Synergistic Effect of Oxygen Vacancy and High Porosity of Nano MIL‐125(Ti) for Enhanced Photocatalytic Nitrogen Fixation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(3)

Опубликована: Дек. 5, 2023

This work reports that a low-temperature thermal calcination strategy was adopted to modulate the electronic structure and attain an abundance of surface-active sites while maintaining crystal morphology. All experiments demonstrate new photocatalyst nano MIL-125(Ti)-250 obtained by has abundant Ti

Язык: Английский

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Synergistic Effect of Oxygen Vacancy and High Porosity of Nano MIL‐125(Ti) for Enhanced Photocatalytic Nitrogen Fixation

Angewandte Chemie, Год журнала: 2023, Номер 136(3)

Опубликована: Дек. 5, 2023

Abstract This work reports that a low‐temperature thermal calcination strategy was adopted to modulate the electronic structure and attain an abundance of surface‐active sites while maintaining crystal morphology. All experiments demonstrate new photocatalyst nano MIL‐125(Ti)‐250 obtained by has abundant Ti 3+ induced oxygen vacancies high specific surface area. facilitates adsorption activation N 2 molecules on active in photocatalytic nitrogen fixation. The NH 3 yield over is enhanced 156.9 μmol g −1 h , twice higher than parent MIL‐125(Ti) (76.2 ). Combined with density function theory (DFT), it shows pattern tends be from “end‐on” “side‐on” mode, which thermodynamically favourable. Moreover, electrochemical tests atomic ratio /Ti 4+ can enhance carrier separation, also promotes efficiency may offer insights into design innovative photocatalysts for various chemical reduction reactions.

Язык: Английский

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Retrofitting Zr-Oxo Nodes of UiO-66 by Ru Single Atoms to Boost Methane Hydroxylation with Nearly Total Selectivity

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(24), С. 13169 - 13180

Опубликована: Июнь 6, 2023

Direct selective oxidation of methane (DSOM) to high value-added oxygenates under mild conditions is attracting considerable interest. Although state-of-the-art supported metal catalysts can improve conversion, it still challenging avoid the deep oxygenates. Here, we develop a highly efficient metal-organic frameworks (MOFs)-supported single-atom Ru catalyst (Ru1/UiO-66) for DSOM reaction using H2O2 as an oxidant. It endows nearly 100% selectivity and excellent turnover frequency 185.4 h-1 production The yield order magnitude higher than that on UiO-66 alone several times nanoparticles or other conventional Ru1 catalysts, which show severe CO2 formation. Detailed characterizations density functional theory calculations reveal synergistic effect between electron-deficient site electron-rich Zr-oxo nodes Ru1/UiO-66. responsible activation CH4 via resulting Ru1═O* species, while undertake formation oxygenic radical species produce In particular, retrofitted by prune excess inactive O2 more •OH helping suppress over-oxidation

Язык: Английский

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Constructing matched active sites for robust photocatalytic dry reforming of methane

Chem, Год журнала: 2023, Номер 9(11), С. 3224 - 3244

Опубликована: Июль 25, 2023

Язык: Английский

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Atomically Strained Metal Sites for Highly Efficient and Selective Photooxidation

Nano Letters, Год журнала: 2023, Номер 23(7), С. 2905 - 2914

Опубликована: Март 24, 2023

Strain engineering is an attractive strategy for improving the intrinsic catalytic performance of heterogeneous catalysts. Manipulating strain on short-range atomic scale to local structure sites still challenging. Herein, we successfully achieved modulation ultrathin layered vanadium oxide nanoribbons by ingenious intercalation chemistry method. When trace sodium cations were introduced between V2O5 layers (Na+-V2O5), V-O bonds stretched atomically strained sites, redistributing charges. The Na+-V2O5 demonstrated excellent photooxidation performance, which was approximately 12 and 14 times higher than that pristine VO2, respectively. Complementary spectroscopy analysis theoretical calculations confirmed had a high surficial charge density, activation oxygen molecules contributing photocatalytic property. This work provides new approach rational design strain-equipped catalysts selective reactions.

Язык: Английский

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Photodriven Methane Conversion on Transition Metal Oxide Catalyst: Recent Progress and Prospects

Advanced Science, Год журнала: 2023, Номер 11(8)

Опубликована: Окт. 26, 2023

Methane as the main component in natural gas is a promising chemical raw material for synthesizing value-added chemicals, but its harsh conversion process often causes severe energy and environment concerns. Photocatalysis provides an attractive path to active convert methane into various products under mild conditions with clean sustainable solar energy, although many challenges remain at present. In this review, recent advances photocatalytic are systematically summarized. As basis of conversion, activation first elucidated from structural molecules. The study committed categorizing elucidating research progress laws intricate reactions according target products, including partial oxidation, reforming, coupling, combustion, functionalization. Advanced reactor designs also designed enrich options reliability performance evaluation. prospects discussed, which turn offers guidelines methane-conversion-related photocatalyst exploration, reaction mechanism investigation, advanced photoreactor design.

Язык: Английский

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In2O3/Bi19Br3S27 S-scheme heterojunction with enhanced photocatalytic CO2 reduction

Science China Materials, Год журнала: 2024, Номер 67(2), С. 514 - 523

Опубликована: Янв. 17, 2024

Язык: Английский

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Selective Photocatalytic Oxidation of Methane to Methanol by Constructing a Rapid O₂ Conversion Pathway over Au–Pd/ZnO

ACS Catalysis, Год журнала: 2024, Номер 14(2), С. 955 - 964

Опубликована: Янв. 5, 2024

Photocatalytic oxidation of methane to methanol is an attractive process under mild conditions, nevertheless confronting significant challenges in achieving high conversion and selectivity simultaneously. Herein, we propose a strategy for the direct rapid generation hydroxyl radicals (•OH) from O2 (O2 → *OOH •OH) by rational design Au–Pd/ZnO photocatalyst, skipping water-soluble H2O2 avoiding diffusion. For photocatalytic at ambient temperature, yield CH3OH over optimized 1.0% AuPd0.5/ZnO catalyst were as 81.0 μmol·h–1 88.2%, respectively, exceeding that most reported systems. The formation Au–Pd alloys could improve adsorption cleavage O–O bond *OOH, facilitating efficient •OH increasing selectivity. This work provides some guidance delicate composite photocatalysts selective utilization.

Язык: Английский

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Continuous Flow System for Highly Efficient and Durable Photocatalytic Oxidative Coupling of Methane

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(4), С. 2465 - 2473

Опубликована: Янв. 17, 2024

Photocatalytic oxidative coupling of methane (OCM) into value-added industrial chemicals offers an appealing green technique for achieving sustainable development, whereas it encounters double bottlenecks in relatively low conversion rate and severe overoxidation. Herein, we engineer a continuous gas flow system to achieve efficient photocatalytic OCM while suppressing overoxidation by synergizing the moderate active oxygen species, surface plasmon-mediated polarization, multipoint intake reactor. Particularly, remarkable CH4 218.2 μmol h–1 with excellent selectivity ∼90% toward C2+ hydrocarbons stability over 240 h is achieved designed Au/TiO2 photocatalyst our homemade three-dimensional (3D) printed This work provides informative concept high-performance design reactor synchronously regulate mass transfer, activation reactants, inhibition

Язык: Английский

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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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