Screened Fe-3 and Ru-3 Single-Cluster Catalysts Anchored on MoS2 Supports for Selective Hydrogenation of CO2

Wang, Gang1,2; Jiang, Xue-Lian1,2; Jiang, Ya-Fei1,2; Wang, Yang-Gang1,2; Li, Jun1,2,3,4

2023-06-01

10.1021/acscatal.3c00617

ACS CATALYSIS   影响因子和分区

2155-5435

Efficient CO2 hydrogenation into valuableproducts isa promising strategy to address environmental issues and achieve greendevelopment goals, yet developing highly active and selective catalystsstill remains a major challenge. The single-cluster catalysts frequentlyexhibit unexpected catalytic performance for complex reactions inheterogeneous catalysis due to the synergistic interaction betweenthe active atoms. In this work, we have proposed candidate catalystswith Fe-3 and Ru-3 clusters anchored at the Svacancies on the MoS2 substrate for highly selective CO2 hydrogenation, which is screened from a series of transition-metalclusters including Fe-3, Co-3, Ni-3,Ru-3, Rh-3, and Pd-3 by employing densityfunctional theory calculations. The electron structure analysis revealsthat the orbital interactions between metal hydride and CO2 dominate the adsorption modes of CO2 molecules on M-3 clusters, wherein CO2 forms a symmetrical eta(1)-C adsorption mode on the Fe-3 cluster andan asymmetric eta(2)-C,O adsorption mode on theRu(3) cluster, thereby leading to different CO2 hydrogenation pathways. Furthermore, the underlying reaction mechanismsfor CO2 hydrogenation on Fe-3/MoS2-v and Ru-3/MoS2-v have been explored, and the M-3 clusters are suggestedto act as electron reservoirs throughout the whole hydrogenation reaction.Combining with microkinetic simulations, we have showed the highlyselective reactivity toward methanol formation on Fe-3/MoS2-v and ethanol formation on Ru-3/MoS2-v . Our work providesin-depth atomic-scale insights into the mechanism of CO2 transformation in transition-metal single-cluster catalysis, whichwould provide ideas for the design and development of highly selectivecatalysts for CO2 hydrogenation.

single-cluster catalysts M-3 MoS2-v CO2 hydrogenation methanol selectivity C-C coupling

SCI ; EI

英语

第一 ; 通讯

National Key R&D Program of China[2022YFA1503102] ; NSFC of China["22022504","22033005","92261111"] ; Shenzhen Science and Technology Program[JCYJ20220818100410023] ; Guangdong "Pearl River" Talent Plan[2019QN01L353] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Physical

WOS:001006223700001

AMER CHEMICAL SOC

20232714333939

Adsorption ; Carbon dioxide ; Catalysis ; Catalyst selectivity ; Density functional theory ; Hydrides ; Hydrogenation ; Iron compounds ; Layered semiconductors ; Methanol ; Ruthenium compounds ; Transition metals

Metallurgy and Metallography:531 ; Semiconducting Materials:712.1 ; Chemical Reactions:802.2 ; Chemical Operations:802.3 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
2.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalyt Chem, Shenzhen 518055, Guangdong, Peoples R China
3.Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China
4.Tsinghua Univ, Engn Res Ctr Adv Rare Earth Mat, Minist Educ, Beijing 100084, Peoples R China

Wang, Gang,Jiang, Xue-Lian,Jiang, Ya-Fei,et al. Screened Fe-3 and Ru-3 Single-Cluster Catalysts Anchored on MoS2 Supports for Selective Hydrogenation of CO2[J]. ACS CATALYSIS,2023,13(13):8413-8422.

Wang, Gang,Jiang, Xue-Lian,Jiang, Ya-Fei,Wang, Yang-Gang,&Li, Jun.(2023).Screened Fe-3 and Ru-3 Single-Cluster Catalysts Anchored on MoS2 Supports for Selective Hydrogenation of CO2.ACS CATALYSIS,13(13),8413-8422.

Wang, Gang,et al."Screened Fe-3 and Ru-3 Single-Cluster Catalysts Anchored on MoS2 Supports for Selective Hydrogenation of CO2".ACS CATALYSIS 13.13(2023):8413-8422.