Role of the Zn atomic arrangements in enhancing the activity and stability of the kinked Cu(2 1 1) site in CH3OH production by CO2 hydrogenation and dissociation: First-principles microkinetic modeling study

Jo, Deok Yeon; Lee, Min Woo; Ham, Hyung Chul; Lee, Kwan‐Young

doi:10.1016/j.jcat.2019.04.009

Cited by 46 publications

(11 citation statements)

References 43 publications

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“…Therefore, a detailed investigation of the kinetics is necessary to understand the actual mechanism. Similar cases can also be found in other reaction systems involving CO 2 hydrogenation and its reverse reactions (carboxyl or formate dehydrogenation), such as CO 2 reduction to methanol, − forward/reverse water–gas shift, − etc. Due to the very small adsorption energy of CO 2 on many surfaces, both the E–R and L–H mechanisms lead to effectively the same energy profiles.…”

Section: Introductionsupporting

confidence: 65%

Involvement of the Unoccupied Site Changes the Kinetic Trend Significantly: A Case Study on Formic Acid Decomposition

et al. 2020

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A qualified heterogeneous catalyst for formic acid decomposition (FAD) should ensure a good H2 production activity and an extremely low CO selectivity. Previous theoretical study applied the well-established “Nørskov–Bligaard” method to screen catalysts for FAD, while some kinetic models for HCOO* and COOH* dehydrogenation involved no extra unoccupied site, which was necessary in some other kinetic models. In the present work, we use FAD as a case study to comprehensively investigate the effects of different kinetic models on the calculated maps for the predictions of the reaction activity and selectivity. The results show that trends of the predicted CO selectivity are significantly different over a series of transition-metal surfaces for two kinetic models, yielding different predictions for catalyst candidates of FAD. Our results call for a close attention to mechanism details in a theoretical catalyst design.

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Section: Introductionsupporting

confidence: 65%

Involvement of the Unoccupied Site Changes the Kinetic Trend Significantly: A Case Study on Formic Acid Decomposition

et al. 2020

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“…Because of the modification of the d -band center of Cu clusters by changing the size of clusters, the adsorption stabilities of reaction intermediates are tuned, giving rise to the observed size-dependent methanol synthesis activity. Moreover, the nature of defects in Cu-based catalysts is found to have a significant impact on methanol synthesis from CO 2 hydrogenation . On the Cu(211) step and kink surfaces, CO 2 hydrogenation barriers to HCOO* and COOH* intermediates are significantly reduced as compared to those obtained on the Cu(111) terrace surface.…”

Section: Mechanistic and Kinetic Studiesmentioning

confidence: 99%

Recent Advances in Carbon Dioxide Hydrogenation to Methanol via Heterogeneous Catalysis

et al. 2020

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The utilization of fossil fuels has enabled an unprecedented era of prosperity and advancement of well-being for human society. However, the associated increase in anthropogenic carbon dioxide (CO2) emissions can negatively affect global temperatures and ocean acidity. Moreover, fossil fuels are a limited resource and their depletion will ultimately force one to seek alternative carbon sources to maintain a sustainable economy. Converting CO2 into value-added chemicals and fuels, using renewable energy, is one of the promising approaches in this regard. Major advances in energy-efficient CO2 conversion can potentially alleviate CO2 emissions, reduce the dependence on nonrenewable resources, and minimize the environmental impacts from the portions of fossil fuels displaced. Methanol (CH3OH) is an important chemical feedstock and can be used as a fuel for internal combustion engines and fuel cells, as well as a platform molecule for the production of chemicals and fuels. As one of the promising approaches, thermocatalytic CO2 hydrogenation to CH3OH via heterogeneous catalysis has attracted great attention in the past decades. Major progress has been made in the development of various catalysts including metals, metal oxides, and intermetallic compounds. In addition, efforts are also put forth to define catalyst structures in nanoscale by taking advantage of nanostructured materials, which enables the tuning of the catalyst composition and modulation of surface structures and potentially endows more promising catalytic performance in comparison to the bulk materials prepared by traditional methods. Despite these achievements, significant challenges still exist in developing robust catalysts with good catalytic performance and long-term stability. In this review, we will provide a comprehensive overview of the recent advances in this area, especially focusing on structure–activity relationship, as well as the importance of combining catalytic measurements, in situ characterization, and theoretical studies in understanding reaction mechanisms and identifying key descriptors for designing improved catalysts.

