Non-enzymatic electrochemical sensors for the determination of hydrogen peroxide(H_(2)O_(2))have attracted more and more concerns.A series of nickel and cobalt double oxides(Ni_(x)Co_(y)-DO)with the different ratios o...Non-enzymatic electrochemical sensors for the determination of hydrogen peroxide(H_(2)O_(2))have attracted more and more concerns.A series of nickel and cobalt double oxides(Ni_(x)Co_(y)-DO)with the different ratios of Ni/Co have been prepared by a polyol-mediated solvothermal method for H_(2)O_(2)detection.The obtained products exhibit honeycomb-like open porous microtubes constituted with the low-dimensional nanostructured Ni_(x)Co_(y)-DO blocks after the calcination treatment.Compared with nickel oxides,the introduced Co ions in Ni_(x)Co_(y)-DO can induce the production of surficial oxygen vacancies,and further enhance the electrode surface activity.In particular,the NiCo-DO sample(with an atomic ratio of Ni/Co=4:3)shows the richest surficial oxygen vacancies and presents the highest H_(2)O_(2)detection activity among all the as-prepared samples,demonstrating an excellent sensitivity of698.60μAL mmol^(-1)cm^(-2)(0~0.4 mmol/L),low detection limit(0.28μmol/L,S/N=3),as well as long stability,high selectivity and good reproducibility.This work lends a new impetus to the potential application of double metal oxides for the next generation of non-enzymatic sensors.展开更多
Pt/WO3/C nanocomposites with parallel WO3 nanorods were synthesized and applied as the cathode catalyst for proton exchange membrane fuel cells （PEMFCs）. Electrochemical results and single cell tests show that an en...Pt/WO3/C nanocomposites with parallel WO3 nanorods were synthesized and applied as the cathode catalyst for proton exchange membrane fuel cells （PEMFCs）. Electrochemical results and single cell tests show that an enhanced activity for the oxygen reduction reaction （ORR） is obtained for the Pt/WO3/C catalyst compared with Pt/C. The higher catalytic activity might be ascribed to the improved Pt dispersion with smaller particle sizes. The Pt/WO3/C catalyst also exhibits a good electrochemical stability under potential cycling. Thus, the Pt/WO3/C catalyst can be used as a potential PEMFC cathode catalyst.展开更多
Durability is one of the critical issues to restrict the commercialization of proton exchange membrane fuel cells(PEMFCs) for the vehicle application.The practical dynamic operation significantly affects the PEMFCs du...Durability is one of the critical issues to restrict the commercialization of proton exchange membrane fuel cells(PEMFCs) for the vehicle application.The practical dynamic operation significantly affects the PEMFCs durability by corroding its key components.In this work,the degradation behavior of a single PEMFC has been investigated under a simulated automotive load-cycling operation,with the aim of revealing the effect of load amplitude(0.8 and 0.2 A/cm2 amplitude for the current density range of0.1-0.9 and 0.1-0.3 A/cm^(2),respectively) on its performance degradation.A more severe degradation on the fuel cell performance is observed under a higher load amplitude of 0.8 A/cm^(2) cycling operation,with$10.5% decrease of cell voltage at a current density of 1.0 A/cm2.The larger loss of fuel cell performance under the higher load amplitude test is mainly due to the frequent fluctuation of a wider potential cycling.Physicochemical characterizations analyses indicate that the Pt nanoparticles in cathodic catalyst layer grow faster with a higher increase extent of particle size under this circumstance because of their repeated oxidation/reduction and subsequent dissolution/agglomeration process,resulting in the degradation of platinum catalyst and thus the cell performance.Additionally,the detected microstructure change of the cathodic catalyst layer also contributes to the performance failure that causes a distinct increase in mass transfer resistance.展开更多
High-purity of hydrogen is vital to the guarantee of end usage in proton exchange membrane fuel cell(PEMFC)electric vehicles(EVs)with superior durability and low expense.However,the currently employed hydrogen,primari...High-purity of hydrogen is vital to the guarantee of end usage in proton exchange membrane fuel cell(PEMFC)electric vehicles(EVs)with superior durability and low expense.However,the currently employed hydrogen,primarily from fossil fuel,still contains some poisoning impurities that significantly affect the durability of PEMFCs.Here,we investigate the poisoning effect of several typical hydrogen impurities(S^(2-),Cl^(-),HCOO^(-)and CO_(3)^(2-))on the hydrogen oxidation reaction(HOR)of the state-of-the-art carbon-supported platinum(Pt/C)catalyst used in the PEMFC anode.Electrochemical results indicate that the electrochemically active surface area of Pt/C is hampered by these hydrogen impurities with reduced effective Pt reactive sites due to the competitive adsorption against hydrogen at Pt sites showing the extent of the poisoning on Pt sites in the order:S^(2-)>Cl^(-)>HCOO^(-)>CO_(3)^(2-).Density functional theory calculations reveal that the adsorption energy of S2-on Pt(111)is greater than that of Cl^(-),HCOO^(-)and CO_(2),and the electronic structure of Pt is found to be changed due to the adsorption of impurities showing the downshift of the d-band centre of Pt that weakens the adsorption of hydrogen on the Pt sites.This work provides valuable guidance for future optimization of hydrogen quality and also emphasizes the importance of anti-poisoning anode catalyst development,especially towards H_(2)S impurities that seriously affect the durability of PEMFCs.展开更多
