From CO₂ methanation to ambitious long-chain hydrocarbons: alternative fuels paving the path to sustainability

The clean and sustainable CO2 reutilization toward products of higher value is of great interest in a background of established environmental concerns and reducing the use of fossil fuels. As promising alternative fuels, hydrocarbons are more valuable than CO, alcohols or formate and can be directly used in existing infrastructures with high energy densities. The prominent development of catalysts capable of selectively converting CO2 into hydrocarbons, from methane to short olefins and long carbon-chains, has been reflected in an expanding volume of exploratory works, which suitably demand interpretive and continuous revision. In the past decades, conventional studies on the thermochemical conversion of CO2 have consistently unlocked meaningful pathways toward the synthesis of hydrocarbons covering a fairly wide range of molecular weights. Conversely, both electrochemically and photochemically driven reactions have only now started to unveil encouraging results, with an extensive number of critical citations outlining the continuous emergence of very recently published reports. In a field in need of urgent development, the authors provide, in a clear form, a detailed retrospective on benchmark catalysts, pioneering approaches and competitive developments in this subject, mechanistic difficulties, emerging stability issues, and reactor design, while highlighting the latest noteworthy reports. Most importantly, this review highlights the advances toward an increase in the hydrocarbon chain-length in the synthesis of highly competitive alternative fuels. Comparisons of valuable thermochemical, electrochemical and photochemically driven strategies in the conversion of CO2 to hydrocarbons are expected to serve as guidelines to disclose promising pathways in a field where mechanistic uncertainties remain a bottleneck for determining the product selectivity. The authors summarize leading and inquisitive perspectives with a focus on the viability and practicability of each approach at a larger scale, while tentatively paving the way to stimulate progress in this field.