物理化学学报 >> 2026, Vol. 42 >> Issue (7): 100212.doi: 10.1016/j.actphy.2025.100212

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无过渡金属聚庚嗪酰亚胺促进的光催化Katritzky盐C–X键构建反应研究

王颖, 杨明成, 尹铸, 王英齐, 成佳佳*()   

  1. 福州大学化学学院, 核生化灾害防护化学全国重点实验室, 能源与环境光催化国家重点实验室, 福建 福州 350116
  • 收稿日期:2025-09-15 修回日期:2025-10-26 录用日期:2025-10-26 发布日期:2026-05-22
  • 通讯作者: Email: jjcheng@fzu.edu.cn (成佳佳)

Transition metal-free poly(heptazine imide) photocatalyst for C–X bond construction from katritzky salts

Ying Wang, Mingcheng Yang, Zhu Yin, Yingqi Wang, Jiajia Cheng*()   

  1. State Key Laboratory of Chemistry for NBC Hazards Protection, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350116, Fujian Province, China
  • Received:2025-09-15 Revised:2025-10-26 Accepted:2025-10-26 Published:2026-05-22
  • Contact: Email: jjcheng@fzu.edu.cn (Jiajia Cheng)

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摘要：

针对聚合物氮化碳光催化剂缺陷调控与界面工程在有机转化中的研究空白，本研究设计并合成了一种新型无过渡金属聚庚嗪酰亚胺光催化剂(PHI-K-alk)。通过熔盐辅助碱化策略，成功构建了具有长程有序骨架结构及丰富N–K表面活性位点的π共轭体系。该策略不仅显著提升了材料电子云极化能力，还通过N–K键协同作用有效降低了Katritzky盐的还原电位(LUMO降低0.33 eV)及C(sp2)–N键裂解能垒(0.7 eV)，从而克服了传统Katritzky盐体系存在的吸附能垒高、反应活性低等瓶颈问题。实验结果表明，PHI-K-alk在可见光驱动下实现了脱氨基Heck型偶联反应的高效转化(转化率90%，选择性94%)，其性能可与当前最优均相光催化剂相媲美。通过原位光谱分析、电化学表征及密度泛函理论计算，揭示了材料中N缺陷位点与K+抗衡离子的协同作用机制：N空位诱导的电子云极化增强了底物吸附能力，而N–K键通过离子交换作用优化了吡啶基团的电荷密度分布，最终实现光生载流子的高效分离。该光催化体系展现出优异的底物普适性，在药物分子衍生化、氨基酸官能团修饰及Minisci反应中均表现出良好适应性，成功实现了C(sp3)–C(sp)、C(sp3)–H等多种化学键的可控构建。本研究为发展高效无金属光催化体系提供了新策略，其结晶度与缺陷态的协同调控策略对可持续光催化合成技术的开发具有重要指导意义。

关键词: 光催化, 聚庚嗪酰亚胺, C–X键构建, 界面电子转移, Katritzky盐

Abstract:

Defect and interface engineering of polymeric carbon nitride photocatalysts remains an under-explored yet powerful strategy for challenging organic transformations. Here we report a crystalline, alkaline-treated poly(heptazine imide) (PHI-K-alk) that enables transition-metal-free activation of Katritzky pyridinium salts for visible-light-driven C–X (C(sp2/sp)–C, C(sp2)–S, etc.) bond construction. A molten-salt/alkalization protocol simultaneously enhances long-range order and installs abundant N–K surface sites, generating a negatively charged, π-extended scaffold that overcomes the intrinsically high reduction potential and poor adsorption of Katritzky salts. PHI-K-alk delivers up to 90% conversion and 94% selectivity in deaminative Heck-type coupling, comparable to state-of-the-art homogeneous photocatalysts. Comprehensive spectroscopic, electrochemical, and DFT investigations elucidate that strategic incorporation of N-defects leads to electron cloud polarization, while N–K bonds facilitate ion exchange with pyridinium counter-anions, lower the substrate LUMO by 0.33 eV, and reduce the C(sp2)–N bond cleavage barrier to 0.7 eV. Additionally, the high crystallinity of the platform suppresses charge recombination, thereby promoting rapid interfacial electron transfer. This photocatalytic system demonstrates broad substrate tolerance, including primary, secondary, amino-acid-derived, and drug-like compounds, and is effective in mediating Minisci reactions, C(sp3)–C(sp) and C(sp3)–H alkylations. Our results offer a blueprint for integrating crystallinity and defects in transition metal-free semiconductors, paving the way toward more sustainable photocatalytic synthesis.

Key words: Photocatalysis, Poly(heptazine imide), C–X bond formation, Interfacial electron transfer, Katritzky pyridinium salts