Shen Yu-Jhih, Hsu Yung-Hsi, Chang Yu-Chia, Ma Jian-Jie, Peng Kang-Shun, Lu Ying-Rui, Hsu Shao-Hui, Hung Sung-Fu
Department of Applied Chemistry and Center for Emergent Functional Matter Science, National Yang Ming Chiao Tung University, Hsinchu 300, Taiwan.
National Synchrotron Radiation Research Center, Hsinchu 300, Taiwan.
ACS Appl Mater Interfaces. 2025 Feb 12;17(6):9378-9390. doi: 10.1021/acsami.4c20586. Epub 2025 Feb 4.
Copper is the catalyst widely used to produce multicarbon products for the carbon dioxide reduction reaction (CORR). The surrounding microenvironment of copper plays a crucial role in determining its catalytic activity and selectivity. In this study, we compare three copper electrocatalysts with different microenvironments: pure metallic copper, a copper metal-organic framework (MOF), and a MOF-derived copper-carbon composite. X-ray absorption spectroscopy, transmission electron microscopy, and Raman spectroscopy reveal that copper in the copper-carbon composite remains in a metallic state, encapsulated by a carbon matrix. The composite catalyst achieves a Faradaic efficiency of 75.6% for C products, including ethylene and ethanol, at a current density of 500 mA cm, with a C current density of 377.9 mA cm. This performance suppresses pure metallic copper, which reaches an optimal Faradaic efficiency of 64.5% for C products at a current density of 300 mA cm, with a C current density of 193.5 mA cm. The copper-carbon composite also significantly overperforms the copper-MOF catalyst, which shows an optimal Faradaic efficiency of 52.0% for C products at a current density of 400 mA cm, with a C current density of 208.0 mA cm. These findings highlight the importance of the microenvironment near active copper sites in determining CORR efficiency. We hope that our results provide valuable insights for advancing catalyst design in carbon dioxide reduction, contributing to reduced carbon emissions and improved environmental sustainability.
铜是广泛用于二氧化碳还原反应（CORR）以生产多碳产物的催化剂。铜周围的微环境在决定其催化活性和选择性方面起着关键作用。在本研究中，我们比较了三种具有不同微环境的铜电催化剂：纯金属铜、铜金属有机框架（MOF）以及MOF衍生的铜 - 碳复合材料。X射线吸收光谱、透射电子显微镜和拉曼光谱表明，铜 - 碳复合材料中的铜保持金属态，被碳基质包裹。在电流密度为500 mA/cm²时，该复合催化剂对于包括乙烯和乙醇在内的C产物实现了75.6%的法拉第效率，C电流密度为377.9 mA/cm²。此性能超过了纯金属铜，纯金属铜在电流密度为300 mA/cm²时对于C产物达到了64.5%的最佳法拉第效率，C电流密度为193.5 mA/cm²。铜 - 碳复合材料也显著优于铜 - MOF催化剂，铜 - MOF催化剂在电流密度为400 mA/cm²时对于C产物显示出52.0%的最佳法拉第效率，C电流密度为208.0 mA/cm²。这些发现突出了活性铜位点附近微环境在决定CORR效率方面的重要性。我们希望我们的结果为推进二氧化碳还原中的催化剂设计提供有价值的见解，有助于减少碳排放并改善环境可持续性。
