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• W3016558044 abstract "Many self-photosensitized bioinorganic hybrid systems have recently been developed by exploiting material–microbe interactions. These hybrids combine the complex functionality of biological systems and inorganic materials to efficiently catalyze the photoreduction of CO2 to chemicals and fuel precursors.The multifaceted mechanism of material–microbe interactions depends on several factors, including the band-gap of the material, biomineralization strategy, biocompatibility, nature of membrane-bound proteins, and electron carriers.Well-organized biohybrid materials can be used to develop bio-inspired materials for biomedical and therapeutic applications. Genetically improving microbes can further improve the biohybrid performance. Sustainable production of solar-based chemicals is possible by mimicking the natural photosynthetic mechanism. To realize the full potential of solar-to-chemical production, the artificial means of photosynthesis and the biological approach should complement each other. The recently developed hybrid microbe–metal interface combines an inorganic, semiconducting light-harvester material with efficient and simple microorganisms, resulting in a novel metal–microbe interface that helps the microbes to capture energy directly from sunlight. This solar energy is then used for sustainable biosynthesis of chemicals from CO2. This review discusses various approaches to improve the electron uptake by microbes at the bioinorganic interface, especially self-photosensitized microbial systems and integrated water splitting biosynthetic systems, with emphasis on CO2 bioelectrosynthesis. Sustainable production of solar-based chemicals is possible by mimicking the natural photosynthetic mechanism. To realize the full potential of solar-to-chemical production, the artificial means of photosynthesis and the biological approach should complement each other. The recently developed hybrid microbe–metal interface combines an inorganic, semiconducting light-harvester material with efficient and simple microorganisms, resulting in a novel metal–microbe interface that helps the microbes to capture energy directly from sunlight. This solar energy is then used for sustainable biosynthesis of chemicals from CO2. This review discusses various approaches to improve the electron uptake by microbes at the bioinorganic interface, especially self-photosensitized microbial systems and integrated water splitting biosynthetic systems, with emphasis on CO2 bioelectrosynthesis. Increasing CO2 concentration, due to anthropogenic activities, is believed to have a serious impact on climate. To reverse such an impact, there is an urge to develop sustainable CO2-capture and -utilization technologies, along with a reliance on renewable energy [1.Chu S. et al.The path towards sustainable energy.Nat. Mater. 2017; 16: 16Crossref Scopus (2161) Google Scholar, 2.Mustafa A. et al.Current technology development for CO2 utilization into solar fuels and chemicals: a review.J. Energy Chem. 2020; 49: 96-123Crossref Scopus (103) Google Scholar, 3.Jiang Y. et al.Carbon dioxide and organic waste valorization by microbial electrosynthesis and electro-fermentation.Water Res. 2019; 149: 42-55Crossref PubMed Scopus (132) Google Scholar, 4.Vidales A.G. et al.Combined energy storage and methane bioelectrosynthesis from carbon dioxide in a microbial electrosynthesis system.Bioresour. Technol. Rep. 2019; 8: 100302Crossref Scopus (22) Google Scholar]. The production and use of renewable energy have recently been increasing [5.Dincer I. Renewable energy and sustainable development: a crucial review.Renew. Sust. Energ. Rev. 2000; 4: 157-175Crossref Scopus (1297) Google Scholar] and the use of surplus renewable energy to convert CO2 into organic fuels and chemical production has appeared as a novel alternative for CO2 utilization. In principle, the amount of CO2 generation should be equal to the amount consumed to create a carbon-neutral, sustainable paradigm [6.Davis S.J. et al.Net-zero emissions energy systems.Science. 