压电增强氢键网络调控氟化氮化碳实现CO2还原的100% CO选择性

doi:10.1016/S1872-2067(26)65035-8

催化学报 ›› 2026, Vol. 85: 130-142.DOI: 10.1016/S1872-2067(26)65035-8

压电增强氢键网络调控氟化氮化碳实现CO₂还原的100% CO选择性

何邢晨^a, 邵俊辉^a, 李娜君^a(), 陈冬赟^a, 李华^a, 徐庆锋^a, 王浩志^b(), 路建美^a^,^c()

^a 苏州大学材料与化学化工学院, 苏州纳米科技协同创新中心, 江苏苏州 215123
^b 海南大学材料科学与工程学院, 热带海洋工程材料与材料评价国家重点实验室, 海南海口 570228
^c 苏州实验室, 江苏苏州 215123

收稿日期:2025-12-17 接受日期:2026-01-09 出版日期:2026-06-18 发布日期:2026-05-18
通讯作者: *电子信箱: linajun@suda.edu.cn (李娜君),
lujm@suda.edu.cn (路建美),
hzwang001@hainanu.edu.cn (王浩志).
基金资助:
国家自然科学基金(22578299);国家自然科学基金(U24A20535);国家自然科学基金(22438009);国家自然科学基金(52301011);江苏省基础研究计划(BK20251897);江苏省基础研究计划(BK20243002);江苏省高等学校重点学科发展计划(PAPD)

Metal-free fluorinated carbon nitride with piezo-boosted hydrogen-bonding networks enable 100% CO selectivity in CO₂ reduction

Xingchen He^a, Junhui Shao^a, Najun Li^a(), Dongyun Chen^a, Hua Li^a, Qingfeng Xu^a, Haozhi Wang^b(), Jianmei Lu^a^,^c()

^a Collaborative Innovation Center of Suzhou Nano Science and Technology, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, Jiangsu, China
^b State Key Laboratory of Tropic Ocean Engineering Materials and Materials Evaluation, School of Materials Science and Engineering, Hainan University, Haikou 570228, Hainan, China
^c Suzhou Laboratory, Suzhou 215123, Jiangsu, China

Received:2025-12-17 Accepted:2026-01-09 Online:2026-06-18 Published:2026-05-18
Contact: *E-mail: linajun@suda.edu.cn (N. Li),
lujm@suda.edu.cn (J. Lu),
hzwang001@hainanu.edu.cn (H. Wang).
Supported by:
National Natural Science Foundation of China(22578299);National Natural Science Foundation of China(U24A20535);National Natural Science Foundation of China(22438009);National Natural Science Foundation of China(52301011);Basic Research Program of Jiangsu province(BK20251897);Basic Research Program of Jiangsu province(BK20243002);Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)

摘要/Abstract

摘要：

随着全球碳排放问题日益严峻, 开发绿色高效的CO₂转化技术已成为催化领域的研究热点. 利用环境中无处不在的机械能驱动化学反应的压电催化技术, 作为一种新兴的能源转化策略, 为CO₂资源化利用提供了全新的视角. 在众多压电材料中, 石墨相氮化碳(g-C₃N₄)因其无金属特性、化学稳定性和易于调控的结构而备受关注. 然而, 原始g-C₃N₄较弱的本征压电响应限制了其在压电催化领域的实际应用. 因此, 利用精准的电子结构工程协同增强压电极化与表面活性, 是突破其在无金属压电催化CO₂还原应用瓶颈的关键所在.

