Thermocatalytic CO2 conversion to value-added C2+ products: Catalyst design and catalytic system modulation

The excessive reliance on fossil fuels has driven a rapid increase in atmospheric CO 2 levels, exacerbating global warming and ocean acidification. The development of carbon-negative technologies is therefore essential, with CO 2 valorization in closed-loop cycles serving as a core strategy. CO 2 conversion generates a broad spectrum of products, from C 1 species to value-added C 2+ compounds with higher energy density and economic relevance. However, C 2+ formation remains challenging because it requires activation of the stable C=O bond and subsequent C-C coupling, both imposing significant thermodynamic and kinetic barriers. To elucidate the diverse conversion mechanisms underlying CO 2 reactions and facilitate the targeted design of pathway-optimized catalysts, this review classifies thermocatalytic CO 2 conversion into fully CO 2 -dependent carbon-supplying reaction (FCCR) and partially CO 2 -dependent carbon-supplying reaction (PCCR). By employing CO 2 hydrogenation and esterification as the respective FCCR and PCCR model reactions, the pathway-oriented design of heterogeneous catalysts is comprehensively evaluated, offering an in-depth dissection of the key mechanisms governing C 2+ selectivity and conversion efficiency. Finally, existing challenges and opportunities are assessed to provide a rational blueprint for next-generation CO 2 valorization.