Clean Production of Hydrogen Peroxide: A Heterogeneous Solar‐Driven Redox Process

Advanced Energy Materials, Год журнала: 2023, Номер 13(36)

Опубликована: Авг. 6, 2023

Abstract Hydrogen peroxide is an essential chemical that attracting strong attention for energy and environmental applications. However, the struggle between growing market demand unsustainability of conventional anthraquinone method motivates exploration alternative H 2 O production processes. Although several new processes have been proposed, environmental‐friendly solar‐driven attracts most because only inputs water, oxygen, light energy. The rational design functional photo‐responsive catalysts promotes in photocatalytic photoelectrocatalytic approaches. These are, general, achieved by facilitating preferential adsorption key intermediates OOH*/OH*/O*, enhancing absorption, promoting charge separation, accelerating surface transfer with selective number involved charges. This review systematically summarizes strategies photo(electro)catalysts toward via both water oxidation oxygen reduction pathways. Though route perceived as more popular community, emerging a convincing alternative. Furthermore, prevailing hypotheses, state‐of‐the‐art catalysts, critical challenges, perspectives are discussed depth. aims to enhance comprehension this research field promote interest sustainable production.

Язык: Английский

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Stabilizing ruthenium dioxide with cation-anchored sulfate for durable oxygen evolution in proton-exchange membrane water electrolyzers

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

Опубликована: Дек. 7, 2023

Ruthenium dioxide is the most promising alternative to prevailing but expensive iridium-based catalysts for oxygen evolution reaction in proton-exchange membrane water electrolyzers. However, under-coordinated lattice of ruthenium prone over-oxidation, and vacancies are formed at high oxidation potentials under acidic corrosive conditions. Consequently, atoms adjacent oxidized into soluble high-valence derivatives, causing collapse crystal structure leading its poor stability. Here, we report an oxyanion protection strategy prevent formation on surface by forming coordination-saturated oxygen. Combining density functional theory calculations, electrochemical measurements, a suite operando spectroscopies, showcase that barium-anchored sulfate can greatly impede loss extend lifetime ruthenium-based during evolution, while maintaining activity. This work paves new way designing stable active anode toward splitting.

Язык: Английский

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Spaced Double Hydrogen Bonding in an Imidazole Poly Ionic Liquid Composite for Highly Efficient and Selective Photocatalytic Air Reductive H₂O₂ Synthesis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(15)

Опубликована: Фев. 15, 2024

Abstract Photocatalytic oxygen reductive H 2 O production is a promising approach to alternative industrial anthraquinone processes while suffering from the requirement of pure feedstock for practical application. Herein, we report spaced double hydrogen bond (IC−H‐bond) through multi‐component Radziszewski reaction in an imidazole poly‐ionic‐liquid composite (SI‐PIL‐TiO ) and levofloxacin hydrochloride (LEV) electron donor highly efficient selective photocatalytic air production. It found that IC−H‐bond formed by imino (−NH−) group SI‐PIL‐TiO carbonyl (−C=O) LEV can switch active sites characteristic covered state fully exposed one shield strong adsorption N air, propel intenser positive potential more orbitals binding patterns surface establish competitive selectivity chemisorption. Moreover, high enrichment as site 2e − reduction ensures rapid . Therefore, enables total utilization conversion efficiency 94.8 % direct reduction, achieving rate 1518 μmol/g/h 16 23 times compared without groups (PIL‐TiO TiO , respectively.

Язык: Английский

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Solar-driven highly selective conversion of glycerol to dihydroxyacetone using surface atom engineered BiVO4 photoanodes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 28, 2024

Abstract Dihydroxyacetone is the most desired product in glycerol oxidation reaction because of its highest added value and large market demand among all possible products. However, selectively oxidative secondary hydroxyl groups for highly efficient dihydroxyacetone production still poses a challenge. In this study, we engineer surface BiVO 4 by introducing bismuth-rich domains oxygen vacancies (Bi-rich 4-x ) to systematically modulate adsorption enhance photo-induced charge separation photoelectrochemical into conversion. As result, Bi-rich increases photocurrent density from 1.42 4.26 mA cm −2 at 1.23 V vs. reversible hydrogen electrode under AM 1.5 G illumination, as well selectivity 54.0% 80.3%, finally achieving rate 361.9 mmol m h −1 that outperforms reported values. The atom customization opens way regulate solar-driven organic transformation pathway toward carbon chain-balanced product.

Язык: Английский

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Enhanced Charge Transfer via Heterogeneous Doping Promotes Hematite Photoelectrodes for Efficient Solar H₂O₂ Synthesis

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 4369 - 4378

Опубликована: Март 7, 2024

Photoelectrochemical (PEC) water splitting into hydrogen peroxide (H2O2) and (H2) is a promising alternative to energy environmentally intensive production. Bulk electronic surface structures affect the charge transport efficiency catalytic activity of photoelectrode. Herein, we design investigate hematite (Fe2O3) nanorod photoelectrode with hafnium titanium binary dopants for highly selective H2O2 The resultant photoanode shows yield 0.41 μmol min–1 cm–2 at 1.5 VRHE Faradaic 72.2%. Experimental investigations theoretical calculations demonstrate synergistic effect Hf gradient Ti doping on performance. effectively improves crystallinity Fe2O3, which favors improving reducing recombination. Gradient inhibits collapse structure, increases specific area, introduces large number active sites surface. Ti- Hf-codoped Ti/Hf:Fe2O3 kinetics generation, leading high selectivity production suppression O2 This work provides importance hematite-based photoanodes toward regulation competition reactions

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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Improving Charge Transfer Beyond Conventional Heterojunction Photoelectrodes: Fundamentals, Strategies and Applications

Advanced Functional Materials, Год журнала: 2024, Номер 34(46)

Опубликована: Июнь 20, 2024

Abstract Photoelectrochemical (PEC) cells are regarded as a promising approach to convert sunlight chemical fuels, whereas the serious photo‐induced charge recombination of semiconductor photoelectrode hinders its solar conversion efficiency. Over past few decades, designing and constructing heterojunction photoelectrodes via thermodynamically favorable transfer have been proven be effective in boosting separation. However, conventional construction strategy generally introduces incompatible, nonconformal, or defective interfaces, leaving considerable room improve efficiency photoelectrodes. To compensate for unsatisfied efficiency, some novel strategies, such grain boundary engineering, band gap field‐effected etc., adopted provide additional driving force, which significantly improves In this review, these strategies discussed beyond construction, prospects development applications photoanodes also proposed.

Язык: Английский

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Supramolecular catalyst with [FeCl4] unit boosting photoelectrochemical seawater splitting via water nucleophilic attack pathway

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Март 6, 2024

Propelled by the structure of water oxidation co-catalysts in natural photosynthesis, molecular have long been believed to possess developable potential artificial photosynthesis. However, interfacial complexity between light absorber and co-catalyst limits its structural stability charge transfer efficiency. To overcome challenge, a supramolecular scaffold with [FeCl

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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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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