A Critical Look at Direct Catalytic Hydrogenation of Carbon Dioxide to Olefins

One of the main initiatives for fighting climate change is to use carbon dioxide as a resource instead of waste. In this respect, thermocatalytic carbon dioxide hydrogenation to high‐added‐value chemicals is a promising process. Among the products of this reaction (alcohols, alkanes, olefins, or aromatics), light olefins are interesting because they are building blocks for making polymers, as well as other important chemicals. Olefins are mainly produced from fossil fuel sources, but the increasing demand of plastics boosts the need to develop more sustainable synthetic routes. This review gives a critical overview of the most recent achievements in direct carbon dioxide hydrogenation to light olefins, which can take place through two competitive routes: the modified Fischer–Tropsch synthesis and methanol‐mediated synthesis. Both routes are compared in terms of catalyst development, reaction performance, and reaction mechanisms. Furthermore, practical aspects of the commercialization of this reaction, such as renewable hydrogen production and carbon dioxide capture, compression, and transport, are discussed. It is concluded that, to date, the catalysts used in the carbon dioxide hydrogenation reaction give a wide product distribution, which reduces the specific selectivity to lower olefins. More efforts are needed to reach better control of the C/H surface ratio and interactions within the functionalities of the catalyst, as well as understanding the reaction mechanism and avoiding deactivation. Renewable H 2 production and carbon dioxide capture and transport technologies are being developed, although they are currently still too expensive for industrial application.