Microenvironment: An efficient avenue for converting CO2 to high-value compounds

The greenhouse gas CO2 is of considerable and particular interest for use as a next generation feedstock in different types of bioconversions to create valuable products on a large scale. However, this gaseous subsrate is a highly stable molecule with strong C=O bonds, non-polarity, low electron, and proton affinity, posing challenges for efficient enzymatic bioconversion in aqueous media. To demonstrate the construction of efficient catalytic systems, in this review, we first discuss recent advances in engineering enzyme structures and optimal microenvironments to improve the bioactivation efficiency of CO2 to C1 compounds. Based on these understandings, we then discuss the construction of artificial multi-enzymatic cascade reaction pathways or enzyme-assisted microbial synthesis pathways for further conversion to multicarbon compounds from CO2. Finally, we highlight the perspectives of microenvironment controlling enzymatic bioconversion of CO2 as feedstock for a future sustainable world.