Precision Molecular Engineering of Carbon Nitride for Efficient and Selective Photoreduction of CO₂ to C₂H₆ in Pure Water

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 7, 2025

Abstract Photocatalytic CO 2 reduction into high‐value C 2+ products such as H 6 is of great importance but challenging due to their multi‐electron steps and high energy barrier C─C coupling. Moreover, improving its solar‐to‐chemical (STC) conversion efficiency in pure water beyond the current 1% empirical value also a significant challenge. Herein, graphite carbon nitride (g‐C 3 N 4 ) nanosheets with controllable (C) doping nitrogen (N) vacancies (PCCN‐x) are designed through biochar‐tailored protocol for efficiently selectively photo‐converting . The optimal PCCN‐10 photocatalyst enables achievement an exceptional activity 99.14 µmol g −1 h selectivity 80.33% over 20 water. A record STC ≈1.13% solar fuel production from O vapor achieved without any other inputs. Outdoor tests demonstrated impressive ‐to‐C photo‐conversion rate 43.17 water, stable 50 period. Critically, experimental theoretical calculations further confirm pivotal role bridged sites activating molecules promoting formation coupling intermediate ( * OCCO), which very beneficial performance this work photocatalytic fuels paves way large‐scale broader sustainable applications.

Язык: Английский

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Ir-O-Mn embedded in porous nanosheets enhances charge transfer in low-iridium PEM electrolyzers

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 2, 2025

Using metal oxides to disperse iridium (Ir) in the anode layer proves effective for lowering Ir loading proton exchange membrane water electrolyzers (PEMWE). However, reported low-Ir-based catalysts still suffer from unsatisfying electrolytic efficiency and durability under practical industrial working conditions, mainly due insufficient catalytic activity mass transport catalyst layer. Herein we report a class of porous heterogeneous nanosheet with abundant Ir-O-Mn bonds, achieving notable 4 A mgIr−1 oxygen evolution reaction at an overpotential 300 mV, which is 150.6 times higher than that commercial IrO2. bonds are unraveled serve as efficient charge-transfer channels between in-situ electrochemically-formed IrOx clusters MnOx matrix, fostering generation stabilization highly active Ir3+ species. Notably, Ir/MnOx-based PEMWE demonstrates comparable performance 10-fold lower (0.2 mgIr cm−2), taking low cell voltage 1.63 V deliver 1 cm−2 over h, positions it among elite Ir-based PEMWEs. Building proton-exchange electrolyzer remains important but challenging. Here, authors Ir/MnOx rich generate stabilize species, enhancing both stability.

Язык: Английский

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Cooperative Atomic Palladium Site and Island-Distributed S-Scheme Heterostructure for Photocatalytic C₂H₆ Production

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 3558 - 3569

Опубликована: Фев. 12, 2025

Язык: Английский

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Constructing an Active Sulfur‐Vacancy‐Rich Surface for Selective *CH₃‐CH₃ Coupling in CO₂‐to‐C₂H₆ Conversion With 92% Selectivity

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 6, 2024

Abstract To achieve high selectivity in photocatalytic CO 2 reduction to C 2+ products, increasing the number of adsorption sites and lowering energy barriers for key intermediates are critical. A ZnIn S 4 (ZIS)/MoO 3‐x (Z‐M) photocatalyst is presented, which plasmonic MoO generates hot electrons, creating a multielectron environment ZIS that facilitates efficient C─C coupling reactions. Density functional theory (DFT) calculations reveal reduces formation sulfur vacancies (S V ) ZIS, thereby enhancing activation. The ‐rich surface lowers barrier forming HCOO * −0.33 eV whereas COOH 0.77 eV. Successive hydrogenation leads CH , converts 3 with an −0.63 ‐CH 0.54 eV, lower than 0.73 form H . Thus, Z‐M preferentially produces 6 over Under visible light, achieves ‐to‐C conversion rate 467.3 µmol g −1 h 92.0% selectivity. This work highlights dual role photocatalysts improving production reduction.