2018; 360eaas9793Crossref PubMed Scopus (634) Google Scholar, 7.Mohan S. et al.A circular bioeconomy with biobased products from CO2 sequestration.Trends Biotechnol. 2016; 34: 506-519Abstract Full Text Full Text PDF PubMed Scopus (174) Google Scholar, 8.Senftle T.P. Carter E.A. The holy grail: chemistry enabling an economically viable CO2 capture, utilization, and storage strategy.Acc. Chem. Res. 2017; 50: 472-475Crossref PubMed Scopus (118) Google Scholar]. Over the years, different methods have been revealed to convert CO2 to chemicals and fuels, such as biocatalytic CO2 transformation via microbes or microalgae [9.Molitor H.R. et al.Maximum CO2 utilization by nutritious microalgae.ACS Sustain. Chem. Eng. 2019; 7: 9474-9479Crossref Scopus (17) Google Scholar, 10.Ghosh A. Kiran B. Carbon concentration in algae: reducing CO2 from exhaust gas.Trends Biotechnol. 2017; 35: 806-808Abstract Full Text Full Text PDF PubMed Scopus (37) Google Scholar, 11.Sultana S. et al.A review of harvesting clean fuels from enzymatic CO2 reduction.RSC Adv. 2016; 6: 44170-44194Crossref Google Scholar, 12.Chiranjeevi P. et al.Current trends in enzymatic electrosynthesis for CO2 reduction.Curr. Opin. Green Sustainable Chem. 2019; 16: 65-70Crossref Scopus (27) Google Scholar, 13.Schievano A. et al.Microbial synthesis, gas-fermentation and bioelectroconversion of CO2 and other gaseous streams.Front. 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Mater. 2014; 26: 4607-4626Crossref PubMed Scopus (1045) Google Scholar, 18.Ma S. Kenis P.J.A. Electrochemical conversion of CO2 to useful chemicals: current status, remaining challenges, and future opportunities.Curr. Opin. Chem. Eng. 2013; 2: 191-199Crossref Scopus (535) Google Scholar], and catalytic hydrogenation of CO2 [19.Rodemerck U. et al.Catalyst development for CO2 hydrogenation to fuels.ChemCatChem. 2013; 5: 1948-1955Crossref Scopus (123) Google Scholar,20.Ashley A.E. et al.Non-metal-mediated homogeneous hydrogenation of CO2 to CH3OH.Angew. Chem. Int. Ed. 2009; 48: 9839-9843Crossref PubMed Scopus (381) Google Scholar]. However, none of the systems can independently address the CO2 capture and utilization issues on a large scale. Microbial electrosynthesis (MES) (see Glossary) -based CO2 reduction has numerous advantages, including being able to operate under mild conditions, high product selectivity based on redox potential, and the use of renewable energy such as solar energy as the driving force without any additional CO2 generation [21.del Pilar Anzola Rojas M. et al.Effect of the electric supply interruption on a microbial electrosynthesis system converting inorganic carbon into acetate.Bioresour. Technol. 2018; 266: 203-210Crossref PubMed Scopus (69) Google Scholar, 22.del Pilar Anzola Rojas M. et al.Microbial electrosynthesis (MES) from CO2 is resilient to fluctuations in renewable energy supply.Energy Convers. Manag. 2018; 177: 272-279Crossref Scopus (81) Google Scholar, 23.Mateos R. et al.Long-term open circuit microbial electrosynthesis system promotes methanogenesis.J. Energy Chem. 2020; 41: 3-6Crossref Scopus (47) Google Scholar, 24.Srikanth S. et al.Electro-biocatalytic conversion of carbon dioxide to alcohols using gas diffusion electrode.Bioresour. Technol. 