本文基于卤素掺杂调控电子结构的策略, 通过两步热缩聚法成功制备了一系列卤素掺杂的氮化碳纳米片, 并筛选出催化性能最优的氟掺杂氮化碳(F-C₃N₄), 揭示了其独特的“压电极化-氢键介导”增强机制. 首先, 密度泛函理论(DFT)计算表明, 氟掺杂引入的F 2p轨道与C 2p轨道在费米能级附近发生强杂化, 形成了能量更高的价带顶, 这种电子态密度的改变不仅优化了能带结构, 还通过显著的电荷再分配在F原子邻近区域构建了局部电场. 通过热缩聚法制备了具有多孔纳米片形貌的F-C₃N₄, X-射线衍射、X-射线光电子能谱及透射电镜表征证实了氟原子的晶格掺杂及材料的结构完整性. 压电力显微镜和电化学测试结果显示, 得益于F原子引入造成的中心对称性破缺, 显著增强了材料的压电响应和载流子分离效率. 压电催化性能表明, 在无牺牲剂的超声振动条件下, F-C₃N₄表现出卓越的CO₂还原活性, CO产率高达201.7 µmol g^-1 h^-1, 是原始g-C₃N₄的19倍, 且实现了100%的CO产物选择性. 此外, 该催化剂在多次循环实验中展现出优异的稳定性. 为了深入探究反应机理, 结合原位傅里叶变换红外光谱、Bader电荷分析及动力学同位素效应实验, 证实了界面微环境的关键作用. 研究发现, 宏观压电极化场与氟诱导的局部偶极场产生协同效应, 动态重构了固-液界面的氢键网络. DFT计算进一步揭示, 这种有序的氢键网络不仅促进了质子的传递, 还有效协助了吸附态CO₂分子的结构扭曲, 显著增强了电子向CO₂的注入, 从而大幅降低了决速步*COOH中间体形成的能垒. 同时, 全路径热力学分析表明, 该体系对*H中间体吸附过强, 导致了H₂脱附困难, 这种动力学限制能够有效抑制析氢副反应, 从而确保了极高的CO选择性.

综上, 本文通过氟掺杂工程成功构建了具有压电增强氢键网络的高效无金属催化剂, 解决了压电催化CO₂还原中选择性低的难题. 这项工作不仅提供了一种低成本、高性能的压电催化剂设计策略, 更重要的是提出了利用机械能动态调控界面氢键网络以优化反应路径的新机制, 为下一代绿色能源催化体系的开发提供了重要的理论启示.

关键词: 氮化碳, 氢键网络, CO₂还原, 压电催化, 选择性

Abstract:

The efficient conversion of CO₂into industrial fuels via piezocatalysis is a compelling solution to carbon emissions but often suffers from low activity and poor selectivity. While many piezocatalysts contain metals, the metal-free and low-cost graphitic carbon nitride (g-C₃N₄) is a promising alternative. However, its modest piezoelectric response and intrinsically low surface activity are unfavorable for efficient CO₂ activation. Here, we demonstrate that halogen doping transforms its catalytic capability by creating highly active hybridized p-states near the Fermi level. Fluorine doping introduces F 2p orbitals that hybridize with C 2p states, forming a new, higher-energy valence band maximum. This modification simultaneously creates electronically potent sites for CO₂ activation and enhances the driving force for charge separation. The resulting F-C₃N₄ converts CO₂ exclusively to CO with 100% selectivity and a high production rate of 201.7 µmol g^-1 h^-1 under ultrasonic vibration without sacrificial agents. Mechanistic investigations reveal macroscopic piezoelectric polarization synergizes with a fluorine-induced local field to drive directional charge separation. Critically, reconstructed interfacial hydrogen-bond networks facilitate CO₂ adsorption and activation, significantly lowering the energy barrier for *COOH formation. This dynamic coupling provides a new paradigm for designing high-efficiency CO₂ reduction systems.

Key words: Carbon nitride, Hydrogen-bonding networks, CO₂ reduction, Piezocatalytic, Selectivity

何邢晨, 邵俊辉, 李娜君, 陈冬赟, 李华, 徐庆锋, 王浩志, 路建美. 压电增强氢键网络调控氟化氮化碳实现CO₂还原的100% CO选择性[J]. 催化学报, 2026, 85: 130-142.

Xingchen He, Junhui Shao, Najun Li, Dongyun Chen, Hua Li, Qingfeng Xu, Haozhi Wang, Jianmei Lu. Metal-free fluorinated carbon nitride with piezo-boosted hydrogen-bonding networks enable 100% CO selectivity in CO₂ reduction[J]. Chinese Journal of Catalysis, 2026, 85: 130-142.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65035-8

https://www.cjcatal.com/CN/Y2026/V85/I6/130

图/表 6

Fig. 1. (a) TDOS for F-C3N4. (b) Comparison of theoretical bandgaps calculated from the TDOS for X-C3N4. (c) PDOS for F-C3N4. (d) Charge density difference plots for X-C3N4, visualizing the charge redistribution and polarization effects induced by halogen doping. (e) Calculated electrostatic potential maps for F-C3N4. (f) Planar-averaged electrostatic potential plot for F-C3N4. (g) Work functions for X-C3N4 (X = F, Cl, Br, I).

