Nano‐Antenna Reactors With Spatially Coordinated Microenvironments Enable Atmospheric CO 2 Photoreduction to C 2 H 6
Dongpo He, Hangtian Hu, Liang Wang, Liang Chen, Peipei Li, Guangbing Huang, Jinyu Ding, Qinyuan Hu, Jun Hu, Junfa Zhu, Wensheng Yan, Xiaowen Ruan, Yuming Dong, Ju Wu, Jinguang Hu, Xingchen JiaoABSTRACT
Photocatalytic CO 2 reduction to multicarbon products is often limited by inefficient proton delivery to metal nanoparticle surfaces, restricting proton‐coupled C─C coupling to a small fraction of metal‐oxide interfacial sites. Here, we report a spatially coordinated microenvironment engineering strategy to activate underutilized metal surface atoms for efficient C 2 H 6 formation, even under low CO 2 concentration. An AuCu‐CeO 2 nano‐antenna‐reactor photocatalyst is constructed where CeO 2 nanosheets serve as oxide antenna supports and Au nanoparticles act as CO 2 reduction reactors. Notably, Cu sites incorporated within Au nanoparticles function as localized water‐activation centers, creating a proton‐rich microenvironment adjacent to CO 2 reduction sites. In situ spectroscopy combined with density functional theory calculations reveals that this proton‐rich microenvironment lowers the rate‐determining *CO to *COH protonation barrier from 1.23 to 0.54 eV, promoting C─C coupling via a *CO─*COH pathway. As a result, AuCu‐CeO 2 achieves a ∼3‐fold enhancement in C 2 H 6 production under pure CO 2 compared with Au‐CeO 2 , while maintaining appreciable rates of 3.3 and 1.67 µmol g −1 h −1 at flue‐gas (15%) and atmospheric (0.03%) CO 2 levels, respectively. This work establishes a general principle for regulating proton‐coupled multi‐electron transformations on catalytic surfaces.