Exploring the Reaction Mechanism of Methanol Steam Reforming on CuZn ₃ O ₃ Cluster: A Density Functional Theory Study

Hydrogen gas is not only an essential industrial raw material but also an important clean energy. The hydrogen production by methanol steam reforming (MSR) has attracted much attention due to its mild reaction conditions and high hydrogen yield. Herein, the MSR reactions on CuZn 3 O 3 cluster are explored using theoretical calculations. It is found that the adjacent Cu and Zn atoms in CuZn 3 O 3 cluster play the synergistic roles in the MSR reaction. Specifically, the reaction starts with the adsorption of H 2 O and CH 3 OH on the Zn atoms. Then, the adsorbed CH 3 OH and H 2 O dehydrogenate, and the produced oxygen‐containing intermediates (CH 3 O* and *OH) remain adsorbed on the Zn atoms. The dissociated H atoms migrate to the nearby Cu atoms. In their subsequent dehydrogenation, this rule is still followed. With the participation of H 2 O, CH 2 O* combines with OH* to form CH 2 OOH*, followed by consecutive dehydrogenation to produce CO 2 and H 2 . Moreover, the formate (HCOO*) pathway is the least energy‐demanding pathway compared with the carboxyl (COOH*) pathway. The synergistic roles of adjacent Cu and Zn atoms in CuZn 3 O 3 cluster may provide insight into the structure‐activity relationship of CuZnO interfacial sites in related MSR catalysts.