Due to its high gravimetric energy density and its extensive sources, hydrogen is a promising energy carrier. However, due to its flammability and explosiveness, there are still challenges for the storage and transportation of hydrogen. In situ methanol reforming is believed to be feasible and promising for hydrogen storage and production. While conventional methanol reforming is carried out at high temperature, it accompanies methanol cracking and CO production. In this research we describe a new reaction pathway for hydrogen production from bioinspired methanol reforming at room temperature. On the one hand, we use alcohol dehydrogenase (ADH) and coenzyme I (NAD +) for methanol dehydrogenation (CH3OH + NAD + → HCHO + NADH + H +). The methanol could be oxidized by NAD +, the oxidation product and the reduction product are formaldehyde or reductive coenzyme I (NADH) during the ADH-assisting methanol dehydrogenation. Then the Ruthenium Metal Organic Frameworks (Ru-MOFs) are made. In addition to high biocompatibility with ADH, this multifunctional catalyst has a high activity in formaldehyde decomposition (HCHO + H2O → CO2 + 2H2) and NADH dehydrogenation (NADH + H + → H2 + NAD +). Finally, the hydrogen is successfully produced through the synergistic effect of ADH and Ru-MOFs through methanol reforming at room temperature. The hydrogen production rate is 51 mmol h-1 mol-1 Ru at 25 ℃ and depends on the pH value and the temperature of the solution. The maximum hydrogen production rate is up to 107 mmol h-1 mol-1Ru at 35 ℃, pH 7.5. This research will provide us with some new inspiration for low temperature methanol reforming as well as the enzymatic catalytic process.

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