Xing Danning, Wang Huixuan, Cui Zheng, Lin Lingtong, Liu Yuanyuan, Dai Ying, Huang Baibiao
Shandong Institute of Advanced Technology, Shandong 250100, PR China.
The First Affiliated Hospital of Shandong First Medical University, Shandong 250100, PR China.
J Colloid Interface Sci. 2024 Feb 15;656:309-319. doi: 10.1016/j.jcis.2023.11.104. Epub 2023 Nov 20.
The poor electrically conductivity of metal-organic frameworks (MOFs) is the main factor hinder their application in electrocatalysis field. In this work, we synthesize a conductive two-dimensional (2D) trimetallic π-d conjugated metal-organic framework (MOF) FeCoNi-BHT (BHT = 1,2,3,4,5,6-benzenehexathiol) through coordinating Co, Fe and Ni ions with 1,2,3,4,5,6-benzenehexathiol ligands. FeCoNi-BHT is demonstrated possessing homogeneously dispersed abundant Co-S, Fe-S, Ni-S single-atom active sites (14.26 wt% of the metal elements) and a large specific surface area (267.05 mg). The room temperature conductivity of FeCoNi-BHT is measured to be 92 S m, indicating its metallic behavior. DFT theoretical calculation reveals that the π-d conjugation structure of FeCoNi-BHT is responsible for its metallic behavior. In addition, FeCoNi-BHT exhibits prominent oxygen evolution reaction (OER) activity (an overpotential of 266 mV vs. RHE at 10 mA cm and a Tafel value of 58 mV dec) in alkaline media. The combined experimental and DFT studies reveal that the synergistic effect of Co, Fe, Ni sites of FeCoNi-BHT contribute to its prominent OER activity. This work paves a new avenue of developing 2D π-d conjugated MOFs with different metal centers as highly efficient eletrocatalysts.
金属有机框架材料（MOFs）较差的导电性是阻碍其在电催化领域应用的主要因素。在本工作中，我们通过将钴、铁和镍离子与1,2,3,4,5,6 - 苯六硫醇配体配位，合成了一种导电的二维（2D）三金属π - d共轭金属有机框架材料FeCoNi - BHT（BHT = 1,2,3,4,5,6 - 苯六硫醇）。结果表明，FeCoNi - BHT具有均匀分散的大量Co - S、Fe - S、Ni - S单原子活性位点（金属元素含量为14.26 wt%）和较大的比表面积（267.05 mg）。FeCoNi - BHT的室温电导率经测量为92 S/m，表明其具有金属特性。密度泛函理论（DFT）计算表明，FeCoNi - BHT的π - d共轭结构是其具有金属特性的原因。此外，FeCoNi - BHT在碱性介质中表现出显著的析氧反应（OER）活性（在10 mA/cm²时相对于可逆氢电极（RHE）的过电位为266 mV，塔菲尔值为58 mV/dec）。结合实验和DFT研究表明，FeCoNi - BHT中Co、Fe、Ni位点的协同作用有助于其显著的OER活性。这项工作为开发具有不同金属中心的二维π - d共轭MOFs作为高效电催化剂开辟了一条新途径。
