Liu Li, Zhu Ting, Xia Mengwei, Zhu Yuanzheng, Ke Hanzhong, Yang Ming, Cheng Hansong, Dong Yuan
Hubei Energy Technology Innovation Center, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430074, P. R. China.
Key of Geological Survey and Evaluation of Ministry of Education, Institute of Advanced Studies, China University of Geosciences, Wuhan 430074, P. R. China.
Inorg Chem. 2023 Oct 23;62(42):17390-17400. doi: 10.1021/acs.inorgchem.3c02721. Epub 2023 Oct 10.
We present a comprehensive theoretical and experimental investigation of the hydrogenation and dehydrogenation of dibenzyltoluene (DBT) using Pd-, Pt-, Ru-, and Rh-supported metal catalysts to identify the optimal catalysts for hydrogen storage and release processes. Our results demonstrated significant variation in the catalytic activity of the metal catalysts. 5 wt % Rh/AlO and 5 wt % Pt/AlO showed the highest activity for hydrogenation and dehydrogenation with the highest selectivity and turnover frequency (TOF), respectively. Conversely, 5 wt % Pd/AlO and 5 wt % Ru/AlO exhibited lower catalytic activity toward full hydrogenation and dehydrogenation. Rh/AlO showed the best catalytic hydrogenation activity with a TOF of 26.49 h and a hydrogenation degree of 92.69% in 2 h, while Pt/AlO exhibited the best catalytic dehydrogenation activity with a released H volume of 3755 mL, a dehydrogenation degree of 78.23%, and a TOF of 39.56 h in 2 h. Additionally, we estimated the activation energies for hydrogenation and dehydrogenation to be 67.20 and 82.78 kJ/mol, respectively. Notably, the produced hydrogen gas was of high purity and suitable for use in fuel cells. Density functional theory (DFT) calculations were used to analyze the adsorption structure and reaction energy changes of all intermediate products of DBT on the surface of the chosen catalysts. Our research provides valuable insights into developing efficient catalysts for liquid organic hydrogen carriers.
我们对使用负载钯、铂、钌和铑的金属催化剂进行二苄基甲苯（DBT）的氢化和脱氢反应展开了全面的理论与实验研究，以确定用于储氢和释氢过程的最佳催化剂。我们的结果表明，金属催化剂的催化活性存在显著差异。5 wt% Rh/AlO和5 wt% Pt/AlO分别在氢化和脱氢反应中表现出最高的活性，具有最高的选择性和周转频率（TOF）。相反，5 wt% Pd/AlO和5 wt% Ru/AlO对完全氢化和脱氢的催化活性较低。Rh/AlO在2小时内表现出最佳的催化氢化活性，TOF为26.49 h，氢化度为92.69%，而Pt/AlO在2小时内表现出最佳的催化脱氢活性，释放的H体积为3755 mL，脱氢度为78.23%，TOF为39.56 h。此外，我们估计氢化和脱氢的活化能分别为67.20和82.78 kJ/mol。值得注意的是，产生的氢气纯度很高，适用于燃料电池。采用密度泛函理论（DFT）计算来分析DBT在所选催化剂表面上所有中间产物的吸附结构和反应能量变化。我们的研究为开发用于液体有机氢载体的高效催化剂提供了有价值的见解。
