Low Temperature Methanol-Water Reforming over the Alcohol Dehydrogenase and Immobilized Ruthenium Complex.

Abstract

Hydrogen is one of the most promising sustainable energy carrier for its high gravimetric energy density and extensive source. Nowadays, hydrogen production and storage are the main constraints for its commercialization. As a current research focus, hydrogen production from methanol-water reforming, especially at low temperature, is particularly important. In this research, we proposed a novel reaction path for low temperature methanol reforming through synergetic catalysis. There are two main steps in this synergetic catalytic process, which are CH 3 OH→HCHO→H 2 and CH 3 OH→NADH→H 2 respectively. We employ the alcohol dehydrogenase (ADH) and coenzyme I (NAD + ) for methanol catalytic dehydrogenation at low temperature, which could generate formaldehyde and reductive coenzyme I (NADH). The covalent triazine framework immobilized ruthenium complex (Ru-CTF) was prepared afterwards. On one hand, the catalyst exhibits high activity for the formaldehyde-water shift reaction, to generate hydrogen and carbon dioxide, namely, CH 3 OH→HCHO→H 2 . On the other hand, the NADH dehydrogenation is also catalyzed by the Ru-CTF, producing NAD + and hydrogen, and that is CH 3 OH→NADH→H 2 . \xa0The hydrogen production rate achieves 157 mmol h -1 mol -1 Ru at the optimum pH (pH=8.1). Additionally, the hydrogen production rate increases linearly with the ADH dosage, the hydrogen production rate reaches 578 mmol h -1 mol -1 Ru when the ADH dosage is 180 unit at 35 ℃.