2018; 265: 45-51Crossref PubMed Scopus (75) Google Scholar]. Bioelectrosynthesis technology depends on the direct utilization of electrons as reducing equivalents from the electrode surface to convert CO2 into chemicals and fuels. However, this process is limited by the extracellular interaction between the living cell membranes of microbes and the electrode, as well as the inability of these microbes to cope with the intermittent nature of renewable electricity [21.del Pilar Anzola Rojas M. et al.Effect of the electric supply interruption on a microbial electrosynthesis system converting inorganic carbon into acetate.Bioresour. Technol. 2018; 266: 203-210Crossref PubMed Scopus (69) Google Scholar,22.del Pilar Anzola Rojas M. et al.Microbial electrosynthesis (MES) from CO2 is resilient to fluctuations in renewable energy supply.Energy Convers. Manag. 2018; 177: 272-279Crossref Scopus (81) Google Scholar]. For instance, a localized basic environment developing around the proton-consuming cathode can damage the immobilized microbial cells during the process of intensifying the CO2-reducing current [25.Rabaey K. Rozendal R.A. Microbial electrosynthesis—revisiting the electrical route for microbial production.Nat. Rev. Microbiol. 2010; 8: 706Crossref PubMed Scopus (1057) Google Scholar, 26.Batlle-Vilanova P. et al.Continuous acetate production through microbial electrosynthesis from CO2 with microbial mixed culture.J. Chem. Technol. Biotechnol. 2016; 91: 921-927Crossref Scopus (99) Google Scholar, 27.Cestellos-Blanco S. et al.Solar-driven carbon dioxide fixation using photosynthetic semiconductor bio-hybrids.Faraday Discuss. 2019; 215: 54-65Crossref PubMed Google Scholar]. Further, electron losses due to various factors like sluggish kinetics of charge transfer across the completely different surfaces of the microbe and the electrode are major challenges. Due to significant developments in nanotechnology, solar energy conversion efficiency by nanostructured semiconducting materials has reached up to 20% (compared with a theoretical limit of 33.7%), yet the solar-assisted CO2-to-chemical selectivity is very low [28.Royanian S. et al.Efficiency enhancement of ultra-thin CIGS solar cells using bandgap grading and embedding Au plasmonic nanoparticles.Plasmonics. 2020; 15: 1173-1182Crossref Scopus (18) Google Scholar]. Solar-driven bioelectrosynthesis through the microbe–material interface is an emerging artificial photosynthesis system that combines the strengths of inorganic materials and living microbial cells to achieve a solar energy conversion efficiency of ~20% with high selectivity towards CO2-to-chemicals [27.Cestellos-Blanco S. et al.Solar-driven carbon dioxide fixation using photosynthetic semiconductor bio-hybrids.Faraday Discuss. 2019; 215: 54-65Crossref PubMed Google Scholar,29.Kornienko N. et al.Interfacing nature’s catalytic machinery with synthetic materials for semi-artificial photosynthesis.Nat. Nanotechnol. 2018; 13: 890-899Crossref PubMed Scopus (206) Google Scholar, 30.Dogutan D.K. Nocera D.G. Artificial photosynthesis at efficiencies greatly exceeding that of natural photosynthesis.Acc. Chem. Res. 2019; 52: 3143-3148Crossref PubMed Scopus (95) Google Scholar, 31.Lin J. et al.Regulations of organism by materials: a new understanding of biological inorganic chemistry.JBIC J. Biol. Inorg. Chem. 2019; 24: 467-481Crossref Scopus (11) Google Scholar, 32.Zhang B. Sun L. Artificial photosynthesis: opportunities and challenges of molecular catalysts.Chem. Soc. Rev. 2019; 48: 2216-2264Crossref PubMed Google Scholar, 33.Sakimoto K.K. et al.Physical biology of the materials–microorganism interface.J. Am. Chem. Soc. 2018; 140: 1978-1985Crossref PubMed Scopus (88) Google Scholar]. Such self-photosensitizing