Core–Shell MIL-125-NH₂@FeOOH Nanocomposites for Highly Selective Photocatalytic Oxidation of Methane to Formaldehyde in Water Vapor

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 21, 2025

Formaldehyde (HCHO), a crucial industrial chemical, finds extensive applications across diverse sectors, including household products, commercial materials, aviation, and medical supplies. Methane (CH4), as an abundant C1 resource, presents promising feedstock for HCHO synthesis. However, the direct conversion of CH4 to remains challenging due its inherent chemical inertness, characterized by low polarizability high C-H bond dissociation energy (439 kJ mol-1), coupled with reactivity intermediate products. The development efficient strategies selective oxidation high-value under mild conditions is therefore significant practical importance. In this study, we developed series MIL-125-NH2@FeOOH-x heterostructured photocatalysts (FM-x) through controlled deposition FeOOH nanoparticles on MIL-125-NH2 surfaces. Comprehensive characterization photocatalytic evaluations reveal that optimized FM-1 catalyst facilitates in situ H2O2 generation subsequent decomposition into hydroxyl radicals (•OH), enabling photooxidation. Remarkably, achieves exceptional production rate 197.79 μmol·gcat-1 >99.99% selectivity water vapor, significantly outperforming both pristine components. This work system conversion, offering new insights design catalysts chemistry.

Язык: Английский

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Theoretical insights into electrochemical CO2 reduction by Bi-based catalysts: single crystals versus mixed phases

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 163047 - 163047

Опубликована: Апрель 1, 2025

Язык: Английский

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Near-Infrared Photon-Triggered CH4-to-CH3OH Conversion over Plasmonic Oxyselenides

Research Square (Research Square), Год журнала: 2025, Номер unknown

Опубликована: Апрель 25, 2025

The direct oxidation of methane into methanol exploiting O2 as oxidant offers an ideal route for utilization. Although the reaction is strongly preferred in thermodynamics, conventional catalytic systems always demand intense energy input like high temperatures or high-energy photons (>2.8 eV) to conquer large kinetic barrier conversion process. In this study, we demonstrate that by creation a suitable plasmonic photocatalyst, namely oxygen-vacancy-rich CuSeO3-x, low-energy near-infrared (NIR) can serve sole complete CH4-to-CH3OH with remarkable activity (AQY 1.5 % at 800 nm Au cocatalyst) and near unity selectivity (ca. 96 %) 25 ℃. Such fascinating performance attributed small activation measured 0.28 eV, enabled existence CuII-Ov species CuSeO3-x. Our study suggests ensemble constitutes exceptional active site, which harness plasmon-induced hot electrons meantime brings kinetically advantageous reducing •OH radicals greatly favoring activation.

Язык: Английский

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Photocatalytic synthesis of ethylene glycol and hydrogen from methyl tert-butyl ether

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 28, 2025

In this work, we have developed a green and sustainable strategy for the synthesis of ethylene glycol, which is highly valuable compound in chemical industry. contrast to currently applied energy-intensive process based on petroleum resources, work demonstrates photocatalytic pathway methanol dehydrogenative coupling produce utilizing methyl tert-butyl ether as substrate protect hydroxyl group against oxidation. Photocatalytic tests reveal efficient C-C with Pt/C-TiO(B)-650 catalyst under light irradiation, target product 1,2-di-tert-butoxyethane at selectivity 67% Pt-based turnover frequency 2754 h-1. Scale up test high stability system, reaching an accumulated number 120 000 well isolation 13 g after 130 h irradiation. The glycol obtained by hydrolysis dimer using regenerable acidic resin catalyst.

Язык: Английский

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Unconventional Carrier Transfer Enabled Direct O₂ Reduction by Oxygen Vacancies for Efficient Photooxidation of CH₄

ACS Applied Materials & Interfaces, Год журнала: 2025, Номер unknown

Опубликована: Май 8, 2025

Photocatalytic oxidation of methane (CH4) to high value-added liquid oxygenates with oxygen (O2) as an oxidant has long been a promising process. In addition the activation CH4, selective reduction O2 hydroperoxyl (·OOH) is also crucial factor in determining efficiency and selectivity overall reaction. thermal catalysis, strong interactions between vacancies (OVs) on catalyst surface are widely adopted means enhancing activation. However, reports this phenomenon limited photocatalysis; attributable fact that dependent upon its reaction photogenerated electrons (e-). For majority photocatalysts, transfer e- metal cocatalysts results spatial separation from OVs. Therefore, intrinsic affinity OVs not fully exploited. study, we discovered H2 treatment at elevated temperatures ZIF-8-derived ZnO led formation OV-enriched amorphous layer surface. After introduction Ag cocatalyst, as-prepared Agx-OVs/ZnO exhibited unconventional carrier direction, whereby holes (h+) transferred Ag, respectively. As result, preferential adsorption sites can be spatially combined together thus drive realize efficient directed generation ·OOH. parallel, h+ weakens capability avoids overoxidation while ensuring CH4 The optimized defect-rich Ag0.5-OVs/ZnO-z photocatalyst reaches oxygenate yield 10148 μmol gcat-1 h-1 95% TOF 2.4 × 106 gAg-1 h-1. This work sheds new light design photocatalytic catalysts via manipulation direction.

Язык: Английский

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Architecting Molecularly Dispersed Cu(I)-Active Sites at UiO-MOF Nodes for Thermocatalytic Oxidation of Methane to Ethanol Using O2

Applied Catalysis B Environment and Energy, Год журнала: 2025, Номер unknown, С. 125474 - 125474

Опубликована: Май 1, 2025

Язык: Английский

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Respective contribution of varied reactive oxygen species formed in methane conversion over calcined ferric sulfate

Journal of environmental chemical engineering, Год журнала: 2025, Номер unknown, С. 117239 - 117239

Опубликована: Май 1, 2025

Язык: Английский

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Photocatalytic CH₄ Upgrading to Multicarbon Products

ACS Catalysis, Год журнала: 2024, Номер 14(22), С. 16673 - 16686

Опубликована: Окт. 29, 2024

Methane is both a greenhouse gas and an abundant C1 fuel resource that exists in nature. The selective photocatalytic upgrading of methane into multicarbon (C2+) chemicals can mitigate the effect promote utilization value methane, which C–C coupling step key to production products. Achieving this targeted under ambient temperature pressure conditions requires efficient activation C–H bonds as well balancing adsorption desorption various free radicals intermediates facilitate coupling. In Review, we delve recent advances C2+ importance catalyst design, including active site assembly, crystal surface, valence reconstruction, first emphasized. Then, discuss how coreactants such carbon dioxide monoxide be introduced enhance chain growth pathways. Furthermore, also summarize developments looping systems photoelectrocatalysis. Finally, conclude with outlook for future advancement field. This Review aims provide general framework investigating reactions toward products, thereby suggesting research directions environmentally friendly strategies.

Язык: Английский

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Scalable In-Situ Synthesis of H2o2 for Highly Selective Converstion of Methane to Methanol in Water at Room Temperature

Опубликована: Янв. 1, 2024

Язык: Английский

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