Efficient photocatalytic H2 evolution, CO2 reduction and N2 fixation coupled with organic synthesis by cocatalyst and vacancies engineering

Meng, Sugang; Chen, Cheng; Gu, Xiaomeng; Wu, Huihui; Meng, Qiangqiang; Zhang, Jinfeng; Chen, Shifu; Fu, Xianliang; Liú, Dan; Lei, Weiwei

doi:10.1016/j.apcatb.2020.119789

Cited by 152 publications

(77 citation statements)

References 46 publications

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“…Aromatic aldehydes represented by anisaldehyde (AA) are important perfumes and medicinal products . Photocatalytic selective conversion of aromatic alcohol to the corresponding aldehyde provides a mild alternative to thermal-driven catalysis. − At present, most photocatalytic systems use acetonitrile or trifluoro toluene as solvents to oxidize 4-methoxybenzyl alcohol (4-MBA) driven by superoxide anion radicals. − Furthermore research studies suggest that using pure water replacing toxic organic solvents with high efficiency would be a worthwhile pursuit for good eco-chemical industry. , In addition, an aqueous system can maximize the utilization of photoexcited electrons to evolve H 2 , which is considered a sustainable source to alleviate the shortage of fossil fuels. − The first attempt of selective oxidation of 4-MBA to AA in aqueous solution was with TiO 2 , showing a low selectivity limited to ca. 41% under visible light irradiation .…”

Section: Introductionmentioning

confidence: 99%

Modulating the Energy Band to Inhibit the Over-oxidation for Highly Selective Anisaldehyde Production Coupled with Robust H₂ Evolution from Water Splitting

et al. 2021

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Aromatic aldehydes are important precursors for pharmaceutical, agricultural, and synthetic chemistry. Compared to thermal catalysis and organic solvent synthesis systems, photocatalytic selective conversion of aromatic alcohol to the corresponding aldehyde coupled with H 2 evolution in pure water represents an alternative due to the mild reaction conditions and the renewable energy production. However, this coupling reaction in aqueous solution is still limited by the low selectivity and conversion due to the over-oxidation. Herein, we demonstrated that the typical type-II heterojunction photocatalysts with a moderate energy band can restrain over-oxidation. This strategy effectively separates the photoexcited charge and hampers the complicated radical oxidation process, thus favoring the generation of aldehyde with the robust evolution of H 2 under visible light illumination without any cocatalyst. The system realizes an anisaldehyde (AA) selectivity of over 99% and a 4-methoxybenzyl alcohol (4-MBA) conversion of over 99% in a low concentration of 4-MBA. Furthermore, when the amount of 4-MBA is expanded to the mL level, the system is able to maintain a robust H 2 evolution rate of 291.8 mmol•g −1 •h −1 at over 99% selectivity for AA. Mechanistic investigation reveals that the photoexcited hole with a moderate potential directly reacts with 4-MBA by promoting the formation of a benzyl carbon radical with abstraction of a hydrogen atom due to the inhibition of •OH formation. Moreover, the effective contact between water, photocatalysts, and 4-MBA also contributes to enhance the conversion activity and improve the practical application potential. The method can be further extended to various aromatic alcohols and offers a concept for highly selective synthesis of high-added value chemicals coupled with H 2 evolution in pure water.

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Section: Introductionmentioning

confidence: 99%

Modulating the Energy Band to Inhibit the Over-oxidation for Highly Selective Anisaldehyde Production Coupled with Robust H₂ Evolution from Water Splitting

et al. 2021

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“…The calculated work functions of CoP, CoS 2 , and the CoP/CoS 2 heterostructure also confirm the direction of electron flow at the interface of the CoP/CoS 2 heterostructure. The work functions of CoP, CoS 2 , and CoP/CoS 2 were calculated to be 4.292, 4.414, and 4.334 eV, respectively, based on DFT calculations (Figure ), signifying that when CoP and CoS 2 are in contact, electrons are transferred from CoP, which has a smaller work function, to CoS 2 , which has a higher work function. , Thus, the DFT calculations confirmed that CoP and CoS 2 formed a lattice-matched CoP/CoS 2 heterostructure with electron redistribution at the interface and also explained that the reason for the better cocatalytic effect of the CoP/CoS 2 heterostructure is that the CoP/CoS 2 heterostructure presented higher electrical conductivity and lower H* adsorption energy.…”

Section: Resultsmentioning

confidence: 76%

Lattice-Matched CoP/CoS₂ Heterostructure Cocatalyst to Boost Photocatalytic H₂ Generation

Hong

Wang

et al. 2021

Inorg. Chem.

