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Oxidation Evolution and Activity Origin of N-Doped Carbon in the Oxygen Reduction Reaction
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作者 Jiaqi Wu Chuanqi Cheng +2 位作者 Shanshan Lu Bin Zhang Yanmei Shi 《Transactions of Tianjin University》 EI CAS 2024年第4期369-379,共11页
N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher ... N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production. 展开更多
关键词 Oxygen reduction reaction N-doped carbon Reaction path Structural evolution oxidation in reduction
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Interfacial and Vacancies Engineering of Copper Nickel Sulfide for Enhanced Oxygen Reduction and Alcohols Oxidation Activity
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作者 Zhaoyang Wang Xiaobin Liao +10 位作者 Min Zhou Fuzhi Huang Kwadwo Asare Owusu Jiantao Li Zifeng Lin Qi Sun Xufeng Hong Congli Sun Yibing Cheng Yan Zhao Liqiang Mai 《Energy & Environmental Materials》 SCIE EI CAS CSCD 2023年第5期288-298,共11页
Rational design and construction of highly efficient nonprecious electrocatalysts for oxygen reduction and alcohols oxidation reactions(ORR,AOR)are extremely vital for the development of direct oxidation alkaline fuel... Rational design and construction of highly efficient nonprecious electrocatalysts for oxygen reduction and alcohols oxidation reactions(ORR,AOR)are extremely vital for the development of direct oxidation alkaline fuel cells,metal-air batteries,and water electrolysis system involving hydrogen and value-added organic products generation,but they remain a great challenge.Herein,a bifunctional electrocatalyst is prepared by anchoring CuS/NiS_(2)nanoparticles with abundant heterointerfaces and sulfur vacancies on graphene(Cu_(1)Ni_(2)-S/G)for ORR and AOR.Benefiting from the synergistic effects between strong interfacial coupling and regulation of the sulfur vacancies,Cu_(1)Ni_(2)-S/G achieves dramatically enhanced ORR activity with long term stability.Meanwhile,when ethanol is utilized as an oxidant for AOR,an ultralow potential(1.37 V)at a current density of 10 mA cm-2 is achieved,simultaneously delivering a high Faradaic efficiency of 96%for ethyl acetate production.Cu_(1)Ni_(2)-S/G also exhibits catalytic activity for other alcohols electrooxidation process,indicating its multifunctionality.This work not only highlights a viable strategy for tailoring catalytic activity through the synergetic combination of interfacial and vacancies engineering,but also opens up new avenues for the construction of a self-driven biomass electrocatalysis system for the generation of value-added organic products and hydrogen under ambient conditions. 展开更多
关键词 alcohols oxidation reaction HETEROINTERFACE metal sulfide oxygen reduction reaction sulfur vacancies
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Deciphering the linear relationship in the activity of the oxygen reduction reaction on Pt electrodes:A decisive role of adsorbates
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作者 Haowen Cui Yan-Xia Chen 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第7期70-77,共8页
Despite substantial efforts in developing high-performance catalysts for the oxygen reduction reaction(ORR),the persistent challenge lies in the high onset overpotential of the ORR,and the effect of the elec-trolyte s... Despite substantial efforts in developing high-performance catalysts for the oxygen reduction reaction(ORR),the persistent challenge lies in the high onset overpotential of the ORR,and the effect of the elec-trolyte solution cannot be ignored.Consequently,we have systematically investigated the impact of adsorbate species and concentration,as well as solution pH,on the ORR activity on Pt(111)and Pt(poly)electrodes.The results all tend to establish a linear quantitative relationship between the onset potential for ORR and the adsorption equilibrium potential of the adsorbate.This finding indicates the decisive role of adsorbates in the onset potential for ORR,suggesting that the adsorption potential of adsorbates can serve as an intuitive criterion for ORR activity.Additional support for this conclusion is derived from experimental results obtained from the oxygen evolution reaction on Pt(poly)with different adsorbate species and from the hydrogen evolution reaction on Pt(111)with iodine adsorption.We further propose both an empirical equation for the onset potential for ORR and the concept of a potential-regulated adsor-bate shielding effect to elucidate the influence of adsorbates on ORR activity.This study provides new insights into the high onset overpotential of the ORR and offers potential strategies for predicting and enhancingORRactivity inthefuture. 展开更多
