The development of high-performance chlorine evolution reaction(CER)catalysts with low noble metal content,superior selectivity,and excellent stability is urgently needed to address the limitations of commercial Ru/Ir...The development of high-performance chlorine evolution reaction(CER)catalysts with low noble metal content,superior selectivity,and excellent stability is urgently needed to address the limitations of commercial Ru/Ir-based catalysts,such as high cost,severe OER competition,and nanoparticle instability.In this study,an innovative strategy is employed to fabricate a CoRu@CN catalyst by leveraging polydopamine-derived nitrogen-doped carbon nanospheres to immobilize cobalt-ruthenium(CoRu)alloy nanoparticles through robust metal-nitrogen coordination bonds,while optimizing the electronic structure via bimetallic synergy and nitrogen-induced modulation.The as-prepared CoRu@CN catalyst exhibits outstanding CER performance,with a remarkably low overpotential of 154 mV at 100 mA cm^(−2),a favorable Tafel slope of 68.18 mV dec^(−1),and a high chlorine selectivity of 97-99%in 5 M NaCl(pH=2),along with a 3.8-fold enhancement in the electrochemically active surface area,attributed to the defect-rich active sites generated by doping.Mechanistic investigations reveal that CoRu@CN operates via the Volmer-Krishtalik(V-K)pathway,where the kinetics of the rate-determining Krishtalik step is significantly promoted at elevated potentials.Meanwhile,the nitrogen-doped carbon scaffold not only suppresses nanoparticle agglomeration and phase separation through metal-nitrogen coordination but also enhances mass transport and conductivity,contributing to the catalyst’s exceptional durability with 99.3%activity retention after 100 hours of testing.This work not only solves the long-standing industrial problem of nanoparticle instability in CER catalysis but also provides a novel design strategy for developing corrosionresistant,high-efficiency electrocatalysts,highlighting the potential of CoRu@CN for scalable and energyefficient chlor-alkali electrolysis.展开更多
Designing highly efficient Pt-free electrocatalysts with low overpotential for an alkaline hydrogen evolution reaction(HER)remains a significant challenge.Here,a novel and efficient cobalt(Co),ruthenium(Ru)bimetallic ...Designing highly efficient Pt-free electrocatalysts with low overpotential for an alkaline hydrogen evolution reaction(HER)remains a significant challenge.Here,a novel and efficient cobalt(Co),ruthenium(Ru)bimetallic electrocatalyst composed of CoRu nanoalloy decorated on the N-doped carbon nanotubes(CoRu@N-CNTs),was prepared by reacting fullerenol with melamine via hydrothermal treatment and followed by pyrolysis.Benefiting from the electronic communication between Co and Ru sites,the as-obtained CoRu@N-CNTs catalyst exhibited superior electrocatalytic HER activity.To deliver a current density of 10 mA·cm^(-2),it required an overpotential of merely 19 mV along with a Tafel slope of 26.19 mV·dec^(-1)in 1 mol·L^(-1)potassium hydroxide(KOH)solution,outperforming the benchmark Pt/C catalyst.The present work would pave a new way towards the design and construction of an efficient electrocatalyst for energy storage and conversion.展开更多
基金supported by the National Natural Science Foundation of China(52272222,52072197,and 52372205)the Natural Science Foundation of Shandong Province,China(ZR2023MB142)+2 种基金the Science and Technology Support Plan for Youth Innovation of Colleges and Universities in Shandong Province(2022KJ308 and 2019KJC004)the Taishan Scholar Young Talent Program(tsqn201909114)the Open Project of the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry(2025-19).
文摘The development of high-performance chlorine evolution reaction(CER)catalysts with low noble metal content,superior selectivity,and excellent stability is urgently needed to address the limitations of commercial Ru/Ir-based catalysts,such as high cost,severe OER competition,and nanoparticle instability.In this study,an innovative strategy is employed to fabricate a CoRu@CN catalyst by leveraging polydopamine-derived nitrogen-doped carbon nanospheres to immobilize cobalt-ruthenium(CoRu)alloy nanoparticles through robust metal-nitrogen coordination bonds,while optimizing the electronic structure via bimetallic synergy and nitrogen-induced modulation.The as-prepared CoRu@CN catalyst exhibits outstanding CER performance,with a remarkably low overpotential of 154 mV at 100 mA cm^(−2),a favorable Tafel slope of 68.18 mV dec^(−1),and a high chlorine selectivity of 97-99%in 5 M NaCl(pH=2),along with a 3.8-fold enhancement in the electrochemically active surface area,attributed to the defect-rich active sites generated by doping.Mechanistic investigations reveal that CoRu@CN operates via the Volmer-Krishtalik(V-K)pathway,where the kinetics of the rate-determining Krishtalik step is significantly promoted at elevated potentials.Meanwhile,the nitrogen-doped carbon scaffold not only suppresses nanoparticle agglomeration and phase separation through metal-nitrogen coordination but also enhances mass transport and conductivity,contributing to the catalyst’s exceptional durability with 99.3%activity retention after 100 hours of testing.This work not only solves the long-standing industrial problem of nanoparticle instability in CER catalysis but also provides a novel design strategy for developing corrosionresistant,high-efficiency electrocatalysts,highlighting the potential of CoRu@CN for scalable and energyefficient chlor-alkali electrolysis.
基金supported by the National Natural Science Foundation of China(No.52072226,U22A20144)Key Research and Development Program of Shaanxi(2024GX-YBXM-466)+1 种基金Science and Technology Program of Xi'an,China(22GXFW0013)Science and Technology Program of Weiyang District of Xi'an,China(202315)。
文摘Designing highly efficient Pt-free electrocatalysts with low overpotential for an alkaline hydrogen evolution reaction(HER)remains a significant challenge.Here,a novel and efficient cobalt(Co),ruthenium(Ru)bimetallic electrocatalyst composed of CoRu nanoalloy decorated on the N-doped carbon nanotubes(CoRu@N-CNTs),was prepared by reacting fullerenol with melamine via hydrothermal treatment and followed by pyrolysis.Benefiting from the electronic communication between Co and Ru sites,the as-obtained CoRu@N-CNTs catalyst exhibited superior electrocatalytic HER activity.To deliver a current density of 10 mA·cm^(-2),it required an overpotential of merely 19 mV along with a Tafel slope of 26.19 mV·dec^(-1)in 1 mol·L^(-1)potassium hydroxide(KOH)solution,outperforming the benchmark Pt/C catalyst.The present work would pave a new way towards the design and construction of an efficient electrocatalyst for energy storage and conversion.
