Currently,dual atomic catalysts(DACs)with neighboring active sites for oxygen reduction reaction(ORR)still meet lots of challenges in the synthesis,especially the construction of atomic pairs of elements from differen...Currently,dual atomic catalysts(DACs)with neighboring active sites for oxygen reduction reaction(ORR)still meet lots of challenges in the synthesis,especially the construction of atomic pairs of elements from different blocks of the periodic table.Herein,a“rare earth(Ce)-metalloid(Se)”non-bonding heteronuclear diatomic electrocatalyst has been constructed for ORR by rational coordination and carbon support defect engineering.Encouraging,the optimized Ce-Se diatomic catalysts(Ce-Se DAs/NC)displayed a half-wave potential of 0.886 V vs.reversible hydrogen electrode(RHE)and excellent stability,which surpass those of separate Ce or Se single atoms and most single/dual atomic catalysts ever reported.In addition,a primary zinc-air battery constructed using Ce-Se DAs/NC delivers a higher peak power density(209.2 mW·cm^(−2))and specific capacity(786.4 mAh·gZn^(−1))than state-of-the-art noble metal catalysts Pt/C.Theoretical calculations reveal that the Ce-Se DAs/NC has improved the electroactivity of the Ce-N_(4)region due to the electron transfer towards the nearby Se specific activity(SA)sites.Meanwhile,the more electron-rich Se sites promote the adsorptions of key intermediates,which results in the optimal performances of ORR on Ce-Se DAs/NC.This work provides new perspectives on electronic structure modulations via non-bonded long-range coordination micro-environment engineering in DACs for efficient electrocatalysis.展开更多
Due to unique electrical properties and high catalytic efficiency,transition metal nitrogen-codoped car-bide(TM-N-C)has attracted tremendous interest as a multifunctional electrocatalyst for water splitting.Unlike tra...Due to unique electrical properties and high catalytic efficiency,transition metal nitrogen-codoped car-bide(TM-N-C)has attracted tremendous interest as a multifunctional electrocatalyst for water splitting.Unlike traditional single-source modification,herein a novel pomegranate-like high-entropy(HE)elec-trocatalyst of Ni_(3)ZnC_(0.7)decorated with homogeneous multimetal(Fe,Co,Cu,and Ni)nitrogen-codoped carbon matrix(Ni_(3)ZnC_(0.7)@CoNiCuFe-NC)is reported.It can be implemented by the simple thermal an-nealing method of multimetal codoped zeolitic imidazolate framework(ZIF).Benefiting from the syn-ergistic effects of plentiful TM-N-C species,template effect of ZIF and distinct nanoporous structure,HE electrocatalyst Ni_(3)ZnC_(0.7)@CoNiCuFe-NC exhibits outstanding electrocatalytic performance.When ap-plied in strong alkaline electrolyte(1.0 M KOH),the overpotentials of Ni_(3)ZnC_(0.7)@CoNiCuFe-NC present as low as 202 and 97 mV for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)at 10 mA cm^(−2)current density.Surprisingly as a bifunctional electrode,it can achieve the low cell voltage of 1.53 V at 10 mA cm^(−2)current density for overall water splitting,which is comparable to conventional IrO_(2)||Pt/C electrode and superior to the recently reported analogous bifunctional catalysts.Thus,the work proposes the direction for the rational design of homogeneous distribution of TM-N-C material for water splitting in the green hydrogen energy industry.展开更多
基金the support from the National Key R&D Program of China(No.2021YFA1501101)the National Natural Science Foundation of China(No.21971117)+12 种基金the National Natural Science Foundation of China/Research Grant Council of Hong Kong Joint Research Scheme(No.N_PolyU502/21)the National Natural Science Foundation of China/Research Grants Council(RGC)of Hong Kong Collaborative Research Scheme(No.CRS_PolyU504/22)the Functional Research Funds for the Central Nankai University(No.63186005)the Tianjin Key Lab for Rare Earth Materials and Applications(No.ZB19500202)the Open Funds(No.RERU2019001)the State Key Laboratory of Rare Earth Resource Utilization,the 111 Project(No.B18030)from Chinathe Beijing-Tianjin-Hebei Collaborative Innovation Project(No.19YFSLQY00030)the Outstanding Youth Project of Tianjin 21 Natural Science Foundation(No.20JCJQJC00130)the Key Project of Tianjin Natural Science Foundation(No.20JCZDJC00650)the funding for Projects of Strategic Importance of The Hong Kong Polytechnic University(Project Code:1-ZE2V)the Shenzhen Fundamental Research Scheme-General Program(No.JCYJ20220531090807017)the Natural Science Foundation of Guangdong Province(No.2023A1515012219)the Departmental General Research Fund(Project Code:ZVUL)from The Hong Kong Polytechnic University.
