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Ethyl-activated carbon nitride for efficient photocatalytic CO2 conversion

乙基修饰的氮化碳增强光催化CO2转化

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Abstract

Surface functional groups of photocatalysts play a key role in the transfer of photogenerated carriers and the active site of the reaction, which severely influence the photocatalytic conversion process. Therefore, reasonable and accurate regulation of surface groups can greatly optimize photocatalytic performance. Herein, we performed optimization on the unpolymerized NH2 group of carbon nitride (g-C3N4) by introducing an ethyl group with a strong electron-donating ability to obtain the E-CN photocatalysts. X-ray photoelectron spectroscopy confirmed the successful embedding of the ethyl group. Time-resolved spectroscopy and density function theory calculations verified that the photogenerated carrier changes in a favorable direction. Finally, the Gibbs free energy showed that E-CN significantly decreases the energy barrier of CO2 conversion to *COOH. The results revealed that the conversion rate of CO2 to CO is 47.08 µmol g−1 h−1. This work offers a reliable reference to improve the performance of photocatalysts by optimizing their surface functional groups.

摘要

光催化剂的表面官能团对光生载体的转移和反应的活性位点起着关键作用, 对光催化转化过程影响很大. 因此, 合理准确地调控表面基团可以极大地优化光催化性能. 本文通过引入给电子能力强的乙基, 对氮化碳(g-C3N4)未聚合的NH2基团进行优化. 通过X射线光电子能谱证实了乙基包埋的成功. 时间分辨光谱和密度泛函理论(DFT)计算证实了光生载流子沿有利方向变化. 最后, Gibbs自由能表明, 乙基改性的氮化碳具有显著降低的CO2转化为*COOH的能垒. 其CO2到CO的转化率为47.08 µmol g−1 h−1. 本研究为通过优化表面官能团来提高光催化剂性能的研究提供了可靠参考.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2022YFE0126500), the National Natural Science Foundation of China (22278169, 22150610467, 52372253, and 51973078), the Excellent Scientific Research and Innovation Team of the Education Department of Anhui Province (2022AH010028), the Major projects of Education Department of Anhui Province (2022AH040068), the Key Foundation of Educational Commission of Anhui Province (2022AH050396 and 2022AH050376), Anhui Provincial Quality Engineering Project (2022sx13), the Innovation Fund for Postgraduates of Huaibei Normal University (CX2023038), Surplus Funds to Expand Research Projects of Huaibei Normal University (2023ZK045), and the Open Project from the Key Laboratory of Green and Precise Synthetic Chemistry and Applications (2020KF07).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, Anhui Province Key Laboratory of Pollutant Sensitive Materials and Environmental Remediation, Huaibei Normal University, Huaibei, 235000, China

    Dongdong Chen  (陈冻冻), Zhongliao Wang  (王中辽), Jinfeng Zhang  (张金锋) & Kai Dai  (代凯)

  2. School of Physics, Central South University, Changsha, 410083, China

    Junwei Fu  (傅俊伟)

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  1. Dongdong Chen  (陈冻冻)
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  2. Zhongliao Wang  (王中辽)
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  3. Junwei Fu  (傅俊伟)
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Contributions

Author contributions Chen D wrote the paper. Wang Z helped with the calculation. Fu J and Zhang J gave some valuable suggestions on the revision. Dai K reviewed the manuscript and finalized the final version. All authors contributed to the general discussion.

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Correspondence to Junwei Fu  (傅俊伟), Jinfeng Zhang  (张金锋) or Kai Dai  (代凯).

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Additional information

Dongdong Chen is currently pursuing an MS degree at the School of Physics and Electronic Information, Huaibei Normal University. His research interests mainly focus on semiconductor photocatalysis.

Jinfeng Zhang received his MS degree from Ningxia University in 2007 and his PhD degree from Wuhan University of Technology in 2016. He carried out postdoctoral research at Wuhan University of Technology from 2016 to 2018. Since the end of 2007, he has been working at Huaibei Normal University. His research interests mainly focus on semiconductor photocatalysis.

Kai Dai is a professor at Huaibei Normal University. He received his PhD degree from Shanghai University in 2007. He worked at Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences in 2007, and then at Huaibei Normal University in 2010. His research interests mainly focus on energy conversion and storage.

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Chen, D., Wang, Z., Fu, J. et al. Ethyl-activated carbon nitride for efficient photocatalytic CO2 conversion. Sci. China Mater. 67, 541–549 (2024). https://doi.org/10.1007/s40843-023-2770-8

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