物理化学学报 >> 2026, Vol. 42 >> Issue (10): 100338.doi: 10.1016/j.actphy.2026.100338

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通过电子给体酚羟基调控芘-COFs的反键轨道占据以促进光催化产氢

刘永康1, 余守希2, 陈丽2, 王中辽2,*(), 张美玉3,*(), 张金峰1,*()   

  1. 1 淮北师范大学物理与电子信息学院, 安徽省智能计算与应用重点实验室, 安徽 淮北 235000
    2 淮北师范大学能源科学与工程学院, 安徽 淮北 235000
    3 聊城大学化学化工学院, 山东省化学储能与新型电池技术重点实验室, 山东 聊城 252059
  • 收稿日期:2026-05-04 修回日期:2026-05-30 录用日期:2026-06-01 发布日期:2026-09-03
  • 通讯作者: Email: wangzl@chnu.edu.cn (王中辽)zhangmeiyu@lcu.edu.cn (张美玉)jfzhang@chnu.edu.cn (张金峰)

Tuning antibonding-orbital occupancy in pyrene-COFs via electron-donating phenolic −OH for boosted photocatalytic H2 evolution

Yongkang Liu1, Shouxi Yu2, Li Chen2, Zhongliao Wang2,*(), Meiyu Zhang3,*(), Jinfeng Zhang1,*()   

  1. 1 Anhui Province Key Laboratory of Intelligent Computing and Applications, College of Physics and Electronic Engineering, Huaibei Normal University, Huaibei 235000, Anhui Province, China
    2 College of Energy Science and Engineering, Huaibei Normal University, Huaibei 235000, Anhui Province, China
    3 Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry & Chemical Engineering, Liaocheng University, Liaocheng 252059, Shandong Province, China
  • Received:2026-05-04 Revised:2026-05-30 Accepted:2026-06-01 Published:2026-09-03
  • Contact: Email: wangzl@chnu.edu.cn (Zhongliao Wang)zhangmeiyu@lcu.edu.cn (Meiyu Zhang)jfzhang@chnu.edu.cn (Jinfeng Zhang)

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摘要：

共价有机框架(COF)作为析氢反应(HER)的光催化剂被广泛研究，但多数设计策略聚焦于光吸收或电荷分离，而非催化位点本身的H*脱附能垒。本研究从键分辨视角重新审视该问题：采用晶体轨道哈密顿布居(COHP)方法，将N−H反键轨道的占据程度作为量化描述符，用于评估希夫碱COF中亚胺氮原子对H*的结合强度。通过合成两种芘基COF (PY-BD与PY-DHBD)验证该描述符：在二醛连接体中引入两个酚羟基后，反键轨道占据率提升(ICOHP从−7.52增至−7.18 eV)，N−H键弱化，ΔGH*从−0.22 eV优化至0.04 eV (接近热中性)。可见光驱动的产氢速率相应从450 μmol g−1 h−1提升至1127 μmol g−1 h−1，达到PY-BD的2.5倍。该研究将COHP解析的反键占据率与金属催化中经典的d带中心理论并列，为调控富氮COF活性位点的HER性能提供了定量描述框架。

关键词: 芘-COFs, 给电子, 酚羟基, 光催化析氢, COHP

Abstract:

Covalent organic frameworks (COFs) are widely studied as photocatalysts for the hydrogen evolution reaction (HER), yet most design strategies target light absorption or charge separation rather than the H* desorption barrier at the catalytic site itself. We re-examine the problem from a bond-resolved view: the crystal orbital Hamilton population (COHP) is used to treat the occupancy of the N−H antibonding manifold as a quantitative descriptor of how strongly the imine nitrogen of a Schiff-base COF binds H*. Two pyrene-based COFs, PY-BD and PY-DHBD, are synthesized to test the descriptor. Adding two phenolic −OH groups to the dialdehyde linker raises the antibonding occupancy (ICOHP from −7.52 to −7.18 eV), weakens the N−H bond, and shifts ΔGH* from −0.22 to 0.04 eV, close to thermoneutrality. The visible-light H2-evolution rate accordingly rises from 450 to 1127 μmol g−1 h−1, 2.5-fold the rate of PY-BD. The work places COHP-resolved antibonding occupancy alongside the d-band-centre framework familiar from metal catalysis as a quantitative descriptor for tuning HER on N-rich COF active sites.

Key words: Pyrene-COFs, Electron-donating, Phenolic ?OH, Photocatalytic HER, COHP