文摘Currently,dual atomic catalysts(DACs)with neighboring active sites for oxygen reduction reaction(ORR)still meet lots of challenges in the synthesis,especially the construction of atomic pairs of elements from different blocks of the periodic table.Herein,a“rare earth(Ce)-metalloid(Se)”non-bonding heteronuclear diatomic electrocatalyst has been constructed for ORR by rational coordination and carbon support defect engineering.Encouraging,the optimized Ce-Se diatomic catalysts(Ce-Se DAs/NC)displayed a half-wave potential of 0.886 V vs.reversible hydrogen electrode(RHE)and excellent stability,which surpass those of separate Ce or Se single atoms and most single/dual atomic catalysts ever reported.In addition,a primary zinc-air battery constructed using Ce-Se DAs/NC delivers a higher peak power density(209.2 mW·cm^(−2))and specific capacity(786.4 mAh·gZn^(−1))than state-of-the-art noble metal catalysts Pt/C.Theoretical calculations reveal that the Ce-Se DAs/NC has improved the electroactivity of the Ce-N_(4)region due to the electron transfer towards the nearby Se specific activity(SA)sites.Meanwhile,the more electron-rich Se sites promote the adsorptions of key intermediates,which results in the optimal performances of ORR on Ce-Se DAs/NC.This work provides new perspectives on electronic structure modulations via non-bonded long-range coordination micro-environment engineering in DACs for efficient electrocatalysis.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22008180 and 21878231)the Natural Science Foundation of Tianjin(Nos.19JCQNJC05700 and 19JCZDJC37300)the Tianjin College Student Innovation and Entrepreneurship Training Program(No.202010058034).This work was also supported by the Analytical&Testing Center of Tiangong University for structural characterization tests.
文摘Due to unique electrical properties and high catalytic efficiency,transition metal nitrogen-codoped car-bide(TM-N-C)has attracted tremendous interest as a multifunctional electrocatalyst for water splitting.Unlike traditional single-source modification,herein a novel pomegranate-like high-entropy(HE)elec-trocatalyst of Ni_(3)ZnC_(0.7)decorated with homogeneous multimetal(Fe,Co,Cu,and Ni)nitrogen-codoped carbon matrix(Ni_(3)ZnC_(0.7)@CoNiCuFe-NC)is reported.It can be implemented by the simple thermal an-nealing method of multimetal codoped zeolitic imidazolate framework(ZIF).Benefiting from the syn-ergistic effects of plentiful TM-N-C species,template effect of ZIF and distinct nanoporous structure,HE electrocatalyst Ni_(3)ZnC_(0.7)@CoNiCuFe-NC exhibits outstanding electrocatalytic performance.When ap-plied in strong alkaline electrolyte(1.0 M KOH),the overpotentials of Ni_(3)ZnC_(0.7)@CoNiCuFe-NC present as low as 202 and 97 mV for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)at 10 mA cm^(−2)current density.Surprisingly as a bifunctional electrode,it can achieve the low cell voltage of 1.53 V at 10 mA cm^(−2)current density for overall water splitting,which is comparable to conventional IrO_(2)||Pt/C electrode and superior to the recently reported analogous bifunctional catalysts.Thus,the work proposes the direction for the rational design of homogeneous distribution of TM-N-C material for water splitting in the green hydrogen energy industry.