关键词 Oxygen reduction reaction activity ADSORBATE Equilibrium potential Pt(111)
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Performance enhancement and active sites identification of Cu-Cd bimetallic oxide derived catalysts for electrochemical CO_(2) reduction
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作者 Cai Wang Xin Hu +7 位作者 Bairong Chen Houan Ren Xiaoyu Wang Yilin Zhang Xinyu Chen Yuping Liu Qingxin Guan Wei Li 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第4期50-58,共9页
The development of earth-abundant electrocatalysts with high performance for electrochemical CO_(2)reduction(ECR)is of great significance.Cu-based catalysts have been widely investigated for ECR due to their unique ab... The development of earth-abundant electrocatalysts with high performance for electrochemical CO_(2)reduction(ECR)is of great significance.Cu-based catalysts have been widely investigated for ECR due to their unique ability to generate various carbonaceous products,but directing selectivity toward one certain product and identifying the real active sites during ECR are still full of challenge.Here,after the incorporation of CdO into CuO,the Cu_(0.5)Cd_(0.5)-O catalyst achieves a 10.3-fold enhancement for CO selectivity in comparison with CuO,and a CO faradic efficiency nearly 90%with a current density around20 mA cm^(-2)could maintain at least 60 h.Interestingly,a wide CO/H_(2)ratio(0.07-10)is reached on Cu_(x)Cd_(1-x)-O catalysts by varying the Cu/Cd ratio,demonstrating the potential of syngas production using such catalysts.The results of ex situ XRD,XPS,and in situ Raman reveal that the real active sites of Cu_(0.5)Cd_(0.5)-O catalysts for CO production during ECR reaction are the reconstructed mixed phases of CuCd alloy and CdCO_(3).In situ FTIR and theoretical calculations further implicate the presence of Cd related species promotes the CO desorption and inhibits the H_(2)evolution,thus leading to an enhanced CO generation. 展开更多
关键词 CO_(2)reduction Cu-Cd bimetallic Real active sites CO production
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Porous metal oxides in the role of electrochemical CO_(2) reduction reaction 被引量:1
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作者 Ziqi Zhang Jinyun Xu +9 位作者 Yu Zhang Liping Zhao Ming Li Guoqiang Zhong Di Zhao Minjing Li Xudong Hu Wenju Zhu Chunming Zheng Xiaohong Sun 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第1期373-398,I0009,共27页
The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous me... The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction. 展开更多
关键词 CO_(2)reduction Carbon dioxide TRANSFORMATION Porous metal oxides ELECTROCATALYSIS
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Revealing the correlation between adsorption energy and activation energy to predict the catalytic activity of metal oxides for HMX using DFT
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作者 Xiurong Yang Chi Zhang +6 位作者 Wujing Jin Zhaoqi Guo Hongxu Gao Shiyao Niu Fengqi Zhao Bo Liu Haixia Ma 《Defence Technology(防务技术)》 SCIE EI CAS CSCD 2024年第1期262-270,共9页
Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculate... Traditional selection of combustion catalysis is time-consuming and labor-intensive.Theoretical calculation is expected to resolve this problem.The adsorption energy of HMX and O atoms on 13 metal oxides was calculated using DMol3,since HMX and O are key substances in decomposition process.And the relationship between the adsorption energy of HMX,O on metal oxides(TiO_(2),Al_(2)O_(3),PbO,CuO,Fe_(2)O_(3),Co_(3)O_(4),Bi_(2)O_(3),NiO)and experimental T30 values(time required for the decomposition depth of HMX to reach 30%)was depicted as volcano plot.Thus,the T30 values of other metal oxides was predicted based on their adsorption energy on volcano plot and validated by previous experimental data.Further,the adsorption energy of HMX on ZrO_(2)and MnO_(2)was predicted based on the linear relationship between surface energy and adsorption energy,and T30 values were estimated based on volcano plot.The apparent activation energy data of HMX/MgO,HMX/SnO_(2),HMX/ZrO_(2),and HMX/MnO_(2)obtained from DSC experiments are basically consistent with our predicted T30 values,indicating that it is feasible to predict the catalytic activity based on the adsorption calculation,and it is expected that these simple structural properties can predict adsorption energy to reduce the large quantities of computation and experiment cost. 展开更多
