Biomimetic Cu<sub>4</sub> Cluster Encapsulated within Hollow Titanium-Oxo Nanoring for Electrochemical CO<sub>2</sub> Reduction to Ethylene
Xi Fan, Jian Cheng, Mei Qiu, Yongfan Zhang, Shuai Chen, Zhangjing Zhang, Yang Peng, Jian Zhang, Lei Zhang
Abstract
The construction of biomimetic cluster catalysts with metalloenzyme-like active sites may open an avenue for the challenging transformation of greenhouse gases (e.g., CO 2 ) to high-value chemicals. Cu-enzymes occur in all three biological kingdoms, with Cu Z clusters serving as representative reaction sites that catalyze challenging transformations. However, artificial Cu clusters with analogous Cu Z structures and high stability are still rare. In this work, we have successfully adopted a Ti 9 -oxo nanoring as an inorganic templating scaffold to isolate a small Cu 4 cluster, which can be regarded as a atomically precise bioinspired cluster with metalloenzyme-like catalytic sites (Cu Z ). Importantly, Cu 4 @Ti 9 displays high selectivity for the electrocatalytic reduction of CO 2 to C 2 H 4 (FE: 47.6 ± 3.4%) at 400 mA cm –2 and good catalytic durability (8 h). The bioinspired Cu 4 @Ti 9 not only represents the first example of Cu cluster directly encapsulated by a metal-oxo shell but also opens the CO 2 electroreduction to ethylene applications of atomically precise metallic clusters.