Cu-based catalysts selectively convert CO2/CO into valuable C2+ oxygenates and hydrocarbons electrochemically, which is regarded as a promising strategy for carbon cycle utilization. Herein, we synthesized CuxP2Ox+5 (x=2, 4, 5) by introducing phosphorous in cupric oxide, which is in situ electrochemically reconstructed into metallic Cu with highly porous structure during CO electrolysis. Physicochemical characterizations demonstrate various degree of grain boundary generation, which depends on Cu atom density in CuxP2Ox+5 cell volume. The reconstructed CuxP2Ox+5 shows a grain boundary-dependent performance in CO electrolysis, with C2+ Faradaic efficiency over 90% at current density greater than 1.0 A cm–2. Among them, the 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 a strong CO adsorption with dominant configurations of atop and bridge. Density functional theory calculation indicates 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

铜基催化剂通过电化学方式选择性地将CO2/CO转化为有价值的C2+含氧化合物和碳氢化合物，这被认为是碳循环利用的一种有前景的策略。在此，我们通过在氧化铜中引入磷合成了CuxP2Ox+5（x=2,4,5），氧化铜在CO电解过程中原位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 CuxP2Ox+5 晶胞体积中的铜原子密度。重建的 CuxP2Ox+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，C2+ 法拉第效率超过 90%。其中，重构的Cu5P2O10具有最高的晶界表面密度，其C2+电流密度为1.70 A cm–2，C2+形成速率为575.8 μmol min–1。 Operando 拉曼光谱显示，CO 具有强烈的吸附作用，其主要构型为顶结构和桥结构。密度泛函理论计算表明，晶界提供了活跃的 C−C 耦合和 H2O 解离位点，有利于 *CO−COH 的形成，从而产生 C2+。