Du Xiaoye, Kim Jaehyun, Gao Bo, Qian Dan, Xiao Chunhui, Ding Shujiang, Song Zhongxiao, Nam Ki Tae
State Key Laboratory for Mechanical Behavior of Materials, Xi'an Jiaotong University, Xi'an, Shaanxi 710049, China.
Department of Materials Science and Engineering, Seoul National University, Seoul 08826, Republic of Korea.
J Colloid Interface Sci. 2025 May;685:537-545. doi: 10.1016/j.jcis.2025.01.132. Epub 2025 Jan 20.
Cuprous oxide (CuO) exhibit significant potential for catalytic activity in the electrochemical carbon dioxide reduction reaction (CORR). However, the rapid reduction of Copper(I) (Cu) to metallic Copper (Cu) leads to catalyst deactivation, significantly impacting product selectivity and stability. This study aims to stabilize the Cu valence state at a metal-CuO heterogeneous interface through interfacial engineering, ultimately enhancing the electrochemical CO reduction performance of CuO. Utilizing comprehensive in situ Raman spectroscopy, we observed that the addition of Palladium (Pd) effectively inhibited the reduction of CuO. Additionally, combined in situ attenuated total reflection Fourier-transform infrared spectroscopy and theoretical calculations revealed that Pd loading enhances *CO intermediate concentration and adsorption energy, and reduces the energy barrier for *CHO formation. The improved stability of the Cu valence state led to the coexistence of two CO adsorption modes including CO and CO, promoting further CO hydrogenation and C-C coupling. Consequently, the Pd-loaded CuO catalyst demonstrated remarkable electrochemical CORR performance, achieving a methanol (CHOH) Faradaic efficiency of 78 %.
氧化亚铜（Cu₂O）在电化学二氧化碳还原反应（CORR）中展现出显著的催化活性潜力。然而，铜（I）（Cu⁺）快速还原为金属铜（Cu）会导致催化剂失活，对产物选择性和稳定性产生重大影响。本研究旨在通过界面工程将铜的价态稳定在金属 - Cu₂O 异质界面处，最终提高 Cu₂O 的电化学 CO 还原性能。利用全面的原位拉曼光谱，我们观察到添加钯（Pd）可有效抑制 Cu₂O 的还原。此外，结合原位衰减全反射傅里叶变换红外光谱和理论计算表明，负载 Pd 提高了 *CO 中间体浓度和吸附能，并降低了 *CHO 形成的能垒。铜价态稳定性的提高导致了包括 CO 和 CO₂ 两种 CO 吸附模式的共存，促进了进一步的 CO 氢化和 C - C 偶联。因此，负载 Pd 的 Cu₂O 催化剂表现出卓越的电化学 CORR 性能，甲醇（CH₃OH）法拉第效率达到 78%。
