Methanol as a Hydrogen Carrier: Kinetic and Thermodynamic Drivers for its CO₂‐Based Synthesis and Reforming over Heterogeneous Catalysts

Abstract

Abstract Methanol is an attractive energy vector in a closed loop including its synthesis from CO 2 and H 2 and on‐demand reforming to the starting feedstocks. Catalytic materials for the two reactions were mostly studied separately, with very few works assessing the feasibility of the same system for both. Here, key kinetic drivers of methanol synthesis (MS) and methanol steam reforming (MSR) were identified for the main catalyst families, with special focus on Cu−ZnO−Al 2 O 3 , In 2 O 3 , and Pd/ZrO 2 . It was shown that the relative activity level was preserved in either direction, whereas the distinctly favored (reverse) water‐gas shift modulated selectivity differently. Low selectivity in kinetically controlled MS could be overcome in MSR by exploiting thermodynamics as the driving force, with many catalysts unfit for MS still comprising appealing candidates for MSR and only few being suited for MS as well as MSR. Overall, readily identifiable properties describing catalyst behavior in the forward and backward reactions were highlighted, effectively linking research in the two fields and setting a stronger basis for developing a methanol‐based hydrogen storage unit with a single reactor.