Wang Keke, Zhang Ruichao, Zhou Bolin, Li Qiang, Zhou Mengmeng, Shen Hai-Min, Wang Qin, Xia Jiexiang, Li Huaming, Yi Qun, She Yuanbin
State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China.
State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China.
J Colloid Interface Sci. 2025 Jan;677(Pt B):872-881. doi: 10.1016/j.jcis.2024.08.114. Epub 2024 Aug 15.
The highly selective conversion of CO into valuable CH is a highly important but particularly challenging reaction. Herein, the metal-organic frameworks MOF-74(Cu) with infinite Cu(II)-O chains and Cu-BTC (BTC=benzene-1,3,5-tricarboxylate) with paddle-wheel binuclear Cu(II) clusters are used as precursors. These MOFs are reduced by NaBH to obtain Cu/Cu-based photocatalysts denoted as R-MOF-74(Cu) and R-Cu-BTC, respectively. Significantly, R-MOF-74(Cu) achieves a high selectivity of 90.2 % for CH with a yield rate of 6.5 μmol g within 5 h due to its high Cu content. To the best of our knowledge, this CH product selectivity is a record high among all the photocatalysts reported so far for photocatalytic CO reduction. In contrast, R-Cu-BTC only forms CO as a product with a cumulative yield of 0.7 μmol g within 5 h. Photoelectrochemical characterization and electron paramagnetic resonance results show that R-MOF-74(Cu) has low interfacial transfer resistance, high photogenerated electron separation efficiency, and excellent CO activation and water oxidation performance. In addition, in situ Fourier transform infrared spectroscopy is used to determine the possible reaction pathway from CO to CH over R-MOF-74(Cu). This work demonstrates the great potential of MOF-derived photocatalysts for the conversion of CO into CH and provides guidance for future photocatalyst development.
将一氧化碳高效选择性地转化为有价值的甲烷是一个极其重要但特别具有挑战性的反应。在此，具有无限铜（II）-氧链的金属有机框架MOF-74（铜）和具有桨轮双核铜（II）簇的铜-均苯三甲酸酯（BTC = 苯-1,3,5-三甲酸酯）用作前驱体。这些金属有机框架通过硼氢化钠还原，分别得到标记为R-MOF-74（铜）和R-铜-均苯三甲酸酯的铜/铜基光催化剂。值得注意的是，由于其高铜含量，R-MOF-74（铜）在5小时内对甲烷的选择性高达90.2%，产率为6.5 μmol g。据我们所知，在迄今为止报道的用于光催化一氧化碳还原的所有光催化剂中，这种甲烷产物选择性是创纪录的高值。相比之下，R-铜-均苯三甲酸酯仅生成一氧化碳作为产物，在5小时内累积产率为0.7 μmol g。光电化学表征和电子顺磁共振结果表明，R-MOF-74（铜）具有低界面转移电阻、高光生电子分离效率以及优异的一氧化碳活化和水氧化性能。此外，采用原位傅里叶变换红外光谱法确定了在R-MOF-74（铜）上从一氧化碳到甲烷的可能反应途径。这项工作证明了金属有机框架衍生的光催化剂在将一氧化碳转化为甲烷方面的巨大潜力，并为未来光催化剂的开发提供了指导。