关键词 Density functional theory HMX Metal oxides Adsorption energy activation energy
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Electrochemical reduction of carbon dioxide to produce formic acid coupled with oxidative conversion of biomass
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作者 Xi Liu Yifan Wang +2 位作者 Zhiwei Dai Daihong Gao Xuebing Zhao 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第5期705-729,共25页
Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(... Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products. 展开更多
关键词 Electrochemical reduction of CO_(2) Formic acid oxidative conversion of biomass LIGNOCELLULOSE Coupled system
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Effects of mechanical activation and oxidation-reduction on hydrochloric acid leaching of Panxi ilmenite concentration 被引量:6
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作者 谭平 胡慧萍 张黎 《Transactions of Nonferrous Metals Society of China》 SCIE EI CAS CSCD 2011年第6期1414-1421,共8页
The effects of oxidation-reduction treatment and mechanical activation on the hydrochloric acid leaching performance of Panxi ilmenite concentration were investigated.The results show that both of oxidation-reduction ... The effects of oxidation-reduction treatment and mechanical activation on the hydrochloric acid leaching performance of Panxi ilmenite concentration were investigated.The results show that both of oxidation-reduction treatment and mechanical activation significantly accelerate the extraction of Fe,Ca and Mg from Panxi ilmenite concentration;however,the CaO and MgO contents of the calcined residues obtained from oxidized-reduced ilmenite concentration are higher than the standard values required by chlorination process.The Ca and Mg in oxidized-reduced ilmenite concentration can be leached much faster after mechanical activation,yielding a synthetic rutile which meets the requirements of chlorination process containing 90.50% TiO2 and 1.37% total iron as well as combined CaO and MgO of 1.00%.The optimum oxidation and reduction conditions are as follows:oxidization at 900 ℃ in the presence of oxygen for 15 min and reduction at 750 ℃ by hydrogen for 30 min. 展开更多
关键词 ilmenite concentration mechanical activation oxidation reduction hydrochloric acid leaching
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Acetic acid-assisted mild dealloying of fine CuPd nanoalloys achieving compressive strain toward high-efficiency oxygen reduction and ethanol oxidation electrocatalysis 被引量:5
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作者 Danye Liu Yu Zhang +5 位作者 Hui Liu Peng Rao Lin Xu Dong Chen Xinlong Tian Jun Yang 《Carbon Energy》 SCIE CSCD 2023年第7期112-120,共9页
Dealloying by which the transition metal is partially or completely leached from an alloy precursor is an effective way to optimize the fundamental effects for further enhancing the electrocatalysis of a catalyst.Here... Dealloying by which the transition metal is partially or completely leached from an alloy precursor is an effective way to optimize the fundamental effects for further enhancing the electrocatalysis of a catalyst.Herein,to address the deficiencies associated with the commonly used dealloying methods,for example,electrochemical and sulfuric acid/nitric acid treatment,we report an acetic acid-assisted mild strategy to dealloy Cu atoms from the outer surface layers of CuPd alloy nanoparticles to achieve high-efficiency electrocatalysis for oxygen reduction and ethanol oxidation in an alkaline electrolyte.The leaching of Cu atoms by acetic acid exerts an additional compressive strain effect on the surface layers and exposes more active Pd atoms,which is beneficial for boosting the catalytic performance of a dealloyed catalyst for the oxygen reduction reaction(ORR)and the ethanol oxidation reaction(EOR).In particular,for ORR,the CuPd nanoparticles with a Pd/Cu molar ratio of 2:1 after acetic dealloying show a half-wave potential of 0.912 V(vs.RHE)and a mass activity of 0.213 AmgPd^(-1) at 0.9 V,respectively,while for EOR,the same dealloyed sample has a mass activity and a specific activity of 8.4 Amg^(-1) and 8.23 mA cm^(-2),respectively,much better than their dealloyed counterparts at other temperatures and commercial Pd/C as well as a Pt/C catalyst. 展开更多
