ZSM-5-confined Cr<sub>1</sub>–O<sub>4</sub> active sites boost methane direct oxidation to C1 oxygenates under mild conditions

Zeng, Mengyu; Cheng, Lu; Gu, Qingqing; Yu, Baiyang; Yang, Bing; Xu, Jiuyang; Zhang, Ying; Pan, Chengsi; Lou, Yang; Cao, Xiaoming; Zhu, Yongfa

doi:10.1039/d2ey00080f

Cited by 17 publications

(5 citation statements)

References 37 publications

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“…[2] Achieving partial CH 4 oxidation reaction can offer dual advantages in both mitigating global warming and producing value-added chemicals, [3,4] while this process often DOI: 10.1002/adfm.202314118 necessitates the use of strong oxidants such as hydrogen peroxide (H 2 O 2 ). [5,6] Most of the commercial methods for large-scale methane conversion involve indirect processes via the production of synthesis gas (H 2 and CO), such as steam reforming, dry reforming, partial oxidation, and autothermal reforming. [7] Among them, the dry reforming of methane (DRM) uses CO 2 as a weak oxidant to react with CH 4 .…”

Section: Introductionmentioning

confidence: 99%

Photocatalytic Coupling of CH₄ and CO₂ to Ethanol on Asymmetric Ce−O−Zn Sites

Hao,

Chen,

Peng

et al. 2023

Adv Funct Materials

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Partial oxidation of methane (CH4) to value‐added products is significantly challenging due to the highly inert chemical property of CH4 at ambient conditions and easy over‐oxidation into carbon dioxide (CO2) or carbon monoxide (CO) at elevated temperatures and pressures. Targeting this challenge, the efficient photocatalytic coupling of CO2 and CH4 into ethanol is demonstrated, using a cerium (Ce)‐doped zinc oxide (ZnO) photocatalyst with abundant Ce─O─Zn units. Under light illumination, CO2 is adsorbed on the Ce atoms and photo‐reduced to CO, and CH4 is captured by the Zn atoms and photo‐oxidized to hydroperoxymethane (CH3OOH). The close proximity of Ce and Zn atoms on the Ce─O─Zn units allowed to further efficiently couple the as‐formed CO and CH3OOH into ethanol. Without additional Oxygen (O2) oxidant or sacrificial regent, the ethanol production rate reached 580 µmol g−1 h−1, substantially exceeding previously reports on photocatalytic CH4 oxidation. This work features to convert two greenhouse gases into value‐added chemicals with adjacent and asymmetric reaction sites, suggesting attractive potentials for CH4 and CO2 utilization.

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Section: Introductionmentioning

confidence: 99%

Photocatalytic Coupling of CH₄ and CO₂ to Ethanol on Asymmetric Ce−O−Zn Sites

Hao,

Chen,

Peng

et al. 2023

Adv Funct Materials

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“…To investigate the effect of promoter on the surface acidity and basicity of these catalysts, NH 3 -TPD and CO 2 -TPD were conducted. The higher desorption temperature indicates the stronger basicity or acidity over the catalysts. , Figure a shows the NH 3 desorption profiles of these commercial catalysts. One can find that the desorption peak of NG is located at ∼378.5 °C, which is significantly higher than that of other catalysts, revealing the strongest acidity of NG.…”

Section: Resultsmentioning

confidence: 99%

Strong Cu/ZnO Interfacial Interaction Induced by ZrO₂ Promoter Suppressing the Ethanol Formation in Industrial Methanol Synthesis

Yu,

Lin,

Song

et al. 2024

Ind. Eng. Chem. Res.

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The presence of ethanol as an impurity in industrial methanol significantly degrades the quality of the downstream products. Addressing the challenge of suppressing ethanol formation remains crucial in the synthesis of industrial methanol. In this context, we systematically characterized a series of commercial catalysts and evaluated their catalytic performance for methanol synthesis to elucidate the relationship between the catalyst structure and ethanol selectivity. Our performance tests indicate that the Cu−Zn−Al commercial catalyst (NG), enhanced with a ZrO 2 promoter, can effectively inhibit ethanol formation, reducing it to approximately 580 ppm after 1000 h. The ZrO 2 promoter stabilizes Cu 0 , ensuring it is highly dispersed and maintains a homogeneous structure, which is pivotal for the catalyst's exceptional performance. Analysis through temperature-programmed desorption and density functional theory (DFT) demonstrates that the high dispersity of Cu 0 enhances the adsorption of CO and H 2 . Additionally, a uniform Cu 0 active site structure contributes to the increased methanol selectivity while simultaneously suppressing ethanol formation. This study underscores the significant potential of incorporating a ZrO 2 promoter in catalysts to effectively suppress ethanol production under industrial operating conditions.

