Benzyl-methylbenzyl-benzene: Improving hydrogen storage and release performance of dibenzyltoluene based liquid organic hydrogen carrier

Liquid organic hydrogen carrier (LOHC) technology enables the safe, easy, and cost-effective storage and transportation of large quantities of hydrogen using inexpensive and mass-produced compounds. The LOHC materials play a crucial role in hydrogen storage capacity, reaction kinetics, reaction temperature, and reversibility. However, the development and optimization of LOHC materials is limited due to using of mass-produced materials for bulk hydrogen logistics. Herein, we propose a molecular engineering approach to overcome the limitations of commercial dibenzyltoluene (DBT)-based LOHC systems, considered one of the most promising LOHC materials based on the heat transfer oil, Marlotherm SH (MSH), owing to its superior physical properties (wide liquid range, and non-flammable properties), low price, and low toxicity. We devised a new chemical structure, benzyl-methylbenzyl-benzene (BMB), with highly improved dehydrogenation/hydrogenation performance achieved by rearranging the methyl group of DBT to overcome the limitations of slow reaction kinetics in terms of its chemical structure. The BMB exhibits a 150 % faster hydrogenation than MSH at 150 °C, and it releases 170 % more hydrogen compared to DBT at 270 °C. In addition, we analyzed the dehydrogenation/hydrogenation pathways according to the structures of DBT and BMB. Furthermore, we found that BMB (27 %) is inevitably generated in the MSH synthesis process alongside DBT (73 %). Based on this, we propose a streamlined and sustainable engineered method for improved MSH material manufacturing with a high BMB ratio (∼70 %). The scientific findings provide a fundamental understanding of DBT-based LOHC systems and new insights into the design of novel LOHC candidates.