systems accompany living systems with light-absorbing materials (in nano, micro, or macro dimensions) and act as chemical factories (Box 1).Box 1Advantages of Self-Photosensitized Bioinorganic Hybrid Systems over MESMES is a promising approach to obtain fuels and chemicals from CO2 using renewable energy sources. In an MES, microorganisms accept electrons from a cathode to reduce CO2 to form organic compounds [21.del Pilar Anzola Rojas M. et al.Effect of the electric supply interruption on a microbial electrosynthesis system converting inorganic carbon into acetate.Bioresour. Technol. 2018; 266: 203-210Crossref PubMed Scopus (69) Google Scholar,22.del Pilar Anzola Rojas M. et al.Microbial electrosynthesis (MES) from CO2 is resilient to fluctuations in renewable energy supply.Energy Convers. Manag. 2018; 177: 272-279Crossref Scopus (81) Google Scholar]. One of the challenges in an MES-based system is the design of the reactor for scale-up production. For instance, in an MES, the cathode potential has to be controlled precisely to prevent the production of H2 and to avoid cell damage. Further, the membrane between the anode chamber and cathode chamber, designed to permit ion flux and restrict oxygen diffusion, also adds cost. Finally, the extracellular interaction between the living cell membranes of microbes and the electrode, as well as the inability of these microbes to cope with the intermittent nature of renewable electricity (mainly from solar, wind, and tidal currents) and electron losses due to various factors like sluggish kinetics of charge transfer need to be addressed [25.Rabaey K. Rozendal R.A. Microbial electrosynthesis—revisiting the electrical route for microbial production.Nat. Rev. Microbiol. 2010; 8: 706Crossref PubMed Scopus (1057) Google Scholar, 26.Batlle-Vilanova P. et al.Continuous acetate production through microbial electrosynthesis from CO2 with microbial mixed culture.J. Chem. Technol. Biotechnol. 2016; 91: 921-927Crossref Scopus (99) Google Scholar, 27.Cestellos-Blanco S. et al.Solar-driven carbon dioxide fixation using photosynthetic semiconductor bio-hybrids.Faraday Discuss. 2019; 215: 54-65Crossref PubMed Google Scholar].Solar-driven bioelectrosynthesis, however, relies on the microbe–material interface. During this process, nonphotosynthetic microorganisms are sensitized by providing them with energy in the form of reducing equivalents from an efficient light-absorbing inorganic or organic light harvester [27.Cestellos-Blanco S. et al.Solar-driven carbon dioxide fixation using photosynthetic semiconductor bio-hybrids.Faraday Discuss. 2019; 215: 54-65Crossref PubMed Google Scholar, 28.Royanian S. et al.Efficiency enhancement of ultra-thin CIGS solar cells using bandgap grading and embedding Au plasmonic nanoparticles.Plasmonics. 2020; 15: 1173-1182Crossref Scopus (18) Google Scholar, 29.Kornienko N. et al.Interfacing nature’s catalytic machinery with synthetic materials for semi-artificial photosynthesis.Nat. Nanotechnol. 2018; 13: 890-899Crossref PubMed Scopus (206) Google Scholar, 30.Dogutan D.K. Nocera D.G. Artificial photosynthesis at efficiencies greatly exceeding that of natural photosynthesis.Acc. Chem. Res. 2019; 52: 3143-3148Crossref PubMed Scopus (95) Google Scholar, 31.Lin J. et al.Regulations of organism by materials: a new understanding of biological inorganic chemistry.JBIC J. Biol. Inorg. Chem. 2019; 24: 467-481Crossref Scopus (11) Google Scholar, 32.Zhang B. Sun L. Artificial photosynthesis: opportunities and challenges of molecular catalysts.Chem. Soc. Rev. 2019; 48: 2216-2264Crossref PubMed Google Scholar, 33.Sakimoto K.K. et al.Physical biology of the materials–microorganism interface.J. Am. Chem. Soc. 2018; 140: 1978-1985Crossref PubMed Scopus (88) Google Scholar]. The biohybrid system acts as a self-sustaining chemical factory. Moreover, the hybrid system is self-regenerating, with low waste generation, and it operates at an efficiency (product yield based on solar energy input) of more than 80% [27.Cestellos-Blanco S. et al.Solar-driven carbon dioxide fixation using photosynthetic semiconductor bio-hybrids.Faraday Discuss. 