关键词 compressive strain effect DEALLOYING ELECTROCATALYSIS ethanol oxidation reaction oxygen reduction reaction
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Activation of Transition Metal(Fe,Co and Ni)-Oxide Nanoclusters by Nitrogen Defects in Carbon Nanotube for Selective CO_(2) Reduction Reaction 被引量:1
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作者 Yi Cheng Jinfan Chen +7 位作者 Chujie Yang Huiping Wang Bernt Johannessen Lars Thomsen Martin Saunders Jianping Xiao Shize Yang San Ping Jiang 《Energy & Environmental Materials》 SCIE EI CAS CSCD 2023年第1期253-263,共11页
The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are u... The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are urgently required.Transition metal oxides such as CoO_(x),FeO_(x),and NiO_(x)are low-cost,low toxicity,and abundant materials for a wide range of electrochemical reactions,but are almost inert for CO_(2)RR.Here,we report for the first time that nitrogen doped carbon nanotubes(N-CNT)have a surprising activation effect on the activity and selectivity of transition metal-oxide(MO_(x)where M=Fe,Ni,and Co)nanoclusters for CO_(2)RR.MO_(x)supported on N-CNT,MO_(x)/N-CNT,achieves a CO yield of 2.6–2.8 mmol cm−2 min−1 at an overpotential of−0.55 V,which is two orders of magnitude higher than MO_(x)supported on acid treated CNTs(MO_(x)/O-CNT)and four times higher than pristine N-CNT.The faraday efficiency for electrochemical CO_(2)-to-CO conversion is as high as 90.3%at overpotential of 0.44 V.Both in-situ XAS measurements and DFT calculations disclose that MO_(x)nanoclusters can be hydrated in CO_(2)saturated KHCO_(3),and the N defects of N-CNT effectively stabilize these metal hydroxyl species under carbon dioxide reduction reaction conditions,which can split the water molecules and provide local protons to inhibit the poisoning of active sites under carbon dioxide reduction reaction conditions. 展开更多
关键词 activation effect electrochemical CO_(2)reduction reaction N defect proton-coupled electron transfer process transition metal oxide nanocluster
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Electrochemical partial reduction of Ni(OH)_(2) to Ni(OH)_(2)/Ni via coupled oxidation of an interfacing NiAl intermetallic compound for robust hydrogen evolution 被引量:1
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作者 Young Hwa Yun Kwangsoo Kim +8 位作者 Changsoo Lee Byeong-Seon An Ji Hee Kwon Sechan Lee MinJoong Kim Jongsu Seo Jong Hyeok Park Byung-Hyun Kim Hyun-Seok Cho 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第7期560-571,I0012,共13页
Ni-based porous electrocatalysts have been widely used in the hydrogen evolution reaction(HER)in alkaline water electrolysis,and the catalysts are produced by selective leaching of Al from Ni-Al alloys.It is well know... Ni-based porous electrocatalysts have been widely used in the hydrogen evolution reaction(HER)in alkaline water electrolysis,and the catalysts are produced by selective leaching of Al from Ni-Al alloys.It is well known that chemical leaching of Ni-Al intermetallic compound(IMC)generates a high surface area in Ni(OH)_(2).However,the Ni(OH)_(2) produced by leaching the Ni-Al intermetallic compound retards the hydrogen evolution reaction,which is attributed to its weak hydrogen adsorption energy.In this study,we controlled the chemical state of Ni using plasma vapor deposition(PVD)followed by heat treatment,selective Al leaching,and electrochemical reduction.X-ray diffraction(XRD),scanning microscopy(SEM),transmission electron microscopy(TEM),and energy-dispersive X-ray spectroscopy(EDS)were used to confirm the phase evolution of the electrocatalysts during fabrication.We reveal that the heat-treated Ni-Al alloy with a thick Ni2Al3surface layer underwent selective Al leaching and produced biphasic interfaces comprising Ni(OH)_(2) and NiAl IMCs at the edges of the grains