DFT and microkinetic investigation of methanol synthesis via CO2 hydrogenation on Ni(111)-based surfaces

Maulana, Arifin Luthfi; Putra, Refaldi Intri Dwi; Saputro, Adhitya Gandaryus; Agusta, Mohammad Kemal; Nugraha, Nugraha; Dipojono, Hermawan Kresno

doi:10.1039/c9cp02970b

Cited by 32 publications

(30 citation statements)

References 42 publications

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“…In methanol synthesis : Maulana et al . recently investigated the CO 2 hydrogenation to methanol on clean Ni(111) and Ni(111)−M (M=Cu, Pd, Pt, Rh) surfaces using DFT and microkinetics.…”

Section: Modelling Catalyst Surfacesmentioning

confidence: 99%

“…They gave insight into the CO 2 /Ni(110)!CO/Ni(110) + O/Ni(110) reaction mechanism and distinguished two decomposition steps: 1) surface diffusion of CO 2 to the H-2 conformation with (depending on the starting geometry) 1-2 transition states; and 2) breaking of the coordinated CÀ O bond with total reaction barrier of 0.44 eV. In methanol synthesis: Maulana et al [202] recently investigated the CO 2 hydrogenation to methanol on clean Ni (111) and Ni(111)À M (M = Cu, Pd, Pt, Rh) surfaces using DFT and microkinetics. The DFT calculations with PBE functional showed that formate-mediated and carboxyl-mediated pathways depicted in Figure 10 seem to be the main routes for production of methanol.…”

Section: Ni Catalytic Surfacesmentioning

confidence: 99%

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Recent Developments in the Modelling of Heterogeneous Catalysts for CO₂ Conversion to Chemicals

et al. 2020

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Density functional theory (DFT) of the CO2 behavior on the catalyst surface provides valuable insights about the C=O bond activation, information about adsorption and dissociation of CO2, understanding the elementary steps involved in the mechanism of the CO2 hydrogenation reaction. Nowadays, DFT computational studies for the catalytic hydrogenation of CO2 are becoming very popular. Therefore, this article is focused on a comprehensive review of the DFT studies in thermocatalytic hydrogenation of CO2 at the gas‐surface interface and discusses three aspects: 1) processes taking place on the surfaces and facets of transition metal heterogeneous catalysts, 2) adsorption of CO2 on surfaces of different transition metals; 3) current understanding of reaction mechanisms taking place on the catalytic surface for the production of different compounds. A detailed schematic overview of the possible CO2 hydrogenation mechanisms and DFT simulations presented here will enhance the current understanding of the CO2 catalytic hydrogenation.

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“…In methanol synthesis : Maulana et al . recently investigated the CO 2 hydrogenation to methanol on clean Ni(111) and Ni(111)−M (M=Cu, Pd, Pt, Rh) surfaces using DFT and microkinetics.…”

Section: Modelling Catalyst Surfacesmentioning

confidence: 99%

Section: Ni Catalytic Surfacesmentioning

confidence: 99%

Recent Developments in the Modelling of Heterogeneous Catalysts for CO₂ Conversion to Chemicals

et al. 2020

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“…Details of the microkinetic model derivation for typical hydrogenation reaction can be found in our recent works [13,[16][17][18].…”

Section: Dft Calculations and Microkinetic Modelingmentioning

confidence: 99%

“…The formation of formate requires two steps: (1) the bending of the linear O-C-O configuration, and (2) the desorption of an adsorbed H from the catalyst to the adsorbed CO2 molecule [13,18,21]. The first condition is already fulfilled on Pd7 and Pd6M clusters due to the formation of CO2 bidentate configuration.…”

Section: Hcooh Vs Co Formationsmentioning

confidence: 99%

Theoretical Study of Direct Carbon Dioxide Conversion to Formic Acid on Transition Metal-doped Subnanometer Palladium Clusters

