A density functional theory study of CO2 hydrogenation to methanol over Pd/TiO2 catalyst: The role of interfacial site

Ou, Zhiliang; Ran, Jingyu; Niu, Juntian; Qin, Changlei; He, Wei; Yang, Lin

doi:10.1016/j.ijhydene.2019.12.099

Cited by 41 publications

(23 citation statements)

References 48 publications

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“…The H 2 O* will be desorbed from the catalyst surface with an energy cost of 0.68 eV. The mild H 2 O formation and easy desorption presentations demonstrate that the OH and H 2 O poisons will be avoided over the Pt 8 /In 2 O 3 catalyst . The remaining CO* will react with H adatoms to create the HCO* radical by climbing TS9.…”

Section: Resultssupporting

confidence: 77%

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Mechanism of Methanol Synthesis from CO₂ Hydrogenation over Pt₈/In₂O₃ Catalysts: A Combined Study on Density Functional Theory and Microkinetic Modeling

Wang

Wei

et al. 2022

J. Phys. Chem. C

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In 2 O 3 -based catalysts have attracted considerable attention in CO 2 hydrogenation to methanol reactions, thanks to their excellent CO 2 conversion rate and methanol selectivity. In this work, density functional theory combined with microkinetic modeling is employed to investigate the methanol synthesis mechanism over a Pt 8 /In 2 O 3 catalyst. First, a stable Pt 8 /In 2 O 3 (110) catalyst is modeled, where the Pt 8 cluster is positively charged. Second, the adsorption properties of the reaction species are optimized. It shows that H 2 is dissociated spontaneously to two H* adatoms on the Pt 8 cluster and the CO 2 * is adsorbed at the interface of Pt 8 /In 2 O 3 . Then three methanol synthesis channels are tested, that is, formate (HCOO), carboxyl (COOH), and RWGS + CO-Hydro routes. The calculations indicate that methanol is produced along with the order of CO 2 * → COOH* → CO* + OH* → HCO* → H 2 CO* → H 2 COH* → H 3 COH*. Finally, the channel is subjected to the microkinetic calculation at a pressure of 5 MPa and in a temperature range of 423 to 873 K. The degree of rate control analysis shows that H* adatom and COOH* dissociation TS7 are the rate-controlling adsorption and transition states, respectively. With the elevation of temperature, the turnover frequencies of CO and CH 3 OH increase, and the CH 3 OH selectivity decreases. They are related to the coverage of H* and COOH*.

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Section: Resultssupporting

confidence: 77%

“…Thus, the follow-up reaction steps of H 2 COO* will not be considered anymore. The rough step is also prohibited over the Pt 46 and Pd 3 /TiO 2 catalysts . On the other hand, HCOOH* is generated when the H* approaches the O b atom of HCOO*.…”

Section: Resultsmentioning

confidence: 99%

Mechanism of Methanol Synthesis from CO₂ Hydrogenation over Pt₈/In₂O₃ Catalysts: A Combined Study on Density Functional Theory and Microkinetic Modeling

Wang

Wei

et al. 2022

J. Phys. Chem. C

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“…The minimum energy path of RWGS pathway from CO 2 to CH 3 OH on FMPA/Mo-MgH 2 (001) surface was shown in Figure 5. The rate-determining step was the HCO * formation, which is consistent with the calculation result in reference [30], whereas the energy barrier was much lower, 1.22 eV here versus 1.50 eV on Pd/TiO 2 . The adsorption energies, rate-determining steps, energy barriers, and reaction energies of C 1 products from CO 2 hydrogenation on FMPA/Mo-MgH 2 (001) surface were summarized in Table 3.…”

Section: Rwgs Pathway On Fmpa/mo-mgh 2 (001) Surfacesupporting

confidence: 90%

Phosphonic Acid Modification to Molybdenum Atom Catalyst for Co2 Hydrogenation on Magnesium Hydride Surface

Manggada,

Zhou

2023

Distilat: J. Tekn. Sep

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Catalytic hydrogenation is one of the most effective ways to convert CO 2 to high value-added chemicals, and it is challenging to improve the catalytic activity and product selectivity based on the understanding of catalysis mechanism of the process. In this work, organic phosphonic acid was innovatively employed to tune single atom catalyst for CO 2 hydrogenation to methanol, and the effect of fluoromethylphosphonic acid (FMPA) on the electronic structure of molybdenum and the reaction energy barriers of CO 2 hydrogenation on MgH 2 surface were investigated by density functional theory (DFT) calculations. The results showed that the reaction energy barriers at the key steps were significantly decreased by the introduction of FMPA, which stabilized the reaction intermediates from CO 2 hydrogenation by reducing the electron density of molybdenum adsorption site with its oxygen atoms. The reverse water gas shift (RWGS) pathway was superior to formate pathway for CO 2 hydrogenation on FMPA/Mo-MgH 2 (001) surface with energy barrier only 1.22 eV at the rate-determining step, and CH 3 OH was the overwhelming product rather than HCOOH, H 2 CO, CO or CH 4 considering the reaction barriers and adsorption energies. The combination of organic phosphonic acid with single atom catalyst can generate the rational design of new catalytic system, which is helpful to control the reaction pathway and product selectivity.

