Reversing sintering effect of Ni particles on γ-Mo2N via strong metal support interaction

Lili Lin; Jinjia Liu; Xi Liu; Zirui Gao; Ning Rui; Siyu Yao; Feng Zhang; Maolin Wang; Chang Liu; Lili Han; Feng Yang; Sen Zhang; Xiao-Dong Wen; Sanjaya D Senanayake; Yichao Wu; Xiaonian Li; José A Rodriguez; Ding Ma

doi:10.1038/s41467-021-27116-8

Reversing sintering effect of Ni particles on γ-Mo₂N via strong metal support interaction

Nat Commun. 2021 Nov 30;12(1):6978. doi: 10.1038/s41467-021-27116-8.

Authors

Lili Lin^#^{1

2}, Jinjia Liu^#^{3

4}, Xi Liu⁵, Zirui Gao², Ning Rui⁶, Siyu Yao⁷, Feng Zhang⁸, Maolin Wang², Chang Liu⁹, Lili Han⁶, Feng Yang¹⁰, Sen Zhang⁹, Xiao-Dong Wen^{3

4}, Sanjaya D Senanayake⁶, Yichao Wu¹, Xiaonian Li¹, José A Rodriguez^{11

12}, Ding Ma¹³

Affiliations

¹ Institute of Industrial Catalysis, State Key Laboratory of Green Chemistry Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, 310014, Hangzhou, Zhejiang, China.
² Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering and College of Engineering and BIC-ESAT Peking University, 100871, Beijing, P. R. China.
³ State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, China.
⁴ National Energy Centre for Coal to Liquids, Synfuels China Co. Ltd, Beijing, China.
⁵ School of Chemistry and Chemical Engineering, In-situ Center for Physical Science, Shanghai Jiao Tong University, Shanghai, China. liuxi@sjtu.edu.cn.
⁶ Chemistry Division, Brookhaven National Laboratory, Upton, NY, 11973, USA.
⁷ Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, 310027, Hangzhou, China.
⁸ Materials Science and Chemical Engineering Department, State University of New York, Stony Brook, NY, USA.
⁹ Department of Chemistry, University of Virginia, Charlottesville, VA, 22904, USA.
¹⁰ Department of Chemistry, Southern University of Science and Technology, 518055, Shenzhen, China.
¹¹ Chemistry Division, Brookhaven National Laboratory, Upton, NY, 11973, USA. rodrigez@bnl.gov.
¹² Materials Science and Chemical Engineering Department, State University of New York, Stony Brook, NY, USA. rodrigez@bnl.gov.
¹³ Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering and College of Engineering and BIC-ESAT Peking University, 100871, Beijing, P. R. China. dma@pku.edu.cn.

^# Contributed equally.

Abstract

Reversing the thermal induced sintering phenomenon and forming high temperature stable fine dispersed metallic centers with unique structural and electronic properties is one of the ever-lasting targets of heterogeneous catalysis. Here we report that the dispersion of metallic Ni particles into under-coordinated two-dimensional Ni clusters over γ-Mo₂N is a thermodynamically favorable process based on the AIMD simulation. A Ni-4nm/γ-Mo₂N model catalyst is synthesized and used to further study the reverse sintering effect by the combination of multiple in-situ characterization methods, including in-situ quick XANES and EXAFS, ambient pressure XPS and environmental SE/STEM etc. The under-coordinated two-dimensional layered Ni clusters on molybdenum nitride support generated from the Ni-4nm/γ-Mo₂N has been demonstrated to be a thermally stable catalyst in 50 h stability test in CO₂ hydrogenation, and exhibits a remarkable catalytic selectivity reverse compared with traditional Ni particles-based catalyst, leading to a chemo-specific CO₂ hydrogenation to CO.