Ordered macroporous superstructure of defective carbon adorned with tiny cobalt sulfide for selective electrocatalytic hydrogenation of cinnamaldehyde

Electrocatalytic selective hydrogenation of α,β-unsaturated aldehydes represents a sustainable approach to achieve the highly value-added products, while the kinetic and selectivity are still greatly depend on the elaborated nanostructure design of electrocatalysts. In this study, by the sulfidation of ordered macroporous ZIF-67 single crystals, the ordered macroporous superstructure of carbon with abundant edge defects was achieved, where the tiny CoS nanoparticles are favorably anchored with homogeneous dispersion. Impressively, this superstructured electrocatalyst exhibited a remarkable activity towards the selective hydrogenation of cinnamaldehyde to hydrocinnamaldehyde with water as hydrogen source, acquiring the highest selectivity up to 92.1 % at 12 mA cm –2 with a cinnamaldehyde conversion of 89.6 %. The further experimental analysis combined with the density functional theory calculations revealed that the preferential absorption of C C over the tiny CoS nanoparticles with the maximal site accessibility, and the facilitated mass and charge transfer enabled by the ordered macropore engineering, jointly contribute to the excellent electrocatalytic performance. Additionally, this electrocatalyst also exhibited good expandability for several kinds of α,β-unsaturated aldehydes/ketones with different functional groups. Our findings offer new insights into the electrocatalytic selective hydrogenation, emphasizing the role of ordered pore engineering in constructing favorable microenvironments and synergizing active sites.