无机纳米材料-微生物杂合系统的研究进展

Design and Construction of Inorganic Nanomaterial-Microorganism Hybrid Systems

摘要

随着CO₂排放问题日益严峻，有效减少碳排放是目前最受关注的热点问题．通过物理封存和化学转化等技术固定CO₂能耗大且安全性有待评估，而微生物固定CO₂技术凭借其环境友好成为可持续碳捕集方案之一．天然固碳微生物通过卡尔文循环等7种途径固定CO₂，然而这些途径的固碳效率仍然面临能量供给不足、关键酶催化效率低等问题，限制了其在工业化碳捕集和转化中的广泛应用．一方面，通过合成生物学和代谢工程等方法可以优化光合自养微生物、化能自养微生物和异养微生物的固碳效率，并将CO₂高效转化为多种高值化学品．另一方面，无机纳米材料-微生物杂合系统将半导体纳米材料与微生物结合，利用材料优良的光-电转化性能不仅可以增强光能的捕获和电子传递效率，同时能够显著提升CO₂转化为高值化学品的效率．本综述总结了微生物天然固定CO₂的7种途径，阐述了光合自养、化能自养和异养微生物固碳途径优化机制的近期进展．同时，总结了这些工程细胞及材料-细胞杂合体系统的设计构建技术，分别介绍了直接电子传递下的无机纳米材料-微生物杂合系统和电子载体介导下的无机纳米材料-微生物杂合系统的重要应用，阐述了纳米材料在固定CO₂过程中的关键作用和原理，并展望了该领域的未来发展趋势．

Abstract

With increasingly serious problems caused by CO₂ emissions，the effective reduction of carbon emissions has become one of the most concerning issues. The fixation of CO₂ through physical storage and chemical conversion technology consumes a considerable amount of energy，and safety needs to be evaluated. Meanwhile，CO₂ fixation technology by microorganisms has transitioned into one of the sustainable carbon capture schemes due to its environmental friendliness. Autotrophic microorganisms fix CO₂ in seven pathways，including the Calvin cycle. However，the carbon fixation efficiency of these pathways still faces the problems of insufficient energy supply and low catalytic efficiency of key enzymes，which limit their wide applications in industrial carbon capture and transformation. On the one hand，optimization of the carbon fixation efficiency of photoautotrophic，chemoautotrophic，and heterotrophic microorganisms can be achieved through synthetic biology and metabolic engineering，enabling the efficient conversion of CO₂ into various high-value chemicals. On the other hand，inorganic nanomaterial-microorganism hybrid systems combine semiconductor nanomaterials with microorganisms. The excellent light-electrical conversion performance of materials can not only enhance the light energy capture and electron transfer efficiency，but also considerably improve the efficiency of CO₂ conversion to high-value chemicals. This review summarizes seven pathways in which microorganisms naturally fix CO₂ and addresses recent advances in the optimization mechanisms of photoautotrophic，chemoautotrophic，and heterotrophic microorganisms. Moreover，this review summarizes the design and construction techniques of these engineered cell and material-cell hybrid systems，inorganic nanomaterial-microorganism hybrid systems with underlying mechanisms of direct electron transfer and mediation by electron carriers，the key role and principles of nanomaterials in CO₂ fixation，and the future development trend of this field.

关键词

二氧化碳捕集 / 微生物 / 合成生物学 / 杂合系统

Key words

CO₂ capture / microorganism / synthetic biology / hybrid system

参考文献

[1] Ripple W J, Wolf C, Newsome T M, et al. World scientists’ warning of a climate emergency[J]. BioScience, 2020, 70(1):8-100.

[2] Friedlingstein P, O’Sullivan M, Jones M W, et al. Global carbon budget 2023[J]. Earth System Science Data, 2023, 15(12):5301-5369.

[3] Irfan M, Bai Y, Zhou L, et al. Direct microbial transformation of carbon dioxide to value—added chemicals：A comprehensive analysis and application potentials[J]. Bioresource Technology, 2019, 288:121401.

[4] Lin Z T, Kuang Y M, Li W Q, et al. Research status and prospects of CO₂ geological sequestration technology from onshore to offshore：A review [J]. Earth—Science Reviews, 2024, 258:104928.

[5] Sun X, Shang A R, Wu P, et al. A review of CO₂ marine geological sequestration [J]. Processes, 2023, 11(7):2206.

