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Dual-facet engineering of surface carboxyl functionalization and interlayer potassium ions regulation in carbon nitride for enhanced CO2 photoreduction

羧基表面修饰与钾离子层间调控双重优化的氮化碳用于增强CO2光还原性能

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Abstract

Simultaneous optimization of surface and interlayer characteristics of graphite-phase carbon nitride (g-C3N4) is crucial for enhanced photogenerated-carrier separation efficiency. Integration of distinct strategies with specific merits for constructing efficacious charge carrier transport pathways from bulk to surface faces challenges. Herein, we proposed a novel carboxyl functional group and potassium (K) ions co-modified g-C3N4 for steering dynamic charge transfer processes. Specifically, carboxyl functional groups were grafted to the surface to substantially improve charge carrier dynamics through the driving force induced by its electron-withdrawing effects. Concurrently, K ions were inserted into the interlayers of g-C3N4 to facilitate interlayer carrier transport by bridging adjacent layers. Such a bi-functional photocatalyst achieves 8.68-fold increase in CO yield compared wtih the pristine g-C3N4 without any cocatalyst or sacrificial agent. This work provides a profound discernment into the directional transport of charge carriers within the surface and interlayers, and presents a promising approach for rational design of photocatalysts with remarkably efficient solar energy conversion.

摘要

对石墨相氮化碳(g-C3N4)的表面和层间结构进行同时优化, 可以显著提高其光生载流子分离效率. 然而, 将具有特定优势的改性策略有效整合, 从而构建由体相到表面的电荷传输通道仍存在巨大挑战. 在此, 我们提出了一种利用羧基和钾离子共修饰g-C3N4的新方法, 用于引导其动态电荷转移过程. 具体而言, 我们将羧基官能团修饰在表面, 通过其吸电子效应产生的驱动力改善表面的载流子动力学. 同时, 我们将钾离子插入g-C3N4层间, 通过连接相邻层间促进载流子的跨层传输. 该双功能光催化剂在无需助催化剂或牺牲剂的气固体系中实现了高达17.93 µmol g−1 h−1的CO产出速率, 比未改性的g-C3N4高出8.68倍. 这项工作有望进一步加深我们对光催化剂材料体相和层间区域载流子定向迁移机制的理解.

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Acknowledgements

This work was partially supported by the National Natural Science Foundation of China (22272019), and Sichuan Science and Technology Program (2022ZYD0039, 2022NSFSC1213 and 2023NSFSC1069). Dr. Tingchuan Zhou is acknowledged for the SEM observation, from the Analysis and Testing Center, University of Electronic Science and Technology of China.

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Authors and Affiliations

  1. State Key Laboratory of Electronic Thin Film and Integrated Devices, School of Electronic Science and Engineering, University of Electronic Science and Technology of China, Chengdu, 610054, China

    Chen Guan  (关晨), Yulong Liao  (廖宇龙) & Quanjun Xiang  (向全军)

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  1. Chen Guan  (关晨)
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  2. Yulong Liao  (廖宇龙)
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  3. Quanjun Xiang  (向全军)
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Contributions

Author contributions Guan C conceived the idea, designed the experiments, and wrote the original draft. Liao Y participated in the design and layout of the pictures and reviewed the manuscript. Xiang Q supervised the work, and reviewed and revised the manuscript.

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Correspondence to Quanjun Xiang  (向全军).

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Conflict of interest The authors declare that they have no conflict of interest.

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Supplementary information Supporting data are available in the online version of the paper.

Chen Guan is a PhD candidate in Prof. Quanjun Xiang’s group at the University of Electronic Science and Technology of China. His current research interests mainly focus on the design of high-performance CO2 photocatalysts and the study of mechanism for CO2 reduction.

Quanjun Xiang received his PhD degree in materials chemistry & physics in 2012 from Wuhan University of Technology. He was a postdoctoral fellow at the City University of Hong Kong from 2013 to 2015 and an associate professor from 2012 to 2017 at Huazhong Agricultural University. He is now a professor at the School of Electronic Science and Engineering, University of Electronic Science and Technology of China. His research interests include semiconductor photocatalytic materials, photocatalytic hydrogen production, and photocatalytic CO2 reduction to hydrocarbon fuels.

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Dual-facet engineering of surface carboxyl functionalization and interlayer potassium ions regulation in carbon nitride for enhanced CO2 photoreduction

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Guan, C., Liao, Y. & Xiang, Q. Dual-facet engineering of surface carboxyl functionalization and interlayer potassium ions regulation in carbon nitride for enhanced CO2 photoreduction. Sci. China Mater. 67, 473–483 (2024). https://doi.org/10.1007/s40843-023-2703-0

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