2019; 215: 54-65Crossref PubMed Google Scholar, 28.Royanian S. et al.Efficiency enhancement of ultra-thin CIGS solar cells using bandgap grading and embedding Au plasmonic nanoparticles.Plasmonics. 2020; 15: 1173-1182Crossref Scopus (18) Google Scholar, 29.Kornienko N. et al.Interfacing nature’s catalytic machinery with synthetic materials for semi-artificial photosynthesis.Nat. Nanotechnol. 2018; 13: 890-899Crossref PubMed Scopus (206) Google Scholar, 30.Dogutan D.K. Nocera D.G. Artificial photosynthesis at efficiencies greatly exceeding that of natural photosynthesis.Acc. Chem. Res. 2019; 52: 3143-3148Crossref PubMed Scopus (95) Google Scholar, 31.Lin J. et al.Regulations of organism by materials: a new understanding of biological inorganic chemistry.JBIC J. Biol. Inorg. Chem. 2019; 24: 467-481Crossref Scopus (11) Google Scholar, 32.Zhang B. Sun L. Artificial photosynthesis: opportunities and challenges of molecular catalysts.Chem. Soc. Rev. 2019; 48: 2216-2264Crossref PubMed Google Scholar, 33.Sakimoto K.K. et al.Physical biology of the materials–microorganism interface.J. Am. Chem. Soc. 2018; 140: 1978-1985Crossref PubMed Scopus (88) Google Scholar]. MES is a promising approach to obtain fuels and chemicals from CO2 using renewable energy sources. In an MES, microorganisms accept electrons from a cathode to reduce CO2 to form organic compounds [21.del Pilar Anzola Rojas M. et al.Effect of the electric supply interruption on a microbial electrosynthesis system converting inorganic carbon into acetate.Bioresour. Technol. 2018; 266: 203-210Crossref PubMed Scopus (69) Google Scholar,22.del Pilar Anzola Rojas M. et al.Microbial electrosynthesis (MES) from CO2 is resilient to fluctuations in renewable energy supply.Energy Convers. Manag. 2018; 177: 272-279Crossref Scopus (81) Google Scholar]. One of the challenges in an MES-based system is the design of the reactor for scale-up production. For instance, in an MES, the cathode potential has to be controlled precisely to prevent the production of H2 and to avoid cell damage. Further, the membrane between the anode chamber and cathode chamber, designed to permit ion flux and restrict oxygen diffusion, also adds cost. Finally, the extracellular interaction between the living cell membranes of microbes and the electrode, as well as the inability of these microbes to cope with the intermittent nature of renewable electricity (mainly from solar, wind, and tidal currents) and electron losses due to various factors like sluggish kinetics of charge transfer need to be addressed [25.Rabaey K. Rozendal R.A. Microbial electrosynthesis—revisiting the electrical route for microbial production.Nat. Rev. Microbiol. 2010; 8: 706Crossref PubMed Scopus (1057) Google Scholar, 26.Batlle-Vilanova P. et al.Continuous acetate production through microbial electrosynthesis from CO2 with microbial mixed culture.J. Chem. Technol. Biotechnol. 2016; 91: 921-927Crossref Scopus (99) Google Scholar, 27.Cestellos-Blanco S. et al.Solar-driven carbon dioxide fixation using photosynthetic semiconductor bio-hybrids.Faraday Discuss. 