Electron-rich pyrimidine rings enabling crystalline carbon nitride for high-efficiency photocatalytic hydrogen evolution coupled with benzyl alcohol selective oxidation

Zhi, Lin; Wang, Yiqing; Nga, Ta Thi Thuy; Zhang, Jie; Wang, Ruizhe; Zhang, Zhengqi; Xu, Yan; Zhao, Daqing; Dong, Chung‐Li; Shen, Shaohua

doi:10.1039/d3ey00055a

Cited by 13 publications

(1 citation statement)

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“…Thus, different approaches, e.g., introducing light‐absorbing groups, increasing crystallinity, constructing heterojunctions and loading cocatalysts, etc., have been explored to modify the molecular, crystal and band structures of PCN for efficient photocatalysis. For example, through self‐assembly and molten‐salt annealing two‐step approach, electron‐rich pyrimidine rings could be introduced into the molecular structure of high crystalline PCN, [ 11 ] which elevated the valence band position to narrow the bandgap and thus extend the optical absorption range, contributing to the improved photocatalytic activity for benzyl alcohol selective oxidation and hydrogen evolution. Wang et al., successfully prepared high crystalline PCN by thermal treatment in KCl/LiCl molten salt, which exhibited a high apparent quantum yield (AQY) of 50.7% at 405 nm for photocatalytic hydrogen production, due to the narrowed bandgap and then the extended optical absorption.…”

Section: Introductionmentioning

confidence: 99%

Cayanamide Group Functionalized Crystalline Carbon Nitride Aerogel for Efficient CO₂ Photoreduction

Li,

Xue,

Gao

et al. 2023

Adv Funct Materials

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For photocatalytic CO2 reduction, traditional amorphous polymeric carbon nitride (PCN) has suffered from fast photoexcited electron‐hole recombination and low specific surface area, resulting in low photocatalytic activity. Herein, starting from thermally polymerized PCN, cayanamide groups (─CN) functionalized crystalline carbon nitride (CCN) self‐supporting aerogels are obtained through a molten‐salt and self‐assembly two‐step strategy, which realized efficient photocatalytic CO2 reduction into CO as the main reduction products and O2 as the oxidation product, with CO evolution rate and selectivity reaching 25.7 µmol g−1 h−1 and 93.8%, respectively. It is revealed that the self‐supporting porous aerogel structure can enhance the mass transport of reactants and products, and increase the light absorption ability via multiple photon reflection. With charge carrier separation greatly enhanced in CCN aerogels with high crystallinity as revealed by charge carrier dynamics investigations, theoretical calculations and in situ spectral characterizations evidence that the introduced ─CN groups would act as the active sites for photoreduction of CO2 into CO, with energy barrier greatly reduced for the formation of COOH* intermediates, the rate‐determining step for CO2─to─CO reduction. This work demonstrates a novel and controllable strategy to develop semiconducting polymers with crystal, molecular and morphological structures synergistically modulated for highly efficient and selective photocatalytic CO2 reduction.

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Section: Introductionmentioning

confidence: 99%

Cayanamide Group Functionalized Crystalline Carbon Nitride Aerogel for Efficient CO₂ Photoreduction

Li,

Xue,

Gao

et al. 2023

Adv Funct Materials

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In Situ Construction of Fuzzy Sea‐Urchin ZnIn₂S₄/W₁₈O₄₉: Leveraging Interfacial Z‐Scheme Redox Sites toward Cooperative Electron–Hole Utilization in Photocatalysis

Ling,

Kok,

Zhang

et al. 2024

Adv Funct Materials

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Despite the significant milestones in the half‐reduction process of photocatalysis, challenges remain in fully utilizing electron–hole pairs in the simultaneous redox reactions. Herein, a Z‐scheme ZnIn2S4/W18O49 (ZW) hybrid with complementary band edge potential is in situ constructed. The resultant fuzzy 1D‐assembled sea‐urchin photocatalyst demonstrates an optimal H2 and benzaldehyde yield of 122 and 106 µmol h−1 under λ > 420 nm light irradiation. This sacrificial‐agent‐free system entails solar‐to‐hydrogen (STH) and apparent quantum efficiency (AQE) values of 0.466% and 2.48% (420 nm), respectively, surpassing most of the recently reported photocatalytic systems without the aid of noble metal cocatalysts. The outstanding performance is mainly attributed to the synergistic formation of intimate Z‐scheme heterojunction and the induction of localized surface plasmon resonances. Comprehensive characterization studies prove the direct injection of energetic hot electrons to promote the number of long‐lived active electrons. Besides, electron paramagnetic resonance and scavenger tests clarify the complicated mechanistic puzzle of the dual‐redox reaction, where benzaldehyde is formed dominantly via O─H activation followed by C─H cleavage of benzyl alcohol over ZW hybrid. Lastly, the universal use of the ZnIn2S4/W18O49 composites is testified in various dual‐redox systems. This study offers a novel outlook for designing dual‐functioning heterojunctions toward a feasible photoredox application.