in the outermost surface layer.Coupled oxidation of the interfacing NiAl IMCs facilitated the partial reduction of Ni(OH)_(2) to Ni(OH)_(2)/Ni in the grains during electrochemical reduction,as confirmed by X-ray photoelectron spectroscopy(XPS).An electrocatalyst containing partially reduced Ni(OH)_(2)/Ni exhibited an overpotential of 54 mV at 10 mA/cm^(2) in a half-cell measurement,and a cell voltage of 1.675 V at 0.4 A/cm2for single-cell operation.A combined experimental and theoretical study(density functional theory calculations)revealed that the superior HER activity was attributed to the presence of partially reduced metallic Ni with various defects and residual Al,which facilitated water adsorption,dissociation,and finally hydrogen evolution. 展开更多
关键词 Raney nickel HERChemical leaching Intrinsic activity Partial reduction
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Catalytic activity of V_(2)CO_(2) MXene supported transition metal single atoms for oxygen reduction and hydrogen oxidation reactions:A density functional theory calculation study
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作者 Zhongjing Deng Xingqun Zheng +3 位作者 Mingming Deng Li Li Li Jing Zidong Wei 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 2021年第10期1659-1666,共8页
Two-dimensional(2D)MXene and single-atom(SA)catalysts are two frontier research fields in catalysis.2D materials with unique geometric and electronic structures can modulate the catalytic performance of supported SAs,... Two-dimensional(2D)MXene and single-atom(SA)catalysts are two frontier research fields in catalysis.2D materials with unique geometric and electronic structures can modulate the catalytic performance of supported SAs,which,in turn,affect the intrinsic activity of 2D materials.Density functional theory calculations were used to systematically explore the potential of O-terminated V2C MXene(V_(2)CO_(2))-supported transition metal(TM)SAs,including a series of 3d,4d,and 5d metals,as oxygen reduction reaction(ORR)and hydrogen oxidation reaction(HOR)catalysts.The combination of TM SAs and V_(2)CO_(2)changes their electronic structure and enriches the active sites,and consequently regulates the intermediate adsorption energy and catalytic activity for ORR and HOR.Among the investigated TM-V_(2)CO_(2)models,Sc-,Mn-,Rh-,and PtMCCh showed high ORR activity,while Sc-,Ti-,V-,Cr-,and Mn-V_(2)CO_(2)exhibited high HOR activity.Specifically,Mn-and Sc-V_(2)CO_(2)are expected to serve as highly efficient and cost-effective bifunctional catalysts for fuel cells because of their high catalytic activity and stability.This work provides theoretical guidance for the rational design of efficient ORR and HOR bifunctional catalysts. 展开更多
关键词 Single atoms catalyst MXenes Oxygen reduction reaction Hydrogen oxidation reaction Density functional theory Fuel cells
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Preparation of nano-platinum and its catalytic activity toward methanol oxidation and oxygen reduction
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作者 黄幼菊 戴宏海 +3 位作者 李伟 张庆龙 赵灵智 李伟善 《中国有色金属学会会刊:英文版》 CSCD 2007年第A02期1006-1009,共4页
Nano-scale platinum catalysts were prepared on a glass carbon electrode by cyclic voltammetry. The surface morphology and active area of the catalysts,and their catalytic activity toward methanol oxidation and oxygen ... Nano-scale platinum catalysts were prepared on a glass carbon electrode by cyclic voltammetry. The surface morphology and active area of the catalysts,and their catalytic activity toward methanol oxidation and oxygen reduction were studied by SEM,linear and cyclic voltammetry. The result shows that the diameters of global Pt particles are affected by the scan rate of cyclic voltammetry:the faster the scan rate is,the smaller the diameters of Pt particles are. The size of the nano-scale platinum catalysts has different effects on their catalytic activity toward oxygen reduction and methanol oxidation:the catalyst with a size of 100 nm shows its best activity toward methanol oxidation,but the catalyst with a size of 65 nm shows its best activity toward oxygen reduction. 展开更多
关键词 纳米材料 纳米铂 催化作用 甲醇氧化作用
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Metal-organic framework-based materials as key components in electrocatalytic oxidation and reduction reactions
