Stable oxygen evolution reaction(OER)catalyst alternatives to the precious IrO_(2) catalysts are of great importance to the next-generation proton-exchange membrane(PEM)electrolyzers.RuO_(2)-based materials are promis...Stable oxygen evolution reaction(OER)catalyst alternatives to the precious IrO_(2) catalysts are of great importance to the next-generation proton-exchange membrane(PEM)electrolyzers.RuO_(2)-based materials are promising candidates but suffer from low stability under highly anodic potentials.Here,we reported a facet-selective etching strategy to improve the stability of polycrystalline RuO_(2) without significantly affecting the activity.The selective etching was enabled by the specific chemisorption of pyridazine(pyd)with contingent N atoms onto the RuO_(2) surface.The pyd-RuO_(2) catalyst,after etching,exhibited a low overpotential 247 mV at 100 mA·cm^(-2) and obvious stability improvement of over 200 h at 100 mA·cm^(-2) with only 0.63% Ru loss in acidic conditions.Combining various characterization techniques and theoretical calculations,we revealed that the crystalline RuO_(2)(110)facet is favorably etched by the coordination of pyridazine while protecting other surfaces,which significantly enriches the RuO_(2)(110)facets toward higher OER stability via the dynamic dissolution and repair mechanism in the ordered manner.This study offers alternative perspectives on the dissolution and stability mechanism of RuO_(2) and the facet-selective modulation of nanocrystals by ligand-driven etching.展开更多
Aqueous zinc-ion batteries(AZIBs)offer promising safety and affordability,but suffer from dendritic Zn growth and parasitic side reactions at the electrode-electrolyte interface.Herein,we construct a dual-region inter...Aqueous zinc-ion batteries(AZIBs)offer promising safety and affordability,but suffer from dendritic Zn growth and parasitic side reactions at the electrode-electrolyte interface.Herein,we construct a dual-region interfacial modulation framework by molecularly reconfiguring the Helmholtz double layer via trace methyl methacrylate(MMA).Exploiting its amphiphilic and functionally asymmetric architecture,MMA enables a coordinated interfacial reconstruction that disrupts Zn^(2+)solvation in the outer Helmholtz plane,builds a chemisorbed coordination layer in the inner plane,and modulates local interfacial chemistry with spatial precision.This dualregion regulation collectively suppresses water reactivity,facilitates Zn^(2+)desolvation,and drives crystallo-graphically preferred deposition along the(101)plane,promoting lateral growth and mitigating dendrite for-mation.As a result,symmetric Zn||Zn cells exhibit over 4200 h of stable cycling at 1 mA cm^(-2) and maintain 1100 h of operation at 2 mA cm^(-2),even at 0℃.Zn||Ti half-cells achieve a Coulombic efficiency of 99.83%,while Zn||NH_(4)V_(4)O_(10) full cells deliver 93.92%capacity retention after 400 cycles at 2 A g^(-1),and preserve 85.3%after 300 cycles at 0℃.This work demonstrates a scalable,mechanism-driven electrolyte design paradigm for dendrite-free and high-performance aqueous Zn metal batteries.展开更多
基金supported by the National Natural Science Foundation of China(No.22172036)the Fundamental Research Funds for the Central Universities(No.20720220011).
文摘Stable oxygen evolution reaction(OER)catalyst alternatives to the precious IrO_(2) catalysts are of great importance to the next-generation proton-exchange membrane(PEM)electrolyzers.RuO_(2)-based materials are promising candidates but suffer from low stability under highly anodic potentials.Here,we reported a facet-selective etching strategy to improve the stability of polycrystalline RuO_(2) without significantly affecting the activity.The selective etching was enabled by the specific chemisorption of pyridazine(pyd)with contingent N atoms onto the RuO_(2) surface.The pyd-RuO_(2) catalyst,after etching,exhibited a low overpotential 247 mV at 100 mA·cm^(-2) and obvious stability improvement of over 200 h at 100 mA·cm^(-2) with only 0.63% Ru loss in acidic conditions.Combining various characterization techniques and theoretical calculations,we revealed that the crystalline RuO_(2)(110)facet is favorably etched by the coordination of pyridazine while protecting other surfaces,which significantly enriches the RuO_(2)(110)facets toward higher OER stability via the dynamic dissolution and repair mechanism in the ordered manner.This study offers alternative perspectives on the dissolution and stability mechanism of RuO_(2) and the facet-selective modulation of nanocrystals by ligand-driven etching.
基金supported by the National Natural Science Foundation of China(Grant Nos.52125405 and U22A20108)Thailand Science Research and Innovation Fund Chulalongkorn University,National Research Council of Thailand(NRCT)and Chulalongkorn University(N42A660383).D.D.Zhang would like to thank the financial support from the Scientific Research Fund of Liaoning Provincial Education Department of China(No.JYTQN2023289)+3 种基金Liaoning Provincial Science and Technology Joint Plan(Fund)Project(No.2023-BSBA-259)and the opening project of State Key Laboratory of Metastable Materials Science and Technology,Yanshan University(No.202404).J.Cao would like to acknowledge the support from National Natural Science Foundation of China(Grant No.52402279)China Postdoctoral Science Foundation Special Funding(Grant Nos.2025T180002,2024M751753)the opening project of State Key Laboratory of Metastable Materials Science and Technology(Yanshan University)(No.202401).
文摘Aqueous zinc-ion batteries(AZIBs)offer promising safety and affordability,but suffer from dendritic Zn growth and parasitic side reactions at the electrode-electrolyte interface.Herein,we construct a dual-region interfacial modulation framework by molecularly reconfiguring the Helmholtz double layer via trace methyl methacrylate(MMA).Exploiting its amphiphilic and functionally asymmetric architecture,MMA enables a coordinated interfacial reconstruction that disrupts Zn^(2+)solvation in the outer Helmholtz plane,builds a chemisorbed coordination layer in the inner plane,and modulates local interfacial chemistry with spatial precision.This dualregion regulation collectively suppresses water reactivity,facilitates Zn^(2+)desolvation,and drives crystallo-graphically preferred deposition along the(101)plane,promoting lateral growth and mitigating dendrite for-mation.As a result,symmetric Zn||Zn cells exhibit over 4200 h of stable cycling at 1 mA cm^(-2) and maintain 1100 h of operation at 2 mA cm^(-2),even at 0℃.Zn||Ti half-cells achieve a Coulombic efficiency of 99.83%,while Zn||NH_(4)V_(4)O_(10) full cells deliver 93.92%capacity retention after 400 cycles at 2 A g^(-1),and preserve 85.3%after 300 cycles at 0℃.This work demonstrates a scalable,mechanism-driven electrolyte design paradigm for dendrite-free and high-performance aqueous Zn metal batteries.
