The selective electrochemical conversion of CO₂/CO into valuable C₂₊ oxygenates and hydrocarbons using Cu-based catalysts is regarded as a promising strategy for carbon cycle utilization. Herein, we synthesized Cu_xP₂O_x+5 (x = 2, 4, and 5) by introducing phosphorous in cupric oxide, which is electrochemically reconstructed into metallic Cu in situ with a highly porous structure during CO electrolysis. Physicochemical characterizations demonstrate various degrees of grain boundary generation, which depends on the Cu atom density in the Cu_xP₂O_x+5 cell volume. Reconstructed Cu_xP₂O_x+5 shows a grain boundary-dependent performance in CO electrolysis, with a C₂₊ faradaic efficiency over 90% at a current density greater than 1.0 A cm⁻². Among them, reconstructed Cu₅P₂O₁₀, with the highest surface density of grain boundary, achieves a C₂₊ current density of 1.70 A cm⁻² and a C₂₊ formation rate of 575.8 μmol min⁻¹. Operando Raman spectra reveal strong CO adsorption with dominant configurations of atop and bridge. Density functional theory calculations indicate that grain boundary provides active C–C coupling and H₂O dissociation sites, which facilitate *CO–COH formation for C₂₊ production.

中文翻译：

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通过控制 CuxP2Ox+5 前体成分生成晶界增强 CO 电解

_{使用Cu基催化剂将CO 2} /CO选择性电化学转化为有价值的C ₂₊含氧化合物和碳氢化合物被认为是碳循环利用的有前途的策略。在此，我们通过在氧化铜中引入磷来合成Cu _x P ₂ O _{x +5} ( x = 2、4和5)，氧化铜在CO电解过程中电化学重构为具有高度多孔结构的金属Cu。物理化学表征表明不同程度的晶界生成，这取决于 Cu _x P ₂ O _{x +5}晶胞体积中的 Cu 原子密度。重构的Cu _x P ₂ O _{x +5}在CO电解中表现出依赖于晶界的性能，在电流密度大于1.0 A cm ^-2时，C ₂₊法拉第效率超过90% 。其中，晶界表面密度最高的重构Cu ₅ P ₂ O ₁₀实现了1.70 A cm ^-2的C ₂₊电流密度和575.8 μmol min ^-1的C ₂₊形成速率。 Operando 拉曼光谱显示，CO 具有很强的吸附能力，主要结构为顶结构和桥结构。密度泛函理论计算表明，晶界提供了活跃的C-C耦合和H ₂ O解离位点，这有利于*CO-COH的形成以用于C _{2+ 的}生产。