Density Functional Theory Based Micro- and Macro-Kinetic Studies of Ni-Catalyzed Methanol Steam Reforming

Ke, Changming; Lin, Zijing

doi:10.3390/catal10030349

Cited by 7 publications

(7 citation statements)

References 38 publications

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“…Similar result has also been observed for the C-H scission on PdZn(111) [40]. As reactions prefer the least resistant paths and the fractional coverage of OH* is in the order of 1% and very low coverages for CH3OH* and CHxO* on Ni(111) [41], the C-H scission is not expected to be adversely impacted by OH*. Due to the high Ea involved in CH3O* → CH2O* + H* or CH3OH* → CH2OH* + H*.…”

Section: Methodssupporting

confidence: 81%

Catalytic Effect of Hydrogen Bond on Oxhydryl Dehydrogenation in Methanol Steam Reforming on Ni(111)

Lin

2020

Molecules

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Dehydrogenation of H3COH and H2O are key steps of methanol steam reforming on transition metal surfaces. Oxhydryl dehydrogenation reactions of HxCOH (x = 0–3) and OH on Ni (111) were investigated by DFT calculations with the OptB88-vdW functional. The transition states were searched by the climbing image nudged elastic band method and the dimer method. The activation energies for the dehydrogenation of individual HxCOH* are 68 to 91 kJ/mol, and reduced to 12–17 kJ/mol by neighboring OH*. Bader charge analysis showed the catalysis role of OH* can be attributed to the effect of hydrogen bond (H-bond) in maintaining the charge of oxhydryl H in the reaction path. The mechanism of H-bond catalysis was further demonstrated by the study of OH* and N* assisted dehydrogenation of OH*. Due to the universality of H-bond, the H-bond catalysis shown here, is of broad implication for studies of reaction kinetics.

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Section: Methodssupporting

confidence: 81%

Catalytic Effect of Hydrogen Bond on Oxhydryl Dehydrogenation in Methanol Steam Reforming on Ni(111)

Lin

2020

Molecules

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“…The analytical rate equation inferred on the basis of the main reaction pathway is proposed to be a good reference for designing and optimization of the reaction conditions during SRM. 249 Table 2 Summarizes Ni-based catalysts used in SRM.…”

Section: Cu-based Catalystsmentioning

confidence: 99%

“…This microkinetic model was utilized to know the dominant reaction pathway and the rate-determining step (RDS). The analytical rate equation inferred on the basis of the main reaction pathway is proposed to be a good reference for designing and optimization of the reaction conditions during SRM Table Summarizes Ni-based catalysts used in SRM.…”

Section: Group Viii–xii Catalystsmentioning

confidence: 99%

Steam Reforming of Methanol for Hydrogen Production: A Critical Analysis of Catalysis, Processes, and Scope

Ranjekar

Yadav

2021

Ind. Eng. Chem. Res.

201

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The hydrogen economy is being pursued quite vigorously since hydrogen is an important and green energy source with a variety of applications as fuel for transportation, fuel cell, feedstock, energy vector, reforming in refineries, carbon dioxide valorization, biomass conversion, etc. Steam reforming of alcohols is a well-established technique to obtain syngas. Methanol is viewed to be a lucrative alternative for fossil fuels, due to its flexibility in being generated from multiple sources, high energy density, and low operating temperatures. The catalysts used for reforming govern the methanol conversion rate and the ratio of gaseous products, i.e., H2, CO, and CO2. Group VIII–XII metals have been widely utilized for methanol steam reforming as they have a higher hydrogen yield. Several other catalysts and novel techniques have been developed and used to date. Quite a few strategies to enhance the performance of catalysts and reduce deactivation have been discussed. This review focuses on the metallic catalysts, mainly Cu, Pd, Zn, with different formulations and compositions for steam reforming of methanol (SRM). Active catalyst components, supports, and their interactions, along with different promoters, are reviewed, and their performances are critically analyzed. The various reaction mechanisms and reaction pathways have been identified and elaborated. A fundamental understanding of the functionality and structure of catalysts is required no matter which alcohol is used as a feedstock, and some general inferences can be obtained from polyhydroxyl feed for the steam reforming of methanol, which is the subject matter of this review. Particularly, the role of copper as a component in mono and multimetallic systems and the nature of support must be studied fundamentally to get high hydrogen yields. It is important to determine how metal support interactions, including oxygen transfer from reducible oxides to the metal site, influence the catalyst activity, selectivity, and stability. Further, the mechanism by which alloying affects the selectivity in multimetallic catalysts must be understood by using high-end characterizations.

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“…3D activity volcano plot under EEFs A detailed study of the microkinetic model of SRM shows that the methanol conversion rate (r M [F]) can be quantified with a simplified pathway [38] We find that the EEF-induced energy change turns out to be rather insensitive to the metal type, which greatly simplifies the problem (see Supplementary Material Sect. VII).…”

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confidence: 92%

Three Dimensional Activity Volcano Plot under External Electric Field

Ke¹,

Lin²,

Shi³

2022

Preprint

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An external electric field (EEF) can impact a broad range of catalytic processes beyond redox systems. Computational design of catalysts under EEFs targeting specific operation conditions essentially requires accurate predictions of the response of a complex physicochemical system to collective parameters such as EEF strength/direction and temperature. Here, we develop a first-principlesbased multiscale approach that enables efficient EEF-dependent kinetic modeling of heterogeneous catalysis. Taking steam reforming of methanol as an example, we find that the methanol conversion rate exhibits strong nonlinear response to temperature and EEF, and the optimal field line and constant carbon concentration line defined in the temperature-EEF parameter space serve as powerful metrics for catalyst design. Assisted with a deep neural network, we establish a three-dimensional activity volcano plot under EEFs for thousands of metallic alloys.

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Density Functional Theory Based Micro- and Macro-Kinetic Studies of Ni-Catalyzed Methanol Steam Reforming

Cited by 7 publications

References 38 publications

Catalytic Effect of Hydrogen Bond on Oxhydryl Dehydrogenation in Methanol Steam Reforming on Ni(111)

Catalytic Effect of Hydrogen Bond on Oxhydryl Dehydrogenation in Methanol Steam Reforming on Ni(111)

Steam Reforming of Methanol for Hydrogen Production: A Critical Analysis of Catalysis, Processes, and Scope

Three Dimensional Activity Volcano Plot under External Electric Field

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