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作者 Soheila Sanati Ali Morsali Hermenegildo García 《Journal of Energy Chemistry》 SCIE EI CSCD 2023年第12期540-567,I0014,共29页
Studies have extensively addressed the development of electrocatalytic technologies for energy storage and conversion,fuel production,and environmental protection.Electrode processes such as different oxidation and re... Studies have extensively addressed the development of electrocatalytic technologies for energy storage and conversion,fuel production,and environmental protection.Electrode processes such as different oxidation and reduction reactions play a vital and significant role in these technologies.In this regard,efficient,inexpensive,and stable electrocatalysts capable can significantly promote electrochemical reactions.Unique features of metal–organic frameworks(MOFs)such as their high porosity,tunable structure,size,and pore shape,high surface area,and redox properties have introduced them as an ideal electrocatalyst candidate.This review is thus aimed at elucidating the role of MOF-based materials(pristine,derivatives and composites)as efficient electrocatalysts in energy and sensing-related oxidation and reduction reactions such as oxygen reduction reaction(ORR),hydrogen oxidation reaction(HOR),carbon dioxide reduction reaction(CO_(2)RR),urea oxidation reaction(UOR),alcohol oxidation reaction(AOR),nitrogen reduction reaction(NRR),and glucose oxidation reaction(GOR)in advanced energy and sensing devices.Also,the structure–property relationship of the electrocatalyst was elaborated for each electrocatalytic reaction.Finally,perspectives on the potential research topics for practical use of MOF-based electrocatalysts are addressed.The present review can improve the interest in MOF-based electrocatalysts to study different oxidation and reduction reactions in energy and sensing systems. 展开更多
关键词 Metal-organic frameworks ELECTROCATALYST oxidation reaction reduction reaction
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Regulation of excitation energy transfer in Sb-alloyed Cs_(4)MnBi_(2)Cl_(12) perovskites for efficient CO_(2) photoreduction to CO and water oxidation toward H_(2)O_(2)
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作者 Haiwen Wei Zhen Li +7 位作者 Honglei Wang Yang Yang Pengfei Cheng Peigeng Han Ruiling Zhang Feng Liu Panwang Zhou Keli Han 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第7期18-24,I0001,共8页
Lead(Pb)-free halide perovskites have recently attracted increasing attention as potential catalysts for CO_(2) photoreduction to CO due to their potential to capture solar energy and drive catalytic reaction.However,... Lead(Pb)-free halide perovskites have recently attracted increasing attention as potential catalysts for CO_(2) photoreduction to CO due to their potential to capture solar energy and drive catalytic reaction.However,issues of the poor charge transfer still remain one of the main obstacles limiting their performance due to the overwhelming radiative and nonradiative charge-carrier recombination losses.Herein,Pb-free Sb-alloyed all-inorganic quadruple perovskite Cs_(4)Mn(Bi_(1-x)Sb_(x))_(2)Cl_(12)(0≤x≤1)is synthesized as efficient photocatalyst.By Sb alloying,the undesired relaxation of photogenerated electrons from conduction band to emission centers of[MnCl6]^(4-)is greatly suppressed,resulting in a weakened PL emission and enhanced charge transfer for photocatalyst.The ensuing Cs_(4)Mn(Bi_(1-x)Sb_(x))_(2)Cl_(12) photocatalyst accomplishes efficient conversion of CO_(2)into CO,accompanied by a surprising production of H_(2)O_(2),a high valueadded product associated with water oxidation.By optimizing Sb^(3+) concentration,a high CO evolution rate of 35.1μmol g^(-1)h^(-1)is achieved,superior to most other Pb and Pb-free halide perovskites.Our findings provide new insights into the mixed-cation alloying strategies for improved photocatalytic performance of Pb-free perovskites and shed light on the rational design of robust band structure toward efficient energy transfer. 展开更多
关键词 Pb-free perovskites Energy band modulation Perovskite photocatalysis photocatalytic CO_(2)reduction Water oxidation to H_(2)O_(2)
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Comparison of 1,2,3-Trichloropropane reduction and oxidation by nanoscale zero-valent iron, zinc and activated persulfate 被引量:1
