TY  - JOUR
AU  - Dong, Wanrong
AU  - Cai, Jinde
AU  - Sun, Qimei
AU  - Luan, Likun
AU  - Ji, Xiuling
AU  - Zeng, Shaojuan
AU  - Huang, Yuhong
PY  - 2025
TI  - Sustainable hybrid photo/electro-enzyme systems for CO2 conversion
JO  - Green Chemical Engineering
SN  - 2096-9147
SP  - 518
EP  - 537
VL  - 6
IS  - 4
AB  - Carbon dioxide (CO2), as an abundant and renewable carbon feedstock, holds immense potential for sustainable biomanufacturing. However, natural carbon fixation pathways, such as the Calvin-Benson-Bassham (CBB) cycle and the reverse tricarboxylic acid (rTCA) cycle, suffer from intrinsic limitations, including low catalytic efficiency, high adenosine triphosphate (ATP) consumption, and oxygen sensitivity. Recent advances in synthetic biology and metabolic engineering have pioneered artificial pathways (e.g., the crotonyl-CoA/ethylmalonyl-CoA/hydroxybutyryl-CoA (CETCH) cycle) that bypass central metabolism, achieving higher fixation rates with reduced ATP consumption. Concurrently, photocatalytic and electrocatalytic systems have emerged as complementary strategies to address cofactor dependency and CO2 activation thermodynamic barriers. This review summarizes breakthroughs in (ⅰ) rational design for CO2 conversion pathway optimization, (ⅱ) photocatalysis, and (ⅲ) electrocatalysis for CO2 activation and cofactor regeneration. By integrating these disciplines, synergistic systems achieve unprecedented efficiency in converting CO2 to Cn compounds (e.g., ethanol, glyoxylate, sugar, and starch) and establish a foundation for scalable carbon-negative biotechnologies. However, challenges remain, including enzyme denaturation under operational stresses, inefficiencies in multi-enzyme cascades due to kinetic mismatches, and the need for sustainable metrics to ensure net-negative carbon footprints. Future research should prioritize material innovation, CO2 assimilation system integration, and optimization to unlock higher efficiency CO2 conversion, aligning with global decarbonization goals while producing high-value chemicals.
UR  - https://doi.org/10.1016/j.gce.2025.06.006
DO  - 10.1016/j.gce.2025.06.006