Huo Debiao, Lin Feifei, Chen Shani, Ni Yueran, Wang Ranhao, Chen Hong, Duan Lele, Ji Yongfei, Zhou Aiju, Tong Lianpeng
School of Chemistry and Chemical Engineering/Institute of Clean Energy and Materials , Guangzhou University , No. 230 Wai Huan Xi Road , Guangzhou 510006 , P. R. China.
School of Environmental Science and Technology , Southern University of Science and Technology , Shenzhen 518055 , P. R. China.
Inorg Chem. 2020 Feb 17;59(4):2379-2386. doi: 10.1021/acs.inorgchem.9b03250. Epub 2020 Feb 3.
Ultrathin two-dimensional (2D) nanosheets with efficient light-driven proton reduction activity were obtained through the exfoliation of novel metal-organic frameworks (MOF), which were synthesized by using a bis(4'-carboxy-2,2':6',2″-terpyridine) ruthenium complex as a linker and transition-metal (Mn, Co, Ni, and Zn) anions as nodes. The nanosheet of the Ni node exhibits a photocatalytic hydrogen evolution rate of 923 ± 40 μmol g h at pH = 4.0, without the presence of any cocatalyst or cosensitizer. A combined experimental and theoretical study suggests a reductive quenched pathway for the photocatalytic hydrogen evolution by the nanosheet. The transition-metal nodes at the edge of the nanosheets are proposed as the active sites. Density functional theory (DFT) calculations attributed the different catalytic activities of the nanosheets to the discrepancy of H adsorption free energy at various transition-metal nodes.
通过剥离新型金属有机框架（MOF）获得了具有高效光驱动质子还原活性的超薄二维（2D）纳米片，该金属有机框架是使用双（4'-羧基-2,2':6',2″-三联吡啶）钌配合物作为连接体，并以过渡金属（Mn、Co、Ni和Zn）阴离子作为节点合成的。在不存在任何助催化剂或共敏化剂的情况下，Ni节点的纳米片在pH = 4.0时表现出923±40 μmol g⁻¹ h⁻¹的光催化析氢速率。一项结合实验和理论的研究表明，纳米片光催化析氢存在还原猝灭途径。纳米片边缘的过渡金属节点被认为是活性位点。密度泛函理论（DFT）计算将纳米片不同的催化活性归因于各种过渡金属节点处H吸附自由能的差异。
