This work is devoted to the development of a low cost dimensionally stable anode with high oxygen evolution catalytic activity for practical applications.For this purpose,a Ti/SnO_(x)/MnO_(2) anode was fabricated thro...This work is devoted to the development of a low cost dimensionally stable anode with high oxygen evolution catalytic activity for practical applications.For this purpose,a Ti/SnO_(x)/MnO_(2) anode was fabricated through an innovative strategy involving Sn electrodeposition,oxidation,and MnO_(2)-layer preparation.The structure of the anode was characterized,and the oxygen evolution performance was evaluated in a H_(2)SO_(4) solution.The results show that compared with the Ti/SnO_(2)/MnO_(2) anode prepared by the conventional brushing-annealing process,the Ti/SnO_(x)/MnO_(2) anode fabricated through the innovative procedure exhibits a lower oxygen evolution potential and a nearly 40%longer accelerated lifespan.The superior oxygen evolution performance of the Ti/SnO_(x)/MnO_(2) anode is attributed to the distinctive SnO_(x) intermediate layer fabricated through Sn electrodeposition followed by oxidation,which indicates the great potential of the anode as a dimensionally stable anode for metal electrowinning and hydrogen production by electrolysis,etc.展开更多
To solve the slow dynamics of catalytic oxygen reaction energy devices,a facile method was developed for the synthesis of methylene alcohol terminated poly(1,4-phenyldiimine)porphyrin cobalt(MPImPorCo),which was synth...To solve the slow dynamics of catalytic oxygen reaction energy devices,a facile method was developed for the synthesis of methylene alcohol terminated poly(1,4-phenyldiimine)porphyrin cobalt(MPImPorCo),which was synthesized by RuCl_(3) catalyzed redox reaction of meso-5,10,15,20-tetra(4-nitrophenyl)porphyrin cobalt(TNO_(2)-PorCo)and 1,4-phenyldimethanol.M-PImPorCo is a fully conjugated covalent organic framework(COF)with high thermal and chemical stability.COFs with different edge groups were synthesized to compare the effect of different groups(–CH_(2)–OH and–NO_(2))on catalytic bifunctional oxygen reaction activity.C=N as nitrogen-rich environment of M-PImPorCo leads to the protonation process of oxygen catalysis and reduces the energy barrier of adsorption in the oxygen intermediate.C=N and–CH_(2)–OH form an“electron pump”structure to deliver electrons to the Co–N4 site in M-PImPorCo,and theπ–πinteraction between M-PImPorCo and three-dimensional graphene(3D-G)can further enrich the electron cloud density of Co–N_(4) sites.M-PImPorCo/3D-G has remarkable oxygen catalytic performance,with a half-wave potential(E_(1/2))of 0.91 V vs.reversible hydrogen electrode(RHE).M-PImPorCo/3D-G has low potential(Ej=10 is 1.49 V vs.RHE)at a current density of 10 mA·cm^(-2).It exhibits a good bifunctional catalytic performance(potential difference(ΔE)=0.58 V).The smaller charge–discharge band gap of zinc-air batteries(ZABs)and flexible ZABs(F-ZABs)equipped with M-PImPorCo/3D-G suggests the potential for catalytic oxygen reaction bifunctional applications.This work provides a new idea for the synthesis of Schiff-base porphyrin-based COF catalyst and its potential application to oxygen reaction catalytic energy storage devices.展开更多
The energy barrier for the rate-determining step(RDS)is exceptionally critical for the catalytic oxygen evolution reaction(OER)efficiency of an electrocatalyst;however,facilely decreasing the energy barrier of RDS and...The energy barrier for the rate-determining step(RDS)is exceptionally critical for the catalytic oxygen evolution reaction(OER)efficiency of an electrocatalyst;however,facilely decreasing the energy barrier of RDS and realizing the precise manipulation of the reaction process remains challenging.Herein,through constructing a nanosheet assembled sunflower-like Co(OH)_(2) with Ir,Fe codoping,the electronic structure and binding strengths with oxygen-involved intermediates of Co active sites are considerably moderated.First-principles calculations and comprehensive characterizations suggest that Fe and Ir codoping significantly lowers the electrochemical reaction barrier and promotes the OER reaction kinetics by precisely accelerating the formation process of*O.Moreover,the nanosheet-assembled open architectures enable the catalyst with plentiful catalytically active sites and facilitate mass transport and electron transfer.As a result,the optimal electrocatalyst can exhibit outstanding oxygen-evolving activity with an ultralow overpotential of 254 mV at 10 mA cm^(-2).This study realizes the precise manipulation of the reaction energy barrier of OER via Ir,Fe dual doping,which will be a generic paradigm for designing advanced yet cost-effective electrocatalysts.展开更多
文摘This work is devoted to the development of a low cost dimensionally stable anode with high oxygen evolution catalytic activity for practical applications.For this purpose,a Ti/SnO_(x)/MnO_(2) anode was fabricated through an innovative strategy involving Sn electrodeposition,oxidation,and MnO_(2)-layer preparation.The structure of the anode was characterized,and the oxygen evolution performance was evaluated in a H_(2)SO_(4) solution.The results show that compared with the Ti/SnO_(2)/MnO_(2) anode prepared by the conventional brushing-annealing process,the Ti/SnO_(x)/MnO_(2) anode fabricated through the innovative procedure exhibits a lower oxygen evolution potential and a nearly 40%longer accelerated lifespan.The superior oxygen evolution performance of the Ti/SnO_(x)/MnO_(2) anode is attributed to the distinctive SnO_(x) intermediate layer fabricated through Sn electrodeposition followed by oxidation,which indicates the great potential of the anode as a dimensionally stable anode for metal electrowinning and hydrogen production by electrolysis,etc.
