Surfactants Used in Colloidal Synthesis Modulate Ni Nanoparticle Surface Evolution for Selective CO<sub>2</sub> Hydrogenation
Xiangru Wei, Grayson Johnson, Yifan Ye, Meiyang Cui, Shen‐Wei Yu, Yihua Ran, Jun Cai, Zhi Liu, Xi Chen, Wenpei Gao, Paul J. L. Bean, Weijie Zhang, Yunpu Zhao, Frédéric A. Perras, Ethan J. Crumlin, Xu Zhang, Robert J. Davis, Zhangxiong Wu, Sen Zhang
Abstract
Colloidal chemistry holds promise to prepare uniform and size-controllable pre-catalysts; however, it remains a challenge to unveil the atomic-level transition from pre-catalysts to active catalytic surfaces under the reaction conditions to enable the mechanistic design of catalysts. Here, we report an ambient-pressure X-ray photoelectron spectroscopy study, coupled with in situ environmental transmission electron microscopy, infrared spectroscopy, and theoretical calculations, to elucidate the surface catalytic sites of colloidal Ni nanoparticles for CO 2 hydrogenation. We show that Ni nanoparticles with phosphine ligands exhibit a distinct surface evolution compared with amine-capped ones, owing to the diffusion of P under oxidative (air) or reductive (CO 2 + H 2 ) gaseous environments at elevated temperatures. The resulting NiP x surface leads to a substantially improved selectivity for CO production, in contrast to the metallic Ni, which favors CH 4 . The further elimination of surface metallic Ni sites by designing multi-step P incorporation achieves unit selectivity of CO in high-rate CO 2 hydrogenation.