Synergy of Pd atoms and oxygen vacancies on In2O3 for methane conversion under visible light

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Май 25, 2022

Methane (CH4) oxidation to high value chemicals under mild conditions through photocatalysis is a sustainable and appealing pathway, nevertheless confronting the critical issues regarding both conversion selectivity. Herein, visible irradiation (420 nm), synergy of palladium (Pd) atom cocatalyst oxygen vacancies (OVs) on In2O3 nanorods enables superior photocatalytic CH4 activation by O2. The optimized catalyst reaches ca. 100 μmol h-1 C1 oxygenates, with selectivity primary products (CH3OH CH3OOH) up 82.5%. Mechanism investigation elucidates that such induced dedicated function Pd single atoms boosting hole electron transfer, respectively. O2 proven be only source for CH3OH production, while H2O acts as promoter efficient ·OH production facilitates product desorption indicated DFT modeling. This work thus provides new understandings simultaneous regulation activity cocatalysts vacancies.

Язык: Английский

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Toward solar-driven carbon recycling

Joule, Год журнала: 2022, Номер 6(2), С. 294 - 314

Опубликована: Янв. 31, 2022

Carbon recycling will become a dominant trend toward alleviating extreme climate change and coping with the increasing energy demand in coming years. Solar-driven strategies have potential to convert CO2 solar fuels chemicals. In this forward-looking perspective, framework is outlined achieve "net-zero emission" blueprint by sorting out raw sources, products, feasible pathways, practical implementation through photocatalysis, photothermal catalysis, photoelectrochemical catalysis techniques. We comprehensively inspect compare state-of-art works framework, including solar-driven C1 fuel production from CO2, as well direct stepwise C2+ involving conversion. This analysis aspires provide most pathway forward finds that converting renewable H2 into can currently obtain best solar-to-fuel conversion efficiency target products high selectivity. Future visions on scientific, technological, economic issues are put determine what should be focus following decades.

Язык: Английский

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Binary Au–Cu Reaction Sites Decorated ZnO for Selective Methane Oxidation to C1 Oxygenates with Nearly 100% Selectivity at Room Temperature

Journal of the American Chemical Society, Год журнала: 2021, Номер 144(2), С. 740 - 750

Опубликована: Дек. 20, 2021

Direct and efficient oxidation of methane to methanol the related liquid oxygenates provides a promising pathway for sustainable chemical industry, while still remaining an ongoing challenge owing dilemma between activation overoxidation. Here, ZnO with highly dispersed dual Au Cu species as cocatalysts enables selective photocatalytic conversion one-carbon (C1) using O2 oxidant operated at ambient temperature. The optimized AuCu-ZnO photocatalyst achieves up 11225 μmol·g-1·h-1 primary products (CH3OH CH3OOH) HCHO nearly 100% selectivity, resulting in 14.1% apparent quantum yield 365 nm, much higher than previous best photocatalysts reported oxygenates. In situ EPR XPS disclose that serve photoinduced electron mediators promote •OOH, simultaneously is hole acceptor enhance H2O •OH, thus synergistically promoting charge separation transformation. This work highlights significances co-modification suitable on simultaneous regulation activity selectivity.

Язык: Английский

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High-performance photocatalytic nonoxidative conversion of methane to ethane and hydrogen by heteroatoms-engineered TiO2

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Май 19, 2022

Abstract Nonoxidative coupling of methane (NOCM) is a highly important process to simultaneously produce multicarbons and hydrogen. Although oxide-based photocatalysis opens opportunities for NOCM at mild condition, it suffers from unsatisfying selectivity durability, due overoxidation CH 4 with lattice oxygen. Here, we propose heteroatom engineering strategy active, selective durable photocatalytic NOCM. Demonstrated by commonly used TiO 2 photocatalyst, construction Pd–O in surface reduces contribution O sites valence band, overcoming the limitations. In contrast state art, 94.3% achieved C H 6 production 0.91 mmol g –1 h along stoichiometric production, approaching level thermocatalysis relatively condition. As benchmark, apparent quantum efficiency reaches 3.05% 350 nm. Further elemental doping can elevate durability over 24 stabilizing This work provides new insights high-performance atomic engineering.

Язык: Английский

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Modulation of the lattice structure of 2D carbon-based materials for improving photo/electric properties

Carbon letters, Год журнала: 2022, Номер 33(5), С. 1321 - 1331

Опубликована: Авг. 2, 2022

Язык: Английский

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Nearly 100% selective and visible-light-driven methane conversion to formaldehyde via. single-atom Cu and Wδ+

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Май 10, 2023

Direct solar-driven methane (CH4) reforming is highly desirable but challenging, particularly to achieve a value-added product with high selectivity. Here, we identify synergistic ensemble effect of atomically dispersed copper (Cu) species and partially reduced tungsten (Wδ+), stabilised over an oxygen-vacancy-rich WO3, which enables exceptional photocatalytic CH4 conversion formaldehyde (HCHO) under visible light, leading nearly 100% selectivity, very yield 4979.0 μmol·g-1 within 2 h, the normalised mass activity 8.5 × 106 μmol·g-1Cu·h-1 HCHO at ambient temperature. In-situ EPR XPS analyses indicate that Cu serve as electron acceptor, promoting photo-induced transfer from conduction band O2, generating reactive •OOH radicals. In parallel, adjacent Wδ+ act hole acceptor preferred adsorption activation site H2O produce hydroxyl radicals (•OH), thus activate methyl (•CH3). The synergy dual active sites boosts overall efficiency selectivity process.

Язык: Английский

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Direct Photocatalytic Synthesis of Acetic Acid from Methane and CO at Ambient Temperature Using Water as Oxidant

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(2), С. 1185 - 1193

Опубликована: Янв. 2, 2023

Direct functionalization of methane selectively to value-added chemicals is still one the main challenges in modern science. Acetic acid an important industrial chemical produced nowadays by expensive and environmentally unfriendly carbonylation methanol using homogeneous catalysts. Here, we report a new photocatalytic reaction route synthesize acetic from CH4 CO at room temperature water as sole external oxygen source. The optimized photocatalyst consists TiO2 support ammonium phosphotungstic polyoxometalate (NPW) clusters anchored with isolated Pt single atoms (Pt1). It enables stable synthesis 5.7 mmol·L–1 solution 60 h selectivity over 90% 66% on liquid-phase carbon basis, respectively, production 99 mol per Pt. Combined isotopic situ spectroscopy investigation suggests that proceeds via oxidative Pt1 sites, activation facilitated water-derived hydroxyl radicals.

Язык: Английский

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Metal–organic frameworks as catalysts and biocatalysts for methane oxidation: The current state of the art

Coordination Chemistry Reviews, Год журнала: 2023, Номер 481, С. 215042 - 215042

Опубликована: Фев. 9, 2023

Язык: Английский

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High-density frustrated Lewis pairs based on Lamellar Nb2O5 for photocatalytic non-oxidative methane coupling

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Апрель 10, 2023

Photocatalytic methane conversion requires a strong polarization environment composed of abundant activation sites with the robust stretching ability for C-H scissoring. High-density frustrated Lewis pairs consisting low-valence acid Nb and base Nb-OH are fabricated on lamellar Nb2O5 through thermal-reduction promoted phase-transition process. Benefitting from planar atomic arrangement Nb2O5, highly exposed accessible to reactants, which results in superior rate 1456 μmol g-1 h-1 photocatalytic non-oxidative coupling without assistance noble metals. The time-dependent DFT calculation demonstrates photo-induced electron transfer LA LB enhances their intensities concerted way, promoting cleavage LB. This work provides in-depth insight into designing constructing micro-environment

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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