Silver nanostructures with hierarchical porosities of multiple length scales have been synthesized through electrochemical reduction of silver benzenethiolate nanoboxes. The porous Ag nanostructures exhibit superior catalytic performance toward electrochemical reduction of CO₂. The Faradaic efficiency of reducing CO₂ to CO can be close to 100% at high cathodic potentials, benefiting from the readsorbed benzenethiolate ions on the Ag surface that can suppress the hydrogen evolution reaction (HER). Density functional theory calculations using the SCAN functional reveal that the disfavored H binding on the benzenethiolate-modified Ag surface is responsible for inhibiting the HER. The mass-specific activity of CO₂ reduction can be over 500 A/g because the multiple-scale porosities maximize the diffusion of reactive species to and away from the Ag surface. The unique multiscale porosities and surface modification of the as-synthesized Ag nanostructures make them a class of promising catalysts for electrochemical reduction of CO₂ in protic electrolytes to achieve maximum activity and selectivity.

中文翻译：

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从苯硫醇银纳米盒衍生的分层3D多孔Ag纳米结构：能够以接近单位的选择性和超过500 A / g的质量比电流密度还原CO ₂

通过电化学还原苯硫醇银纳米盒已经合成了具有多个长度尺度的分级孔隙率的银纳米结构。多孔的Ag纳米结构对电化学还原CO ₂表现出优异的催化性能。在高阴极电位下，将CO ₂还原为CO的法拉第效率可得益于在Ag表面上重新吸附的苯硫醚离子，该离子可抑制氢释放反应（HER），在高阴极电势下可达到100％。使用SCAN官能团的密度泛函理论计算表明，苯硫醇酯修饰的Ag表面上不利的H结合是抑制HER的原因。CO ₂的质量比活度由于多尺度的孔隙率使反应性物质扩散到银表面和从银表面扩散出的最大程度的减少，其还原可以超过500 A / g。刚合成的Ag纳米结构的独特的多尺度孔隙率和表面改性使其成为一类有希望的催化剂，用于电化学还原质子电解质中的CO ₂以获得最大的活性和选择性。