基金supported by the National Natural Science Foundation of China(Nos.22172093 and 21776167)the Natural Science Foundation of Shandong Province,China(No.ZR2023MB061).
文摘To solve the slow dynamics of catalytic oxygen reaction energy devices,a facile method was developed for the synthesis of methylene alcohol terminated poly(1,4-phenyldiimine)porphyrin cobalt(MPImPorCo),which was synthesized by RuCl_(3) catalyzed redox reaction of meso-5,10,15,20-tetra(4-nitrophenyl)porphyrin cobalt(TNO_(2)-PorCo)and 1,4-phenyldimethanol.M-PImPorCo is a fully conjugated covalent organic framework(COF)with high thermal and chemical stability.COFs with different edge groups were synthesized to compare the effect of different groups(–CH_(2)–OH and–NO_(2))on catalytic bifunctional oxygen reaction activity.C=N as nitrogen-rich environment of M-PImPorCo leads to the protonation process of oxygen catalysis and reduces the energy barrier of adsorption in the oxygen intermediate.C=N and–CH_(2)–OH form an“electron pump”structure to deliver electrons to the Co–N4 site in M-PImPorCo,and theπ–πinteraction between M-PImPorCo and three-dimensional graphene(3D-G)can further enrich the electron cloud density of Co–N_(4) sites.M-PImPorCo/3D-G has remarkable oxygen catalytic performance,with a half-wave potential(E_(1/2))of 0.91 V vs.reversible hydrogen electrode(RHE).M-PImPorCo/3D-G has low potential(Ej=10 is 1.49 V vs.RHE)at a current density of 10 mA·cm^(-2).It exhibits a good bifunctional catalytic performance(potential difference(ΔE)=0.58 V).The smaller charge–discharge band gap of zinc-air batteries(ZABs)and flexible ZABs(F-ZABs)equipped with M-PImPorCo/3D-G suggests the potential for catalytic oxygen reaction bifunctional applications.This work provides a new idea for the synthesis of Schiff-base porphyrin-based COF catalyst and its potential application to oxygen reaction catalytic energy storage devices.
基金supported by the start-up funding to H.Xu from Changzhou University(ZMF22020055)grants from Advanced Catalysis and Green Manufacturing Collaborative Innovation Center(ACGM2022-10-01),Changzhou University.
文摘The energy barrier for the rate-determining step(RDS)is exceptionally critical for the catalytic oxygen evolution reaction(OER)efficiency of an electrocatalyst;however,facilely decreasing the energy barrier of RDS and realizing the precise manipulation of the reaction process remains challenging.Herein,through constructing a nanosheet assembled sunflower-like Co(OH)_(2) with Ir,Fe codoping,the electronic structure and binding strengths with oxygen-involved intermediates of Co active sites are considerably moderated.First-principles calculations and comprehensive characterizations suggest that Fe and Ir codoping significantly lowers the electrochemical reaction barrier and promotes the OER reaction kinetics by precisely accelerating the formation process of*O.Moreover,the nanosheet-assembled open architectures enable the catalyst with plentiful catalytically active sites and facilitate mass transport and electron transfer.As a result,the optimal electrocatalyst can exhibit outstanding oxygen-evolving activity with an ultralow overpotential of 254 mV at 10 mA cm^(-2).This study realizes the precise manipulation of the reaction energy barrier of OER via Ir,Fe dual doping,which will be a generic paradigm for designing advanced yet cost-effective electrocatalysts.
