Pauling‐Type Adsorption of O₂ Induced by Heteroatom Doped ZnIn₂S₄ for Boosted Solar‐Driven H₂O₂ Production

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(5)

Опубликована: Дек. 12, 2023

Abstract Breaking the trade‐off between activity and selectivity has perennially been a formidable endeavor in field of hydrogen peroxide (H 2 O ) photosynthesis, especially side‐on configuration oxygen (O on catalyst surface will cause cleavage O−O bonds, which drastically hinders H production performance. Herein, we present an atomically heteroatom P doped ZnIn S 4 with tunable adsorption to accelerate ORR kinetics essential for solar‐driven production. Indeed, spectroscopy characterizations (such as EXAFS situ FTIR) DFT calculations reveal that at substitutional interstitial sites, not only optimizes coordination environment Zn active but also facilitates electron transfer sites improves charge density, avoiding breakage bonds reducing energy barriers As result, is regulated from (Yeager‐type) end‐on (Pauling‐type), resulting accelerated 874.94 2107.66 μmol g −1 h . This finding offers new avenue toward strategic tailoring by rational design photocatalyst.

Язык: Английский

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Covalent organic frameworks bearing Ni active sites for free radical-mediated photoelectrochemical organic transformations

Science Advances, Год журнала: 2023, Номер 9(45)

Опубликована: Ноя. 8, 2023

Photoelectrochemical (PEC) organic transformations occurring at anodes are a promising strategy for circumventing the sluggish kinetics of oxygen evolution reaction. Here, we report free radical-mediated reaction instead direct hole transfer solid/liquid interface PEC oxidation benzyl alcohol (BA) to benzaldehyde (BAD) with high selectivity. A bismuth vanadate (BiVO4) photoanode coated 2,2'-bipyridine-based covalent framework bearing single Ni sites (Ni-TpBpy) was developed drive transformation. Experimental studies reveal that Ni-TpBpy/BiVO4 followed first-order kinetics, boosting formation surface-bound ·OH radicals, which suppressed further BAD and provided nearly 100% selectivity rate 80.63 μmol hour-1 BA-to-BAD conversion. Because alcohol-to-aldehyde conversions involved in valorizations biomass plastics, this work is expected open distinct avenues producing key intermediates great value.

Язык: Английский

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Solar-driven photoelectrochemical conversion of biomass: recent progress, mechanistic insights and potential scalability

Energy & Environmental Science, Год журнала: 2024, Номер 17(20), С. 7459 - 7511

Опубликована: Янв. 1, 2024

This review provides a comprehensive overview on the mechanism of photoelectrochemical biomass conversion and highlights extension dual-function cells for valorization paired with more valuable half-reactions.

Язык: Английский

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Cycad-leaf-like crystalline-amorphous heterostructures for efficient urea oxidation-assisted water splitting

Chinese Journal of Structural Chemistry, Год журнала: 2024, Номер 43(7), С. 100290 - 100290

Опубликована: Апрель 4, 2024

Язык: Английский

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Rapid Surface Reconstruction of In₂S₃ Photoanode via Flame Treatment for Enhanced Photoelectrochemical Performance

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Май 9, 2024

Abstract Surface reconstruction, reorganizing the surface atoms or structure, is a promising strategy to manipulate materials' electrical, electrochemical, and catalytic properties. Herein, rapid reconstruction of indium sulfide (In 2 S 3 ) demonstrated via high‐temperature flame treatment improve its charge collection The process selectively transforms In into diffusionless O layer with high crystallinity. Additionally, it controllably generates bulk sulfur vacancies within few seconds, leading surface‐reconstructed (sr‐In ). When using those sr‐In as photoanode for photoelectrochemical water splitting devices, these dual functions /bulk reduce recombination in region, thus improving photocurrent density stability. With optimized demonstrates significant 8.5 mA cm −2 at 1.23 V versus reversible hydrogen electrode (RHE), marking 2.5‐fold increase compared pristine (3.5 More importantly, exhibits an impressive 7.3 0.6 RHE iodide oxidation reaction. A practical scalable also showcased treatment. This work provides new insights engineering sulfide‐based semiconductors, making breakthrough developing efficient solar‐fuel energy devices.