Fig. 2. (a) Schematic illustration of the preparation process for X-C3N4. (b) SEM image of F-C3N4. (c) TEM image of F-C3N4. (d) EDS elemental mapping of F-C3N4. (e) XRD patterns. (f) High-resolution N 1s XPS spectra. (g) High-resolution F 1s XPS spectrum of F-C3N4.

Fig. 3. (a) Yields of CO2 reduction products obtained via piezoelectric catalysis with different samples. (b) Control experiments for piezoelectric CO2 reduction using F-C3N4 under various conditions. (c) Recycling stability test of F-C3N4 for piezoelectric CO2 reduction over multiple cycles. (d) Comparison of CO generation performance of this work (photocatalyst is carbon nitride-based materials). (e) LSV curves of F-C3N4 recorded in a CO2-saturated electrolyte under static, stirring, and ultrasonic conditions. (f) Mass spectrometry verification of CO production from CO2 using F-C3N4 via 13CO2 isotope-labeling experiment. (g) CO2 adsorption isotherms for the different samples.

Fig. 4. (a) PFM topography image of F-C3N4. (b) PFM amplitude image of F-C3N4. (c) PFM phase image of F-C3N4. (d) PFM butterfly amplitude loop and phase hysteresis loop obtained for F-C3N4. (e) Piezoelectric current response curves under periodic mechanical stress. (f) EIS Nyquist plot. (g) KPFM surface potential map. (h) Calculated electronic band structure. (i) DFT calculated Gibbs free energy profiles for CO generation pathways on halogen-doped carbon nitride catalysts. (Detailed optimized geometric structures and adsorption configurations of the reaction intermediates are provided in Fig. S35.)

Fig. 5. (a) In-situ FTIR spectra of C3N4. (b) In-situ FTIR spectra of F-C3N4. (c) Enlarged view of the H2O characteristic peaks region from the in-situ FTIR spectra presented in (a) and (b). (d) DFT calculated changes in key bond lengths and angles on F-C3N4 after CO2 adsorption. (e) DFT calculated Gibbs free energy profile for the complete hydrogen evolution reaction pathway on F-C3N4 considering the participation of different numbers of H2O molecules. (f) DFT calculated Gibbs free energy profiles for CO generation pathways on F-C3N4, considering the participation of different numbers of H2O molecules. (Detailed optimized geometric structures and adsorption configurations of the reaction intermediates are provided in Fig. S36.)

Fig. 6. Proposed schematic diagram illustrating the piezocatalytic CO2 reduction mechanism on F-C3N4.