Saputro

Maulana

Aprilyanti

et al. 2021

J. Eng. Technol. Sci.

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We studied the direct conversion of CO2 to HCOOH through hydrogenation reaction without the presence of base additives on the transition metal-doped subnanometer palladium (Pd7) cluster (PdxM: M = Cu, Ni, Rh) by using a combination of density functional theory and microkinetic calculations. It was shown that the CO2 hydrogenation on Pd7 and Pd6M clusters are more selective towards the formate pathway to produce HCOOH than the reverse water gas shift pathway to produce CO. Inclusion of Ni and Rh doping in the subnanometer Pd7 cluster could successfully enhance the turnover frequency (TOF) for CO2 hydrogenation to formic acid at low temperature. The order of TOF for formic acid formation is as follows: Pd6Ni > Pd6Rh > Pd7 > Pd6Cu. This order can be explained by the trend of the activation energy of CO2 hydrogenation to formate (HCOO*). The Pd6Ni cluster has the highest TOF value because it has the lowest activation energy for the formate formation reaction. The Pd6Ni system also has a superior TOF profile for HCOOH formation compared to several metal surfaces in low and high-temperature regions. This finding suggests that the subnanometer PdxNi cluster is a promising catalyst candidate for direct CO2 hydrogenation to formic acid.

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“…These authors identified the dissociation of HCO * as the RDS, which is supported by Zhou et al 15 from DFT calculations with the same functional. In addition to these models of CO 2 hydrogenation on Ni(111), other studies focused on the (reverse) water-gas shift reaction, [19][20][21] methanol synthesis, 22 and formic acid formation. 23 Apart from the general role/activity of the Ni(111) facet, the dominant reaction network for CO 2 hydrogenation has not been conclusively determined; the aforementioned computational studies disagree about important intermediates, pathways, and the RDS.…”

mentioning

confidence: 99%

Quantifying the Impact of Parametric Uncertainty on Automatic Mechanism Generation for CO2 Hydrogenation on Ni(111)

Kreitz¹,

Goldsmith²,

West³

et al. 2021

Preprint

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Automatic mechanism generation is used to determine mechanisms for the CO2 hydrogenation on Ni(111) in a two-stage process, while considering the uncertainty in energetic parameters systematically. In a coarse stage, all the possible chemistry is explored with gas-phase products down to the ppb level, while a refined stage discovers the core methanation submechanism. 5,000 unique mechanisms were generated, which contain minor perturbations in all parameters. Global uncertainty assessment, global sensitivity analysis, and degree of rate control analysis are performed to study the effect 1 of this parametric uncertainty on the microkinetic model predictions. Comparison of the model predictions with experimental data on a Ni/SiO2 catalyst find a feasible set of microkinetic mechanisms that are in quantitative agreement with the measured data, without relying on explicit parameter optimization. Global uncertainty and sensitivity analyses provide tools to determine the pathways and key factors that control the methanation activity within the parameter space. Together, these methods reveal that the degree of rate control approach can be misleading if parametric uncertainty is not considered. The procedure of considering uncertainties in the automated mechanism generation is not unique to CO2 methanation and can be easily extended to other challenging heterogeneously catalyzed reactions

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DFT and microkinetic investigation of methanol synthesis via CO₂ hydrogenation on Ni(111)-based surfaces

Abstract: The kinetic performance of methanol synthesis on a clean Ni(111) surface can be improved by doping the surface with a transition metal atom.

Cited by 32 publications

References 42 publications

Recent Developments in the Modelling of Heterogeneous Catalysts for CO₂ Conversion to Chemicals

Recent Developments in the Modelling of Heterogeneous Catalysts for CO₂ Conversion to Chemicals

Theoretical Study of Direct Carbon Dioxide Conversion to Formic Acid on Transition Metal-doped Subnanometer Palladium Clusters

Quantifying the Impact of Parametric Uncertainty on Automatic Mechanism Generation for CO2 Hydrogenation on Ni(111)

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DFT and microkinetic investigation of methanol synthesis via CO2 hydrogenation on Ni(111)-based surfaces

Abstract: The kinetic performance of methanol synthesis on a clean Ni(111) surface can be improved by doping the surface with a transition metal atom.

Cited by 32 publications

References 42 publications

Recent Developments in the Modelling of Heterogeneous Catalysts for CO2 Conversion to Chemicals

Recent Developments in the Modelling of Heterogeneous Catalysts for CO2 Conversion to Chemicals

Theoretical Study of Direct Carbon Dioxide Conversion to Formic Acid on Transition Metal-doped Subnanometer Palladium Clusters

Quantifying the Impact of Parametric Uncertainty on Automatic Mechanism Generation for CO2 Hydrogenation on Ni(111)

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Product

Resources

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DFT and microkinetic investigation of methanol synthesis via CO₂ hydrogenation on Ni(111)-based surfaces

Recent Developments in the Modelling of Heterogeneous Catalysts for CO₂ Conversion to Chemicals

Recent Developments in the Modelling of Heterogeneous Catalysts for CO₂ Conversion to Chemicals