How enzyme modifications influence sustainable CO2 fixation? A tradeoff between enzyme structures and functions

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Green Chem., 2026, Accepted ManuscriptDOI: 10.1039/D6GC02548J, Critical Review Open Access &nbsp This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.Arnab Sil, Aaftaab Sethi, Diksha Dhiman, Meena Bisht, Gregory Franklin, Dibyend…

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How enzyme modifications influence sustainable CO2 fixation? A tradeoff between enzyme structures and functions

Abstract

Rising atmospheric CO2 concentrations, driven by industrial activity and fossil fuel combustion, have intensified global climate challenges. Among various existing CO2 capture and conversion methods, the enzymatic approach stands out for its high stereospecificity, chemical selectivity, and ability to operate under ambient, environmentally benign conditions. Despite its promise, enzymatic CO2 fixation faces key challenges, including limited catalytic activity, insufficient stability, oxygen sensitivity, high operational costs, poor CO2 solubility, and an incomplete understanding of reaction mechanisms. To address these issues and improve economic viability, researchers have explored diverse approaches to enzyme modification, such as surface, protein, and solvent engineering. Recent reviews have typically emphasized narrow themes, like biomimetic systems or surface functionalization. This review critically examined the progress in surface engineering/immobilization, protein engineering, solvent engineering and computational design including artificial intelligence and machine learning strategies. This study highlights the structure-function relationships of 14 representative enzymes (carboxylases, dehydrogenases, and anhydrases) with strong relevance to CO2 conversion. Enzymatic CO2 fixation has been explored predominantly using only three enzymes-CA, FDH, and RuBisCo-with limited number of tandem cascade systems, while, surface immobilization and protein engineering are the most widely reported strategies. The discussion outlines a progression from single-enzyme optimization to multi-enzyme cascade systems capable of producing valuable compounds such as bio-alcohols, polymers including bioplastics, sugars, organic acids, and amino acids. A central challenge lies in balancing activity and stability, as improvements in one often compromise the other. Future progress will depend on system-level design that harmonizes enzyme efficiency, durability, cofactor use, and process costs to enable scalable, economically and environmentally sustainable CO2 utilization technologies.

• This article is part of the themed collections: 2026 Green Chemistry Reviews and Green Chemistry Emerging Investigators Series