CuZnAl-Oxide Nanopyramidal Mesoporous Materials for the Electrocatalytic CO2 Reduction to Syngas: Tuning of H2/CO Ratio

Inspired by the knowledge of the thermocatalytic CO₂ reduction process, novel nanocrystalline CuZnAl-oxide based catalysts with pyramidal mesoporous structures are here proposed for the CO₂ electrochemical reduction under ambient conditions. The XPS analyses revealed that the co-presence of ZnO and Al₂O₃ into the Cu-based catalyst stabilize the CuO crystalline structure and introduce basic sites on the ternary as-synthesized catalyst. In contrast, the as-prepared CuZn- and Cu-based materials contain a higher amount of superficial Cu⁰ and Cu¹⁺ species. The CuZnAl-catalyst exhibited enhanced catalytic performance for the CO and H₂ production, reaching a Faradaic efficiency (FE) towards syngas of almost 95% at −0.89 V vs. RHE and a remarkable current density of up to 90 mA cm⁻² for the CO₂ reduction at −2.4 V vs. RHE. The physico-chemical characterizations confirmed that the pyramidal mesoporous structure of this material, which is constituted by a high pore volume and small CuO crystals, plays a fundamental role in its low diffusional mass-transfer resistance. The CO-productivity on the CuZnAl-catalyst increased at more negative applied potentials, leading to the production of syngas with a tunable H₂/CO ratio (from 2 to 7), depending on the applied potential. These results pave the way to substitute state-of-the-art noble metals (e.g., Ag, Au) with this abundant and cost-effective catalyst to produce syngas. Moreover, the post-reaction analyses demonstrated the stabilization of Cu₂O species, avoiding its complete reduction to Cu⁰ under the CO₂ electroreduction conditions.