Nanoscale Ni–NiO–ZnO Heterojunctions for Switchable Dehydrogenation and Hydrogenation through Modulation of Active Sites

Catalysts consisting of metal–metal hydroxide/oxide interfaces are highly in demand for advanced catalytic applications as their multicomponent active sites will enable different reactions to occur in close proximity through synergistic cooperation when a single component fails to promote it. To address this, herein we disclosed a simple, scalable, and affordable method for synthesizing catalysts consisting of nanoscale nickel–nickel oxide–zinc oxide (Ni–NiO–ZnO) heterojunctions by a combination of complexation and pyrolytic reduction. The modulation of active sites of catalysts was achieved by varying the reaction conditions of pyrolysis, controlling the growth, and inhibiting the interlayer interaction and Ostwald ripening through the efficient use of coordinated acetate and amide moieties of Zn–Ni materials ( ZN–O ), produced by the reaction between hydrazine hydrate and Zn–Ni–acetate complexes. We found that the coordinated organic moieties are crucial for forming heterojunctions and their superior catalytic activity. We analyzed two antagonistic reactions to evaluate the performance of the catalysts and found that while the heterostructure of Ni–NiO–ZnO and their cooperative synergy were crucial for managing the effectiveness and selectivity of the catalyst for dehydrogenation of aryl alkanes/alkenes, they failed to enhance the hydrogenation of nitro arenes. The hydrogenation reaction was influenced by the shape, surface properties, and interaction of the hydroxide and oxide of both zinc and nickel, particularly accessible Ni(0). The catalysts showed functional group tolerance, multiple reusabilities, broad substrate applicability, and good activity for both reactions.