[6] Ling Z Y, Pan J Y, Kontchouo F M B, et al. Current situation of marine CO₂ sequestration and analysis of related environmental issues[J]. Fuel, 2024, 366:131288.

[7] Wang F, Dreisinger D, Jarvis M, et al. Kinetic evaluation of mineral carbonation of natural silicate samples[J]. Chemical Engineering Journal, 2021, 404:126522.

[8] Li J J, Hitch M. Mechanical activation of ultramafic mine waste rock in dry condition for enhanced mineral carbonation[J]. Minerals Engineering, 2016, 95:1-4.

[9] Song C F, Liu Q L, Deng S, et al. Cryogenic—based CO₂ capture technologies：State—of—the—art developments and current challenges [J]. Renewable and Sustainable Energy Reviews, 2019, 101:265-278.

[10] Li Y Y, Zhang J, Chen X L. Microbial conversion of CO₂ to organic compounds [J]. Energy & Environmental Science, 2024, 17(19):7017-7034.

[11] Sieborg M U, Oliveira J M S, Ottosen L D M, et al. Flue—to—fuel：Bio—integrated carbon capture and utilization of dilute carbon dioxide gas streams to renewable methane[J]. Energy Conversion and Management, 2024, 302:118090.

[12] Chu N, Liang Q J, Jiang Y, et al. Microbial electrochemical platform for the production of renewable fuels and chemicals[J]. Biosensors and Bioelectronics, 2020, 150:111922.

[13] Karishma S, Kamalesh R, Saravanan A, et al. A review on recent advancements in biochemical fixation and transformation of CO₂ into constructive products [J]. Biochemical Engineering Journal, 2024, 208:109366.

[14] Agarwal P, Soni R, Kaur P, et al. Cyanobacteria as a promising alternative for sustainable environment：Synthesis of biofuel and biodegradable plastics[J]. Frontiers in Microbiology, 2022, 13:939347.

[15] Kushkevych I, Procházka V, Vítězová M, et al. Anoxygenic photosynthesis with emphasis on green sulfur bacteria and a perspective for hydrogen sulfide detoxification of anoxic environments[J]. Frontiers in Microbiology, 2024, 15:1417714.

[16] Hatti—Kaul R, Mamo G, Mattiasson B. Anaerobes in Biotechnology[M]. Cham： Springer Nature, 2016.

[17] Doni L, Azzola A, Oliveri C, et al. Genome—resolved metagenomics revealed novel microbial taxa with ancient metabolism from macroscopic microbial mat structures inhabiting anoxic deep reefs of a maldivian blue hole[J]. Environmental Microbiology Reports, 2024, 16(5):e13315.

[18] Bourgade B, Islam M A. Progresses and challenges of engineering thermophilic acetogenic cell factories[J]. Frontiers in Microbiology, 2024, 15:1476253.

[19] Widberger J, Wittgens A, Klaunig S, et al. Recombinant production of pseudomonas aeruginosa rhamnolipids in P. putida KT2440 on acetobacterium woodii cultures grown chemo—autotrophically with carbon dioxide and hydrogen[J]. Microorganisms, 2024, 12(3):529.

[20] Elisiário M P, van Hecke W, de Wever H, et al. Acetic acid，growth rate，and mass transfer govern shifts in CO metabolism of clostridium autoethanogenum[J]. Applied Microbiology and Biotechnology, 2023, 107(17):5329-5340.

[21] Montgomery B L, Lechno—Yossef S, Kerfeld C A. Interrelated modules in cyanobacterial photosynthesis：The carbon—concentrating mechanism，photorespiration，and light perception[J]. Journal of Experimental Botany, 2016, 67(10):2931-2940.

[22] Walker B, Schmiege S C, Sharkey T D. Re—evaluating the energy balance of the many routes of carbon flow through and from photorespiration[J]. Plant，Cell & Environment, 2024, 47(9):3365-3374.

[23] Sharkey T D. The discovery of RuBisco[J]. Journal of Experimental Botany, 2023, 74(2):510-519.

[24] Garritano A N, Song W, Thomas T. Carbon fixation pathways across the bacterial and archaeal tree of life[J]. PNAS Nexus, 2022, 1(5):pgac226.

