Sun Na, Si Xiuwen, Wei Xiaoqi, Zhou Xue, Yu Han, Ding Fu, Kong Xiangru, Sun Yaguang
Key Laboratory of Inorganic Molecule-Based Chemistry of Liaoning Province, Shenyang University of Chemical Technology, Shenyang, 110142, China.
School of Materials Science and Engineering National Institute for Advanced Materials TKL of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin, 300350, China.
Small. 2025 Jan;21(1):e2407933. doi: 10.1002/smll.202407933. Epub 2024 Oct 31.
Elucidating the correlation of active sites and catalytic activity in multi-component metal-organic frameworks (MOFs) is key to understanding the mechanism of oxygen evolution reaction (OER), yet it remains nebulous. Herein, a direct pathway combining theoretical prediction with anchoring high-valence metals is proposed on MOFs to reveal the mechanism of the OER reaction. Density functional theory (DFT) predicts that the co-modulation by Mo and Co atoms can enhance the conductance of CoMOF and optimize the adsorption-free energies of the OER intermediates. Guided by the theoretical prediction, the Co-based MOFs grown on Ni foams are doped with high valence Mo, which is used as model catalysts for the quantitative study of the composition-dependent OER performance. With Co/Mo in the ratio of 5:1 for the highest OER activity (impressively overpotential of 324 mV at 100 mA cm and a Tafel slope of 96.07 mV dec) and excellent stability (maintains for 200 h at 100 mA cm), the catalysts in this work is superior to commercial benchmarks electrocatalysts (RuO/NF, 420 mV, 199.12 mV dec). This work sheds light on the tailoring of the active sites of MOFs, which is highly correlated with the activity of the OER.
阐明多组分金属有机框架（MOF）中活性位点与催化活性之间的相关性是理解析氧反应（OER）机理的关键，但目前仍不清楚。在此，提出了一种将理论预测与锚定高价金属相结合的直接途径，以揭示MOF上OER反应的机理。密度泛函理论（DFT）预测，Mo和Co原子的共调制可以提高CoMOF的电导率，并优化OER中间体的吸附自由能。在理论预测的指导下，在泡沫镍上生长的Co基MOF被高价Mo掺杂，用作定量研究成分依赖的OER性能的模型催化剂。Co/Mo比例为5:1时具有最高的OER活性（在100 mA cm时过电位低至324 mV，塔菲尔斜率为96.07 mV dec）和出色的稳定性（在100 mA cm下可保持200 h），这项工作中的催化剂优于商业基准电催化剂（RuO/NF，420 mV，199.12 mV dec）。这项工作为MOF活性位点的调控提供了思路，这与OER的活性高度相关。