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作者 LI Hui HAN Zhan-tao +1 位作者 MA Chun-xiao GUI Jian-ye 《Journal of Groundwater Science and Engineering》 2015年第2期156-163,共8页
Trichloropropane(TCP) is a chlorinated solvent which derives from chemical manufacturing as a precursor, and it is also an important constituent of solvent formulations in cleaning/degreasing operations. The control... Trichloropropane(TCP) is a chlorinated solvent which derives from chemical manufacturing as a precursor, and it is also an important constituent of solvent formulations in cleaning/degreasing operations. The control and remediation of TCP in polluted sites is a challenge for many conventional remediation techniques due to its refractory behaviour. This challenge in mind, some nano-materials and oxidants were tested to evaluate their effectiveness as in TCP degradation in a laboratory setting. Experimental results indicate that the use of nanoscale zero-valent iron prepared by green tea(GT) as a reductant has negligible degradation effect on TCP under normal temperature and pressure conditions. However, zinc powders of similar size but higher surface reactivity, demonstrated stronger dechlorination capacity in the breakdown of TCP, as almost all of TCP was degraded by carboxymethocel(CMC) stabilized nanoscale zinc within 24 h. Activated persulfate by citric acid(CA) and chelated Fe(Ⅱ) was also used for TCP treatment with a TCP removal efficiency rate of nearly 50% within a 24 h reaction period, and a molar ratio of S2O82-, Fe2+ and CA is 20:5:1. Both the reduction and oxidation reactions are in accordance with the pseudo-first order kinetic equation. These results are promising for future use of TCP for the remediation of polluted sites. 展开更多
关键词 1 2 3-Trichloropropane reduction Advanced oxidation NANOPARTICLES activated persulfate
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Achieving exceptional activity and durability toward oxygen reduction based on a cobalt-free perovskite for solid oxide fuel cells 被引量:1
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作者 Feifei Dong Zhenghui Gao +5 位作者 Bingkai Zhang Lu Li Ziqi Kong Zilin Ma Meng Ni Zhan Lin 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2021年第11期653-659,I0016,共8页
In response to the shortcomings of cobalt-rich cathodes, iron-based perovskite oxides appear as promising alternatives for solid oxide fuel cells (SOFCs). However, their inferior electrochemical performance at reduced... In response to the shortcomings of cobalt-rich cathodes, iron-based perovskite oxides appear as promising alternatives for solid oxide fuel cells (SOFCs). However, their inferior electrochemical performance at reduced temperatures (<700 ℃) becomes a major bottleneck for future progress. Here, a novel cobalt-free perovskite Ba_(0.75)Sr_(0.25)Fe_(0.875)Ga_(0.125)O_(3−δ) (BSFG) is developed as an efficient oxygen reduction electrode for SOFCs, featuring cubic-symmetry structure, large oxygen vacancy concentration and fast oxygen transport. Benefiting from these merits, cells incorporated with BSFG achieve exceptionally high electrochemical performance, as evidenced by a low polarization area-specific resistance of 0.074 Ω cm^(2) and a high peak power density of 1145 mW cm^(−2) at 600 ℃. Meanwhile, a robust short-term performance stability of BSFG cathode can be ascribed to the stable crystalline structure and favorable thermal expansion behavior. First-principles computations are also conducted to understanding the superior activity and durability toward oxygen reduction reaction. These pave the way for rationally developing highly active and robust cobalt-free perovskite-type cathode materials for reduced-temperature SOFCs. 展开更多
关键词 Solid oxide fuel cell CATHODE PEROVSKITE Oxygen reduction reaction Cobalt-free
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Influence of Oxidation and Reduction Treatments on the Photorefractive Properties of Mg:In:Fe:LiNbO_3 Crystals
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作者 王锐 王佳 +4 位作者 徐衍岭 王淼 杨春晖 徐玉恒 石连升 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 北大核心 2007年第9期1102-1106,共5页