[25] Atomi H. Microbial enzymes involved in carbon dioxide fixation[J]. Journal of Bioscience and Bioengineering, 2002, 94(6):497-505.

[26] Strauss G, Fuchs G. Enzymes of a novel autotrophic CO₂ fixation pathway in the phototrophic bacterium Chloroflexus aurantiacus，the 3—hydroxypropionate cycle[J]. European Journal of Biochemistry, 1993, 215(3):633-643.

[27] Tang K H, Barry K, Chertkov O, et al. Complete genome sequence of the filamentous anoxygenic phototrophic bacterium Chloroflexus aurantiacus[J]. BMC Genomics, 2011, 12:334.

[28] Hawkins A S, Han Y, Bennett R K, et al. Role of 4—hydroxybutyrate—CoA synthetase in the CO₂ fixation cycle in Thermoacidophilic archaea [J]. Journal of Biological Chemistry, 2013, 288(6):4012-4022.

[29] Chapman R D, Heidemann M, Albert T K, et al. Transcribing RNA polymerase Ⅱ is phosphorylated at ctd residue serine—7[J]. Science, 2007, 318(5857):1780-1782.

[30] Liu L, Huber H, Berg I A. Enzymes catalyzing crotonyl—coa conversion to acetoacetyl—CoA during the autotrophic CO₂ fixation in Metallosphaera sedula [J]. Frontiers in Microbiology, 2020, 11:354.

[31] Jennings R D M, Moran J J, Jay Z J, et al. Integration of metagenomic and stable carbon isotope evidence reveals the extent and mechanisms of carbon dioxide fixation in high—temperature microbial communities[J]. Frontiers in Microbiology, 2017, 8:88.

[32] Martin W F. Older than genes：The acetyl—CoA pathway and origins[J]. Frontiers in Microbiology, 2020, 11:817.

[33] Schuchmann K, Müller V, Stams A J M. Energetics and application of heterotrophy in acetogenic bacteria[J]. Applied and Environmental Microbiology, 2016, 82(14):4056-4069.

[34] Song Y, Lee J S, Shin J, et al. Functional cooperation of the glycine synthase—reductase and Wood—Ljungdahl pathways for autotrophic growth of Clostridium drakei[J]. Proceedings of the National Academy of Sciences, 2020, 117(13):7516-7523.

[35] Sánchez—Andrea I, Guedes I A, Hornung B, et al. The reductive glycine pathway allows autotrophic growth of Desulfovibrio desulfuricans[J]. Nature Communications, 2020, 11(1):5090.

[36] Figueroa I A, Barnum T P, Somasekhar P Y, et al. Metagenomics—guided analysis of microbial chemolithoautotrophic phosphite oxidation yields evidence of a seventh natural CO₂ fixation pathway[J]. Proceedings of the National Academy of Sciences, 2018, 115(1):285-291.

[37] Campbell D, Hurry V, Clarke A K, et al. Chlorophyll fluorescence analysis of cyanobacterial photosynthesis and acclimation[J]. Microbiology and Molecular Biology Reviews, 1998, 62(3):667-683.

[38] Lockhart J. Shedding new light on the ancient process of photosynthesis in Cyanobacteria[J]. The Plant Cell, 2019, 31(4):755-756.

[39] Eaton—Rye J J, Sobotka R. Editorial：Assembly of the photosystem II membrane—protein complex of oxygenic photosynthesis[J]. Frontiers in Plant Science, 2017, 8:884.

[40] Han T J, Sinha R P, Häder D P. Effects of intense PAR and UV radiation on photosynthesis，growth and pigmentation in the rice—field cyanobacterium Anabaena sp.[J]. Photochemical & Photobiological Sciences, 2003, 2(6):649-654.

[41] Srivastava A K, Alexova R, Jeon Y J, et al. Assessment of salinity—induced photorespiratory glycolate metabolism in Anabaena sp. PCC 7120[J]. Microbiology, 2011, 157(3):911-917.

[42] Hernández—Herreros N, Rodríguez A, Galán B, et al. Boosting hydrogen production in Rhodospirillum rubrum by syngas—driven photoheterotrophic adaptive evolution[J]. Bioresource Technology, 2024, 406:130972.