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“…In addition, DFT calculations over Pd/TiO 2 catalyst also demonstrated that the CAMERE pathway is the primary route for MeOH production, and CO*‐to‐HCO* conversion is the rate‐determining step. [ 25 ] The other pathway proposes that the first step of MeOH synthesis is the direct CO 2 hydrogenation through formate (HCOO*) or carboxylate (COOH*) intermediate, and the subsequent formate/carboxylate hydrogenation is regarded as the rate‐determining step (formate pathway). [ 26 ] In situ DRIFT measurement confirmed that CO 2 was first activated and converted into HCOO* intermediate at a relatively low temperature in the presence of Co 4 N nanosheets and then generated CH 2 O* species with a further increase of reaction temperature.…”

Section: Thermocatalysismentioning

confidence: 99%

Recent Progress in Materials Exploration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO₂‐to‐Fuel Conversion

Zhang

Pérez‐Ramírez

et al. 2021

Adv Energy and Sustain Res

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The excess depletion of carbon‐rich fossil fuels and agroforest biomass resources has aggravated the energy crisis and environmental pollution, causing increased CO2 emissions. Accordingly, the goal of “peak CO2 emissions and carbon neutrality” is proposed to alleviate global warming. CO2‐to‐fuel conversion is considered as a preferable move for reducing the atmospheric CO2 concentration and further upgrading to chemical feedstocks. However, the highly efficient CO2 conversion remains challenging due to the thermodynamic limits and kinetic barriers, which require high energy input through conventional thermocatalysis. Inspired by “artificial photosynthesis,” photocatalytic CO2 transformation has received tremendous attention and makes remarkable progress over the past decades, although it is still far from practical application. Recently, the integrated photothermocatalysis has emerged as an intelligent strategy to utilize solar energy to induce local heating and energetic hot carriers, which synergistically promote CO2‐to‐fuel conversion. The key to the success of CO2 upgradation is catalysts’ development with improved activity, selectivity, and stability. This review highlights the recent advancements in materials designing for practical CO2 conversion through thermocatalysis, photocatalysis, and photothermocatalysis during the past five years, emphasizing the reaction pathways and mechanism on the CO bond activation and intermediates formation. Finally, the current challenges and future opportunities are described.

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A density functional theory study of CO2 hydrogenation to methanol over Pd/TiO2 catalyst: The role of interfacial site

Cited by 41 publications

References 48 publications

Mechanism of Methanol Synthesis from CO₂ Hydrogenation over Pt₈/In₂O₃ Catalysts: A Combined Study on Density Functional Theory and Microkinetic Modeling

Mechanism of Methanol Synthesis from CO₂ Hydrogenation over Pt₈/In₂O₃ Catalysts: A Combined Study on Density Functional Theory and Microkinetic Modeling

Phosphonic Acid Modification to Molybdenum Atom Catalyst for Co2 Hydrogenation on Magnesium Hydride Surface

Recent Progress in Materials Exploration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO₂‐to‐Fuel Conversion

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A density functional theory study of CO2 hydrogenation to methanol over Pd/TiO2 catalyst: The role of interfacial site

Cited by 41 publications

References 48 publications

Mechanism of Methanol Synthesis from CO2 Hydrogenation over Pt8/In2O3 Catalysts: A Combined Study on Density Functional Theory and Microkinetic Modeling

Mechanism of Methanol Synthesis from CO2 Hydrogenation over Pt8/In2O3 Catalysts: A Combined Study on Density Functional Theory and Microkinetic Modeling

Phosphonic Acid Modification to Molybdenum Atom Catalyst for Co2 Hydrogenation on Magnesium Hydride Surface

Recent Progress in Materials Exploration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO2‐to‐Fuel Conversion

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Mechanism of Methanol Synthesis from CO₂ Hydrogenation over Pt₈/In₂O₃ Catalysts: A Combined Study on Density Functional Theory and Microkinetic Modeling

Mechanism of Methanol Synthesis from CO₂ Hydrogenation over Pt₈/In₂O₃ Catalysts: A Combined Study on Density Functional Theory and Microkinetic Modeling

Recent Progress in Materials Exploration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO₂‐to‐Fuel Conversion