参考文献

[1]	S. Navarro-Jaén, M. Virginie, J. Bonin, M. Robert, R. Wojcieszak, A. Y. Khodakov, Nat. Rev. Chem., 2021, 5, 564-579.
[2]	S. Chu Y,. Cui N. Liu, Nat. Mater., 2017, 16, 16-22.
[3]	C. Li J,. He T,. Cai X,. Chen H,. Tao Y,. Zhou M. Zhu, Chin. J. Catal., 2025, 74, 130-143.
[4]	L. Qin D,. Sun D,. Ma Z,. Wang Y,. Liu Q,. Li F,. Song K,. Wu L,. Gan T,. Zhou J. Zhang, Adv. Mater., 2025, 37, 2504205.
[5]	H. Lv Z,. Li P,. Yin P,. Wan M. Zhu, Chin. Chem. Lett., 2025, 36, 110457.
[6]	C. Li W,. Liu X,. Chen L,. Li S,. Lan M. Zhu, Chin. Chem. Lett., 2024, 35, 109652.
[7]	H. Wang, L. Song, X. Lv, H. Wang, F. Zhang, S. Hao, R. Wei, L. Zhang, Q. Han, G. Zheng, Angew. Chem. Int. Ed., 2025, 64, e202500928.
[8]	H. Shi Y,. Liang J,. Hou H,. Wang Z,. Jia J,. Wu F,. Song H,. Yang X. Guo, Angew. Chem. Int. Ed., 2024, 63, e202404884.
[9]	J. He X,. Wang S,. Jin Z.-Q., Liu M. Zhu, Chin. J. Catal., 2022, 43, 1306-1315.
[10]	N. Meng, W. Liu, R. Jiang, Y. Zhang, S. Dunn, J. Wu, H. Yan, Prog. Mater. Sci., 2023, 138, 101161.
[11]	Z. Ye R,. Zheng S,. Li Q,. Wang R,. Zhang C,. Yu J,. Lei X,. Liu D. Zhang, Nanomaterials, 2024, 14, 1641.
[12]	P. Zhao, Q. Zhang, Y. Liu, Z. Yin, Y. Wang, X. Zheng, H. Wang, Y. Deng, X. Fan, ACS Appl. Mater. Interfaces, 2024, 16, 49286-49292.
[13]	H. Zheng, Y. Wang, J. Liu, J. Wang, K. Yan, K. Zhu, Appl. Catal. B, 2024, 341, 123335.
[14]	W. Tian, N. Li, D. Chen, Q. Xu, H. Li, C. Yan, J. Lu, Angew. Chem. Int. Ed., 2023, 62, e202306964.
[15]	N. Tian, H. Huang, X. Du, F. Dong, Y. Zhang, J. Mater. Chem. A, 2019, 7, 11584-11612.
[16]	C. Zhu K,. Zhong B,. Zhu S,. Li H,. Li J,. Yang H. Xu, Appl. Catal. B, 2025, 371, 125200.
[17]	C. Hu F,. Chen Y,. Wang N,. Tian T,. Ma Y,. Zhang H. Huang, Adv. Mater., 2021, 33, 2101751.
[18]	Q. Ye Y,. Zhou Y,. Xu Q,. Zhang X,. Shi D,. Li D,. Tian D. Jiang, Chem. Eng. J., 2023, 463, 142395.
[19]	Y. Shang, Y. Hou, X. Cao, H. Liu, X. Jin, J. Liu, C. Yan, Y. Qian, L. Song, Z. Qi, P. Song, Y. Zhou, D. Liu, Z. Liu, F. Jing, Q. Yan, G. Chen, C. Lv, Chem. Eng. J., 2024, 486, 150306.
[20]	L. Zhang, X. Zhao, M. Liu, Q. Li, Y. Yin, X. Ma, H. Gu, B. Jiang, Chem. Eng. J., 2024, 479, 147912.
[21]	S. Cao J,. Low J,. Yu M. Jaroniec, Adv. Mater., 2015, 27, 2150-2176.
[22]	A. Ismail, M. Zahid, B. Ahmad, S. Hayat, S. Ali, S. U. H. Bakhtiar, A. N. Alodhayb, X. Wu, Q. Alam, S. Ali, L. Qiao, Chem. Eng. J., 2025, 513, 163023.
[23]	E. Gong, S. Ali, C. B. Hiragond, H. S. Kim, N. S. Powar, D. Kim, H. Kim, S.-I. In, Energy Environ. Sci., 2022, 15, 880-937.
