The development of efficient catalysts is one of the main challenges in CO₂ conversion to valuable chemicals and fuels. Herein, inspired by the knowledge of the thermocatalytic (TC) processes, Cu/ZnO and bare Cu catalysts enriched with Cu⁺¹ were studied to convert CO₂ via the electrocatalytic (EC) pathway. Integrating Cu with ZnO (a CO-generation catalyst) is a strategy explored in the EC CO₂ reduction to reduce the kinetic barrier and enhance C–C coupling to obtain C₂₊ chemicals and energy carriers. Herein, ethanol was produced with the Cu/ZnO catalyst, reaching a productivity of about 5.27 mmol·g_cat^–1·h^–1 in a liquid-phase configuration at ambient conditions. In contrast, bare copper preferentially produced C₁ products like formate and methanol. During CO₂ hydrogenation, a methanol selectivity close to 100% was achieved with the Cu/ZnO catalysts at 200 °C, a value that decreased at higher temperatures (i.e., 23% at 300 °C) because of thermodynamic limitations. The methanol productivity increased to approximately 1.4 mmol·g_cat^–1·h^–1 at 300 °C. Ex situ characterizations after testing confirmed the potential of adding ZnO in Cu-based materials to stabilize the Cu¹⁺/Cu⁰ interface at the electrocatalyst surface because of Zn and O enrichment by an amorphous zinc oxide matrix; while in the TC process, Cu⁰ and crystalline ZnO prevailed under CO₂ hydrogenation conditions. It is envisioned that the lower *CO binding energy at the Cu⁰ catalyst surface in the TC process than in the Cu¹⁺ present in the EC one leads to preferential CO and methanol production in the TC system. Instead, our EC results revealed that an optimum local CO production at the ZnO surface in tandem with a high amount of superficial Cu¹⁺ + Cu⁰ species induces ethanol formation by ensuring an appropriate local amount of *CO intermediates and their further dimerization to generate C₂₊ products. Optimizing the ZnO loading on Cu is proposed to tune the catalyst surface properties and the formation of more reduced CO₂ conversion products.

Advances and strategies of electrocatalytic CO ₂ conversion to alcohols on Cu-based catalysts is assessed with an outlook of current challenges for a practical application of this technology.

Electrochemical CO₂ reduction is a promising carbon capture and utilisation technology. Herein, a continuous flow gas diffusion electrode (GDE)-cell configuration has been studied to convert CO₂ via electrochemical reduction under atmospheric conditions. To this purpose, Cu-based electrocatalysts immobilised on a porous and conductive GDE have been tested. Many system variables have been evaluated to find the most promising conditions able to lead to increased production of CO₂ reduction liquid products, specifically: applied potentials, catalyst loading, Nafion content, KHCO₃ electrolyte concentration, and the presence of metal oxides, like ZnO or/and Al₂O₃. In particular, the CO productivity increased at the lowest Nafion content of 15%, leading to syngas with an H₂/CO ratio of ~1. Meanwhile, at the highest Nafion content (45%), C₂₊ products formation has been increased, and the CO selectivity has been decreased by 80%. The reported results revealed that the liquid crossover through the GDE highly impacts CO₂ diffusion to the catalyst active sites, thus reducing the CO₂ conversion efficiency. Through mathematical modelling, it has been confirmed that the increase of the local pH, coupled to the electrode-wetting, promotes the formation of bicarbonate species that deactivate the catalysts surface, hindering the mechanisms for the C₂₊ liquid products generation. These results want to shine the spotlight on kinetics and transport limitations, shifting the focus from catalytic activity of materials to other involved factors.

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.

This research is a significant step forward in understanding how the electrochemical cell setup influences CO₂ conversion. The performance of Cu–Zn–Al metal oxide-based catalysts was compared in two reactor configurations: a gas diffusion electrode (GDE) cell with an aqueous electrolyte and a Membrane Electrode Assembly (MEA) cell operating in the gas phase without catholyte. The different operations induced significant morphological and crystalline structural changes, profoundly impacting the catalytic behaviour. The MEA configuration, for instance, led to the formation of a higher Cu⁰/Cu¹⁺ ratio in the catalysts, promoting C–C coupling for C₂H₄ production. Conversely, the GDE operation favoured alcohol (ethanol and methanol) production by balancing copper oxidation states formed in situ in the presence of the aqueous catholyte. Zn and Al oxides also played a role in stabilising the resulting Cu species, some of which remained oxidised on the electrode surface. These findings underscore the crucial influence of varying cell operation conditions on catalyst reconstruction, shaping the quantity of Cu⁰ + Cu¹⁺ species formed in situ to tailor catalyst selectivity.

Carbon dioxide (CO₂) hydrogenation to obtain valuable chemicals and fuels via thermocatalysis or electrocatalysis is a promising and sustainable method for CO₂ utilization.