2019; 215: 54-65Crossref PubMed Google Scholar]. Solar-driven bioelectrosynthesis, however, relies on the microbe–material interface. During this process, nonphotosynthetic microorganisms are sensitized by providing them with energy in the form of reducing equivalents from an efficient light-absorbing inorganic or organic light harvester [27.Cestellos-Blanco S. et al.Solar-driven carbon dioxide fixation using photosynthetic semiconductor bio-hybrids.Faraday Discuss. 2019; 215: 54-65Crossref PubMed Google Scholar, 28.Royanian S. et al.Efficiency enhancement of ultra-thin CIGS solar cells using bandgap grading and embedding Au plasmonic nanoparticles.Plasmonics. 2020; 15: 1173-1182Crossref Scopus (18) Google Scholar, 29.Kornienko N. et al.Interfacing nature’s catalytic machinery with synthetic materials for semi-artificial photosynthesis.Nat. Nanotechnol. 2018; 13: 890-899Crossref PubMed Scopus (206) Google Scholar, 30.Dogutan D.K. Nocera D.G. Artificial photosynthesis at efficiencies greatly exceeding that of natural photosynthesis.Acc. Chem. Res. 2019; 52: 3143-3148Crossref PubMed Scopus (95) Google Scholar, 31.Lin J. et al.Regulations of organism by materials: a new understanding of biological inorganic chemistry.JBIC J. Biol. Inorg. Chem. 2019; 24: 467-481Crossref Scopus (11) Google Scholar, 32.Zhang B. Sun L. Artificial photosynthesis: opportunities and challenges of molecular catalysts.Chem. Soc. Rev. 2019; 48: 2216-2264Crossref PubMed Google Scholar, 33.Sakimoto K.K. et al.Physical biology of the materials–microorganism interface.J. Am. Chem. Soc. 2018; 140: 1978-1985Crossref PubMed Scopus (88) Google Scholar]. The biohybrid system acts as a self-sustaining chemical factory. Moreover, the hybrid system is self-regenerating, with low waste generation, and it operates at an efficiency (product yield based on solar energy input) of more than 80% [27.Cestellos-Blanco S. et al.Solar-driven carbon dioxide fixation using photosynthetic semiconductor bio-hybrids.Faraday Discuss. 2019; 215: 54-65Crossref PubMed Google Scholar, 28.Royanian S. et al.Efficiency enhancement of ultra-thin CIGS solar cells using bandgap grading and embedding Au plasmonic nanoparticles.Plasmonics. 2020; 15: 1173-1182Crossref Scopus (18) Google Scholar, 29.Kornienko N. et al.Interfacing nature’s catalytic machinery with synthetic materials for semi-artificial photosynthesis.Nat. Nanotechnol. 2018; 13: 890-899Crossref PubMed Scopus (206) Google Scholar, 30.Dogutan D.K. Nocera D.G. Artificial photosynthesis at efficiencies greatly exceeding that of natural photosynthesis.Acc. Chem. Res. 2019; 52: 3143-3148Crossref PubMed Scopus (95) Google Scholar, 31.Lin J. et al.Regulations of organism by materials: a new understanding of biological inorganic chemistry.JBIC J. Biol. Inorg. Chem. 2019; 24: 467-481Crossref Scopus (11) Google Scholar, 32.Zhang B. Sun L. Artificial photosynthesis: opportunities and challenges of molecular catalysts.Chem. Soc. Rev. 2019; 48: 2216-2264Crossref PubMed Google Scholar, 33.Sakimoto K.K. et al.Physical biology of the materials–microorganism interface.J. Am. Chem. Soc. 2018; 140: 1978-1985Crossref PubMed Scopus (88) Google Scholar]. In a breakthrough development, Sakimoto and colleagues studied the efficacy of a Morella thermoacetica–cadmium sulfide (CdS) quantum dot hybrid to convert CO2 to chemicals under visible radiation [34.Sakimoto K.K. et al.Self-photosensitization of nonphotosynthetic bacteria for solar-to-chemical production.Science. 2016; 351: 74-77Crossref PubMed Scopus (559) Google Scholar]. Thereafter, several hybrid photosynthesis systems were developed, where the metabolic adaptability of microbes was tailored by integrating light-harvesting inorganic materials to drive the bioelectrosynthesis of CO2 into fuels and chemicals [35.Liu C. et al.Nanowire–bacteria hybrids for unassisted solar carbon dioxide fixation to value-added chemicals.Nano Lett. 2015; 15: 3634-3639Crossref PubMed Scopus (273) Google Scholar, 36.Kumar M. et al.Photosensitization of electro-active microbes for solar assisted carbon dioxide transformation.Bioresour. Technol. 