A quasi-stable molybdenum sub-oxide with abundant oxygen vacancies that promotes CO<sub>2</sub> hydrogenation to methanol

Kuwahara, Yasutaka; Mihogi, Takashi; Hamahara, Koji; Kusu, Kazuki; Kobayashi, Hisayoshi; Yamashita, Hiromi

doi:10.1039/d1sc02550c

Cited by 50 publications

(49 citation statements)

References 78 publications

(124 reference statements)

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“…The 1.8 wt % Ru/TiO 2 and 1.8 wt % Ru/CeO 2 catalysts all present dominant methanation activity below 500 °C, which are different from those observed in the 1.9 wt % Ru–Mo–O x catalyst (Figure a). These suggest that MoO 3 is easier to be reduced and form the SMSI structure than TiO 2 and CeO 2 , which are generally thermal-induced above 500 °C. ,, Thus, the MoO 3 support is unique for the formation of the SMSI state under the relatively mild conditions.…”

Section: Resultssupporting

confidence: 76%

Overturning CO₂ Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

et al. 2022

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Encapsulation of metal nanoparticles by support-derived materials known as the classical strong metal–support interaction (SMSI) often happens upon thermal treatment of supported metal catalysts at high temperatures (≥500 °C) and consequently lowers the catalytic performance due to blockage of metal active sites. Here, we show that this SMSI state can be constructed in a Ru–MoO3 catalyst using CO2 hydrogenation reaction gas and at a low temperature of 250 °C, which favors the selective CO2 hydrogenation to CO. During the reaction, Ru nanoparticles facilitate reduction of MoO3 to generate active MoO3–x overlayers with oxygen vacancies, which migrate onto Ru nanoparticles’ surface and form the encapsulated structure, that is, Ru@MoO3–x . The formed SMSI state changes 100% CH4 selectivity on fresh Ru particle surfaces to above 99.0% CO selectivity with excellent activity and long-term catalytic stability. The encapsulating oxide layers can be removed via O2 treatment, switching back completely to the methanation. This work suggests that the encapsulation of metal nanocatalysts can be dynamically generated in real reactions, which helps to gain the target products with high activity.

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Section: Resultssupporting

confidence: 76%

Overturning CO₂ Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

et al. 2022

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“…). − Besides, molybdenum-based catalysts are also commonly used in the catalytic conversion of synthesis gas with favorable selectivity toward oxygenate products (i.e., H 2 + CO → alcohols) . In recent years, Mo-containing solids (e.g., MoP, , β-Mo 2 C, MoS 2 , − MoO x , − molybdate, etc.) have garnered significant research attention in the field of catalytic CO 2 utilization, including the hydrogenation of CO 2 to methanol.…”

Section: Introductionmentioning

confidence: 99%

Boxlike Assemblages of Few-Layer MoS₂ Nanosheets with Edge Blockage for High-Efficiency Hydrogenation of CO₂ to Methanol

Zhou

Zeng

2022

ACS Catal.

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Direct hydrogenation of CO2 into methanol is a promising strategy for reducing excessive dependence on fossil fuels and alleviating environmental concerns. Recently, in-plane sulfur vacancies in two-dimensional MoS2 nanosheets were unveiled as efficient catalytic active sites for methanol synthesis from CO2, whereas edge vacancies facilitated hydrogenation of CO2 to methane. Herein, we developed boxlike assemblages of quasi-single-layer MoS2 nanosheets, which were edge-blocked by ZnS crystallites (denoted as h-MoS2/ZnS) via a metal–organic framework (MOF)-engaged solvothermal route and subsequent heat treatments. The spatial confinement of the ZnS can restrain the growth and aggregation of MoS2 and ensure the stability of few-layer or even single-layer MoS2 in the assemblages. More importantly, the presence of ZnS can prevent reactants from approaching the edge sulfur vacancies of MoS2. With more exposed in-plane sulfur vacancies and less edge sulfur vacancies, the h-MoS2/ZnS exhibits 67.3% methanol selectively, 9.0% CO2 conversion, and a high methanol space-time yield of up to 0.93 gMeOH·gMoS2 –1·h–1 at 260 °C, 5 MPa, and 15 000 mL·gcat. –1·h–1. The catalytic activity was stable for at least 120 h. By removing the ZnS phase from h-MoS2/ZnS and thus deliberately creating more edge sulfur vacancies, it was further confirmed that edge sulfur vacancies are active catalytic sites for excessive hydrogenation of CO2 to methane. Furthermore, the reaction mechanism of our catalyst was also investigated by a high-pressure in situ DRIFTS study. Thus, this MOF-templated strategy for assembling and confining quasi-single-layer MoS2 provides insights into the development of highly efficient transition-metal dichalcogenide catalysts for CO2 hydrogenation with excellent stability.

