Highly Selective Photocatalytic Methane Coupling by Au-Modified Bi₂WO₆

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 1855 - 1861

Опубликована: Янв. 19, 2024

Photocatalytic oxidative coupling of methane (OCM) to ethane promises a route value-added C2 products from an abundant and low-cost feedstock. However, selective activation the C–H bond CH4 without overoxidation CO2 has been major challenge. In this work, we present use Au-modified Bi2WO6 as prototypical photocatalyst, demonstrating high performance OCM through photocatalysis. A C2H6 production rate at 1.69 × 103 μmol·g–1·h–1 with approximately 85% selectivity was achieved, which ranks among top-performing photocatalytic systems. Efforts were also made in establishing correlation between improved photocatalyst system by examining nature oxide photocatalyst. Our findings indicated that oxygen within surface, likely adsorbed subsequently dissociated vacancy sites, afforded desired reactivity selectively activate significant overoxidation. Surprisingly, it revealed Au cocatalyst plays dual roles activating for enhanced promoting C–C yield main product.

Язык: Английский

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Solar‐Driven Hydrogen Evolution from Value‐Added Waste Treatment

Advanced Energy Materials, Год журнала: 2024, Номер 14(15)

Опубликована: Фев. 13, 2024

Abstract Hydrogen is one of the most important energy alternatives to conventional fossil‐based fuel. Solar based photocatalytic hydrogen evolution (PHE) a salient approach produce fuel but its efficiency generally limited by sluggish and energy‐unfavorable oxidation reaction. Meanwhile, waste treatment has become worldwide problem clean highly demanded avoid vast greenhouse emission currently. Inspiringly, PHE can be effectively coupled with favorable photooxidation many wastes, which kills two birds stone. In this review, recent progress in presented, where typical solid, liquid, gas wastes have been briefly discussed. Focusing on understanding complicated reaction mechanism revelation products, cutting‐edge techniques for photophysics surface chemistry characterization analyzed, are imperative facilitate following investigation. Finally, developing trend existing issues current research also discussed detail so that holistic blueprint portrayed accelerate their application realistic world.

Язык: Английский

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Pauling‐Type Adsorption of O₂ Induced by Heteroatom Doped ZnIn₂S₄ for Boosted Solar‐Driven H₂O₂ Production

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(5)

Опубликована: Дек. 12, 2023

Abstract Breaking the trade‐off between activity and selectivity has perennially been a formidable endeavor in field of hydrogen peroxide (H 2 O ) photosynthesis, especially side‐on configuration oxygen (O on catalyst surface will cause cleavage O−O bonds, which drastically hinders H production performance. Herein, we present an atomically heteroatom P doped ZnIn S 4 with tunable adsorption to accelerate ORR kinetics essential for solar‐driven production. Indeed, spectroscopy characterizations (such as EXAFS situ FTIR) DFT calculations reveal that at substitutional interstitial sites, not only optimizes coordination environment Zn active but also facilitates electron transfer sites improves charge density, avoiding breakage bonds reducing energy barriers As result, is regulated from (Yeager‐type) end‐on (Pauling‐type), resulting accelerated 874.94 2107.66 μmol g −1 h . This finding offers new avenue toward strategic tailoring by rational design photocatalyst.

Язык: Английский

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Steering Photooxidation of Methane to Formic Acid over A Priori Screened Supported Catalysts

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(23), С. 16039 - 16051

Опубликована: Июнь 4, 2024

Efficient methane photooxidation to formic acid (HCOOH) has emerged as a sustainable approach simultaneously generate value-added chemicals and harness renewable energy. However, the persistent challenge lies in achieving high yield selectivity for HCOOH formation, primarily due complexities associated with modulating intermediate conversion desorption after activation. In this study, we employ first-principles calculations comprehensive guiding tool discover that by precisely controlling O2 activation process on noble metal cocatalysts adsorption strength of carbon-containing intermediates oxide supports, one can finely tune products. Specifically, bifunctional catalyst comprising Pd nanoparticles monoclinic WO3 (Pd/WO3) would possess optimal kinetics an oxidation/desorption barrier, thereby promoting formation. As evidenced experiments, Pd/WO3 achieves exceptional 4.67 mmol gcat–1 h–1 62% under full-spectrum light irradiation at room temperature using molecular O2. Notably, these results significantly outperform state-of-the-art photocatalytic systems operated identical condition.

