Experimental and theoretical insights into an enhanced CO2 methanation mechanism over a Ru-based catalyst

Li, Yangyang; Liu, Zhisong; Rao, Zhiqiang; Yu, Feng; Bao, Wentao; Tang, Ying; Zhao, Huanhuan; Zhang, Jie; Wang, Zijun; Li, Jiangbing; Huang, Zeai; Zhou, Ying; Li, Yongsheng; Dai, Bin

doi:10.1016/j.apcatb.2022.121903

Cited by 27 publications

(8 citation statements)

References 54 publications

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“…Nevertheless, the charge transfer from TiO 2 to Ru contributes to the high electron density in the Ru surface, which is not conducive to the activation of CH 4 reactant and desorption of CO product, whereas electrophilic CO 2 molecules can be adsorbed and activated by Ru atoms due to the accumulated electrons. [22] Therefore, we speculate that CH 4 tends to react with generated holes in the VB band of TiO 2 for the Ru/TiO 2 catalyst, while CO 2 more likely reacts with the photo-generated electrons on Ru NPs, consistent with the reported reaction model. [23] As for Ru/ TiO 2 À H 2 , due to the weakened SMSI effect, excited electrons in the CB of TiO 2 À H 2 and hot electrons with high energies from Ru NPs can be trapped by abundant OVs on the surface of TiO 2 À H 2 .…”

Section: Methodssupporting

confidence: 85%

Suppressive Strong Metal‐Support Interactions on Ruthenium/TiO₂ Promote Light‐Driven Photothermal CO₂ Reduction with Methane

Wang

Zhang

et al. 2023

Angew Chem Int Ed

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Strong metal‐support interactions (SMSI) have gained great attention in the heterogeneous catalysis field, but its negative role in regulating light‐induced electron transfer is rarely explored. Herein, we describe how SMSI significantly restrains the activity of Ru/TiO2 in light‐driven CO2 reduction by CH4 due to the photo‐induced transfer of electrons from TiO2 to Ru. In contrast, on suppression of SMSI Ru/TiO2−H2 achieves a 46‐fold CO2 conversion rate compared to Ru/TiO2. For Ru/TiO2−H2, a considerable number of photo‐excited hot electrons from Ru nanoparticles (NPs) migrate to oxygen vacancies (OVs) and facilitate CO2 activation under illumination, simultaneously rendering Ruδ+ electron deficient and better able to accelerate CH4 decomposition. Consequently, photothermal catalysis over Ru/TiO2−H2 lowers the activation energy and overcomes the limitations of a purely thermal system. This work offers a novel strategy for designing efficient photothermal catalysts by regulating two‐phase interactions.

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Section: Methodssupporting

confidence: 85%

Suppressive Strong Metal‐Support Interactions on Ruthenium/TiO₂ Promote Light‐Driven Photothermal CO₂ Reduction with Methane

Wang

Zhang

et al. 2023

Angew Chem Int Ed

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“…Moreover, as shown in Supplementary Fig. 35 , compared with Ru/Mn 3 O 4−x (321) slabs that simulated dark state, the conduction band that simulated the light state moved to the low energy region, indicating that the involved photons were conducive to electron transfer, which is favorable to CO 2 hydrogenation toward CH 4 47 – 49 . Together with the FT-IR spectroscopic characterization above, it was rationalized that the synergy between photon energy and thermal energy favored the formation of COOH*, thus exerting a positive impact on the CO 2 methanation over Ru/MnO x , which is generated by the partial reduction of Mn 3 O 4 by Ru-mediated H-spillover effect in CO 2 hydrogenation 50 .…”

