A controlled non-radical chlorine activation pathway on hematite photoanodes for efficient oxidative chlorination reactions

Tang, Daojian; Wu, Lei; Li, Liubo; Fu, Niankai; Chen, Chuncheng; Zhang, Yuchao; Zhao, Jincai

doi:10.1039/d3sc06337b

Cited by 6 publications

(1 citation statement)

References 50 publications

(91 reference statements)

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“…The reaction order ( β ) of surface-trapped holes in water oxidation can be obtained by fitting the data. where k is the rate constant of the reaction, and β is the reaction order 56 .…”

Section: Methodsmentioning

confidence: 99%

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

Lu,

Lee,

Lin

et al. 2024

Nat Commun

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Dihydroxyacetone is the most desired product in glycerol oxidation reaction because of its highest added value and large market demand among all possible oxidation products. However, selectively oxidative secondary hydroxyl groups of glycerol for highly efficient dihydroxyacetone production still poses a challenge. In this study, we engineer the surface of BiVO4 by introducing bismuth-rich domains and oxygen vacancies (Bi-rich BiVO4-x) to systematically modulate the surface adsorption of secondary hydroxyl groups and enhance photo-induced charge separation for photoelectrochemical glycerol oxidation into dihydroxyacetone conversion. As a result, the Bi-rich BiVO4-x increases the glycerol oxidation photocurrent density of BiVO4 from 1.42 to 4.26 mA cm−2 at 1.23 V vs. reversible hydrogen electrode under AM 1.5 G illumination, as well as the dihydroxyacetone selectivity from 54.0% to 80.3%, finally achieving a dihydroxyacetone production rate of 361.9 mmol m−2 h−1 that outperforms all reported values. The surface atom customization opens a way to regulate the solar-driven organic transformation pathway toward a carbon chain-balanced product.

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“…The reaction order ( β ) of surface-trapped holes in water oxidation can be obtained by fitting the data. where k is the rate constant of the reaction, and β is the reaction order 56 .…”

Section: Methodsmentioning

confidence: 99%

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

Lu,

Lee,

Lin

et al. 2024

Nat Commun

View full text Add to dashboard Cite

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Regulating Chlorine and Hydrogen Atom Transfer for Selective Photoelectrochemical C─C Coupling by Cu‐coordination Effect at Semiconductor/Electrolyte Interfaces

Li,

Dang,

et al. 2024

Advanced Science

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Semiconductor‐based photoelectrochemical (PEC) organic transformations usually show radical characteristics, in which the reaction selectivity is often difficult to precisely control due to the nonselectivity of radicals. Accordingly, several simple organic reactions (e.g., oxidations of alcohols, aldehydes, and other small molecules) have been widely studied, while more complicated processes like C─C coupling remain challenging. Herein, a synergistic heterogeneous/homogeneous PEC strategy is developed to achieve a controllable radical‐induced C─C coupling reaction mediated by the copper‐coordination effect at the semiconductor/electrolyte interfaces, which additionally exerts a significant impact on the product regioselectivity. Through experimental studies and theoretical simulations, this study reveals that the copper‐chloride complex effectively regulates the formation of chloride radicals, a typical hydrogen atom transfer agent, on semiconductor surfaces and stabilizes the heterogeneous interfaces by suppressing the radical‐induced surface passivation. Taking the Minisci reaction (the coupling between 2‐phenylquinoline and cyclohexane) as a model, the yield of the target C─C coupling product reaches up to 90% on TiO2 photoanodes with a selectivity of 95% and long‐term stability over 100 h. Moreover, such a strategy exhibits a broad scope and can be used for the functionalization of various heteroaromatic hydrocarbons.

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Customized Photoelectrochemical C−N and C−P Bond Formation Enabled by Tailored Deposition on Photoanodes

Wang,

Yang,

Gao

et al. 2024

Angewandte Chemie

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Photoelectrochemistry (PEC) is burgeoning as an innovative solution to organic synthesis. However, the current PEC system suffers limited reaction types and unsatisfactory performances. Herein, we employ efficient BiVO4 photoanode with tailored deposition layers for customizing two PEC approaches toward C–N and C–P formation. Notably, our process proceeds under mild reaction conditions, easily available substrates, and ultra‐low potentials. Beyond photocatalysis and electrocatalysis, customized PEC offers high efficiency, good functional group tolerance, and substantial applicability for decorating drug molecules, highlighting its promising potential to enrich the synthetic toolbox for broader organic chemistry of practical applications.

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A controlled non-radical chlorine activation pathway on hematite photoanodes for efficient oxidative chlorination reactions

Abstract: Photo(electro)catalytic chlorine oxidation has been emerging as a useful method for chemical transformation and environmental remediation. However, the reaction selectivity usually remains low due to the high activity and non-selectivity...

Cited by 6 publications

References 50 publications

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

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

Regulating Chlorine and Hydrogen Atom Transfer for Selective Photoelectrochemical C─C Coupling by Cu‐coordination Effect at Semiconductor/Electrolyte Interfaces

Customized Photoelectrochemical C−N and C−P Bond Formation Enabled by Tailored Deposition on Photoanodes

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