东北师范大学李云锋团队报道了以g-C3N4晶体为电荷转移模块的，增强光催化析氢的高效供体-π-受体体系的制备。相关研究成果于2024年11月8日发表在《结构化学》。

以g-C3N4为π模的供体-π-受体（D-π-A）型光催化剂，因其优化的共轭结构和增强的电子定向驱动而受到广泛关注。然而，由于其非晶态或半晶态结构以及可用官能团的限制，g-C3N4的低效电荷迁移是目前的挑战。

该文中，研究人员通过在高结晶度Melon框架中原位引入酰胺和氰化物基团，获得了D-π-A型高结晶氮化碳（HCCN）。官能团改性和结晶度调节的协同作用，大大提高了电子感应驱动和电荷载流子密度。

此外，密度泛函理论计算表明，D-π-A结构可以诱导Melon单元的局部电荷分布，为光诱导电荷迁移提供独特而稳定的途径。所制备的HCCN样品在420±15nm处显示出优异的可见光光催化析氢性能，表观量子效率（AQE）为12.2%，是原始g-C3N4的23.7倍。最后，还研究了HCCN样品的电荷分离和转移过程，以及可能的光催化反应机理。

附：英文原文

Title: Preparation of high-efficient donor-π-acceptor system with crystalline g-C3N4 as charge transfer module for enhanced photocatalytic hydrogen evolution

Author: Guixu Pan, Zhiling Xia, Ning Wang, Hejia Sun, Zhaoqi Guo, Yunfeng Li, Xin Li

Issue&Volume: 2024-11-08

Abstract: Donor-π-acceptor (D-π-A) type photocatalysts with g-C3N4 as π-module have attracted much attention due to their optimized conjugate structure and enhanced electron directed driving. However, the inefficient charges migration of g-C3N4 due to its amorphous or semi-crystalline structure and limitation of available functional groups are present challenges. In this work, the D-π-A type high crystalline carbon nitride (HCCN) has been obtained by in-situ introducing amide and cyanide groups into the high-crystallinity melon framework. The synergistic effect of functional group modification and crystallinity regulation greatly enhances the electron induction driving and charge carrier density. Moreover, the density functional theory calculations demonstrate that the D-π-A structure could induce the local charge distribution of melon units to provide a unique and stable pathway for photoinduced charges migration. The as-prepared HCCN sample shows a superior visible-light photocatalytic performance for hydrogen evolution with an apparent quantum efficiency (AQE) of 12.2% at 420 ± 15 nm, which is 23.7 times higher than that of original g-C3N4. Finally, the charge separation and transfer processes as well as the possible photocatalytic reaction mechanisms of HCCN sample are also investigated.

DOI: 10.1016/j.cjsc.2024.100463

Source: http://cjsc.ac.cn/cms/issues/725