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Transition-metal phosphides and sulfides are considered as promising cocatalysts for the photocatalytic hydrogen evolution reaction (HER), and the cocatalytic effect can be improved by directed heterostructure engineering. In this study, a novel lattice-matched CoP/CoS 2 heterostructure having a nanosheet morphology was developed as an HER cocatalyst and integrated in situ onto graphitic carbon nitride (g-C 3 N 4 ) nanosheets via a successive phosphorization and vulcanization route. First-principles density functional theory calculations evidenced that the construction of the lattice-matched CoP/CoS 2 heterostructure resulted in the redistribution of interface electrons, enhanced metallic characteristics, and improved H* adsorption. As a result of these effects, the CoP/CoS 2 heterostructure cocatalyst formed a 2D/2D Schottky junction with the g-C 3 N 4 nanosheets, thus promoting photoelectron transfer to CoP/CoS 2 and realizing fast charge-carrier separation and good HER activity. As expected, the CoP/CoS 2 heterostructure exhibited excellent cocatalytic activity, and the optimal loading of the cocatalyst on g-C 3 N 4 enhanced its HER activity to 3.78 mmol g −1 h −1 . This work furnishes a new perspective for the development of highly active noble-metal-free cocatalysts via heterostructure engineering for water splitting applications.

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“…The TRPL decay plots are fitted via the bi-exponential kinetic function ( I ( t ) = A 1 exp(− t / τ 1 ) + A 2 exp(− t / τ 2 )), in which two decay components are obtained. 48 In detail, τ 1 and τ 2 are regarded as the non-radiative recombination of charge carriers in the defects and the recombination of free excitons, respectively. The average lifetime of Bi 2 WO 6 -OVs and 1% FeS 2 /Bi 2 WO 6 is displayed in Fig.…”

Section: Resultsmentioning

confidence: 99%

Photo-Fenton and oxygen vacancies' synergy for enhancing catalytic activity with S-scheme FeS₂/Bi₂WO₆ heterostructure

Zhang

Wang

et al. 2022

Catal. Sci. Technol.

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Efficient photocatalytic H2 evolution, CO2 reduction and N2 fixation coupled with organic synthesis by cocatalyst and vacancies engineering

Cited by 152 publications

References 46 publications

Modulating the Energy Band to Inhibit the Over-oxidation for Highly Selective Anisaldehyde Production Coupled with Robust H₂ Evolution from Water Splitting

Modulating the Energy Band to Inhibit the Over-oxidation for Highly Selective Anisaldehyde Production Coupled with Robust H₂ Evolution from Water Splitting

Lattice-Matched CoP/CoS₂ Heterostructure Cocatalyst to Boost Photocatalytic H₂ Generation

Photo-Fenton and oxygen vacancies' synergy for enhancing catalytic activity with S-scheme FeS₂/Bi₂WO₆ heterostructure

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Efficient photocatalytic H2 evolution, CO2 reduction and N2 fixation coupled with organic synthesis by cocatalyst and vacancies engineering

Cited by 152 publications

References 46 publications

Modulating the Energy Band to Inhibit the Over-oxidation for Highly Selective Anisaldehyde Production Coupled with Robust H2 Evolution from Water Splitting

Modulating the Energy Band to Inhibit the Over-oxidation for Highly Selective Anisaldehyde Production Coupled with Robust H2 Evolution from Water Splitting

Lattice-Matched CoP/CoS2 Heterostructure Cocatalyst to Boost Photocatalytic H2 Generation

Photo-Fenton and oxygen vacancies' synergy for enhancing catalytic activity with S-scheme FeS2/Bi2WO6 heterostructure

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Modulating the Energy Band to Inhibit the Over-oxidation for Highly Selective Anisaldehyde Production Coupled with Robust H₂ Evolution from Water Splitting

Modulating the Energy Band to Inhibit the Over-oxidation for Highly Selective Anisaldehyde Production Coupled with Robust H₂ Evolution from Water Splitting

Lattice-Matched CoP/CoS₂ Heterostructure Cocatalyst to Boost Photocatalytic H₂ Generation

Photo-Fenton and oxygen vacancies' synergy for enhancing catalytic activity with S-scheme FeS₂/Bi₂WO₆ heterostructure