基金supported by the National Natural Science Foundation of China(Nos.51432003,51802011 and 51125007)the Start-Up Fund for Talent Introduction of Beijing University of Chemical Technology(No.buctrc201806)the Fundamental Research Funds for the Central Universities(No.JD2010)。
文摘Non-enzymatic electrochemical sensors for the determination of hydrogen peroxide(H_(2)O_(2))have attracted more and more concerns.A series of nickel and cobalt double oxides(Ni_(x)Co_(y)-DO)with the different ratios of Ni/Co have been prepared by a polyol-mediated solvothermal method for H_(2)O_(2)detection.The obtained products exhibit honeycomb-like open porous microtubes constituted with the low-dimensional nanostructured Ni_(x)Co_(y)-DO blocks after the calcination treatment.Compared with nickel oxides,the introduced Co ions in Ni_(x)Co_(y)-DO can induce the production of surficial oxygen vacancies,and further enhance the electrode surface activity.In particular,the NiCo-DO sample(with an atomic ratio of Ni/Co=4:3)shows the richest surficial oxygen vacancies and presents the highest H_(2)O_(2)detection activity among all the as-prepared samples,demonstrating an excellent sensitivity of698.60μAL mmol^(-1)cm^(-2)(0~0.4 mmol/L),low detection limit(0.28μmol/L,S/N=3),as well as long stability,high selectivity and good reproducibility.This work lends a new impetus to the potential application of double metal oxides for the next generation of non-enzymatic sensors.
基金financially supported by the National Natural Science Fundation of China(No.51125007)the National Basic Research Program(No.2012CB215500)
文摘Pt/WO3/C nanocomposites with parallel WO3 nanorods were synthesized and applied as the cathode catalyst for proton exchange membrane fuel cells （PEMFCs）. Electrochemical results and single cell tests show that an enhanced activity for the oxygen reduction reaction （ORR） is obtained for the Pt/WO3/C catalyst compared with Pt/C. The higher catalytic activity might be ascribed to the improved Pt dispersion with smaller particle sizes. The Pt/WO3/C catalyst also exhibits a good electrochemical stability under potential cycling. Thus, the Pt/WO3/C catalyst can be used as a potential PEMFC cathode catalyst.
基金supported by the National Key R&D Program of China (No.2018YFB0105503)。
文摘Durability is one of the critical issues to restrict the commercialization of proton exchange membrane fuel cells(PEMFCs) for the vehicle application.The practical dynamic operation significantly affects the PEMFCs durability by corroding its key components.In this work,the degradation behavior of a single PEMFC has been investigated under a simulated automotive load-cycling operation,with the aim of revealing the effect of load amplitude(0.8 and 0.2 A/cm2 amplitude for the current density range of0.1-0.9 and 0.1-0.3 A/cm^(2),respectively) on its performance degradation.A more severe degradation on the fuel cell performance is observed under a higher load amplitude of 0.8 A/cm^(2) cycling operation,with$10.5% decrease of cell voltage at a current density of 1.0 A/cm2.The larger loss of fuel cell performance under the higher load amplitude test is mainly due to the frequent fluctuation of a wider potential cycling.Physicochemical characterizations analyses indicate that the Pt nanoparticles in cathodic catalyst layer grow faster with a higher increase extent of particle size under this circumstance because of their repeated oxidation/reduction and subsequent dissolution/agglomeration process,resulting in the degradation of platinum catalyst and thus the cell performance.Additionally,the detected microstructure change of the cathodic catalyst layer also contributes to the performance failure that causes a distinct increase in mass transfer resistance.
基金supported by the National Key R&D Program of China (No.2019YFB1505004).
文摘High-purity of hydrogen is vital to the guarantee of end usage in proton exchange membrane fuel cell(PEMFC)electric vehicles(EVs)with superior durability and low expense.However,the currently employed hydrogen,primarily from fossil fuel,still contains some poisoning impurities that significantly affect the durability of PEMFCs.Here,we investigate the poisoning effect of several typical hydrogen impurities(S^(2-),Cl^(-),HCOO^(-)and CO_(3)^(2-))on the hydrogen oxidation reaction(HOR)of the state-of-the-art carbon-supported platinum(Pt/C)catalyst used in the PEMFC anode.Electrochemical results indicate that the electrochemically active surface area of Pt/C is hampered by these hydrogen impurities with reduced effective Pt reactive sites due to the competitive adsorption against hydrogen at Pt sites showing the extent of the poisoning on Pt sites in the order:S^(2-)>Cl^(-)>HCOO^(-)>CO_(3)^(2-).Density functional theory calculations reveal that the adsorption energy of S2-on Pt(111)is greater than that of Cl^(-),HCOO^(-)and CO_(2),and the electronic structure of Pt is found to be changed due to the adsorption of impurities showing the downshift of the d-band centre of Pt that weakens the adsorption of hydrogen on the Pt sites.This work provides valuable guidance for future optimization of hydrogen quality and also emphasizes the importance of anti-poisoning anode catalyst development,especially towards H_(2)S impurities that seriously affect the durability of PEMFCs.
