Enabling Specific Photocatalytic Methane Oxidation by Controlling Free Radical Type

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(4), P. 2698 - 2707

Published: Jan. 17, 2023

Selective CH4 oxidation to CH3OH or HCHO with O2 in H2O under mild conditions provides a desired sustainable pathway for synthesis of commodity chemicals. However, manipulating reaction selectivity while maintaining high productivity remains huge challenge due the difficulty kinetic control formation oxygenate against its overoxidation. Here, we propose highly efficient strategy, based on precise type as-formed radicals by rational design photocatalysts, achieve both and photooxidation first time. Through tuning band structure size active sites (i.e., single atoms nanoparticles) our Au/In2O3 catalyst, show alternative two important radicals, •OOH •OH, which leads distinctly different paths HCHO, respectively. This approach gives rise remarkable yield 97.62% 6.09 mmol g-1 In2O3-supported Au (Au1/In2O3) an exceptional 89.42% 5.95 nanoparticles (AuNPs/In2O3), respectively, upon photocatalytic 3 h at room temperature. work opens new avenue toward selective delicate composite photocatalysts.

Language: Английский

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Elevating Photooxidation of Methane to Formaldehyde via TiO₂ Crystal Phase Engineering

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(35), P. 15977 - 15987

Published: Aug. 15, 2022

Photocatalytic conversion of methane to value-added products under mild conditions, which represents a long sought-after goal for industrial sustainable production, remains extremely challenging afford high production and selectivity using cheap catalysts. Herein, we present the crystal phase engineering commercially available anatase TiO2 via simple thermal annealing optimize structure-property correlation. A biphase catalyst with (90%) rutile (10%) optimal interface concentration exhibits exceptional performance in oxidation formaldehyde reaction conditions water solvent, oxygen atmosphere, full-spectrum light irradiation. An unprecedented 24.27 mmol gcat-1 an excellent 97.4% toward is acquired at room temperature after 3 h reaction. Both experimental results theoretical calculations disclose that lengthens lifetime photogenerated carriers favors formation intermediate methanol species, thus maximizing efficiency aerobic formaldehyde. More importantly, feasibility scale-up demonstrated by inventing "pause-flow" reactor. This work opens avenue transformation economical way.

Language: Английский

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Engineering a Copper Single‐Atom Electron Bridge to Achieve Efficient Photocatalytic CO₂ Conversion

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(13)

Published: Feb. 7, 2023

Developing highly efficient and stable photocatalysts for the CO2 reduction reaction (CO2 RR) remains a great challenge. We designed Z-Scheme photocatalyst with N-Cu1 -S single-atom electron bridge (denoted as Cu-SAEB), which was used to mediate RR. The production of CO O2 over Cu-SAEB is high 236.0 120.1 μmol g-1 h-1 in absence sacrificial agents, respectively, outperforming most previously reported photocatalysts. Notably, as-designed throughout 30 cycles, totaling 300 h, owing strengthened contact interface Cu-SAEB, mediated by atomic structure. Experimental theoretical calculations indicated that SAEB greatly promoted Z-scheme interfacial charge-transport process, thus leading enhancement photocatalytic RR Cu-SAEB. This work represents promising platform development have potential conversion applications.

Language: Английский

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

Advanced Science, Journal Year: 2023, Volume and Issue: 11(8)

Published: Oct. 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.

Language: Английский

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Ultrathin two-dimensional materials: New opportunities and challenges in ultra-sensitive gas sensing

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 505, P. 215691 - 215691

Published: Jan. 31, 2024

Language: Английский

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Photocatalytic aerobic oxidation of C(sp3)-H bonds

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 15, 2024

Abstract In modern industries, the aerobic oxidation of C(sp 3 )-H bonds to achieve value-added conversion hydrocarbons requires high temperatures and pressures, which significantly increases energy consumption capital investment. The development a light-driven strategy, even under natural sunlight ambient air, is therefore great significance. Here we develop series hetero-motif molecular junction photocatalysts containing two bifunctional motifs. With these materials, reduction O 2 can be effectively accomplished, thus realizing efficient in e.g., toluene ethylbenzene. Especially for ethylbenzene reactions, excellent catalytic capacity (861 mmol g cat −1 ) observed. addition direct bonds, CeBTTD-A also applied other types reactions highlighting their potential industrial applications.

Language: Английский

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Best Practices for Experiments and Reports in Photocatalytic Methane Conversion

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 4, 2024

Efficiently converting methane into valuable chemicals via photocatalysis under mild condition represents a sustainable route to energy storage and value-added manufacture. Despite continued interest in this area, the achievements have been overshadowed by absence of standardized protocols for conducting photocatalytic oxidation experiments as well evaluating corresponding performance. In review, we present structured solution aimed at addressing these challenges. Firstly, introduce norms underlying reactor design outline various configurations gas-solid gas-solid-liquid reaction systems. This discussion helps choosing suitable reactors conversion experiments. Subsequently, offer comprehensive step-by-step protocol applicable diverse methane-conversion reactions. Emphasizing meticulous verification accurate quantification products, highlights significance mitigating contamination sources selecting appropriate detection methods. Lastly, propose performance metrics crucial conversion. By defining metrics, community could obtain consensus assessing across different studies. Moving forward, future necessitates further refinement stringent experimental standards evaluation criteria. Moreover, development scalable is essential facilitate transition from laboratory proof-of-concept potentially industrial production.

Language: Английский

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Optimizing the reaction pathway of methane photo-oxidation over single copper sites

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Oct. 21, 2024

Language: Английский

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Carbon dioxide, global boiling, and climate carnage, from generation to assimilation, photocatalytic conversion to renewable fuels, and mechanism

The Science of The Total Environment, Journal Year: 2025, Volume and Issue: 965, P. 178629 - 178629

Published: Jan. 28, 2025

Language: Английский

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Selective Liquid Chemical Production in Waste Polyolefin Photorefinery by Controlling Reactive Species

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 29, 2025

Photocatalytic upcycling of waste polyolefins into value-added chemicals provides promise in plastic management and resource utilization. Previous works demonstrate that can be converted carboxylic acids, with CO2 as the final oxidation product. It is still challenging to explore more transformation products, particularly mild-oxidation products such alcohols, because their instability compared polymer substrates, which are prone during catalytic reactions. In this work, we propose an efficient strategy regulate product type through precise control radicals, intermediates, reaction paths. Taking commonly used photocatalyst C3N4 example, its major acids CO2. When MoS2 introduced construct a Z-scheme heterostructure, gas significantly reduced alcohols appear high yield 1358.8 μmol gcat-1 selectivity up 80.3%. This primarily attributed presence •OH radicals from oxygen reduction, acting key role alcohol formation while simultaneously suppressing competing pathways •O2- 1O2, thus reducing overoxidation products. The β-scission C-C bonds chains generates intermediate alkyl species, followed by combination produce methanol, energetically favorable for MoS2/C3N4. contrast, species couple form formic acid, C3N4. work new approaches controlling types offers insights involved polyolefin photorefinery.

Language: Английский

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