In this work,the oxidation of a mixture of dimethyl ether(DME) and methyl formate(MF) was studied in both an aqueous electrochemical cell and a vapor-fed polymer electrolyte membrane fuel cell(PEMFC)utilizing a multi-...In this work,the oxidation of a mixture of dimethyl ether(DME) and methyl formate(MF) was studied in both an aqueous electrochemical cell and a vapor-fed polymer electrolyte membrane fuel cell(PEMFC)utilizing a multi-metallic alloy catalyst,Pt_(3)Pd_(3)Sn_(2)/C,discovered earlier by us.The current obtained during the bulk oxidation of a DME-saturated 1 M MF was higher than the summation of the currents provided by the two fuels separately,suggesting the cooperative effect of mixing these fuels.A significant increase in the anodic charge was realized during oxidative stripping of a pre-adsorbed DME+MF mixture as compared to DME or MF individually.This is ascribed to greater utilization of specific catalytic sites on account of the relatively lower adsorption energy of the dual-molecules than of the sum of the individual molecules as confirmed by the density fu nctional theory(DFT) calculations.Fuel cell polarization was also conducted using a Pt_(3)Pd_(3)Sn_(2)/C(anode) and Pt/C(cathode) catalysts-coated membrane(CCM).The enhanced surface coverage and active site utilization resulted in providing a higher peak power density by the DME+MF mixture-fed fuel cell(123 mW cm^(-2)at 0.45 V) than with DME(84mW cm^(-2)at 0.35 V) or MF(28 mW cm^(-2)at 0.2 V) at the same total anode hydrocarbon flow rate,temperature,and ambient pressure.展开更多
Iridium(Ir)-based catalysts are highly efficient for the anodic oxygen evolution reaction(OER)due to high stability and anti-corrosion ability in the strong acid electrolyte.Recently,intensive attention has been direc...Iridium(Ir)-based catalysts are highly efficient for the anodic oxygen evolution reaction(OER)due to high stability and anti-corrosion ability in the strong acid electrolyte.Recently,intensive attention has been directed to novel,efficient,and low-cost Ir-based catalysts to overcome the challenges of their application in the water electrolysis technique.To make a comprehensive understanding of the recently developed Ir-based catalysts and their catalytic properties,the mechanism and catalytic promotion principles of Ir-based catalysts were discussed for OER in the acid condition aimed for the proton exchange membrane water electrolyzer(PEMWE)in this review.The OER catalytic mechanisms of the adsorbate evolution mechanism and the lattice oxygen mechanism were first presented and discussed for easy understanding of the catalytic mechanism;a brief perspective analysis of promotion principles from the aspects of geometric effect,electronic effect,synergistic effect,defect engineering,support effect was concluded.Then,the latest progress and the practical application of Ir-based catalysts were introduced in detail,which was classified into the varied composition of Ir catalyst in terms of alloys,hetero-element doping,perovskite,pyrochlore,heterostructure,core-shell structure,and supported catalysts.Finally,the problems and challenges faced by the current Ir-based catalyst in the acidic electrolyte were put forward.It is concluded that highly efficient catalysts with low Ir loading should be developed in the future,and attention should be paid to probing the structural and performance correlation,and their application in real PEMWE devices.Hopefully,the current effort can be helpful in the catalysis mechanism understanding of Ir-based catalysts for OER,and instructive to the novel efficient catalysts design and fabrication.展开更多
Methanol as an important hydrogen-rich fuel has received increasing attention in energy storage and conversion techniques,and energy release can be realized in the methanol oxidation reaction(MOR)process.Note that hig...Methanol as an important hydrogen-rich fuel has received increasing attention in energy storage and conversion techniques,and energy release can be realized in the methanol oxidation reaction(MOR)process.Note that highly efficient catalysts are still required to drive methanol oxidation,and the Ni-based catalysts have received intensive attention due to their facile active site generation based on the electrochemical-chemical oxidation mechanisms.In light of the significant advances made recently,herein,we reviewed the recent advances of Ni-based catalysts for methanol oxidation in the alkaline medium.The fundamental of methanol oxidation in the alkaline medium was first presented,and then the catalyst design principles including synergistic effect,electronic effect,defect construction,doping effect,as well as surface reconstruction were presented;and the advances of various Ni-based catalysts for MOR are summarized and discussed by combining with some typical examples.The problems and challenges were also concluded for the Ni-based catalyst fabrication,the performance evaluation,and their application.We believe that the summary of this review will be helpful in the design of nickel-based catalysts and understanding the catalysis mechanism of nickel-based materials in alcohol fuel electrochemical reactions.展开更多