[24]	J.-J. Fang, Z. Liu, Z.-Y. Wang, Y.-P. Xie, X. Lu, Angew. Chem. Int. Ed., 2025, 64, e202504989.
[25]	Y. Yu Z,. Zhu F,. Chen T,. Ma H. Huang, Adv. Mater., 2024, 36, 2413835.
[26]	J. Wang, H. Zhang, Y. Nian, Y. Chen, H. Cheng, C. Yang, Y. Han, X. Tan, J. Ye, T. Yu, Adv. Funct. Mater., 2024, 34, 2406549.
[27]	H. Li J,. Zhao L,. Luo J,. Du J. Zeng, Acc. Chem. Res., 2021, 54, 1454-1464.
[28]	Y. Li T,. Wang Z,. Yao Q.-A., Chen Q. Li, Chin. J. Catal., 2024, 56, 51-73.
[29]	W. Tian, J. Han, N. Li, D. Chen, Q. Xu, H. Li, J. Lu, Chin. J. Catal., 2024, 64, 166-179.
[30]	S. Sriram, M. Bhaskaran, R. Ahluwalia, T. G. Nguyen, N. Ng, D. J. Srolovitz, K. Kalantar-zadeh, A. Mitchell, ACS Nano, 2011, 5, 1067-1072.
[31]	J. Ye H,. Gong Y,. Zhang Q,. Xu X,. Zhou M,. Yan D,. Zhai K,. Zhou D,. Zhang C. Bowen, Addit. Manuf., 2024, 79, 103915.
[32]	X. Shan, G. Ge, Z. Zhao, ChemCatChem, 2019, 11, 1534-1544.
[33]	L. I. Isaenko, A. A. Merkulov, A. Y. Tarasova, V. M. Pashkov, V. A. Drebushchak, J. Therm. Anal. Calorim., 2009, 95, 323-325.
[34]	J. Medina-Ramos, J. L. DiMeglio, J. Rosenthal, J. Am. Chem. Soc., 2014, 136, 8361-8367.
[35]	S. Jiang, Y. Chen, X. Cui, Y. Sun, G. Ma, Y. Bao, Y. Yao, T. Ma, ACS Appl. Mater. Interfaces, 2024, 16, 14965-14973.
[36]	Q. Li X,. Li M,. Zheng F,. Luo L,. Zhang B,. Zhang B. Jiang, Adv. Funct. Mater., 2025, 35, 2417279.
[37]	M. Zhang, K. Wang, C. Han, M. Zhang, J. Vongsvivut, T. Dong, L. Liu, S. Wang, S. Liu, Adv. Funct. Mater., 2025, 35, 2412258.
[38]	J. Dai Z,. Fan Y,. Long W,. Yue F,. Huang Y,. Jiao Y,. Deng Y,. Chang D. Wang, Adv. Funct. Mater., 2024, 34, 2408754.
[39]	Y. Bian, Y. Wang, Z. Yang, Z. Yin, H. Zhao, Y. Liu, H. Shi, Y. Su, Y. Deng, H. Wang, Adv. Energy Mater., 2025, 15, e03855.
[40]	S. Jin Z,. Hao K,. Zhang Z,. Yan J. Chen, Angew. Chem. Int. Ed., 2021, 60, 20627-20648.
[41]	Y. Liu J,. Wang H,. Wang Z,. Yin Y,. Wang W,. Huang X,. Hu Z. J. Xu, J. Am. Chem. Soc., 2025, 147, 20318-20328.
[42]	X. Zheng, Y. Wang, J. Guan, X. Liu, Y. Bai, Y. Chen, P. Yang, J. Zhang, H. Ou, M. Wang, Y. Xiong, H. Wang, Y. Lei, Adv. Powder Mater., 2025, 4, 100308.
[43]	J. Ma S,. Jing Y,. Wang X,. Liu L.-Y., Gan C,. Wang J.-Y., Dai X,. Han X. Zhou, Adv. Energy Mater., 2022, 12, 2200253.
[44]	J. Zhou, X. Zha, Z. Chen, K. Li, H. Sun, J. Wang, K. Lv, S. Cong, Z. Zhao, Appl. Catal. B, 2024, 350, 123911.
[45]	Y. Li Y,. Xue X,. Gao L,. Wang X,. Liu Z,. Wang S. Shen, Adv. Funct. Mater., 2024, 34, 2312634.
[46]	W. Shang, Y. Li, W. Che, T. Liu, W. Peng, J. Guo, W. Fan, J.-B. Baek, J. Hou, W. Liu, Y. Shi, Angew. Chem. Int. Ed., 2025, 64, e202510799.

