Resolving the Active Role of Isolated Transition Metal Species in Ni-Based Catalysts for Dry Reforming of Methane

Zhou, Chuan1; Zhang, Yafeng2; Li, Bai1; Yang, Bing2; Li, Lei1

2024-03-04

10.1021/acscatal.3c05737

ACS CATALYSIS   影响因子和分区

2155-5435

["Ni-based catalysts have demonstrated high catalytic activity and stability toward the dry reforming of methane (DRM). However, the nature of the active sites and the origin of high catalytic activity remain unclear. Herein, we developed a three-step microkinetic model and constructed a volcano-type contour plot to study the catalytic activity of transition metal (TM) catalysts. Our findings revealed that the active sites in Ni-M (M = Mo, W, and Ru) catalysts predominantly consist of isolated M species, such as monomers (M-1), dimers (M-2), and trimers (M3), rather than uniformly distributed Ni-M species. Experimental observations validated our theoretical findings, demonstrating that the diluted Ni90Mo10 alloy containing isolated Mo1-3 species exhibits an activity significantly higher than those of NiMo alloys and Ni catalysts. We further confirmed that the superior catalytic activity originates from the highly localized electronic density, which enables continuous fine-tuning of the adsorption energies of C and O. These results demonstrate the critical role of precise surface composition manipulation in bimetallic catalysts. Furthermore, our three-step reaction model largely reduces the parameter dimension of DRM by requiring only the computation of 6 elementary steps rather than the original 38 elementary steps. These findings hold significant potential to facilitate the theoretical study of catalytic mechanisms and the rational design of DRM catalysts.","[GRAPHICS]"]

dry reforming of methane Ni-based alloys volcano plot reaction kinetics isolated Mo sites rational design of catalysts

SCI ; EI

英语

第一 ; 通讯

Shenzhen Key Laboratory of Micro/Nano-Porous Functional Materials[2022YFA1503102] ; National Key R&D Program of China[ZDSYS20210709112802010] ; Shenzhen Key Laboratory of Micro/Nano-Porous Functional Materials (SKLPM)["22179058","22072151"] ; National Natural Science Foundation of China[JCYJ20210324115809026] ; Shenzhen fundamental research funding[YSBR-022] ; CAS Project for Young Scientists in Basic Research[2023M733452]

Chemistry

Chemistry, Physical

WOS:001179733700001

AMER CHEMICAL SOC

Web of Science

1.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen Key Lab Micro Nanoporous Funct Mat SKLPM, Shenzhen 518055, Peoples R China
2.Chinese Acad Sci, Dalian Inst Chem Phys, CAS Key Lab Sci & Technol Appl Catalysis, Dalian 116023, Peoples R China

Zhou, Chuan,Zhang, Yafeng,Li, Bai,et al. Resolving the Active Role of Isolated Transition Metal Species in Ni-Based Catalysts for Dry Reforming of Methane[J]. ACS CATALYSIS,2024,14(6).

Zhou, Chuan,Zhang, Yafeng,Li, Bai,Yang, Bing,&Li, Lei.(2024).Resolving the Active Role of Isolated Transition Metal Species in Ni-Based Catalysts for Dry Reforming of Methane.ACS CATALYSIS,14(6).

Zhou, Chuan,et al."Resolving the Active Role of Isolated Transition Metal Species in Ni-Based Catalysts for Dry Reforming of Methane".ACS CATALYSIS 14.6(2024).