Mechanistic Insights into Selective CO2 Conversion via RWGS on Transition Metal Phosphides: A DFT Study

doi:10.1021/acs.jpcc.9b04122

	Mechanistic Insights into Selective CO2 Conversion via RWGS on Transition Metal Phosphides: A DFT Study
	Guharoy, Utsab 1,2; Reina, Tomas Ramirez 1; Gu, Sai 1; Cai, Qiong 1
刊名	JOURNAL OF PHYSICAL CHEMISTRY C
	2019-09-19
卷号	123 期号:37 页码:22918-22931
ISSN号	1932-7447
DOI	10.1021/acs.jpcc.9b04122
通讯作者	Cai, Qiong(q.cai@surrey.ac.uk)
英文摘要	Selective conversion of CO2 to CO via the reverse water gas shift TMPs (RWGS) reaction is an attractive CO2 conversion process, which may be integrated with many industrial catalytic processes such as Fischer-Tropsch synthesis to generate added value products. The development of active and cost friendly catalysts is of paramount importance. Among the available catalyst materials, transition metal phosphides (TMPs) such as MoP and Ni2P have remained unexplored in the context of the RWGS reaction. In the present work, we have employed density functional theory (DFT) to first investigate the stability and geometries of selected RWGS intermediates on the MoP (0001) surface, in comparison to the Ni2P (0001) surface. Higher adsorption energies and Bader charges are observed on MoP (0001), indicating better stability of intermediates on the MoP (0001) surface. Furthermore, mechanistic investigation using potential energy surface (PES) profiles showcased that both MoP and Ni2P were active toward RWGS reaction with the direct path (CO2* -> CO* + O) favorable on MoP (0001), whereas the COOH-mediated path (CO2 + H* -> COOH) favors Ni2P (0001) for product (CO and H2O) gas generation. Additionally, PES profiles of initial steps to CO activation revealed that direct CO decomposition to C and O* is favored only on MoP (0001), while H-assisted CO activation is more favorable on Ni2P (0001) but could also occur on MoP (0001). Furthermore, our DFT calculations also ascertained the possibility of methane formation on Ni2P (0001) during the RWGS process, while MoP (0001) remained more selective toward CO generation.
资助项目	Department of Chemical and Process Engineering at the University of Surrey ; EPSRC[EP/M027066/1] ; EPSRC[EP/R512904] ; EPSRC[EP/J020184/2] ; EPSRC[EP/P003354/1]
WOS关键词	GAS SHIFT REACTION ; CARBON-MONOXIDE ; HYDROGEN EVOLUTION ; ADSORPTION ; CATALYSTS ; MOLYBDENUM ; ACTIVATION ; SURFACE ; CARBIDE ; DISSOCIATION
WOS研究方向	Chemistry ; Science & Technology - Other Topics ; Materials Science
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000487349600023
资助机构	Department of Chemical and Process Engineering at the University of Surrey ; Department of Chemical and Process Engineering at the University of Surrey ; EPSRC ; EPSRC ; Department of Chemical and Process Engineering at the University of Surrey ; Department of Chemical and Process Engineering at the University of Surrey ; EPSRC ; EPSRC ; Department of Chemical and Process Engineering at the University of Surrey ; Department of Chemical and Process Engineering at the University of Surrey ; EPSRC ; EPSRC ; Department of Chemical and Process Engineering at the University of Surrey ; Department of Chemical and Process Engineering at the University of Surrey ; EPSRC ; EPSRC
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/172842]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
通讯作者	Cai, Qiong
作者单位	1.Univ Surrey, Fac Engn & Phys Sci, Dept Chem & Proc Engn, Guildford GU2 7XH, Surrey, England 2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, 457 Zhongshan Rd, Dalian 116023, Peoples R China
推荐引用方式 GB/T 7714	Guharoy, Utsab,Reina, Tomas Ramirez,Gu, Sai,et al. Mechanistic Insights into Selective CO2 Conversion via RWGS on Transition Metal Phosphides: A DFT Study[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2019,123(37):22918-22931.
APA	Guharoy, Utsab,Reina, Tomas Ramirez,Gu, Sai,&Cai, Qiong.(2019).Mechanistic Insights into Selective CO2 Conversion via RWGS on Transition Metal Phosphides: A DFT Study.JOURNAL OF PHYSICAL CHEMISTRY C,123(37),22918-22931.
MLA	Guharoy, Utsab,et al."Mechanistic Insights into Selective CO2 Conversion via RWGS on Transition Metal Phosphides: A DFT Study".JOURNAL OF PHYSICAL CHEMISTRY C 123.37(2019):22918-22931.