在用于增强光催化剂的捐赠者-接受者共价有机框架中基于计算调节激发效应
Yunyang Qian1, Yulan Han2, Xiyuan Zhang1
1Department of Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China.
Nature communications
|May 29, 2023
概括
研究人员开发了新的捐赠者-受体共价有机框架 (COFs),以克服因巨大的刺激子结合能引起的光催化局限性. 一种经过修改的COF,TAPT-OMe-alkyne-COF,显示生产活动显著增加了20倍.
科学领域:
- 材料科学 材料科学 材料科学
- 光催化作用的光催化
- 计算化学的计算化学
背景情况:
- 聚合物半导体中的强烈刺激效应导致高刺激子结合能 (Eb),阻碍光催化.
- 捐赠者-接受者 (D-A) 共价有机框架 (COF) 提供可调节的电子特性,以提高性能.
研究的目的:
- 通过计算评估和实验合成具有调节激子结合能量的D-A COF,以增强光催化.
- 研究D-A COF中激素结合能和光催化活性之间的相关性.
主要方法:
- 密度函数理论 (DFT) 的计算用于预测D-A COF中的带对齐和电荷转移.
- 使用 1,3,5-tris(4-aminophenyl) triazine (TAPT) 或 1,3,5-tris(4-aminophenyl) benzene (TAPB) 作为受体的 D-A COF 的合成.
- 通过基环添加进行合成后的修饰,以提高COF的稳定性.
主要成果:
- DFT计算显示,激子结合能量 (Eb) 可以通过不同的D-A相互作用强度系统调整,TAPT-OMe显示最小的Eb.
- 合成的TAPT-OMe-COF表现出优异的光催化H2生产活性,与计算的Eb相关.
- 基因循环添加显著改善了COF的稳定性,并进一步降低了Eb,导致TAPT-OMe-alkyne-COF的活性增加了约20倍.
结论:
- 在D-ACOF中对Eb进行系统的调整,可以通过对供体和受体单元的合理设计来实现.
- 减少COF中的EB直接提高光催化性能,特别是用于生产.
- 通过合成后修改提高稳定性和降低 Eb,为开发先进光催化剂提供了一个有前途的战略.
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