Developing non-precious metal-based inexpensive and highly active electrocatalysts for the oxygen reduction reaction(ORR)in alkaline media is important for fuel cell applications.Herein,we report a simple and effectiv...Developing non-precious metal-based inexpensive and highly active electrocatalysts for the oxygen reduction reaction(ORR)in alkaline media is important for fuel cell applications.Herein,we report a simple and effective synthesis of transition-metal-doped zeolitic imidazolate framework-8(ZIF-8)and carbon nanotube(CNT)composite catalysts(ZIF-8@CNT)prepared via high-temperature pyrolysis at 900℃.The catalysts were characterized using different physicochemical techniques and employed as cathode materials in anion exchange membrane fuel cells(AEMFC).The prepared metal-free(ZNT-900),single-metal-doped(Fe-ZNT-900,Co-ZNT-900)and binary-metal-doped(Fe_(1)Co_(1)-ZNT-900,Fe_(1)Co_(2)-ZNT-900)catalysts had a sufficient amount of N-doping with the presence of FeCo moieties in the carbon skeleton of the latter two materials.N_(2) adsorption–desorption isotherms showed that all the prepared catalysts possess a sufficient Brunauer–Emmett–Teller surface area with more micropores present in ZNT-900,while a combined micro–mesoporous structure was obtained for transition-metal-doped catalysts.Binary-metal-doped catalysts showed the highest number of ORR-active sites(pyridinic-N,pyrrolic-N,graphitic-N,M–Nx)and exhibited a half-wave potential(E_(1/2))of 0.846 and 0.847 V vs.RHE for Fe_(1)Co_(1)-ZNT-900 and Fe_(1)Co_(2)-ZNT-900,respectively,which surpassed that of the commercial Pt/C catalyst(E_(1/2)=0.834 V).In H_(2)–O_(2) AEMFCs,the Fe_(1)Co_(2)-ZNT-900 catalyst delivered a maximum power density(P_(max))of 0.171 W cm^(-2) and current density at 0.5 V(j_(0.5))of 0.326 A cm^(-2),which is very close to that of the Pt/C catalyst(P_(max)=0.215 W cm^(-2) and j_(0.5)=0.359 A cm^(-2)).The prepared ZIF-8@CNT catalysts showed remarkable electrocatalytic ORR activity in 0.1 M KOH solution and fuel cell performance comparable to that of the benchmark Pt/C catalyst.展开更多
基金The present work was financially supported by the Estonian Research Council(grants PRG723,PRG4 and PRG1509).
文摘Developing non-precious metal-based inexpensive and highly active electrocatalysts for the oxygen reduction reaction(ORR)in alkaline media is important for fuel cell applications.Herein,we report a simple and effective synthesis of transition-metal-doped zeolitic imidazolate framework-8(ZIF-8)and carbon nanotube(CNT)composite catalysts(ZIF-8@CNT)prepared via high-temperature pyrolysis at 900℃.The catalysts were characterized using different physicochemical techniques and employed as cathode materials in anion exchange membrane fuel cells(AEMFC).The prepared metal-free(ZNT-900),single-metal-doped(Fe-ZNT-900,Co-ZNT-900)and binary-metal-doped(Fe_(1)Co_(1)-ZNT-900,Fe_(1)Co_(2)-ZNT-900)catalysts had a sufficient amount of N-doping with the presence of FeCo moieties in the carbon skeleton of the latter two materials.N_(2) adsorption–desorption isotherms showed that all the prepared catalysts possess a sufficient Brunauer–Emmett–Teller surface area with more micropores present in ZNT-900,while a combined micro–mesoporous structure was obtained for transition-metal-doped catalysts.Binary-metal-doped catalysts showed the highest number of ORR-active sites(pyridinic-N,pyrrolic-N,graphitic-N,M–Nx)and exhibited a half-wave potential(E_(1/2))of 0.846 and 0.847 V vs.RHE for Fe_(1)Co_(1)-ZNT-900 and Fe_(1)Co_(2)-ZNT-900,respectively,which surpassed that of the commercial Pt/C catalyst(E_(1/2)=0.834 V).In H_(2)–O_(2) AEMFCs,the Fe_(1)Co_(2)-ZNT-900 catalyst delivered a maximum power density(P_(max))of 0.171 W cm^(-2) and current density at 0.5 V(j_(0.5))of 0.326 A cm^(-2),which is very close to that of the Pt/C catalyst(P_(max)=0.215 W cm^(-2) and j_(0.5)=0.359 A cm^(-2)).The prepared ZIF-8@CNT catalysts showed remarkable electrocatalytic ORR activity in 0.1 M KOH solution and fuel cell performance comparable to that of the benchmark Pt/C catalyst.