Section: Resultsmentioning

confidence: 93%

Photo-thermal coupling to enhance CO2 hydrogenation toward CH4 over Ru/MnO/Mn3O4

Zhai,

Xia,

Zhou

et al. 2024

Nat Commun

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Upcycling of CO2 into fuels by virtually unlimited solar energy provides an ultimate solution for addressing the substantial challenges of energy crisis and climate change. In this work, we report an efficient nanostructured Ru/MnOx catalyst composed of well-defined Ru/MnO/Mn3O4 for photo-thermal catalytic CO2 hydrogenation to CH4, which is the result of a combination of external heating and irradiation. Remarkably, under relatively mild conditions of 200 °C, a considerable CH4 production rate of 166.7 mmol g−1 h−1 was achieved with a superior selectivity of 99.5% at CO2 conversion of 66.8%. The correlative spectroscopic and theoretical investigations suggest that the yield of CH4 is enhanced by coordinating photon energy with thermal energy to reduce the activation energy of reaction and promote formation of key intermediate COOH* species over the catalyst. This work opens up a new strategy for CO2 hydrogenation toward CH4.

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“…[11,12] For instance, chain growth and termination steps suffice to describe the spectrum based on similarity of the steps irrespective of the specific hydrocarbon chain length. [12] Third, Ru/TiO2 is reported to exhibit light-induced effects with emphasis on apparent activity, [5,6,8,13,14,15] while it provides high intrinsic activity in CO2 hydrogenation even at low temperatures. [16,17] The exothermicity of CO2 hydrogenation potentially interferes with light-induced effects and thus requires a sound strategy for disentangling the different effects.…”

Section: Resultsmentioning

confidence: 99%

Photoassisted amplification of chain-growth in CO2 hydrogenation: Switching selectivities of heterogeneously catalyzed reactions with light

Becker,

Ziegenbalg,

Güttel

2024

Preprint

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Selective carbon-carbon bond formation is a major challenge for chemical transformations to meet the global sustainability targets, which requires game-changing concepts instead of further improvement of conventional catalyst materials. In this work, a new paradigm to tune the selectivity of thermal catalytic systems is presented by using light as an external trigger to switch the selectivity from pure reduction to carbon-carbon bond formation. In a ruthenium-catalyzed CO2 hydrogenation reaction, chain-growth is initiated through irradiation with light, eventually leading to the formation of higher hydrocarbons instead of solely methane. Photoassisted reaction control was differentiated from photokinetic and photothermal effects by sophisticated thermal imaging and kinetic modelling. A light-induced change of the sorption properties of the solid catalyst surface was identified as reason for the changes in selectivity. The results render the exploitation of photoassisted effects as highly potent general strategy for comprehensive reaction control of reactions catalyzed by solids.

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Experimental and theoretical insights into an enhanced CO2 methanation mechanism over a Ru-based catalyst

Cited by 27 publications

References 54 publications

Suppressive Strong Metal‐Support Interactions on Ruthenium/TiO₂ Promote Light‐Driven Photothermal CO₂ Reduction with Methane

Suppressive Strong Metal‐Support Interactions on Ruthenium/TiO₂ Promote Light‐Driven Photothermal CO₂ Reduction with Methane

Photo-thermal coupling to enhance CO2 hydrogenation toward CH4 over Ru/MnO/Mn3O4

Photoassisted amplification of chain-growth in CO2 hydrogenation: Switching selectivities of heterogeneously catalyzed reactions with light

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Experimental and theoretical insights into an enhanced CO2 methanation mechanism over a Ru-based catalyst

Cited by 27 publications

References 54 publications

Suppressive Strong Metal‐Support Interactions on Ruthenium/TiO2 Promote Light‐Driven Photothermal CO2 Reduction with Methane

Suppressive Strong Metal‐Support Interactions on Ruthenium/TiO2 Promote Light‐Driven Photothermal CO2 Reduction with Methane

Photo-thermal coupling to enhance CO2 hydrogenation toward CH4 over Ru/MnO/Mn3O4

Photoassisted amplification of chain-growth in CO2 hydrogenation: Switching selectivities of heterogeneously catalyzed reactions with light

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Suppressive Strong Metal‐Support Interactions on Ruthenium/TiO₂ Promote Light‐Driven Photothermal CO₂ Reduction with Methane

Suppressive Strong Metal‐Support Interactions on Ruthenium/TiO₂ Promote Light‐Driven Photothermal CO₂ Reduction with Methane