2019; 272: 300-307Crossref PubMed Scopus (24) Google Scholar, 37.Guo J. et al.Light-driven fine chemical production in yeast biohybrids.Science. 2018; 362: 813-816Crossref PubMed Scopus (155) Google Scholar, 38.Wang B. et al.Enhanced CO2 reduction and valuable C2+ chemical production by a CdS-photosynthetic hybrid system.Nanoscale. 2019; 11: 9296-9301Crossref PubMed Google Scholar, 39.Ye J. et al.Light-driven carbon dioxide reduction to methane by Methanosarcina barkeri-CdS biohybrid.Appl. Catal. B Environ. 2019; 257: 117916Crossref Scopus (63) Google Scholar]. Such hybrid photosynthesis systems are distinct as they can couple with numerous inorganic light-harvesting 2D or 3D materials, such as nanoparticles (NPs), quantum dots, nanowires (NWs), and biological catalysts, including enzymes and autotrophic or heterotrophic microbes [35.Liu C. et al.Nanowire–bacteria hybrids for unassisted solar carbon dioxide fixation to value-added chemicals.Nano Lett. 2015; 15: 3634-3639Crossref PubMed Scopus (273) Google Scholar, 36.Kumar M. et al.Photosensitization of electro-active microbes for solar assisted carbon dioxide transformation.Bioresour. Technol. 2019; 272: 300-307Crossref PubMed Scopus (24) Google Scholar, 37.Guo J. et al.Light-driven fine chemical production in yeast biohybrids.Science. 2018; 362: 813-816Crossref PubMed Scopus (155) Google Scholar, 38.Wang B. et al.Enhanced CO2 reduction and valuable C2+ chemical production by a CdS-photosynthetic hybrid system.Nanoscale. 2019; 11: 9296-9301Crossref PubMed Google Scholar, 39.Ye J. et al.Light-driven carbon dioxide reduction to methane by Methanosarcina barkeri-CdS biohybrid.Appl. Catal. B Environ. 2019; 257: 117916Crossref Scopus (63) Google Scholar]. However, the working mechanism of these hybrid systems remains poorly understood, especially at the material–microbe interface. Understanding this interaction will help to develop new solar-to-chemical conversion systems. Recent pioneering works have focused on various photosensitized microbial systems as well as integrated water splitting–biosynthetic systems to understand the entire solar–chemical pathway (Figure 1) [40.Liu C. et al.Solar-powered CO2 reduction by a hybrid biological inorganic system.J. Photochem. Photobiol. A Chem. 2018; 358: 411-415Crossref Scopus (20) Google Scholar, 41.Torella J.P. et al.Efficient solar-to-fuels production from a hybrid microbial–water-splitting catalyst system.Proc. Natl. Acad. Sci. U.S.A. 2015; 112: 2337-2342Crossref PubMed Scopus (249) Google Scholar, 42.Liu C. et al.Water splitting–biosynthetic system with CO2 reduction efficiencies exceeding photosynthesis.Science. 2016; 352: 1210-1213Crossref PubMed Scopus (558) Google Scholar]. This review summarizes advances in the transfer of energy or signals at the interface between inorganic or organic material and whole-cell organisms to fix CO2 into fuels and chemicals. In solar-driven bioelectrosynthesis, inorganic sunlight absorbers capture solar energy and transfer reducing equivalents to biological systems to drive CO2 reduction. In the biological system, CO2 is converted via the Wood-Ljungdahl (WL) pathway [43.Ragsdale S.W. Pierce E. Acetogenesis and the Wood–Ljungdahl pathway of CO2 fixation.Biochim. Biophys. Acta Proteins Proteomics. 