Density functional theory study of propane steam reforming on Rh–Ni bimetallic surface: Sulfur tolerance and scaling/Brønsted–Evans–Polanyi relations

Lee, Kyungtae; Lee, Eunmin; Song, Chunshan; Janik, Michael J.

doi:10.1016/j.jcat.2013.10.006

Cited by 30 publications

(25 citation statements)

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“…Most of them concentrate on extended metal facets, such as Ir(111), 7 Pt(111), 8 , 9 Pt with step sites, 10 Ni(111), 11 , 12 and Rh–Ni bimetallic surface. 13 Recently, the density functional theory (DFT) study has been carried out for n -butane dehydrogenation and cracking on Ni(111). 14 While many of those studies take C–C bond cleavage into account as well, the coking is still not well understood from the theoretical perspective.…”

Section: Introductionmentioning

confidence: 99%

First-Principles-Based Multiscale Modelling of Nonoxidative Butane Dehydrogenation on Cr₂O₃(0001)

et al. 2020

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Propane (C 3 H 8 ) and butane (C 4 H 10 ) are short straight-chain alkane molecules that are difficult to convert catalytically. Analogous to propane, butane can be dehydrogenated to butenes (also known as butylenes) or butadiene, which are used industrially as raw materials when synthesizing various chemicals (plastics, rubbers, etc.). In this study, we present results of detailed first-principles-based multiscale modelling of butane dehydrogenation, consisting of three size- and time-scales. The reaction is modelled over Cr 2 O 3 (0001) chromium oxide, which is commonly used in the industrial setting. A complete 108-step reaction pathway of butane (C 4 H 10 ) dehydrogenation was studied, yielding 1-butene (CH 2 CHCH 2 CH 3 ) and 2-butene (CH 3 CHCHCH 3 ), 1-butyne (CHCCH 2 CH 3 ) and 2-butyne (CH 3 CCCH 3 ), butadiene (CH 2 CHCHCH 2 ), butenyne (CH 2 CHCCH), and ultimately butadiyne (CHCCCH). We include cracking and coking reactions (yielding C 1 , C 2 , and C 3 hydrocarbons) in the model to provide a thorough description of catalyst deactivation as a function of the temperature and time. Density functional theory calculations with the Hubbard U model were used to study the reaction on the atomistic scale, resulting in the complete energetics and first-principles kinetic parameters for the dehydrogenation reaction. They were cast in a kinetic model using mean-field microkinetics and kinetic Monte Carlo simulations. The former was used to obtain gas equilibrium conditions in the steady-state regime, which were fed in the latter to provide accurate surface kinetics. A full reactor simulation was used to account for the macroscopic properties of the catalytic particles: their loading, specific surface area, and density and reactor parameters: size, design, and feed gas flow. With this approach, we obtained first-principles estimates of the catalytic conversion, selectivity to products, and time dependence of the catalyst activity, which can be paralleled to experimental data. We show that 2-butene is the most abundant product of dehydrogenation, with selectivity above 90% and turn-over frequency above 10 –3 s –1 at T = 900 K. Butane conversion is below 5% at such low temperature, but rises above 40% at T > 1100 K. Activity starts to drop after ∼6 h because of surface poisoning with carbon. We conclude that the dehydrogenation of butane is a viable alternative to conventiona...

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Section: Introductionmentioning

confidence: 99%

First-Principles-Based Multiscale Modelling of Nonoxidative Butane Dehydrogenation on Cr₂O₃(0001)

et al. 2020

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“…LPG is a mixture of petroleum gases that exists in a liquid state at ambient temperatures under moderate pressures (less than 1.5 MPa). It is inexpensive and mainly consists of propane in many countries such as U.S./Canadian LPG [9,10]. Hence, propane has also been accepted as a practical feedstock for hydrogen production due to its abundance and its well-established infrastructure in modern cities.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen production from propane steam reforming over Ir/Ce 0.75 Zr 0.25 O 2 catalyst

