Cooperative Coupling of Oxidative Organic Synthesis and Hydrogen Production over Semiconductor-Based Photocatalysts

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(21), P. 13051 - 13085

Published: Aug. 11, 2021

Merging hydrogen (H2) evolution with oxidative organic synthesis in a semiconductor-mediated photoredox reaction is extremely attractive because the clean H2 fuel and high-value chemicals can be coproduced under mild conditions using light as sole energy input. Following this dual-functional photocatalytic strategy, dreamlike pathway for constructing C–C/C–X (X = C, N, O, S) bonds from abundant readily available X–H bond-containing compounds concomitant release of fulfilled without need external chemical reagents, thus offering green fascinating synthetic strategy. In review, we begin by presenting concise overview on general background traditional production then focus fundamental principles cooperative coupling selective simultaneous utilization photoexcited electrons holes over semiconductor-based catalysts to meet economic sustainability goal. Thereafter, put dedicated emphasis recent key progress various transformations, including alcohol oxidation, methane conversion, amines coupling, cross-coupling, cyclic alkanes dehydrogenation, reforming lignocellulosic biomass, so on. Finally, remaining challenges future perspectives flourishing area have been critically discussed. It anticipated that review will provide enlightening guidance rational design such system, thereby stimulating development economical environmentally benign solar generation value-added fine chemicals.

Language: Английский

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Electrocatalytic Refinery for Sustainable Production of Fuels and Chemicals

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(36), P. 19572 - 19590

Published: Feb. 19, 2021

Abstract Compared to modern fossil‐fuel‐based refineries, the emerging electrocatalytic refinery (e‐refinery) is a more sustainable and environmentally benign strategy convert renewable feedstocks energy sources into transportable fuels value‐added chemicals. A crucial step in conducting e‐refinery processes development of appropriate reactions optimal electrocatalysts for efficient cleavage formation chemical bonds. However, compared well‐studied primary (e.g., O 2 reduction, water splitting), mechanistic aspects materials design complex are yet be settled. To address this challenge, herein, we first present fundamentals heterogeneous electrocatalysis some reactions, then implement these establish framework by coupling situ generated intermediates (integrated reactions) or products (tandem reactions). We also set principles strategies efficiently manipulate reaction pathways.

Language: Английский

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Direct and Selective Photocatalytic Oxidation of CH₄ to Oxygenates with O₂ on Cocatalysts/ZnO at Room Temperature in Water

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(51), P. 20507 - 20515

Published: Dec. 13, 2019

Direct conversion of methane into methanol and other liquid oxygenates still confronts considerable challenges in activating the first C-H bond inhibiting overoxidation. Here, we report that ZnO loaded with appropriate cocatalysts (Pt, Pd, Au, or Ag) enables direct oxidation to formaldehyde water using only molecular oxygen as oxidant under mild light irradiation at room temperature. Up 250 micromoles ∼95% selectivity is achieved for 2 h over 10 mg 0.1 wt % Au. Experiments isotopically labeled reveal O2, rather than water, source CH4 oxidation. We find cocatalyst could concertedly activate O2 methyl radical mildly oxidative intermediate (hydroperoxyl radical) which are two key precursor intermediates generating oxygenated products Our study underlines equally significant aspects realizing selective photooxidation oxygenates, i.e., efficient activation controllable O2.

Language: Английский

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Methane transformation by photocatalysis

Nature Reviews Materials, Journal Year: 2022, Volume and Issue: 7(8), P. 617 - 632

Published: Feb. 28, 2022

Language: Английский

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Pd-Modified ZnO–Au Enabling Alkoxy Intermediates Formation and Dehydrogenation for Photocatalytic Conversion of Methane to Ethylene

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 143(1), P. 269 - 278

Published: Dec. 29, 2020

Photocatalysis provides an intriguing approach for the conversion of methane to multicarbon (C2+) compounds under mild conditions; however, with methyl radicals as sole reaction intermediate, current C2+ products are dominated by ethane, a negligible selectivity toward ethylene, which, key chemical feedstock, possesses higher added value than ethane. Herein, we report direct photocatalytic methane-to-ethylene pathway involving formation and dehydrogenation alkoxy (i.e., methoxy ethoxy) intermediates over Pd-modified ZnO–Au hybrid catalyst. On basis various in situ characterizations, it is revealed that Pd-induced capability catalyst holds turning on pathway. During reaction, molecules first dissociated into surface ZnO assistance Pd. Then these further dehydrogenated coupled radical ethoxy, which can be subsequently converted ethylene through dehydrogenation. As result, optimized ZnO–AuPd atomically dispersed Pd sites Au lattice achieves 536.0 μmol g–1 compound 96.0% (39.7% C2H4 54.9% C2H6 total produced compounds) after 8 h light irradiation. This work fresh insight conditions highlights significance enhanced activity unsaturated hydrocarbon product selectivity.

Language: Английский

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Selective photocatalytic oxidation of methane by quantum-sized bismuth vanadate

Nature Sustainability, Journal Year: 2021, Volume and Issue: 4(6), P. 509 - 515

Published: Feb. 4, 2021

Language: Английский

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Toward solar-driven carbon recycling

Joule, Journal Year: 2022, Volume and Issue: 6(2), P. 294 - 314

Published: Jan. 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.

Language: Английский

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Photocatalytic C–H activation and the subtle role of chlorine radical complexation in reactivity

Science, Journal Year: 2021, Volume and Issue: 372(6544), P. 847 - 852

Published: May 21, 2021

A complex role for chlorine radicals Radicals are atoms or molecules that highly reactive because they have an unpaired electron. common means of investigating whether involved in a particular reaction is to try trap them with acceptor compound. Yang et al. reinvestigated photoinduced alkane oxidation which trapping study had previously implicated alkoxy radicals. Their spectroscopic, kinetic, and isotopic labeling studies revealed chlorine, rather than alkoxy, was the key radical intermediate; prior results stemmed from its complexation alcohols. Science , abd8408, this issue p. 847

Language: Английский

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Catalysis for Selected C1 Chemistry

Chem, Journal Year: 2020, Volume and Issue: 6(10), P. 2497 - 2514

Published: Sept. 24, 2020

Language: Английский

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The reformation of catalyst: From a trial-and-error synthesis to rational design

Nano Research, Journal Year: 2023, Volume and Issue: 17(4), P. 3261 - 3301

Published: Sept. 27, 2023

Language: Английский

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