Liu Ning, Jiang Jialong, Xu Mingming, Zhang Shiqi, Zhang Runhao, Chen Zhonghang, Mao Yue, Cheng Peng, Shi Wei
Frontiers Science Center for New Organic Matter, Key Laboratory of Advanced Energy Materials Chemistry (MOE), and State Key Laboratory of Advanced Chemical Power Sources, College of Chemistry, Nankai University, Tianjin, 300071, China.
ChemSusChem. 2025 Jan 14;18(2):e202401338. doi: 10.1002/cssc.202401338. Epub 2024 Oct 23.
The local charge distribution of photocatalyst is crucial to the catalytic activity due to its influence on the charge separation process. Herein, we report two one-dimensional Ni-based metal-organic assemblies for efficient photocatalytic hydrogen evolution without using noble-metal cocatalysts. By adjusting the aromatic ring in the center of the tricarboxylic ligand, the photocatalytic hydrogen evolution activity was increased from 1715 to 2652 μmol h g. The detailed mechanism study shows that the introduced nitrogen atoms in the ligands of the metal-organic coordination assembly could modulate the local charge distribution, and yielding a significant enhancement of the molecular dipole moment which engenders a propulsive force for the effective separation and transport of photoinduced charge carriers. This work provides insights into the local charge distribution via ligand modulation for enhancing the activity of photocatalysts.
光催化剂的局部电荷分布对催化活性至关重要，因为它会影响电荷分离过程。在此，我们报道了两种一维镍基金属有机组装体，可在不使用贵金属助催化剂的情况下实现高效光催化析氢。通过调整三羧酸配体中心的芳香环，光催化析氢活性从1715 μmol h g提高到2652 μmol h g。详细的机理研究表明，金属有机配位组装体配体中引入的氮原子可以调节局部电荷分布，并显著增强分子偶极矩，从而为光生电荷载流子的有效分离和传输产生推进力。这项工作通过配体调控为增强光催化剂活性的局部电荷分布提供了见解。