Язык: Английский

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S-Scheme-Heterojunction LaNiO₃/CdLa₂S₄ Photocatalyst for Solar-Driven CO₂-to-CO Conversion

ACS Applied Nano Materials, Год журнала: 2023, Номер 6(10), С. 8927 - 8936

Опубликована: Май 9, 2023

Visible-light-driven semiconductor-catalyzed CO2 conversion into valuable chemicals and industrial feedstocks is one of the superior pathways to address excess carbon emissions energy shortages. Herein, an innovative step-scheme (S-scheme) heterojunction assembled from bulk CdLa2S4 surface rare-earth perovskite-type oxide LaNiO3 with precisely engineered suitable band alignment employed for selective photocatalytic CO. The optimized 8%-LaNiO3/CdLa2S4 photocatalyst exhibits outstanding CO output up 102.43 μmol h–1 a selectivity about 83.4%, rivaling all similar incumbent reaction systems CO2-to-CO conversion. It highlights effectiveness S-scheme LaNiO3/CdLa2S4 in hindering recombination photogenerated electron–hole pairs. Meanwhile, remarkable apparent quantum efficiency (AQE) as high 6.76% achieved, well still maintained at 99.5% initial value after five cycle tests, revealing repeatability reliability solar-to-chemical In addition, experimentally verified alignment-boosted mechanism proposed. This study construction structurally flexible highly designable heterojunctions, demonstrating potential application carbon-negative

Язык: Английский

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Plasmon-Driven Reaction Selectivity Tuning for Photoelectrochemical H₂O₂ Production

ACS Energy Letters, Год журнала: 2023, Номер 8(12), С. 5192 - 5200

Опубликована: Ноя. 27, 2023

Photoelectrochemical (PEC) H2O2 production has gained interest as a green, promising route to produce valuable chemicals. However, it suffers from low Faradaic efficiency due competing O2 generation. Here, we propose plasmon-driven band structure engineering strategy thermodynamically regulate the product selectivity of metal oxide based PEC photoanode. It is demonstrated that plasmonic near-field generated by periodically patterned Au nanosphere arrays (Au-PAT) effectively modulates surface photovoltage and energy BiVO4 This modulation helps photoinduced charge carriers satisfy thermodynamic potential required shift water oxidation reaction (WOR) high-value H2O2. As result, BiVO4/Au-PAT achieves approximately 3.3 times higher than pristine BiVO4. These findings suggest effectiveness external modulation, originating effect, in regulating WOR pathway, providing an efficient selective value-added production.

Язык: Английский

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Prussian-blue-analogue derived FeNi2S4/NiS nanoframes supported by N-doped graphene for highly efficient methanol oxidation electrocatalysis

Journal of Colloid and Interface Science, Год журнала: 2023, Номер 647, С. 246 - 254

Опубликована: Май 24, 2023

Язык: Английский

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Organic Upgrading through Photoelectrochemical Reactions: Toward Higher Profits

Small Methods, Год журнала: 2023, Номер 8(2)

Опубликована: Июнь 29, 2023

Abstract Aqueous photoelectrochemical (PEC) cells have long been considered a promising technology to convert solar energy into hydrogen. However, the solar‐to‐H 2 (STH) efficiency and cost‐effectiveness of PEC water splitting are significantly limited by sluggish oxygen evolution reaction (OER) kinetics low economic value produced O , hindering practical commercialization cells. Recently, organic upgrading reactions, especially for alternative OERs, received tremendous attention, which improves not only STH but also effectiveness overall reaction. In this review, fundamentals reactant‐product cost analysis reactions briefly reviewed, recent advances made in categorized their reactant substrates, such as methanol, ethanol, glycol, glycerol, complex hydrocarbons, then summarized discussed. Finally, current status, further outlooks, challenges toward industrial applications

Язык: Английский

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Direct generation of high-valent iron-oxo species to eliminate oxytetracycline at circumneutral pH via paper mill sludge ash activating peroxymonosulfate

Chemical Engineering Journal, Год журнала: 2024, Номер 484, С. 150021 - 150021

Опубликована: Март 1, 2024

Язык: Английский

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