Язык: Английский

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Synergetic Effect of Heterojunction and Sulfur Vacancy on ZnIn₂S₄/CeO₂ to Enhance the Photocatalytic Performance of 5‐Hydroxymethylfurfural into 2,5‐Diformylfuran

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Окт. 18, 2024

Abstract The efficient separation of photocarriers and facile generation superoxide radicals are crucial for enhancing the performance photocatalysts in selectively photo‐oxidizing 5‐hydroxymethylfurfural (HMF) into 2,5‐diformylfuran (DFF). Herein, a ZnIn 2 S 4 /CeO composite with S‐scheme heterojunction sulfur vacancies (S V ) is successfully developed through one‐step hydrothermal method. optimal catalyst ‐ZnIn exhibits excellent catalytic activity 100% conversion HMF 96.1% selectivity DFF 80 min under ambient conditions, production rate up to 952.6 µmol g −1 h . Intriguingly, remains significant even when concentration increased from 8 100 mм. Experimental theoretical investigations discover that synergistic effect contribute activation oxygen, which facilitate radicals, thus boosting oxidation reactions.

Язык: Английский

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Study on the high-efficiency CO2 mineralization reaction mechanism of thermally modified materials from neutralized gypsum residue driven by sulfur vacancies in an aqueous environment

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 163591 - 163591

Опубликована: Май 1, 2025

Язык: Английский

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Computational Screening of Asymmetric Dual Sites by Bader Charge Variation Facilitates C–C Coupling for CO₂ Photoreduction to C₂H₄

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 12(47), С. 17336 - 17346

Опубликована: Ноя. 12, 2024

Constructing asymmetric dual active sites is an effective strategy to promote formation of the C2 product in photocatalytic CO2 reactions, attributed suppressed dipole–dipole repulsion facilitating C–C coupling. However, information about extent asymmetry still absent, making precise design a challenge. Herein, Bader charge variation (Δq) intermetallics was chosen as descriptor select sites, where linear relation between Δq and adsorption energy intermediate found. From 66 intermetallic candidates, FePt stood out, with = 0.503 e–, predicted be promising candidate. Experimentally, nanoparticles were synthesized loaded onto substrate TiO2 (denoted FePt/TiO2), CoPt NiPt also reference samples. X-ray photoelectron spectroscopy absorption results reveal electron enrichment on Pt depletion Fe, DFT calculations uncover that distribution strengthened intermediate's coupling, reducing free barrier 0.68 eV. As result, FePt/TiO2 showed efficient production C2H4 (4.8 μmol g–1 h–1) absence photosensitizers scavengers, higher than amounts obtained CoPt/TiO2, NiPt/TiO2, (2.1, 1.5, 0 h–1, respectively). This study offers insights into criteria motivate photoreduction.

Язык: Английский

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Employing facile molten-salt strategy towards erbium ornamentation over CuInS2 for upgrading visible-light-driven hydrogen production and Cr(VI) reduction

Journal of environmental chemical engineering, Год журнала: 2024, Номер 12(6), С. 114788 - 114788

Опубликована: Ноя. 13, 2024

Язык: Английский

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Anti-Site Defect-Induced Cascaded Sub-Band Transition in CuInS₂ Enables Infrared Light-Driven CO₂ Reduction

ACS Nano, Год журнала: 2024, Номер 18(52), С. 35480 - 35489

Опубликована: Дек. 18, 2024

Photocatalytic CO2 conversion is a promising approach to simultaneously mitigate climate change and alleviate the energy crisis. However, infrared light, which constitutes nearly half of solar energy, has not been effectively utilized yet. In this work, we discover photogenerated charge transition mechanism in CuInS2 with intrinsic InCu antisite defects for synergistic utilization full-spectrum photons. Femtosecond transient absorption spectroscopy DFT calculation unveil an intermediate band induced by defects, where cascaded sub-band could be realized high-energy photons (UV–vis) low-energy (IR), thus improving range light as well efficiency carriers. situ Kelvin probe force microscopy demonstrates that generation photoexcited electrons greatly enhanced through full spectrum light. Moreover, X-ray photoelectron diffuse reflectance Fourier transform reveal also enhance adsorption activation H2O on catalyst surface. As result, CO production rate under reaches 19.9 μmol g–1 h–1, more than 7-fold increase over UV–vis irradiation.

Язык: Английский

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Pt single atoms promoting the construction of asymmetric double sites to achieve highly selective photoreduction of CO2 to ethylene

Journal of Colloid and Interface Science, Год журнала: 2024, Номер 683, С. 301 - 309

Опубликована: Дек. 20, 2024

Язык: Английский

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