Climate change is an escalating global issue, visibly affecting ecosystems and human societies. Balancing environmental protection with industrial and technological growth now becomes the key challenge. Among mitigation strategies, the capture and utilization of greenhouse gases, particularly the conversion of CO2 to valuable chemicals via hydrogenation, has attracted substantial attention. Yet, the practical application of CO2 as chemical feedstock is complicated by its inherent chemical stability and the lack of effective catalysts optimized at atomic and nanoscale levels. Indeed, the complexity of the catalytic reaction network for CO2 hydrogenation into C2+ oxygenates and hydrocarbons significantly exceeds the notorious complexity of the CO hydrogenation reaction. Experimental observations suggest the existence of numerous intermediates on the surface of transition metal catalysts in this process, including CO*, CHO*, HCOO*, COOH*, and CHx*. Although the modeling of catalytic reaction networks is incredibly helpful for understanding key factors driving various chemical reactions, the construction and analysis of microkinetic models covering reaction networks for CO2 and CO hydrogenation is greatly complicated by hundreds of the involved intermediates. In particular, the complexity of these models serves as the bottleneck for the rational design of new catalysts through identifying key intermediates and constructing Sabatier volcano plots. Moreover, realistic modeling of chemical processes needs to account for the nanostructure of the applied catalysts to minimize the gap between the computational predictions and the experimental observations. Indeed, nanostructuring is well-known for generating uniquely active sites with coordinatively unsaturated metal atoms on the catalyst surface. Moreover, surface intermediates may diffuse between active sites under the high temperatures typical of heterogeneous catalytic hydrogenation. Thus, advancing beyond simplistic models of ideal surfaces to more nuanced representations is essential for accurate microkinetic simulations of complex, multistep catalytic processes.