Bio-integrated nano-biocatalytic hybrid interfacial systems for efficient CO ₂ conversion and utilization into valuable fuels and chemicals

Constant economic expansion, development, sustainability and agricultural progress raise energy consumption and CO2 emissions, which contribute to significant global climate change and pose enormous environmental risks. Therefore, developing technical solutions to reduce CO2 emissions and create a variety of useful goods, including materials, chemicals, copolymers and fuels, is essential to solve this problem. Breakthroughs, such as protein-inorganic nanoflowers, supercritical CO2-soluble polymers, and engineered metal–organic frameworks (MOFs) for enzyme immobilization, as well as precipitation-based nanoscale enzyme reactors (p-NERs), are paving the way for stable, cost-effective, and highly efficient CO2 conversion platforms. The interaction with nanostructured support is analysed for enhancing operational stability or activity retention, and depicts the ∼85% retention capacity after multiple cycles with elevated reaction conditions (pH ∼8.5). Hybrid nano bio systems have achieved catalytic benchmarks, in electro-assisted CO2 reduction to CO, as well as CO2 to methanol conversion with 95% efficiencies and ∼99% selectivity in nanoflower-based catalytic modification. The synergistic coupling of enzymatic catalysis with innovative materials presents a clear path toward sustainable and efficient CO2 conversion, significantly contributing to GHG emission reduction and accelerating the transition to a circular, carbon-neutral economy. This synergistic coupling shows how material characteristics, electron/proton transport and enzyme orientation procedures all have a direct effect on catalytic performance. The development of efficient catalysts and processes for the selective conversion of CO2 into specific chemicals remains a major challenge. Therefore, this review focuses on the material design, current mechanistic findings and challenges involved in setting up and maintaining such systems for efficient CO2 conversion.Abbreviations: ADH: Alcohol dehydrogenase; AgNCs: Silver nanoclusters; APTES: Aminopropyltriethoxysilane; bCA: bovine carbonic anhydrase; CA: Carbonic anhydrase; CAPEX: Capital expenditures; CCUS: Carbon capture, utilization, and storage; CDR: Carbon dioxide removal; CE: Current efficiency; CETCH: Crotonyl-Enoyl-Thiolase and Carboxylase/Hydratase cycle; CLEAs: Cross-linked enzyme aggregates; CmFDH: Candida methylica formate dehydrogenase; CNTs: Carbon nanotubes; CODH: Carbon-Monoxide Dehydrogenase; COFs: Covalent organic frameworks; CtFDH: Chaetomium thermophilum formate dehydrogenase; Cys: Cystein; EPC: Enzyme precipitate coating; FalDH: Fatty Aldehyde Dehydrogenase; FDH: Formate dehydrogenase; GDE: Gas Diffusion Electrode; GDH: Glutamate dehydrogenase; GHG: Greenhouse Gas; Gt: Gigatons; H2ase: Hydrogenase; HER: Hydrogen evolution reaction; HOMO: Highest occupied molecular orbital; HRP: Horseradish peroxidase; LCA: life-cycle assessment; LDHs: Layered double hydroxide; LUMO: Lowest unoccupied molecular orbital; MES: Microbial electrosynthesis system; MES: Multilayer electrolyser stack; ML: Machine learning; MOF’s: Metal–organic frameworks; MOG: Metal–organic gel; MRs: Membrane reactors; NADH: Nicotinamide Adenine Dinucleotide; NCs: Nanoclusters; NF: Nanoflower; NPs: Nanoparticles; NZs: Nanozymes; OF: Oligofluorene; OPEX: Operating expenses; ORR: Oxygen reduction reactions; Ovs: Oxygen vacancies; PDA: Polydopamine; PDMS: Polydimethylsiloxane; PEC: Photoelectrochemical; PEG: Polyethylene glycol; PEI: Polyethyleneimine; PES: Polyethersulfone; PMAA: Polymethacrylic acid; p-NERs: Precipitation-based nanoscale enzyme reactor; POPs: Porous organic polymers; PSA: Pressure swing adsorption; PTP: Polythiophene; PVDF: Polyvinylidene fluoride; RR: Reduction reactions; RuP: Phosphonated Ruthenium(II) photosensitizer; SFNs: Solvent-free nanofluids; SVM: Support vector machine; SWCNHs: Single-walled carbon nano horns; TCA: Tricarboxylic acid; TEA: Techno-economic analysis; TOF: Turnover frequency; TON: Turnover number; TSA: Temperature swing adsorption; WGI: World Greenhouse Gas Initiative; ZIFs: Zeolite imidazolate frameworks.