed NO. All these enhanced the catalytic performance for the NO+CO model reaction. A reaction mecha‐nism was proposed to explain the excellent catalytic performance of CeO2‐MnOx‐Al2O3 catalysts for NO reduction by CO.
文摘First-row transition metal compounds have been widely explored as oxygen evolution reaction(OER)electrocatalysts due to their impressive performance in this application.However,the activity trends of these electrocatalysts remain elusive due to the effect of inevitable iron impurities in alkaline electrolytes on the OER;the inhomogeneous structure of iron-based(oxy)hydroxides further complicates this situation.Bimetallic metal-organic frameworks(MOFs)have the advantages of well-defined and uniform atomic structures and the tunable coordination environments,allowing the structure-activity relationships of bimetallic sites to be precisely explored.Therefore,we prepared a series of iron-based bimetallic MOFs(denoted as Fe_(2)M-MIL-88B,M=Mn,Co,or Ni)and systematically compared their electrocatalytic performance in the OER in this work.All the bimetallic MOFs exhibited higher OER activity than their monometallic iron-based counterpart,with their activity following the order FeNi>FeCo>FeMn.In an alkaline electrolyte,Fe2Ni-MIL-88B showed the lowest overpotential to achieve a current density of 10 mA cm^(–2)(307 mV)and the smallest Tafel slope(38 mV dec^(–1)).The experimental and calculated results demonstrated that iron and nickel exhibited the strongest coupling effect in the series,leading to modification of the electronic structure,which is crucial for tuning the electrocatalytic activity.
基金Project(20376086) supported by the National Natural Science Foundation of ChinaProject(2005037700) supported by the Postdoctoral Science Foundation of China+1 种基金Project(07A058) supported by the Scientific Research Fund of Hunan Provincial Education DepartmentProject(07JJ3014) supported by Hunan Provincial Natural Science Foundation of China
文摘The SnO2-polyaniline(SnO2-PAn) composite was prepared by microemulsion polymerization method using aniline,ammonium peroxodisulfate and SnO2 as starting materials.The SnO2-PAn composite was characterized by X-ray diffractometer,scanning electron microscope and electrochemical techniques.The results show that PAn in the composites is amorphous.PAn formed in the reaction is deposited preferentially on the SnO2 particles,giving a SnO2-PAn composite,in which SnO2 is coated with PAn.SnO2-PAn composite shows a reversible capacity of 657.6 mA·h/g and the capacity loss per cycle is only 0.092% after 80 cycles,suggesting that SnO2-PAn composite is a promising anode material for lithium ion batteries.
基金supported by the Major Research plan(91751112)the General Programme(41371257,41573071)of the National Natural Science Foundation of China+2 种基金Shandong Natural Science Fund for Distinguished Young Scholars(JQ201608)the Young Taishan Scholars Programme of Shandong Province(tsqn20161054)the Key Research Project for Frontier Science of the Chinese Academy of Sciences(QYZDJ-SSW-DQC015)
文摘Both activated carbon and magnetite have been reported to promote the syntrophic growth of Geobacter metallireducens and Geobacter sulfurreducens co-cultures, the first model to show direct interspecies electron transfer (DIET); however, differential transcriptomics of the promotion on co-cultures with these two conductive materials are unknown. Here, the comparative transcriptomic analysis of G. metallireducens and G. sulfurreducens co-cultures with granular activated carbon (GAC) and magnetite was reported. More than 2.6-fold reduced transcript abundances were determined for the uptake hydrogenase genes of G. sulfurreducens as well as other hydrogenases in those co-cultures to which conductive materials had been added. This is consistent with electron transfer in G. metallireducens-G. sulfurreducens co-cultures as evinced by direct interspecies electron transfer (DIET). Transcript abundance for the structural component of electrically conductive pili (e-pili), PilA, was 2.2-fold higher in G. metallireducens, and, in contrast, was 14.9-fold lower in G. sulfurreducens in co-cultures with GAC than in Geobacters co-cultures without GAC. However, it was 9.3-fold higher in G. sulfurreducens in co-cultures with magnetite than in Geobacters co-cultures. Mutation results showed that GAC can be substituted for the e-pili of both strains but magnetite can only compensate for that of G. sulfurreducens, indicating that the e-pili is a more important electron acceptor for the electron donor strain of G. metallireducens than for G. sulfurreducens. Transcript abundance for G. metallireducens c-type cytochrome gene GMET_RS14535, a homologue to c-type cytochrome gene omcE of G. sulfurreducens was 9.8-fold lower in co-cultures with GAC addition, while that for OmcS of G. sulfurreducens was 25.1-fold higher in co-cultures with magnetite, than in that without magnetite. Gene deletion studies showed that neither GAC nor magnetite can completely substitute the cytochrome (OmcE homologous) of G. metallireducens but compensate for the cytochrome (OmcS) of G. sulfurreducens. Moreover, some genes associated with central metabolism were up-regulated in the presence of both GAC and magnetite; however, tricarboxylic acid cycle gene transcripts in G. sulfurreducens were not highly-expressed in each of these amended co-cultures, suggesting that there was considerable redundancy in the pathways utilised by G. sulfurreducens for electron transfer to reduce fumarate with the amendment of GAC or magnetite. These results support the DIET model of G. metallireducens and G. sulfurreducens and suggest that e-pili and cytochromes of the electron donor strain are more important than that of the electron acceptor strain, indicating that comparative transcriptomics may be a promising route by which to reveal different responses of electron donor and acceptor during DIET in co-cultures.
基金supported by the National Natural Science Foundation of China (Grant Nos. 10974138 and 10774103)
文摘This paper presents the complete energy matrix of the 3d2system containing the electron-electron interaction, the ligand-fieldinteraction, the spin-orbit coupling interaction, and the Zeeman interaction, in which the optical spectra and g-factor of V3+andTi2+ions in the series of tetrahedral AIIBVI(AII=Zn, Cd, BVI=S, Se, Te) semiconductor materials are determined. In the inves-tigation of the optical and magnetic properties of these transition-metal ions in the tetrahedral coordination complexes, wecompared the data obtained from the transition-metal ions in the tetrahedral coordination complexes with those obtained fromthe corresponding ions in the octahedral ones, and found that the tetrahedral complexes have weaker crystal-field strength, in-verse energy level ordering and stronger covalence effect.