物理化学学报

上一篇    下一篇

D-π-A介导的能带工程与定向电荷分离用于双路径H2O2光合成

付保岗1,2, 苏楠1, 罗建民3, 王赟1, 胡博4, 成亮2, 董红军1, 李春梅1   

  1. 1 江苏大学化学化工学院, 绿色化学与化工技术研究院, 江苏 镇江 212013;
    2 江苏大学环境与安全工程学院, 江苏 镇江 212013;
    3 韶关学院化学与土木工程学院, 广东 韶关 512005;
    4 白城师范学院化学学院, 吉林省西部清洁能源重点实验室, 吉林 白城 137000
  • 收稿日期:2026-07-22 修回日期:2026-08-13 录用日期:2026-08-21
  • 通讯作者: 成亮, 董红军, 李春梅 E-mail:lcheng@ujs.edu.cn;donghongjun6698@aliyun.com;lichun_mei_happy@126.com
  • 基金资助:
    本工作得到国家自然科学基金项目(52072153)、江苏省研究生科研创新计划项目(KYCX24_4008)、大学生创新创业项目(202410299511X,202410299498X,X2025102990467,X2025102990460)的资助。

D-π-A mediated band engineering with directional charge separation for dual-pathway H2O2 photosynthesis

Baogang Fu1,2, Nan Su1, Jianmin Luo3, Yun Wang1, Bo Hu4, Liang Cheng2, Hongjun Dong1, Chunmei Li1   

  1. 1 Institute of Green Chemistry and Chemical Technology, School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu Province, China;
    2 School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu Province, China;
    3 School of Chemistry and Civil Engineering, Shaoguan University, Shaoguan 512005, Guangdong Province, China;
    4 Jilin Provincial Key Laboratory of Western Jilin's Clean Energy, College of Chemistry, Baicheng Normal University, Baicheng 137000, Jilin Province, China
  • Received:2026-07-22 Revised:2026-08-13 Accepted:2026-08-21
  • Contact: Liang Cheng, Hongjun Dong, Chunmei Li E-mail:lcheng@ujs.edu.cn;donghongjun6698@aliyun.com;lichun_mei_happy@126.com

PDF

42

赞

补充材料

1

摘要： 光催化H2O2合成通常由氧还原反应(ORR)主导，而通过能带结构调控同时实现水氧化反应(WOR)与定向电荷分离仍具有挑战性。本文将硫掺杂和吡啶修饰相结合，在氮化碳骨架内构建了分子内供体-π-受体(D-π-A)网络。由此产生的电子极化促进了光生载流子的定向分离，并优化了能带结构，从而在热力学上同时满足ORR和WOR两条反应路径。因此，所合成的SCN-AP光催化剂在纯水中2 h内实现了1030 μmol g-1的H2O2产量，是原始PCN的3.73倍，并对临床相关病原体Acinetobacter beijerinckii和Klebsiella variicola表现出有效的抗菌活性。原位电子顺磁共振(EPR)光谱和原位漫反射红外傅里叶变换光谱(DRIFTS)共同支持ORR和WOR路径的共存。其中，ORR作为主要路径，涉及·O2-介导的逐步还原路径以及与1O2相关的反应路径，WOR则提供互补的空穴驱动贡献以促进H2O2生成。本工作展示了一种可行的能带工程策略，用于构建具有定向电荷转移和双路径H2O2光合成的聚合物光催化剂。

关键词: 氮化碳, D-π-A网络结构, 双路径反应, H2O2光合成, 抗菌活性

Abstract: Photocatalytic H2O2 synthesis is commonly dominated by the oxygen reduction reaction (ORR), whereas simultaneously enabling water oxidation reaction (WOR) and directional charge separation through band-structure regulation remains challenging. Herein, sulfur doping and pyridine modification were integrated to construct an intramolecular donor-π-acceptor (D-π-A) network within the carbon nitride framework. The resulting electronic polarization promotes directional separation of photogenerated charge carriers and optimizes the band structure to thermodynamically enable both ORR and WOR pathways. Consequently, the as-synthesized SCN-AP photocatalyst achieves an H2O2 yield of 1030 μmol g-1 within 2 h in pure water, 3.73 times that of pristine PCN, and exhibits effective antibacterial activity against clinically relevant pathogens including Acinetobacter beijerinckii and Klebsiella variicola. The in situ electron paramagnetic resonance (EPR) spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) collectively support the coexistence of ORR and WOR pathways. The ORR serves as the predominant route and involves a ·O2--mediated stepwise reduction pathway together with a 1O2- associated pathway, while WOR provides a complementary hole-driven contribution to H2O2 formation. This work demonstrates a feasible band-engineering strategy for constructing polymeric photocatalysts with directional charge transfer and dual-pathway H2O2 photosynthesis.

Key words: Carbon nitride, D-π-A network structure, Dual-pathway reactions, H2O2 Photosynthesis, Antibacterial activity