Ni-Zn Dual Sites Switch the CO2 Hydrogenation Selectivity via Tuning of the d-Band Center

被引：66

作者：

Lin, Shuangxi ^{[1
]}

Wang, Qiang ^{[1
]}

Li, Maoshuai ^{[1
]}

Hao, Ziwen ^{[2
]}

Pan, Yutong ^{[1
]}

Han, Xiaoyu ^{[2
]}

Chang, Xiao ^{[1
]}

Huang, Shouying ^{[1
]}

Li, Zhenhua ^{[1
]}

Ma, Xinbin ^{[1
,2
]}

机构：

[1] Tianjin Univ, Sch Chem Engn & Technol, Collaborat Innovat Ctr Chem Sci & Engn, Key Lab Green Chem Technol,Minist Educ, Tianjin 300350, Peoples R China

[2] Joint Sch Natl Univ Singapore & Tianjin Univ, Fuzhou 350207, Peoples R China

来源：

ACS CATALYSIS | 2022年 / 12卷 / 06期

基金：

中国国家自然科学基金;

关键词：

CO2; hydrogenation; Ni-based catalyst; electronic interaction; Ni-Zn alloy; reaction pathway; METAL-SUPPORT INTERACTIONS; HETEROGENEOUS CATALYSTS; ELECTRONIC-STRUCTURE; METHANATION ACTIVITY; LOW-TEMPERATURE; PERFORMANCE; ACTIVATION; VACANCIES; PRESSURE; SURFACES;

D O I：

10.1021/acscatal.1c05582

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Controlling the selectivity of CO2 hydrogenation by catalysis is a fundamental challenge. This study examines the interrelation between active sites and reaction pathways in Ni-catalyzed CO2 hydrogenation. The alloying of Ni with Zn to charged (Ni sigma--Zn-sigma(+)) active sites modifies the electronic structure and d-band center, weakens the interaction with CO/H-2, and preferentially catalyzes the reverse water gas shift to CO with the thermodynamically favored methanation pathway switched off. The charged dual sites can stabilize the activated CO2 species in a eta(2)(C, 0) bridge configuration, directly dissociate the C=0 bond to *CO, and promote CO desorption. The mechanistic investigation has elucidated the reaction pathways in the Ni-catalyzed CO2 hydrogenation and identified the crucial intermediates that impacted the product selectivity, which can provide a theoretical guide for the Ni-based catalyst design.

引用

页码：3346 / 3356

页数：11

共 58 条

[1] Catalytic Performance of γ-Al2O3-ZrO2-TiO2-CeO2 Composite Oxide Supported Ni-Based Catalysts for CO2 Methanation [J].