Theoretical Insight into the Reaction Mechanism of Ethanol Steam Reforming on Co(0001)

Lin, Sen; Huang, Jing; Gao, Xiaomei; Ye, Xinxin; Guo, Hua

doi:10.1021/jp512000k

Cited by 26 publications

(35 citation statements)

References 64 publications

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“…This calculated reaction mechanism is in agreement with that proposed before. 31 The rate-limiting step on Co 0 site is found to be the form of CH 3 CHO resulting CO.…”

Section: Bond Scission In Ch 3 Cho(a-3) Species Ch 3 Chomentioning

confidence: 94%

“…Hence, path (i) is favored over path (ii). 31 ). The CH 3 and H species will locate at hcp sites stably, and H then could approach the fcc site neighboring CH 3 species in the less stable configuration.…”

Section: Bond Scission In Ch 3 Cho(a-3) Species Ch 3 Chomentioning

confidence: 99%

“…The DFT result is in agreement with the small amount of CH 4 detected in experiment and the reported DFT calculation results that CH 3 species tends to remove H yielding CH 2 species. 31,32 The length of breaking C−H in CH 3 species increases to 1.64 Å in TS. Then the detached H reaches the hcp site at FS.…”

Section: Bond Scission In Ch 3 Cho(a-3) Species Ch 3 Chomentioning

confidence: 99%

“…A similar adsorption energy of −6.39 eV is found in a previous study. 31 The binding lengths of C−Co are 1.86, 1.88, and 1.88 Å, respectively. The CH species on the Co 3+ site is adsorbed occupying the fcc site of the Co with an adsorption energy of −4.04 eV (d(C−Co 3+ ) = 1.91 and 1.93 Å and d(C− Co 2+ ) = 1.94 Å).…”

Section: Introductionmentioning

confidence: 99%

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Reaction Mechanism of Ethanol on Model Cobalt Catalysts: DFT Calculations

Chen

Wang

2016

J. Phys. Chem. C

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In the present work, the density functional theory calculations analysis are performed to study the reaction mechanisms and catalytic activity of ethanol reactions over Co 0 , Co 2+ , and Co 3+ sites. Adsorption situations and the reaction cycles for ethanol reactions on cobalt catalysts were clarified. The mechanisms include the dehydrogenation steps of ethanol and the C−C cleavage step. The present calculation results show that the mechanism of ethanol reaction on Co 0 site is CH 3 CH 2 OH → CH 3 CH 2 O → CH 3 CHO → CH 3 CO → CH 3 +CO, and the final products are CO and H 2 . H 2 is formed by the combination of adsorbed H species. On Co 2+ site, the mechanism is CH 3 CH 2 OH → CH 3 CH 2 O → CH 3 CHO, and the main final product is CH 3 CHO species. On Co 3+ site, the mechanism is CH 3 CH 2 OH → CH 3 CH 2 O → CH 3 CHO → CH 2 CHO → CH 2 CO → CHCO → CCO → COCO → CO → CO 2 , and the final products are CO 2 and H 2 O. The rate-limiting step on Co 0 , Co 2+ , and Co 3+ sites is the form of CH 3 CHO species. The possible reasons for the different catalytic activities may be the following two facts: First, Co 3+ sites density in Co 3 O 4 (110)-A is larger than that of Co 2+ and tends to break the C−C bond to produce CO; second, Co 3+ binds more oxygen atoms that the further oxidation of ethanol requires, which leads to the full oxidation of ethanol to CO 2 on Co 3+ sites. The present result may help people to design an ESR (ethanol stream reaction) catalyst by controlling its oxidation state, and the catalyst with modest oxidation state is benefit for the H 2 formation. The proper catalyst should own the ability to break C−C to form CO but avoid the full oxidation of CO into CO 2 which is needed to react with H 2 O in the water−gas shift reaction generating CO 2 and H 2 .

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“…This calculated reaction mechanism is in agreement with that proposed before. 31 The rate-limiting step on Co 0 site is found to be the form of CH 3 CHO resulting CO.…”

Section: Bond Scission In Ch 3 Cho(a-3) Species Ch 3 Chomentioning

confidence: 94%

Section: Bond Scission In Ch 3 Cho(a-3) Species Ch 3 Chomentioning

confidence: 99%

Section: Bond Scission In Ch 3 Cho(a-3) Species Ch 3 Chomentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Reaction Mechanism of Ethanol on Model Cobalt Catalysts: DFT Calculations

Chen

Wang

2016

J. Phys. Chem. C

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“…The adsorption energy ( E ads ) is calculated as follows:

E_{ads} = E_{total} - ((), E_{adsorbate} + E_{Fe / normalg - normalC 3 N4})

where E total is the total energy of the adsorbate on Fe/g‐C 3 N 4 , E Fe/g‐C3N4 is the energy of the g‐C 3 N 4 adsorbed by the Fe atom and E adsorbate is the energy of methanol or intermediates.…”

Section: Methodsmentioning

confidence: 99%

Methanol dissociation and oxidation on single Fe atom supported on graphitic carbon nitride

Feng

Yang

et al. 2019

Applied Organom Chemis

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Considering environmental protection and sustainable development, fuel cells have always been an ideal choice for clean energy. For the performance of fuel cells, the anode catalysts are a key consideration. In the work reported, we designed a new type of anode catalyst, in which graphitic carbon nitride was used as the substrate and transition metal iron as the supported atom. The calculation results were characterized by adsorption energy, reaction energy barrier, potential energy surface and charge analysis. Based on density functional theory, the gradual decomposition of methanol molecules on the catalyst is realized; the decomposition products are oxidized to reduce the formation of CO, and the efficiency of anode catalysis is improved, which provides a new idea for the design of anode materials for methanol fuel cells.

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From Ensemble Electrochemistry to Nano‐Impact Electrochemistry: Altered Reaction Selectivity

et al. 2022

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Selective electrochemical production of valued chemicals is of significant importance but remains a great challenge in chemistry. Conventional approaches for enhancing reaction selectivity focus on the improvement of the catalysts themselves. In this work, we systematically studied the reaction kinetics and mass transport behavior of LaNiO3 nanocubes (LaNiO3 NCs) catalyzed hydrogen peroxide reduction reaction (HPRR) at ensemble and single nanoparticle levels using nano‐impact electrochemistry (NIE). We find that the selectivity of HPRR was altered at individual random‐walk nanoparticles as compared to their ensemble counterpart without changing the reaction kinetics, due to the significantly enhanced mass transport at single nanoparticles. This discovery offers the scope of new catalytic approaches for engineering electrochemical reactions in general.

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Theoretical Insight into the Reaction Mechanism of Ethanol Steam Reforming on Co(0001)

Cited by 26 publications

References 64 publications

Reaction Mechanism of Ethanol on Model Cobalt Catalysts: DFT Calculations

Reaction Mechanism of Ethanol on Model Cobalt Catalysts: DFT Calculations

Methanol dissociation and oxidation on single Fe atom supported on graphitic carbon nitride

From Ensemble Electrochemistry to Nano‐Impact Electrochemistry: Altered Reaction Selectivity

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