压电增强氢键网络调控氟化氮化碳实现CO₂还原的100% CO选择性

Metal-free fluorinated carbon nitride with piezo-boosted hydrogen-bonding networks enable 100% CO selectivity in CO₂ reduction

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 6

参考文献

相关文章 15

编辑推荐

Metrics

[1]	林哲冠, 何舒怡, 李铁森, 崔勍焱, 闫文付, 岳源源. CuO/Cu-SSZ-13界面结构的设计调控及其对NO_x选择性催化还原与CO氧化的协同催化[J]. 催化学报, 2026, 85(6): 286-297.
[2]	兰青, 靳素娟, 焦莹莹, 张志明. 单/双金属中心锚定在氮化碳: 温室气体转化和有机光合成的可持续路线[J]. 催化学报, 2026, 85(6): 13-33.
[3]	李婧宇, 徐艺军. 光催化环氧化合物的区域选择性开环反应[J]. 催化学报, 2026, 85(6): 34-46.
[4]	赖可溱, 孙雨鑫, 李林萍, 施晓庆, 周小松, 李宁, 高旸钦, 戈磊. 缺陷介导的Zn-CuInS₂双位点协同催化: 轨道调控实现高效光催化CO₂转化制乙烯[J]. 催化学报, 2026, 85(6): 153-167.
[5]	陈兰兰, 圣利, 周亚男, 罗其全, 李震宇, 张文华, 杨金龙. Ni₁-MoS₂单原子催化剂用于CO₂加氢制甲醇的优越性: 密度泛函理论与微观动力学研究[J]. 催化学报, 2026, 85(6): 143-152.
[6]	胡瑞文, 郭志勇, 彭小刚, 石晓琪, 乔玉本, 李倩, 高成华, 李爱涛. 祖先序列重建与理性设计赋能非特异性过加氧酶实现高效甾体母核氧化官能团化[J]. 催化学报, 2026, 84(5): 417-427.
[7]	陈榕兴, 权永康, 蔡伟龙, 吴永豪, 黄剑莹, 赖跃坤. 氰氧共功能化氮化碳中的协同能带和电子工程用于高效光催化合成H₂O₂[J]. 催化学报, 2026, 84(5): 250-260.
[8]	陈杨林, 方瑞明, 赵慧博, 封敏君, 侯卫东, Tze Chien Sum, Wen Liu, 王亮, Lydia Helena Wong, 薛灿. 褐色聚合氮化碳纳米线双极光催化体系实现生物多元醇氧化与CO₂还原协同产CO[J]. 催化学报, 2026, 84(5): 214-225.
[9]	胡碧华, 曹海邻, 陈振, 雷志伟, 王新, Panagiotis Tsiakaras, 陈忠伟, 徐保民. 氮基载体调控酞菁钴的电子结构实现高选择性电化学还原二氧化碳产甲醇[J]. 催化学报, 2026, 83(4): 330-340.
[10]	李佳幸, 彭悦, 李一凡, 隆云鹏, William Orbell, 高传, 朱晓, 袁兴, 陈琳, 李俊华. 调控Pt/Cu-SSZ-13界面相互作用优化氨选择性催化氧化性能[J]. 催化学报, 2026, 83(4): 376-387.
[11]	唐克山, 邓莞沂, 王宁远, 夏阳, 吴新鹤, 杨恒. 富含氧空位的三嗪基-COF/TiO₂ S-型异质结用于高效光催化CO₂还原[J]. 催化学报, 2026, 83(4): 244-257.
[12]	尤长君, 任宇奇, 贺红斌, 彭若轩, 朱元皓, 程淼, 丁培根, 张刘娜, 兰盛楠, 张虹扬, 章毅琴, 朱丰帆, 李敬, 周建成. Ru单原子与Ni团簇双位点协同构筑CeO₂纳米棒实现高效太阳能驱动CO₂甲烷化[J]. 催化学报, 2026, 83(4): 183-197.
[13]	刘鑫, 杨烨舟, 杨敬茹, 王茂弟, 杨启华. 镍铁双金属催化剂中铁对糠醛选择性加氢的促进作用[J]. 催化学报, 2026, 83(4): 411-418.
[14]	李俊青, 何科林, 陶英, 陈超, 谢林富, 马云飞, 王骏鹏, 许长文, 李杨, 张启涛. 阴阳离子对促进结晶氮化碳激子解离实现过氧化氢高效人工光合成[J]. 催化学报, 2026, 82(3): 174-186.
[15]	张婧, 张锡东, 王开颜, 王雪飞, 王苹, 陈峰, 余火根. 柠檬酸的定向配位用于高效光合成过氧化氢以及高附加值β-酮戊二酸[J]. 催化学报, 2026, 82(3): 201-211.