Boosting CO hydrogenation towards C2+ hydrocarbons over interfacial TiO2-x/Ni catalysts

Ming Xu; Xuetao Qin; Yao Xu; Xiaochen Zhang; Lirong Zheng; Jin-Xun Liu; Meng Wang; Xi Liu; Ding Ma

doi:10.1038/s41467-022-34463-7

Boosting CO hydrogenation towards C₂₊ hydrocarbons over interfacial TiO_2-x/Ni catalysts

Nat Commun. 2022 Nov 7;13(1):6720. doi: 10.1038/s41467-022-34463-7.

Authors

Ming Xu^#^{1

2}, Xuetao Qin^#¹, Yao Xu¹, Xiaochen Zhang¹, Lirong Zheng³, Jin-Xun Liu⁴, Meng Wang⁵, Xi Liu^{6

7}, Ding Ma⁸

Affiliations

¹ College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China.
² State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, P. R. China.
³ Institute of High Energy Physics, the Chinese Academy of Sciences, Beijing, 100049, P. R. China.
⁴ Department of Chemical Physics, University of Science and Technology of China, Hefei, 230026, P. R. China. jxliu86@ustc.edu.cn.
⁵ College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China. m.wang@pku.edu.cn.
⁶ School of Chemistry and Chemical Engineering, In-situ Center for Physical Sciences, Shanghai Jiaotong University, Shanghai, 200240, P. R. China. liuxi@sjtu.edu.cn.
⁷ Syncat@Beijing, Synfuels China Co., Ltd, Beijing, 101400, P. R. China. liuxi@sjtu.edu.cn.
⁸ College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China. dma@pku.edu.cn.

^# Contributed equally.

Abstract

Considerable attention has been drawn to tune the geometric and electronic structure of interfacial catalysts via modulating strong metal-support interactions (SMSI). Herein, we report the construction of a series of TiO_2-x/Ni catalysts, where disordered TiO_2-x overlayers immobilized onto the surface of Ni nanoparticles (~20 nm) are successfully engineered with SMSI effect. The optimal TiO_2-x/Ni catalyst shows a CO conversion of ~19.8% in Fischer-Tropsch synthesis (FTS) process under atmospheric pressure at 220 °C. More importantly, ~64.6% of the product is C₂₊ paraffins, which is in sharp contrast to the result of the conventional Ni catalyst with the main product being methane. A combination study of advanced electron microscopy, multiple in-situ spectroscopic characterizations, and density functional theory calculations indicates the presence of Ni^δ-/TiO_2-x interfacial sites, which could bind carbon atom strongly, inhibit methane formation and facilitate the C-C chain propagation, lead to the production of C₂₊ hydrocarbon on Ni surface.