Ethylene glycol reforming on Pt(111): first-principles microkinetic modeling in vapor and aqueous phases

	Ethylene glycol reforming on Pt(111): first-principles microkinetic modeling in vapor and aqueous phases
	Lu, Jianmin 1,3; Faheem, Muhammad 1,2; Saleheen, Mohammad 1; Heyden, Andreas 1
刊名	Catalysis Science & Technology
	2016
卷号	6 期号:23 页码:8242-8256
英文摘要	First-principles, periodic density functional theory (DFT) calculations and mean-field microkinetic modeling have been used to investigate the decomposition of ethylene glycol for hydrogen production on Pt(111) in vapor and aqueous phases. All dehydrogenated species derived from ethylene glycol (C2HxO2, x = 0-6) and methanol (CHyO, y = 0-4), and all elementary C-C, C-H, and O-H bond breaking steps are included in the microkinetic model. Reaction path analysis in vapor phase indicates that both initial C-H and O-H dehydrogenation steps are kinetically relevant at all temperatures (470-530 K). Initial O-H bond cleavage is reversible at low temperatures but accounts for an increasingly dominant fraction of the total reaction flux at higher temperatures. C-C bond scission is observed only after significant dehydrogenation (x = 3) and is more likely to happen in surface intermediates where one of the cleavage products is CO. The process is highly selective to the production of H-2 compared to methanol. For aqueous-phase model development, free energies of solvation were computed for all surface intermediates and transition states using a continuum solvation approach. Our aqueous-phase microkinetic model predicts a 0.4 eV lower apparent activation energy and an order of magnitude larger turnover frequencies. Initial C-H bond cleavage becomes more important but the general trends are similar to the vapor phase, suggesting that the reaction chemistry is similar in both vapor and aqueous phases.
WOS标题词	Science & Technology ; Physical Sciences
类目[WOS]	Chemistry, Physical
关键词[WOS]	SUPPORTED PLATINUM CATALYSTS ; FINDING SADDLE-POINTS ; RATE-DETERMINING STEP ; ZETA VALENCE QUALITY ; BASIS-SETS ; METHANOL DECOMPOSITION ; TRANSITION-METALS ; OXYGENATED HYDROCARBONS ; RENEWABLE HYDROGEN ; ENERGY
收录类别	SCI
语种	英语
WOS记录号	WOS:000389224400006
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/150448]
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
作者单位	1.Univ South Carolina, Dept Chem Engn, 301 South Main St, Columbia, SC 29208 USA 2.Univ Engn & Technol, Dept Chem Engn, Lahore 54890, Pakistan 3.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian Natl Lab Clean Energy, State Key Lab Catalysis, Dalian 116023, Liaoning, Peoples R China
推荐引用方式 GB/T 7714	Lu, Jianmin,Faheem, Muhammad,Saleheen, Mohammad,et al. Ethylene glycol reforming on Pt(111): first-principles microkinetic modeling in vapor and aqueous phases[J]. Catalysis Science & Technology,2016,6(23):8242-8256.
APA	Lu, Jianmin,Faheem, Muhammad,Saleheen, Mohammad,&Heyden, Andreas.(2016).Ethylene glycol reforming on Pt(111): first-principles microkinetic modeling in vapor and aqueous phases.Catalysis Science & Technology,6(23),8242-8256.
MLA	Lu, Jianmin,et al."Ethylene glycol reforming on Pt(111): first-principles microkinetic modeling in vapor and aqueous phases".Catalysis Science & Technology 6.23(2016):8242-8256.