Язык: Английский

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Contact‐Electro‐Catalysis for Direct Oxidation of Methane under Ambient Conditions

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(20)

Опубликована: Март 16, 2024

Abstract The conversion of methane under ambient conditions has attracted significant attention. Although advancements have been made using active oxygen species from photo‐ and electro‐ chemical processes, challenges such as complex catalyst design, costly oxidants, unwanted byproducts remain. This study exploits the concept contact‐electro‐catalysis, initiating reactions through charge exchange at a solid–liquid interface, to report novel process for directly converting conditions. Utilizing electrification commercially available Fluorinated Ethylene Propylene (FEP) with water ultrasound, we demonstrate how this interaction promote activation molecules. Our results show that yield HCHO CH 3 OH can reach 467.5 151.2 μmol ⋅ g cat −1 , respectively. We utilized electron paramagnetic resonance (EPR) confirm evolution hydroxyl radicals (⋅OH) superoxide (⋅OOH). Isotope mass spectrometry (MS) was employed analyze elemental origin OH, which be further oxidized HCHO. Additionally, conducted density functional theory (DFT) simulations assess reaction energies FEP H 2 O, O 4 these implications methodology, its potential applicability wider array gas‐phase catalytic reactions, underscore advance in catalysis.

Язык: Английский

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Interstitial Zinc Defects Enriched ZnO Tuning O₂ Adsorption and Conversion Pathway for Superior Photocatalytic CH₄ Oxygenation

ACS Catalysis, Год журнала: 2024, Номер 14(12), С. 9104 - 9114

Опубликована: Май 30, 2024

Photocatalytic methane conversion into liquid oxygenates using O2 oxidants provides a promising approach for high-value chemicals. The generation of reactive oxygen species and their reaction pathway are key to determine the oxygenate selectivity. Here, an interstitial Zni defect ZnO (ZnO(Zni)) is developed through thermal decomposition ZnO2 precursor. favors adsorption at terminal configuration induces effectively desired •OOH instead •OH improving yield selectivity oxygenates. For comparison, adsorbed in lateral tends be converted excessive on typical Au/ZnO. As result, ZnO(Zni) shows 6080 μmol g–1 with 98.6% selectivity, which leads 10 times lower than Au/ZnO CO2 release overoxidation. This work activation regulate photocatalytic CH4 oxidation

Язык: Английский

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Product Peroxidation Inhibition in Methane Photooxidation into Methanol

Advanced Science, Год журнала: 2024, Номер 11(12)

Опубликована: Янв. 17, 2024

Abstract Methane photooxidation into methanol offers a practical approach for the generation of high‐value chemicals and efficient storage solar energy. However, propensity C─H bonds in desired products to cleave more easily than those methane molecules results continuous dehydrogenation process, inevitably leading peroxidation. Consequently, inhibiting peroxidation is perceived as one most formidable challenges field direct conversion methanol. This review thorough overview typical mechanisms involved radical mechanism active site regulatory methods employed inhibit product photooxidation. Additionally, several perspectives on future research direction this crucial are proposed.

Язык: Английский

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Light-driven propane dehydrogenation by a single-atom catalyst under near-ambient conditions

Nature Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 21, 2025

Язык: Английский

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Photocatalytic nonoxidative coupling of methane to ethylene over carbon-doped ZnO/Au catalysts

Science China Chemistry, Год журнала: 2023, Номер 66(11), С. 3252 - 3261

Опубликована: Авг. 25, 2023

Язык: Английский

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Single Dispersion of Fe(H₂O)₂‐based Polyoxometalate on Polymeric Carbon Nitride for Biomimetic CH₄ Photooxidation

Advanced Materials, Год журнала: 2024, Номер 36(31)

Опубликована: Май 21, 2024

Direct methane conversion to value-added oxygenates under mild conditions with in-depth mechanism investigation has attracted wide interest. Inspired by monooxygenase, the K

Язык: Английский

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