Efficacious regulation of the geometric and electronic structures of carbon nanomaterials via the introduction of defects and their synergy is essential to achieving good electrochemical performance.However,the guidel...Efficacious regulation of the geometric and electronic structures of carbon nanomaterials via the introduction of defects and their synergy is essential to achieving good electrochemical performance.However,the guidelines for designing hybrid materials with advantageous structures and the fundamental understanding of their electrocatalytic mechanisms remain unclear.Herein,superfine Pt and PtCu nanoparticles supported by novel S,N‐co‐doped multi‐walled CNT(MWCNTs)were prepared through the innovative pyrolysis of a poly(3,4‐ethylenedioxythiophene)/polyaniline copolymer as a source of S and N.The uniform wrapping of the copolymer around the MWCNTs provides a high density of evenly distributed defects on the surface after the pyrolysis treatment,facilitating the uniform distribution of ultrafine Pt and PtCu nanoparticles.Remarkably,the Pt_(1)Cu_(2)/SN‐MWCNTs show an obviously larger electroactive surface area and higher mass activity,stability,and CO poisoning resistance in methanol oxidation compared to Pt/SN‐MWCNTs,Pt/S‐MWCNTs,Pt/N‐MWCNTs,and commercial Pt/C.Density functional theory studies confirm that the co‐doping of S and N considerably deforms the CNTs and polarizes the adjacent C atoms.Consequently,both the adsorption of Pt1Cu2 onto the SN‐MWCNTs and the subsequent adsorption of methanol are enhanced;in addition,the catalytic activity of Pt_(1)Cu_(2)/SN‐MWCNTs for methanol oxidation is thermodynamically and kinetically more favorable than that of its CNT and N‐CNT counterparts.This work provides a novel method to fabricate high‐performance fuel cell electrocatalysts with highly dispersed and stable Pt‐based nanoparticles on a carbon substrate.展开更多
As the kinetically sluggish oxygen evolution reaction(OER)is considered to be a bottleneck in overall water splitting,it is necessary to develop a highly active and stable electrocatalyst to overcome this issue.Herein...As the kinetically sluggish oxygen evolution reaction(OER)is considered to be a bottleneck in overall water splitting,it is necessary to develop a highly active and stable electrocatalyst to overcome this issue.Herein,we successfully fabricated a three-dimensional iron-dysprosium oxide co-regulated in-situ formed MOF-Ni arrays on carbon cloth(FeDy@MOF-Ni/CC)through a facile two-step hydrothermal method.Electrochemical studies demonstrate that the designed FeDy@MOF-Ni/CC catalyst requires an overpotential of only 251 mV to reach 10 mA cm-2 with a small Tafel slope of 52.1 mV dec-1.Additionally,the stability declined by only 5.5%after 80 h of continuous testing in 1.0 M KOH.Furthermore,a cell voltage of only 1.57 V in the overall water splitting system is sufficient to achieve 10 mA cm-2;this value is far better than that of most previously reported catalysts.The excellent catalytic performance originates from the unique 3D rhombus-like structure,as well as coupling synergies of Fe-Dy-Ni species.The combination of lanthanide and transition metal species in the synthesis strategy may open entirely new possibilities with promising potential in the design of highly active OER electrocatalysts.展开更多
文摘Efficacious regulation of the geometric and electronic structures of carbon nanomaterials via the introduction of defects and their synergy is essential to achieving good electrochemical performance.However,the guidelines for designing hybrid materials with advantageous structures and the fundamental understanding of their electrocatalytic mechanisms remain unclear.Herein,superfine Pt and PtCu nanoparticles supported by novel S,N‐co‐doped multi‐walled CNT(MWCNTs)were prepared through the innovative pyrolysis of a poly(3,4‐ethylenedioxythiophene)/polyaniline copolymer as a source of S and N.The uniform wrapping of the copolymer around the MWCNTs provides a high density of evenly distributed defects on the surface after the pyrolysis treatment,facilitating the uniform distribution of ultrafine Pt and PtCu nanoparticles.Remarkably,the Pt_(1)Cu_(2)/SN‐MWCNTs show an obviously larger electroactive surface area and higher mass activity,stability,and CO poisoning resistance in methanol oxidation compared to Pt/SN‐MWCNTs,Pt/S‐MWCNTs,Pt/N‐MWCNTs,and commercial Pt/C.Density functional theory studies confirm that the co‐doping of S and N considerably deforms the CNTs and polarizes the adjacent C atoms.Consequently,both the adsorption of Pt1Cu2 onto the SN‐MWCNTs and the subsequent adsorption of methanol are enhanced;in addition,the catalytic activity of Pt_(1)Cu_(2)/SN‐MWCNTs for methanol oxidation is thermodynamically and kinetically more favorable than that of its CNT and N‐CNT counterparts.This work provides a novel method to fabricate high‐performance fuel cell electrocatalysts with highly dispersed and stable Pt‐based nanoparticles on a carbon substrate.
文摘As the kinetically sluggish oxygen evolution reaction(OER)is considered to be a bottleneck in overall water splitting,it is necessary to develop a highly active and stable electrocatalyst to overcome this issue.Herein,we successfully fabricated a three-dimensional iron-dysprosium oxide co-regulated in-situ formed MOF-Ni arrays on carbon cloth(FeDy@MOF-Ni/CC)through a facile two-step hydrothermal method.Electrochemical studies demonstrate that the designed FeDy@MOF-Ni/CC catalyst requires an overpotential of only 251 mV to reach 10 mA cm-2 with a small Tafel slope of 52.1 mV dec-1.Additionally,the stability declined by only 5.5%after 80 h of continuous testing in 1.0 M KOH.Furthermore,a cell voltage of only 1.57 V in the overall water splitting system is sufficient to achieve 10 mA cm-2;this value is far better than that of most previously reported catalysts.The excellent catalytic performance originates from the unique 3D rhombus-like structure,as well as coupling synergies of Fe-Dy-Ni species.The combination of lanthanide and transition metal species in the synthesis strategy may open entirely new possibilities with promising potential in the design of highly active OER electrocatalysts.
基金Project supported by the National Natural Science Foundation of China(No.21362002)the Bagui Scholar Program of Guangxi Province of China(No.2016A13)~~