A series of Mg:In:Fe:LiNbO3 crystals were grown by Czochralski technique; their absorption spectra and photo scattering resistance ability after oxidation or reduction treatment were measured by light spot distorti... A series of Mg:In:Fe:LiNbO3 crystals were grown by Czochralski technique; their absorption spectra and photo scattering resistance ability after oxidation or reduction treatment were measured by light spot distortion method, and their response time and exponential gain coefficient were tested by two-beam coupling experiment. Besides, the effective carrier concentration has been calculated. The results showed that the absorption edges of reduced and oxidized crystals are respectively shifted to violet and Einstein compared with those of the growth state crystal. From oxidation state to growth state to reduction state of the samples, the photo scattering resistance ability and response time decrease while the exponential gain coefficient and concentration of effective carriers increase. The reduction treatment was necessary for the Mg:In:Fe:LiNbO3 crystals to enhance their photorefractive properties. 展开更多
关键词 Mg:In:Fe:LiNbO3 crystals oxidation reduction photorefractive properties
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Characterization of apparent sulfur oxidation activity of thermophilic archaea in bioleaching of chalcopyrite 被引量:5
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作者 朱薇 夏金兰 +2 位作者 彭安安 聂珍媛 邱冠周 《Transactions of Nonferrous Metals Society of China》 SCIE EI CAS CSCD 2013年第8期2383-2388,共6页
The apparent sulfur oxidation activities of four pure thermophilic archaea, Acidianus brierleyi (JCM 8954), Metallosphaera sedula (YN 23), Acidianus manzaensis (YN 25) and Sulfolobus metallicus (YN 24) and the... The apparent sulfur oxidation activities of four pure thermophilic archaea, Acidianus brierleyi (JCM 8954), Metallosphaera sedula (YN 23), Acidianus manzaensis (YN 25) and Sulfolobus metallicus (YN 24) and their mixture in bioleaching chalcopyrite were compared, which were characterized indirectly by the evolution of the cells concentration, pH value and sulfate ions concentration in solution. The results show that the mixed culture contributed significantly to the raising of leaching rate, which suggests that the mixed culture had a higher sulfur oxidation activity than the pure culture. Meanwhile, the results also indicate that the changes of parameters characterizing the sulfur oxidation activity of thermophilic archaea are often influenced by many factors, so it is hard to reflect accurately the specific sulfur oxidation activities among the different sulfur-oxidizing microbes when bioleaching chalcopyrite at different conditions. Accordingly, an efficient method to characterize microbial sulfur oxidation activity appears to be desirable. 展开更多
关键词 thermophilic archaea sulfur oxidation activity CHARACTERIZATION BIOLEACHING
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Effect of preparation routes on activity of Ag-MnO_x/C as electrocatalysts for oxygen reduction reaction in alkaline media 被引量:2
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作者 伍秋美 阮建明 +1 位作者 周忠诚 桑商斌 《Transactions of Nonferrous Metals Society of China》 SCIE EI CAS CSCD 2015年第2期510-519,共10页
The effect of preparation routes on the physical characteristics and activity of the Ag-MnOx/C composites toward the oxygen reduction reaction (ORR) in alkaline media were studied by X-ray diffraction (XRD), X-ray... The effect of preparation routes on the physical characteristics and activity of the Ag-MnOx/C composites toward the oxygen reduction reaction (ORR) in alkaline media were studied by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy-dispersion spectroscopy (EDS) as well as scanning electron microscopy (SEM) and electrochemical techniques. The results show that more Ag and Mn species present on the surface of the Ag-MnOx/C composite prepared by two-step route (Ag-MnOx/C-2) compared to the one prepared by one-step route (Ag-MnOx/C-1), which contributes to its superior activity toward the ORR. The higher electron transfer number involved in the ORR can be observed on the Ag-MnOx/C-2 composite and its specific mass kinetic current at -0.6 V (vs Hg/HgO) is 46 mA/μg, which is 23 times that on the Ag/C. The peak power density of zinc-air battery with the Ag-MnOx/C-2 air electrode reaches up to 117 mW/cm^2. 展开更多
关键词 SILVER manganese oxide oxygen reduction reaction zinc-air battery ELECTROCATALYST full cell
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