物理化学学报 >> 2026, Vol. 42 >> Issue (5): 100183.doi: 10.1016/j.actphy.2025.100183

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离子极化工程调控聚合物氮化碳框架结构实现双氧水高效人工光合成

谢垚1, 李双军2, 陈超1, 樊思宇3, 陶英1,*(), 张启涛1,*()   

  1. 1 深圳大学微纳光电子学研究院, 二维材料光电科技国际合作联合实验室, 广东 深圳 518060
    2 上海大学纳米科学与技术研究中心, 上海 200444
    3 Department of Applied Chemistry, Faculty of Engineering, Kyushu Institute of Technology, Kitakyushu 804-8550, Japan
  • 收稿日期:2025-08-20 修回日期:2025-09-04 录用日期:2025-09-04 发布日期:2026-01-23
  • 通讯作者: Email: taoying951223@163.com (陶英)qitao-zhang@szu.edu.cn (张启涛)

Ionic polarization engineering of polymeric carbon nitride toward efficient H2O2 photosynthesis

Yao Xie1, Shuangjun Li2, Chao Chen1, Siyu Fan3, Ying Tao1,*(), Qitao Zhang1,*()   

  1. 1 International Collaborative Laboratory of 2D Materials for Optoelectronic Science & Technology, Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen 518060, Guangdong Province, China
    2 Research Center of Nano Science and Technology, Shanghai University, Shanghai 200444, China
    3 Department of Applied Chemistry, Faculty of Engineering, Kyushu Institute of Technology, Kitakyushu 804-8550, Japan
  • Received:2025-08-20 Revised:2025-09-04 Accepted:2025-09-04 Published:2026-01-23
  • Contact: Email: taoying951223@163.com (Ying Tao)qitao-zhang@szu.edu.cn (Qitao Zhang)

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摘要：

熔盐极化技术利用高温熔盐中的离子相互作用，成为一种强大但尚未充分开发的结构工程策略。该技术能实现对聚合氮化碳(PCN)的精确结构调控，为提升光催化H2O2合成效率提供了新思路。本研究通过调控LiCl/KCl熔盐比例，成功构建了两种不同晶相结构：以七嗪单元为主的LKCN-0.95和七嗪-三嗪给受体(D-A)结结构的LKCN-0.2。结合实验与理论分析发现，富Li+熔盐体系促进高度有序七嗪骨架形成，而K+主导体系则有利于三嗪单元的引入。优化后的七嗪主导结构和七嗪-三嗪结结构分别展现出27倍和42倍的光合成H2O2性能提升(3.3和5.2 mmol L−1 h−1)，较原始PCN(0.12 mmol L−1 h−1)显著提高，并保持五个循环的优异稳定性。机理研究表明，结构调控可增强电荷分离效率并优化氧吸附/活化过程，从而促进选择性2e−氧还原反应。该工作不仅深化了对熔盐驱动结构演变的理解，更为设计高效太阳能驱动H2O2人工光合成催化剂提供了可规模化制备的新方法。

关键词: 聚合碳氮化物, 七嗪-三嗪, 离子极化, 过氧化氢, 光合成

Abstract:

Molten salt polarization, leveraging ionic interactions in high-temperature molten salts, emerges as a powerful yet underexplored strategy for structural engineering. It enables precise structural engineering of polymeric carbon nitride (PCN), offering a promising strategy to boost photocatalytic H2O2 synthesis. Herein, we report a controlled modulation strategy by varying LiCl/KCl ratios in molten salts to tailor the framework structures of PCN, achieving two distinct crystalline phases: heptazine-dominated (LKCN-0.95) and heptazine-triazine donor-acceptor (D-A) junction (LKCN-0.2). By integrating experimental and theoretical analyses, we revealed that Li+-rich molten salts promote highly ordered heptazine frameworks, while K+-dominated systems enable triazine incorporation. The optimized heptazine-dominated and heptazine-triazine junction exhibited 27-fold and 42-fold enhancements in H2O2 photosynthesis (3.3 and 5.2 mmol L−1 h−1) compared to pristine PCN (0.12 mmol L−1 h−1), alongside exceptional stability over five cycles. Mechanistic studies demonstrated that structural modulation enhances charge separation and optimizes oxygen adsorption/activation for selective 2e− oxygen reduction. This work not only advances the understanding of molten salt-driven structural evolution but also provides a scalable approach for designing efficient photocatalysts toward solar-driven H2O2 photosynthesis.

Key words: Polymeric carbon nitride, Heptazine-Triazine, Ionic polarization, Hydrogen peroxide, Photosynthesis