Room-temperature photosynthesis of propane from CO2 with Cu single atoms on vacancy-rich TiO2

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

Опубликована: Фев. 27, 2023

Photochemical conversion of CO2 into high-value C2+ products is difficult to achieve due the energetic and mechanistic challenges in forming multiple C-C bonds. Herein, an efficient photocatalyst for C3H8 prepared by implanting Cu single atoms on Ti0.91O2 atomically-thin layers. promote formation neighbouring oxygen vacancies (VOs) matrix. These modulate electronic coupling interaction between adjacent Ti form a unique Cu-Ti-VO unit A high electron-based selectivity 64.8% (product-based 32.4%), 86.2% total hydrocarbons 50.2%) are achieved. Theoretical calculations suggest that may stabilize key *CHOCO *CH2OCOCO intermediates reduce their energy levels, tuning both C1-C1 C1-C2 couplings thermodynamically-favourable exothermal processes. Tandem catalysis mechanism potential reaction pathway tentatively proposed formation, involving overall (20e- - 20H+) reduction three molecules at room temperature.

Язык: Английский

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Reticular framework materials for photocatalytic organic reactions

Chemical Society Reviews, Год журнала: 2023, Номер 52(22), С. 7949 - 8004

Опубликована: Янв. 1, 2023

Photocatalytic organic reactions, harvesting solar energy to produce high value-added chemicals, have attracted increasing attention as a sustainable approach address the global crisis and environmental issues. Reticular framework materials, including metal-organic frameworks (MOFs) covalent (COFs), are widely considered promising candidates for photocatalysis owing their crystallinity, tailorable pore environment extensive structural diversity. Although design synthesis of MOFs COFs been intensively developed in last 20 years, applications photocatalytic transformations still preliminary stage, making systematic summary necessary. Thus, this review aims provide comprehensive understanding useful guidelines exploration suitable MOF COF photocatalysts towards appropriate reactions. The commonly used reactions categorized facilitate identification reaction types. From practical viewpoint, fundamentals experimental design, active species, performance evaluation external conditions, discussed detail easy experimentation. Furthermore, latest advances COFs, composites, comprehensively summarized according actual sites, together with discussion structure-property relationship. We believe that study will be helpful researchers novel reticular various synthetic applications.

Язык: Английский

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Molecular engineering of biomimetic donor-acceptor conjugated microporous polymers with full-spectrum response and an unusual electronic shuttle for enhanced uranium(VI) photoreduction

Chemical Engineering Journal, Год журнала: 2023, Номер 466, С. 143285 - 143285

Опубликована: Май 2, 2023

Язык: Английский

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Cobaloximes: selective nitrite reduction catalysts for tandem ammonia synthesis

Energy & Environmental Science, Год журнала: 2023, Номер 16(4), С. 1590 - 1596

Опубликована: Янв. 1, 2023

Herein, we demonstrate cobaloximes as a bioinspired molecular platform for exclusive ammonia synthesis via electrocatalytic NO 2 − reduction (eNO RR), which attained 98.5% faradaic efficiency (FE) under close-to-neutral conditions.

Язык: Английский

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Single-Electron Oxidation-Initiated Enantioselective Hydrosulfonylation of Olefins Enabled by Photoenzymatic Catalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(4), С. 2748 - 2756

Опубликована: Янв. 12, 2024

Controlling the enantioselectivity of hydrogen atom transfer (HAT) reactions has been a long-standing synthetic challenge. While recent advances on photoenzymatic catalysis have demonstrated great potential non-natural photoenzymes, all transformations are initiated by single-electron reduction substrate, with only one notable exception. Herein, we report an oxidation-initiated enantioselective hydrosulfonylation olefins using novel mutant gluconobacter ene-reductase (GluER-W100F-W342F). Compared to known systems, our approach does not rely formation electron donor–acceptor complex between substrates and enzyme cofactor simplifies reaction system obviating addition regeneration mixture. More importantly, GluER variant exhibits high reactivity broad substrate scope. Mechanistic studies support proposed mechanism reveal that tyrosine-mediated HAT process is involved.

Язык: Английский

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Recent advances in FeCl3-photocatalyzed organic reactions via hydrogen-atom transfer

Chinese Chemical Letters, Год журнала: 2024, Номер 35(9), С. 109517 - 109517

Опубликована: Янв. 21, 2024

Язык: Английский

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Red-Light-Based Effective Photocatalysis of a Photosensitive Covalent Organic Framework Triggered Singlet Oxygen

ACS Catalysis, Год журнала: 2024, Номер 14(4), С. 2631 - 2641

Опубликована: Фев. 6, 2024

The direct application of low-energy red light for photochemical transformations is synthetically appealing but practically challenging. Covalent organic frameworks (COFs) exhibit significant potential within this domain, owing to their broad spectrum absorption and prevalence in reactions, despite the fact that these photocatalysts are now mainly focused on using ultraviolet (UV) blue light. In study, an imidazole-linked porphyrin-based COF, PyPor-COF, which exhibits a wide band ranging from 200 700 nm, especially strong 630 expected be applied photocatalytic reactions. PyPor-COF possesses capacity selectively generate singlet oxygen (1O2) with high efficiency, renders it efficient photosensitizer reactions olefin cleavages thioanisole photooxidation under present study demonstrates intriguing prospect photoactive COFs as type II utilization photocatalyses.

Язык: Английский

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Multi‐Functional Integration of Phosphor, Initiator, and Crosslinker for the Photo‐Polymerization of Flexible Phosphorescent Polymer Gels

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(18)

Опубликована: Март 8, 2024

A general approach to constructing room temperature phosphorescence (RTP) materials involves the incorporation of a phosphorescent emitter into rigid host or polymers with high glass transition temperature. However, these often suffer from poor processability and suboptimal mechanical properties, limiting their practical applications. In this work, we developed benzothiadiazole-based dialkene (BTD-HEA), multifunctional remarkable yield intersystem crossing (Φ

Язык: Английский

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Decoupled Artificial Photosynthesis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)

Опубликована: Фев. 27, 2023

Natural photosynthesis (NP) generates oxygen and carbohydrates from water CO2 utilizing solar energy to nourish lives balance levels. Following nature, artificial (AP), typically, overall or splitting, produces fuels chemicals renewable energy. However, hydrogen evolution reduction is inherently coupled with kinetically sluggish oxidation, lowering efficiencies raising safety concerns. Decoupled systems have thus emerged. In this review, we elaborate how decoupled (DAP) evolves NP AP unveil their distinct photoelectrochemical mechanisms in capture, transduction conversion. Advances of DAP are summarized terms photochemical (PC), (PEC), photovoltaic-electrochemical (PV-EC) catalysis based on material device design. The process emphasized. Challenges perspectives future researches also presented.

Язык: Английский

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Interfacial Charge Transfer Regulates Photoredox Catalysis

ACS Central Science, Год журнала: 2024, Номер 10(3), С. 529 - 542

Опубликована: Фев. 26, 2024

Photoredox catalytic processes offer the potential for precise chemical reactions using light and materials. The central determinant is identified as interfacial charge transfer, which simultaneously engenders distinctive behavior in overall reaction. An in-depth elucidation of main mechanism highlighting complexity transfer can occur through both diffusive direct models, revealing its sophisticated design complex transformations. fundamental photophysics uncover these comprehensive applications a clue future development. This research contributes to growing body knowledge on photoredox catalysis sets stage further exploration this fascinating area research.

Язык: Английский

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