Localized Phase Transformation Triggering Lattice Matching of Metal Oxide and Carbonate Hydroxide for Efficient CO₂ Photoreduction

Abstract

Orderly heterostructured catalysts, which integrate nanomaterials of complementary structures and dimensions into single‐entity structures, have hold great promise for sustainability applications. In this work, it is showcased that air as green reagent can trigger in situ localized phase transformation and transform the metal carbonate hydroxide nanowires into ordered heterostructured catalyst. In single‐crystal nanowire heterostructure, the in situ generated and nanosized Co3O4 will be anchored in single‐crystal Co6(CO3)2(OH)8 nanowires spontaneously, triggered by the lattice matching between the (220) plane of Co3O4 and the (001) plane of Co6(CO3)2(OH)8. The lattice matching allows intimate contact at heterointerface with well‐defined orientation and strong interfacial coupling, and thus significantly expedites the transfer of photogenerated electrons from tiny Co3O4 to catalytically active Co6(CO3)2(OH)8 in single‐crystal nanowire, which elevates the catalytic efficiency of metal carbonate catalyst in the CO2 reduction reaction (VCO = 19.46 mmol g−1 h−1 and VH2 = 11.53 mmol g−1 h−1). The present findings add to the growing body of knowledge on exploiting Earth‐abundant metal‐carbonate catalysts, and demonstrate the utility of localized phase transformation in constructing advanced catalysts for energy and environmental sustainability applications.

Revealing the Lattice Carbonate Mediated Mechanism in Cu2(OH)2CO3 for Electrocatalytic Reduction of CO2 to C2H4

“…Regarding the possible carbon‐containing species, carbonates are being found to be reactive intermediates during CO 2 RR due to their equilibrium with bicarbonate. [ 12 ] Moreover, carbonate intermediates in situ generated on catalyst surface during CO 2 RR have been found to promote CO 2 RR kinetics, both in photocatalysis [ 13 ] and electrocatalysis. [ 14 ] Further, recently, Ma et al.…”

Coupling homogeneous and heterogeneous catalysis for the efficient and selective activation of H2O2

“…In contrast, heterogeneous catalysts are readily recyclable and can offer tailorable active sites for a given catalytic reaction. Nevertheless, it is hard to engineer their complex catalytic sites in a uniform geometrical and electronic environment, 6–8 and a low level of atom utilization is typical of heterogeneous catalysts. 9 Therefore, it is an exciting approach to bridge the gap between these two important fields of chemistry and design homogeneous and heterogeneous catalysts can complement each other with their respective advantages.…”