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“…Apparently, for the most studied active phase, such as CuO–ZnO, the reduced Cu (as Cu + ), located at the interface of ZnO, is involved during the activated adsorption of CO 2 , while ZnO activates H 2 via Zn–OH entities . Such a conclusion was reached for both unsupported CuO–ZnO catalysts and the corresponding catalysts supported on oxidic supports.…”

Section: Nature Of Active Site and Mechanism Of Hyd Of Co2mentioning

confidence: 91%

“…This confirmed that the Cu + species was an important part of the active site, in agreement with the study by Li et al 136 An over-reduction may result in the formation of Cu 0 rather than Cu + . 137 Beneficial effects facilitated by ZnO on the activity and stability of Cu + were described by Jo et al 138 These effects can be fine-tuned by Zn and Cu precursors used for catalyst preparation. 139,140 Thus, among precursors such as Cunitrate, Cu-acetate, and Cu-amine complex, the catalyst prepared using Cu-acetate exhibited the highest activity and selectivity to methanol.…”

Section: Table 2 Effect Of Temperature (K) On the Free Energies (Kj/m...mentioning

confidence: 97%

CO₂ Hydrogenation to Methanol and Methane over Carbon-Supported Catalysts

Furimsky¹

2020

Ind. Eng. Chem. Res.

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Methanol and methane are among the important products obtained during the hydrogenation (HYD) of CO2. The distribution of products and their yields can be influenced by operating conditions. In this case, the type of catalyst has a dominant effect. Gradual transformation of CO2 involves several surface intermediates. Special geometry of active site is required for maximizing the yield of methanol and for minimizing the reaction run-away to methane. Such a state can be attained over catalysts that contain CuO-ZnO components. Catalysts containing other transition metals and noble metals are less suitable, while the same catalysts exhibit good performance during the HYD of CO2 to methane. In industrial applications, catalysts supported on oxidic supports, i.e., Al2O3, SiO2, TiO2, etc., have been used. During HYD of CO2, 1 and 2 mol of water are generated for every mole of methanol and methane, respectively. The stability of catalysts used for HYD of CO2 can be enhanced by replacing oxidic supports with carbon supports. Amorphous carbons, such as activated carbon, and carbon nanomaterials, such as carbon nanotubes, carbon nanofibers, and graphene-derived solids, have been tested both as catalysts and supports. For methanol synthesis, CuO-ZnO catalysts supported on these carbons have been evaluated. Similar carbon supports have been used for the preparation and testing of methanation catalysts consisting of a wide range of transition and noble metals as active metals. Both monometallic and bimetallic catalysts were evaluated.

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Role of the Zn atomic arrangements in enhancing the activity and stability of the kinked Cu(2 1 1) site in CH3OH production by CO2 hydrogenation and dissociation: First-principles microkinetic modeling study

Cited by 46 publications

References 43 publications

Involvement of the Unoccupied Site Changes the Kinetic Trend Significantly: A Case Study on Formic Acid Decomposition

Involvement of the Unoccupied Site Changes the Kinetic Trend Significantly: A Case Study on Formic Acid Decomposition

Recent Advances in Carbon Dioxide Hydrogenation to Methanol via Heterogeneous Catalysis

CO₂ Hydrogenation to Methanol and Methane over Carbon-Supported Catalysts

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Role of the Zn atomic arrangements in enhancing the activity and stability of the kinked Cu(2 1 1) site in CH3OH production by CO2 hydrogenation and dissociation: First-principles microkinetic modeling study

Cited by 46 publications

References 43 publications

Involvement of the Unoccupied Site Changes the Kinetic Trend Significantly: A Case Study on Formic Acid Decomposition

Involvement of the Unoccupied Site Changes the Kinetic Trend Significantly: A Case Study on Formic Acid Decomposition

Recent Advances in Carbon Dioxide Hydrogenation to Methanol via Heterogeneous Catalysis

CO2 Hydrogenation to Methanol and Methane over Carbon-Supported Catalysts

Contact Info

Product

Resources

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Role of the Zn atomic arrangements in enhancing the activity and stability of the kinked Cu(2 1 1) site in CH3OH production by CO2 hydrogenation and dissociation: First-principles microkinetic modeling study

CO₂ Hydrogenation to Methanol and Methane over Carbon-Supported Catalysts