Cobalt carbonate hydroxide nanowires (Co(CO₃)_0.5(OH)·0.11H₂O, CCO NWs) have gained significant attention as promising catalysts; however, their potential towards photocatalytic CO₂ reduction (PCR) has not yet been explored. Herein, orthorhombic CCO NWs with rich oxygen vacancies (Vo-CCO NWs) have been manufactured by the self-photoetching approach under vacuum. Notably, the unsaturated coordinated cobalt centers, formed by destroying the interlayer carbonate ions bonded with Co species, act as the active sites, which can preferably adsorb and activate CO₂ molecules, effectively inhibiting hydrogen evolution. Surprisingly, the Vo-CCO NWs manifest remarkable activity for CO₂ reduction with a high CO evolution rate (1333.20 μmol h⁻¹ g⁻¹) and remarkable selectivity (98.2%) under visible light irradiation. Insightfully, a typical Co^II/I reaction pathway can be demonstrated as the reduction mechanism supported by the combined evidence including in situ FTIR, CV, and in situ EPR results. This work provides a mild strategy for controllable oxygen vacancy generation on the surface of CCO, and also a deeper mechanistic study to understand the reaction process of PCR.

中文翻译：

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碳酸钴氢氧化物纳米线中氧空位设计的不饱和配位使高选择性光催化二氧化碳还原成为可能

碳酸钴氢氧化物纳米线（Co(CO ₃ ) _0.5 (OH)·0.11H ₂ O，CCO NWs ）作为一种有前景的催化剂已受到广泛关注。然而，尚未探索它们在光催化 CO ₂还原 (PCR) 方面的潜力。在此，具有丰富氧空位的正交 CCO NW（Vo-CCO NW）已通过真空下的自光刻方法制造。值得注意的是，通过破坏与Co物种键合的层间碳酸根离子而形成的不饱和配位钴中心作为活性位点，可以优先吸附和活化CO ₂分子，有效抑制析氢。令人惊讶的是，Vo-CCO NW 对 CO ₂表现出显着的活性在可见光照射下具有高 CO 析出率 (1333.20 μmol h ^-1 g ^-1 ) 和显着的选择性 (98.2%)。有见地，典型的 Co ^II/I反应途径可以证明是由原位FTIR、CV 和原位EPR 结果等综合证据支持的还原机制。这项工作为CCO表面可控氧空位的产生提供了一种温和的策略，也为理解PCR反应过程提供了更深入的机理研究。