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“…As the H 2 reduction process continues, the lattice oxygen atoms around Mo are thermally expelled at around 200 °C (2H + + 2e − + O lattice → V O + H 2 O), thereby driving the generation of a large number of oxygen vacancies. According to previous studies, 34,38,43 the intercalation of H atoms and the introduction of oxygen vacancies into MoWO y increase the free electron concentration, consequently causing the emergence of SPR.…”

Section: Resultsmentioning

confidence: 85%

“…[34][35][36][37] In addition, the oxygen vacancies (V O ) in Pt/H x MoO 3Ày provide effective sites for activating molecular CO 2 and weakening the C]O bonds, facilitating the generation of CO in the photothermal catalytic CO 2 reaction, while Pt nanoparticles (NPs) act as H 2 dissociation sites, continuously supplying active H atoms to increase the concentration of free electrons in MoO 3 and regenerating the oxygen vacancies. 38,39 Given the foregoing background information, Mo-doped Pt/WO y can be expected to enhance the number of defects (oxygen vacancies) and the free electron (H + ) concentration via H 2 reduction to facilitate CO 2 activation and solar energy utilization, realizing highly efficient photothermal catalytic CO 2 reduction.…”

Section: Introductionmentioning

confidence: 99%

Enhanced visible-NIR absorption and oxygen vacancy generation of Pt/H_xMoWO_y by H-spillover to facilitate photothermal catalytic CO₂ hydrogenation

Kuwahara

Kusu

et al. 2022

J. Mater. Chem. A

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A quasi-stable molybdenum sub-oxide with abundant oxygen vacancies that promotes CO₂ hydrogenation to methanol

Abstract: Production of methanol from anthropogenic carbon dioxide (CO2) is a promising chemical process that can alleviate both the environmental burden and the dependence on fossil fuels. In catalytic CO2 hydrogenation...

Cited by 50 publications

References 78 publications

Overturning CO₂ Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

Overturning CO₂ Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

Boxlike Assemblages of Few-Layer MoS₂ Nanosheets with Edge Blockage for High-Efficiency Hydrogenation of CO₂ to Methanol

Enhanced visible-NIR absorption and oxygen vacancy generation of Pt/H_xMoWO_y by H-spillover to facilitate photothermal catalytic CO₂ hydrogenation

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A quasi-stable molybdenum sub-oxide with abundant oxygen vacancies that promotes CO2 hydrogenation to methanol

Abstract: Production of methanol from anthropogenic carbon dioxide (CO2) is a promising chemical process that can alleviate both the environmental burden and the dependence on fossil fuels. In catalytic CO2 hydrogenation...

Cited by 50 publications

References 78 publications

Overturning CO2 Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

Overturning CO2 Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

Boxlike Assemblages of Few-Layer MoS2 Nanosheets with Edge Blockage for High-Efficiency Hydrogenation of CO2 to Methanol

Enhanced visible-NIR absorption and oxygen vacancy generation of Pt/HxMoWOy by H-spillover to facilitate photothermal catalytic CO2 hydrogenation

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A quasi-stable molybdenum sub-oxide with abundant oxygen vacancies that promotes CO₂ hydrogenation to methanol

Overturning CO₂ Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

Overturning CO₂ Hydrogenation Selectivity with High Activity via Reaction-Induced Strong Metal–Support Interactions

Boxlike Assemblages of Few-Layer MoS₂ Nanosheets with Edge Blockage for High-Efficiency Hydrogenation of CO₂ to Methanol

Enhanced visible-NIR absorption and oxygen vacancy generation of Pt/H_xMoWO_y by H-spillover to facilitate photothermal catalytic CO₂ hydrogenation