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“…Actually, impressive oxygenate yield and selectivity in the direct oxidation of CH 4 have been demonstrated in aqueous medium with single‐atom catalysts such as zeolites, [ 86 ] oxides, [ 87 ] etc. Similar to the photocatalytic oxidation of CH 4 in gas‐phase systems, photooxidation of CH 4 in an aqueous medium could also deliver C1 oxygenates such as CH 3 OH with H 2 O 2 or H 2 O [ 88 ] as oxidant.…”

Section: Methane Conversion Driven By Sustainable Energymentioning

confidence: 99%

Sustainable Energy Resources for Driving Methane Conversion

Chen

Weng

2023

Advanced Energy Materials

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The conversion of methane to value‐added chemicals by traditional reforming processes suffers from intensive energy consumption due to its particularly strong C─H bonds. Thus, it is urgent to optimize the driving force structure for methane conversion by accelerating the integration of sustainable energy. In this review, the advances in sustainable energy‐driven methane conversion are systematically summarized to provide a scientific understanding of methane conversion in operation/storage concepts, reactor design, technological maturity, system optimization, and remaining issues. Furthermore, the essence, economic evaluations, energy balance, and social impacts of methane conversion driven by sustainable energy are carefully discussed, paving a path for the future course of research and development. Diversifying the energy mix can play an important role in the future of sustainable energy‐driven methane conversion industries, being used as a crucial step for the transition to sustainable energy, especially the combination of solar/nuclear energy with fossil fuels to produce value‐added chemicals. Additionally, this review intends to bridge the studies of methane conversion and sustainable energy‐driven development, with the ultimate goal of offering a robust framework to understand the current status of sustainable energy‐driven methane conversion and provide guidance for the design of sustainable solutions for a greener future.

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ZSM-5-confined Cr₁–O₄ active sites boost methane direct oxidation to C1 oxygenates under mild conditions

Abstract: Direct oxidation of methane (DOM) to value-added chemicals is of great significance but still challenging under mild conditions. Herein, we report that Cr1-O4 as an active site in ZSM-5 anchored...

Cited by 17 publications

References 37 publications

Photocatalytic Coupling of CH₄ and CO₂ to Ethanol on Asymmetric Ce−O−Zn Sites

Photocatalytic Coupling of CH₄ and CO₂ to Ethanol on Asymmetric Ce−O−Zn Sites

Strong Cu/ZnO Interfacial Interaction Induced by ZrO₂ Promoter Suppressing the Ethanol Formation in Industrial Methanol Synthesis

Sustainable Energy Resources for Driving Methane Conversion

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ZSM-5-confined Cr1–O4 active sites boost methane direct oxidation to C1 oxygenates under mild conditions

Abstract: Direct oxidation of methane (DOM) to value-added chemicals is of great significance but still challenging under mild conditions. Herein, we report that Cr1-O4 as an active site in ZSM-5 anchored...

Cited by 17 publications

References 37 publications

Photocatalytic Coupling of CH4 and CO2 to Ethanol on Asymmetric Ce−O−Zn Sites

Photocatalytic Coupling of CH4 and CO2 to Ethanol on Asymmetric Ce−O−Zn Sites

Strong Cu/ZnO Interfacial Interaction Induced by ZrO2 Promoter Suppressing the Ethanol Formation in Industrial Methanol Synthesis

Sustainable Energy Resources for Driving Methane Conversion

Contact Info

Product

Resources

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ZSM-5-confined Cr₁–O₄ active sites boost methane direct oxidation to C1 oxygenates under mild conditions

Photocatalytic Coupling of CH₄ and CO₂ to Ethanol on Asymmetric Ce−O−Zn Sites

Photocatalytic Coupling of CH₄ and CO₂ to Ethanol on Asymmetric Ce−O−Zn Sites

Strong Cu/ZnO Interfacial Interaction Induced by ZrO₂ Promoter Suppressing the Ethanol Formation in Industrial Methanol Synthesis