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Bio‐Inspired Supramolecular Self‐Assembled Carbon Nitride Nanostructures for Photocatalytic Water Splitting

Dharmarajan,

Vidyasagar,

Yang

et al. 2023

Advanced Materials

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Fast production of hydrogen and oxygen in large amounts at an economic rate is the need of the hour to cater to the needs of the most awaited hydrogen energy, a futuristic renewable energy solution. Production of hydrogen through a simple water splitting through visible light photocatalytic approach using sunlight is considered as one of the most promising and sustainable approaches for generating clean fuels. For this purpose, a variety of catalytic techniques and novel catalysts are being investigated. Among these catalysts, carbon nitride is presently deemed as one of the best candidates for the visible light photocatalysis due to its unique molecular structure and adequate visible‐range band gap. Its band gap can further be engineered by structural and morphological manipulation or by, doping/hybridization. Among numerous synthetic approaches for carbon nitrides, supramolecular self‐assembly is one of the recently developed elegant bottom‐up strategies as it is bio‐inspired and provides a facile and eco‐friendly route to synthesise high surface area carbon nitride with superior morphological features and other semiconducting and catalytic properties. The current review article broadly covers supramolecular self‐assembly synthesis of carbon nitride nanostructures and their photocatalytic water splitting application and provides a comprehensive outlook on the future directions.This article is protected by copyright. All rights reserved

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Electron-rich pyrimidine rings enabling crystalline carbon nitride for high-efficiency photocatalytic hydrogen evolution coupled with benzyl alcohol selective oxidation

Abstract: Photocatalytic water splitting over polymeric carbon nitride (PCN) has been seriously limited by the poor charge carrier transfer ability and the sluggish four-electron water oxidation kinetics. Herein, crystalline carbon nitride...

Cited by 13 publications

References 46 publications

Cayanamide Group Functionalized Crystalline Carbon Nitride Aerogel for Efficient CO₂ Photoreduction

Cayanamide Group Functionalized Crystalline Carbon Nitride Aerogel for Efficient CO₂ Photoreduction

In Situ Construction of Fuzzy Sea‐Urchin ZnIn₂S₄/W₁₈O₄₉: Leveraging Interfacial Z‐Scheme Redox Sites toward Cooperative Electron–Hole Utilization in Photocatalysis

Bio‐Inspired Supramolecular Self‐Assembled Carbon Nitride Nanostructures for Photocatalytic Water Splitting

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Electron-rich pyrimidine rings enabling crystalline carbon nitride for high-efficiency photocatalytic hydrogen evolution coupled with benzyl alcohol selective oxidation

Abstract: Photocatalytic water splitting over polymeric carbon nitride (PCN) has been seriously limited by the poor charge carrier transfer ability and the sluggish four-electron water oxidation kinetics. Herein, crystalline carbon nitride...

Cited by 13 publications

References 46 publications

Cayanamide Group Functionalized Crystalline Carbon Nitride Aerogel for Efficient CO2 Photoreduction

Cayanamide Group Functionalized Crystalline Carbon Nitride Aerogel for Efficient CO2 Photoreduction

In Situ Construction of Fuzzy Sea‐Urchin ZnIn2S4/W18O49: Leveraging Interfacial Z‐Scheme Redox Sites toward Cooperative Electron–Hole Utilization in Photocatalysis

Bio‐Inspired Supramolecular Self‐Assembled Carbon Nitride Nanostructures for Photocatalytic Water Splitting

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Product

Resources

About

Cayanamide Group Functionalized Crystalline Carbon Nitride Aerogel for Efficient CO₂ Photoreduction

Cayanamide Group Functionalized Crystalline Carbon Nitride Aerogel for Efficient CO₂ Photoreduction

In Situ Construction of Fuzzy Sea‐Urchin ZnIn₂S₄/W₁₈O₄₉: Leveraging Interfacial Z‐Scheme Redox Sites toward Cooperative Electron–Hole Utilization in Photocatalysis