Hou

Zhang

et al. 2015

Applied Catalysis B: Environmental

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“…MO x -CeO 2 materials can be used to adsorb sulfur [3][4][5][6][7][8] as well as reform hydrocarbons [8][9][10][11][12][13]. These two processes have mostly been studied independently from one another on oxides, though reforming in the presence of sulfur species has been examined on metal catalysts [14,15]. There are several studies (both experimental and computational) examining hydrocarbon reforming over ceria, with most of them focused on methane [9][10][11][12][13][16][17][18].…”

Section: Introductionmentioning

confidence: 99%

“…DFT studies have examined how sulfur affects hydrocarbon reforming over metals [14,15]. The presence of sulfur on Ni (1 1 1) will deactivate the step sites on Ni, leaving only terrace sites active for the activation of methane [14].…”

Section: Introductionmentioning

confidence: 99%

“…The presence of sulfur on Ni (1 1 1) will deactivate the step sites on Ni, leaving only terrace sites active for the activation of methane [14]. Rh has a low sulfur resistance, which can be improved with the addition of Ni forming a bimetallic surface [15]. The impact of S absorption into oxides may be expected to be more complex, as surface S atoms may alter the surface redox properties, impact the binding of adsorbates on nearby O atoms, or themselves bind surface adsorbates.…”

Section: Introductionmentioning

confidence: 99%

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Alkane reforming on partially sulfided CeO2 (1 1 1) surfaces

Krcha

Dooley

Janik

2015

Journal of Catalysis

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a b s t r a c tCleanup of biomass gasification effluent requires a catalyst that can reform methane and larger hydrocarbons while tolerating the presence of H 2 S or, ideally, that can act as a sulfur sorbent while reforming hydrocarbons. We utilize density functional theory (DFT) methods to examine the impact of oxide sulfidation on the reforming of methane and the initial steps of propane reforming, using M-doped CeO 2 catalysts. On a ceria oxy-sulfide surface, surface oxygen atoms remain active for CAH bond activation via hydride abstraction whereas surface sulfur atoms are significantly less active. Methyl adsorption is slightly favored at a surface sulfur site, and though subsequent dehydrogenation steps remain viable, the final steps of methane decomposition may lead to carbon buildup on the surface. However, surface sulfur sites will be less active globally for the initial rate limiting H abstraction step, and these sites can nucleate carbon buildup. Doping CeO 2 with Mn accelerates CAH bond activation, aids eventual CO product desorption, and may induce sulfur tolerance by motivating CH x intermediates to bind to surface O atoms rather than surface S atoms. This work represents an initial step in the development of S-tolerant oxide catalysts for hydrocarbon reforming.

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Density functional theory study of propane steam reforming on Rh–Ni bimetallic surface: Sulfur tolerance and scaling/Brønsted–Evans–Polanyi relations

Cited by 30 publications

References 48 publications

First-Principles-Based Multiscale Modelling of Nonoxidative Butane Dehydrogenation on Cr₂O₃(0001)

First-Principles-Based Multiscale Modelling of Nonoxidative Butane Dehydrogenation on Cr₂O₃(0001)

Hydrogen production from propane steam reforming over Ir/Ce 0.75 Zr 0.25 O 2 catalyst

Alkane reforming on partially sulfided CeO2 (1 1 1) surfaces

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Density functional theory study of propane steam reforming on Rh–Ni bimetallic surface: Sulfur tolerance and scaling/Brønsted–Evans–Polanyi relations

Cited by 30 publications

References 48 publications

First-Principles-Based Multiscale Modelling of Nonoxidative Butane Dehydrogenation on Cr2O3(0001)

First-Principles-Based Multiscale Modelling of Nonoxidative Butane Dehydrogenation on Cr2O3(0001)

Hydrogen production from propane steam reforming over Ir/Ce 0.75 Zr 0.25 O 2 catalyst

Alkane reforming on partially sulfided CeO2 (1 1 1) surfaces

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First-Principles-Based Multiscale Modelling of Nonoxidative Butane Dehydrogenation on Cr₂O₃(0001)

First-Principles-Based Multiscale Modelling of Nonoxidative Butane Dehydrogenation on Cr₂O₃(0001)