文摘实现绿色甲醇电解制氢需要高效的双功能催化剂。本文采用热处理结合乙二醇还原法成功制备了MoP-NC纳米球负载的超细Pt纳米粒子(平均粒径为2.53 nm)复合催化剂(Pt/MoP-NC)用于高效甲醇电解制氢。MoP-NC纳米球不仅能提高Pt纳米粒子的分散性并且增强Pt的抗中毒能力。电化学测试表明Pt/MoP-NC催化剂在酸性甲醇氧化反应(MOR)和析氢反应(HER)中具有较高的催化性能;其中,MOR的正向扫描峰值电流密度为90.7 m A·cm^(-2),是商业Pt/C催化剂的3.2倍,在10 mA·cm^(-2)的电流密度下,HER的过电位低至30 m V,与商业Pt/C接近。由Pt/MoP-NC||Pt/MoP-NC组装的两电极电解槽驱动10 mA·cm^(-2)的电流密度仅需要0.67 V的电压,比相同条件下电解水的电压低1.02 V,大大降低了能量输入。Pt/MoP-NC的高催化性能主要来源于Pt活性中心与相邻层状多孔球形结构的MoP-NC载体之间电子效应及配体效应引起的抗一氧化碳中毒能力的提升和含氧物种的容易生成。
基金Ariel UniversityIsrael National Research Center for Electrochemical PropulsionNew Technologies Research Centre,University of West Bohemia,Pilsen for financially supporting this research。
文摘In this work,the oxidation of a mixture of dimethyl ether(DME) and methyl formate(MF) was studied in both an aqueous electrochemical cell and a vapor-fed polymer electrolyte membrane fuel cell(PEMFC)utilizing a multi-metallic alloy catalyst,Pt_(3)Pd_(3)Sn_(2)/C,discovered earlier by us.The current obtained during the bulk oxidation of a DME-saturated 1 M MF was higher than the summation of the currents provided by the two fuels separately,suggesting the cooperative effect of mixing these fuels.A significant increase in the anodic charge was realized during oxidative stripping of a pre-adsorbed DME+MF mixture as compared to DME or MF individually.This is ascribed to greater utilization of specific catalytic sites on account of the relatively lower adsorption energy of the dual-molecules than of the sum of the individual molecules as confirmed by the density fu nctional theory(DFT) calculations.Fuel cell polarization was also conducted using a Pt_(3)Pd_(3)Sn_(2)/C(anode) and Pt/C(cathode) catalysts-coated membrane(CCM).The enhanced surface coverage and active site utilization resulted in providing a higher peak power density by the DME+MF mixture-fed fuel cell(123 mW cm^(-2)at 0.45 V) than with DME(84mW cm^(-2)at 0.35 V) or MF(28 mW cm^(-2)at 0.2 V) at the same total anode hydrocarbon flow rate,temperature,and ambient pressure.
基金This work is supported by the National Natural Science Foundation of China(Nos.21972124 and 22272148),a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institution was also appreciated by the authors.
文摘Iridium(Ir)-based catalysts are highly efficient for the anodic oxygen evolution reaction(OER)due to high stability and anti-corrosion ability in the strong acid electrolyte.Recently,intensive attention has been directed to novel,efficient,and low-cost Ir-based catalysts to overcome the challenges of their application in the water electrolysis technique.To make a comprehensive understanding of the recently developed Ir-based catalysts and their catalytic properties,the mechanism and catalytic promotion principles of Ir-based catalysts were discussed for OER in the acid condition aimed for the proton exchange membrane water electrolyzer(PEMWE)in this review.The OER catalytic mechanisms of the adsorbate evolution mechanism and the lattice oxygen mechanism were first presented and discussed for easy understanding of the catalytic mechanism;a brief perspective analysis of promotion principles from the aspects of geometric effect,electronic effect,synergistic effect,defect engineering,support effect was concluded.Then,the latest progress and the practical application of Ir-based catalysts were introduced in detail,which was classified into the varied composition of Ir catalyst in terms of alloys,hetero-element doping,perovskite,pyrochlore,heterostructure,core-shell structure,and supported catalysts.Finally,the problems and challenges faced by the current Ir-based catalyst in the acidic electrolyte were put forward.It is concluded that highly efficient catalysts with low Ir loading should be developed in the future,and attention should be paid to probing the structural and performance correlation,and their application in real PEMWE devices.Hopefully,the current effort can be helpful in the catalysis mechanism understanding of Ir-based catalysts for OER,and instructive to the novel efficient catalysts design and fabrication.
基金National Natural Science Foundation of China(21972124 and 22272148)a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institution was also appreciated by the authors.
文摘Methanol as an important hydrogen-rich fuel has received increasing attention in energy storage and conversion techniques,and energy release can be realized in the methanol oxidation reaction(MOR)process.Note that highly efficient catalysts are still required to drive methanol oxidation,and the Ni-based catalysts have received intensive attention due to their facile active site generation based on the electrochemical-chemical oxidation mechanisms.In light of the significant advances made recently,herein,we reviewed the recent advances of Ni-based catalysts for methanol oxidation in the alkaline medium.The fundamental of methanol oxidation in the alkaline medium was first presented,and then the catalyst design principles including synergistic effect,electronic effect,defect construction,doping effect,as well as surface reconstruction were presented;and the advances of various Ni-based catalysts for MOR are summarized and discussed by combining with some typical examples.The problems and challenges were also concluded for the Ni-based catalyst fabrication,the performance evaluation,and their application.We believe that the summary of this review will be helpful in the design of nickel-based catalysts and understanding the catalysis mechanism of nickel-based materials in alcohol fuel electrochemical reactions.
