Catalytic CO₂ hydrogenation toward net-zero fuels and chemicals

Heterogeneous catalytic CO₂ hydrogenation has emerged as a versatile route for converting captured CO₂ and renewable H₂ into fuels and chemicals, with relevance to carbon circularity, energy storage, and the progressive defossilisation of chemical manufacturing. This review describes CO₂ hydrogenation as a complex network capable of delivering CO, methanol, methane, formates, dimethyl ether, and a broad range of C₂₊ products. We examine how catalyst composition and structure, including metal nuclearity, metal-oxide interfaces, oxygen vacancies, acid-base properties, and pore confinement, govern pathway competition and product selectivity, and we discuss the growing importance of tandem and multifunctional catalytic platforms. Particular attention is given to the dynamic evolution of active phases under reaction conditions, and to the role of in situ and operando characterisation, together with theoretical and kinetic analysis, in establishing meaningful structure-performance relationships. We further consider the emerging contribution of data-driven methods to catalyst screening, descriptor discovery, and optimisation. Beyond catalyst-level advances, this review addresses reactor and process constraints, including transport effects, scale-up, separation, feed variability, and system integration, and examines how life-cycle assessment, techno-economic analysis, and pilot-scale validation are needed to distinguish laboratory performance from deployable value. Taken together, this review provides an integrated framework for evaluating the scientific basis and practical prospects of CO₂ hydrogenation in a net-zero context.