We report a simple procedure that drastically reduces the E(Feⁱ/Fe⁰) and E0cat of the Fe^IIITPP·Cl catalyst via a synergetic effect with the imidazolium dications of the IL electrolyte, and its application in tandem carbonylations.

New hybrid photocathode assemblies were used in the photoelectrochemical CO₂ reduction in the presence of an ionic liquid that acts as both absorbent and electrolyte.

The industrial application of CO₂ methanation in Power-to-X (P2X) systems requires the development of highly active catalysts capable of operating at milder temperatures to ensure energy efficiency, while exhibiting high activity, stability and selectivity. This study reports the synthesis and optimization of Ni-based catalysts on Al₂O₃ supports, guided by a Design of Experiments (DoE, 2⁴ factorial design) approach. Initial optimization afforded a robust catalyst achieving 80% CO₂ conversion and >99% CH₄ selectivity at 325 °C. Remarkably, the incorporation of CeO₂ traces to the Ni-based catalyst substantially boosted catalytic activity, enabling higher conversions at temperatures up to 75 °C lower than the unpromoted catalyst. This improvement is attributed to Ni–CeO_x synergy, which facilitates CO₂ activation and Ni reducibility. Both formulations exhibited exceptional long-term stability over 100 h. Furthermore, process intensification via the Sorption-Enhanced Reaction Process (SERP) with the Ni-based catalyst demonstrated even superior efficiency, rapidly increasing CO₂ conversion beyond 95% with the same selectivity range. Our findings establish a clear and consistent pathway for industrial CO₂ valorization through next-generation P2X technology for high-purity synthetic natural gas (SNG) production. This process offers an efficient and sustainable route toward industrial defossilization by converting captured CO₂ and green H₂ into SNG that is readily usable within the existing energy infrastructure.

The electrochemical reduction of CO ₂ into valuable products is a promising strategy for mitigating atmospheric CO ₂ emissions, particularly coupled with solar energy. Among the possible products, CO is currently most attractive, both because it can combine with hydrogen to produce syngas, and because CO is a key reactant in the chemical industry. Copper‐based electrocatalysts are extensively investigated for CO ₂ reduction; however, their morphological and chemical evolution under operating conditions still needs to be clarified, to understand the relationship between morphology, structure, and catalytic activity. This paper discusses a Cu ₂ O–SnO ₂ based‐catalyst, designed to enhance CO selectivity, and studies its evolution under reaction conditions by operando electrochemical liquid‐phase transmission electron microscopy (EC‐LPTEM). First, the morphology and composition of the as‐prepared catalyst is characterized. Then, operando EC‐LPTEM is discussed and compared to the post mortem catalyst characterization, together with electrochemical behavior evaluated in the lab‐scale device. Different experimental conditions were studied to provide insights on how the catalyst modifies during the electrochemical activity. This characterization contributes to a better understanding of the possible mechanisms involved in the CO ₂ reduction, and of the factors influencing the catalyst stability and selectivity, supporting the development of improved catalysts for CO ₂ to syngas conversion.