2008; 1784: 1873-1898Crossref Scopus (692) Google Scholar] (Figure 2). In the WL pathway, acetic acid is synthesized from CO2 by autotrophic and anaerobic microorganisms, including Proteobacteria, Planctomycetes, Spirochaetes, and Euryarchaeota. Such microorganisms use hydrogen as the electron donor and CO2 as the electron acceptor for the biosynthesis of cellular precursors through simultaneous oxidation and reduction of CO2. Sakimoto and colleagues studied the photoreductive ability of an M. thermoacetica–CdS hybrid under visible light [34.Sakimoto K.K. et al.Self-photosensitization of nonphotosynthetic bacteria for solar-to-chemical production.Science. 2016; 351: 74-77Crossref PubMed Scopus (559) Google Scholar]. In this system, electron (e–) and hole (h+) pairs are generated by the absorption of visible light via CdS as a semiconducting light harvester. The photoinduced electrons generate CO2-reducing equivalent, [H+], which then passes through the WL pathway to produce acetic acid from CO2. The holes are quenched by cysteine molecules, leading to the formation of cystine (CySS), the oxidized form of cysteine. The overall equation is given here:2CO2+8Cysteine+8photon→CH3COOH+2H2O+4CySS[1] Ye and coworkers studied an exhaustive mechanistic model for photoreductive reactions in microbial systems to convert CO2 to methane [39.Ye J. et al.Light-driven carbon dioxide reduction to methane by Methanosarcina barkeri-CdS biohybrid.Appl. Catal. B Environ. 2019; 257: 117916Crossref Scopus (63) Google Scholar]. According to this model, electron transfer from an inorganic photosensitizer to the microbial cell is facilitated by membrane-bound proteins. Membrane-bound proteins like hydrogenases and cytochromes play a key role in electron transport during e–/h+ separation and facilitate the conversion of CO2 to CH4 [44.Shi L. et al.Extracellular electron transfer mechanisms between microorganisms and minerals.Nat. Rev. Microbiol. 2016; 14: 651Crossref PubMed Scopus (769) Google Scholar]. Further, various concentrations of proteinase K, an enzyme that exhibits specific cleavage and denaturation of membrane-bound proteins, were used to establish the importance of membrane-bound proteins in an Methanosarcina barkeri–CdS biohybrid system. The results suggested that with a rising concentration of proteinase K, the CO2 to CH4 conversion efficiency in M. barkeri–CdS biohybrid steadily decreased, which demonstrates the major role of membrane-bound proteins. Natural photosynthetic organisms are more selective than chemical catalysts for CO2 reduction to valuable chemicals, yet they are limited by extremely low efficiency [41.Torella J.P. et al.Efficient solar-to-fuels production from a hybrid microbial–water-splitting catalyst system.Proc. Natl. Acad. Sci. U.S.A. 2015; 112: 2337-2342Crossref PubMed Scopus (249) Google Scholar,42.Liu C. et al.Water splitting–biosynthetic system with CO2 reduction efficiencies exceeding photosynthesis.Science. 2016; 352: 1210-1213Crossref PubMed Scopus (558) Google Scholar]. At the same time, using inorganic semiconducting materials, up to 20% solar energy conversion efficiency has been achieved against a maximum theoretical limit of 33.7% [28.Royanian S. et al.Efficiency enhancement of ultra-thin CIGS solar cells using bandgap grading and embedding Au plasmonic nanoparticles.Plasmonics." @default.
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• W3016558044 date "2020-11-01" @default.
• W3016558044 modified "2023-10-16" @default.
• W3016558044 title "Material–Microbe Interfaces for Solar-Driven CO2 Bioelectrosynthesis" @default.
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• W3016558044 doi "https://doi.org/10.1016/j.tibtech.2020.03.008" @default.
• W3016558044 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/32305152" @default.
• W3016558044 hasPublicationYear "2020" @default.

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