[43] Cao P, Bracun L, Yamagata A, et al. Structural basis for the assembly and quinone transport mechanisms of the dimeric photosynthetic Rc—Lh1 supercomplex[J]. Nature Communications, 2022, 13(1):1977.

[44] Gabrielyan L, Sargsyan H, Hakobyan L, et al. Regulation of hydrogen photoproduction in Rhodobacter sphaeroides batch culture by external oxidizers and reducers[J]. Applied Energy, 2014, 131:20-25.

[45] Zhuang X Y, Zhang Y H, Xiao A F, et al. Applications of synthetic biotechnology on carbon neutrality research：A review on electrically driven microbial and enzyme engineering[J]. Frontiers in Bioengineering and Biotechnology, 2022, 10:826008.

[46] Meng X, Liu L M, Chen X L. Bacterial photosynthesis：State—of—the—art in light—driven carbon fixation in engineered bacteria[J]. Current Opinion in Microbiology, 2022, 69:102174.

[47] Nürnberg D J, Morton J, Santabarbara S, et al. Photochemistry beyond the red limit in chlorophyll f—containing photosystems[J]. Science, 2018, 360(6394):1210-1213.

[48] de Mooij T, Janssen M, Cerezo—Chinarro O, et al. Antenna size reduction as a strategy to increase biomass productivity：A great potential not yet realized[J]. Journal of Applied Phycology, 2015, 27(3):1063-1077.

[49] Zhou J, Zhang F L, Meng H K, et al. Introducing extra nadph consumption ability significantly increases the photosynthetic efficiency and biomass production of Cyanobacteria[J]. Metabolic Engineering, 2016, 38:217-227.

[50] Andersson I, Backlund A. Structure and function of Rubisco[J]. Plant Physiology and Biochemistry, 2008, 46(3):275-291.

[51] Du Y C, Hong S, Spreitzer R J. RbcS suppressor mutations improve the thermal stability and CO₂/O₂ specificity of rbcL mutant ribulose—1，5—bisphosphate carboxy—lase/oxygenase[J]. Proceedings of the National Academy of Sciences of the United States of America, 2000, 97(26):14206-14211.

[52] Nishitani Y, Yoshida S, Fujihashi M, et al. Structure—based catalytic optimization of a type Ⅲ Rubisco from a hyperthermophile[J]. Journal of Biological Chemistry, 2010, 285(50):39339-39347.

[53] Yang F, Zhang J L, Cai Z, et al. Exploring the oxygenase function of form Ⅱ Rubisco for production of glycolate from CO₂ [J]. AMB Express, 2021, 11(1):65.

[54] Wilson R H, Alonso H, Whitney S M. Evolving Methanococcoides burtonii archaeal Rubisco for improved photosynthesis and plant growth[J]. Scientific Reports, 2016, 6(1):22284.

[55] Liang F Y, Englund E, Lindberg P, et al. Engineered Cyanobacteria with enhanced growth show increased ethanol production and higher biofuel to biomass ratio[J]. Metabolic Engineering, 2018, 46:51-59.

[56] Tharasirivat V, Jantaro S. Increased biomass and polyhydroxybutyrate production by Synechocystis sp. PCC 6803 overexpressing RuBisCO genes[J]. International Journal of Molecular Sciences, 2023, 24(7):6415.

[57] Price G D, Badger M R, Woodger F J, et al. Advances in understanding the cyanobacterial CO₂—concentrating—mechanism(Ccm)：Functional components，transporters，diversity，genetic regulation and prospects for engineering into plants[J]. Journal of Experimental Botany, 2008, 59(7):1441-1461.

[58] Ludwig M, Sültemeyer D, Price G D. Isolation of ccmKLMN genes from the marine cyanobacterium，Synechococcus sp. PCC 7002(Cyanophyceae)，and evidence that CcmM is essential for carboxysome assembly[J]. Journal of Phycology, 2000, 36(6):1109-1119.

[59] Li D Y, Dong H, Cao X P, et al. Enhancing photosynthetic CO₂ fixation by assembling metal—organic frameworks on Chlorella pyrenoidosa [J]. Nature Communications, 2023, 14(1):5337.

[60] Lim J M, Jung S, Min S R, et al. Isolation and characterization of high—CO₂ sensitive Nannochloropsis salina mutant [J]. Plant Biotechnology Reports, 2023, 17(5):677-686.

[61] Moroney J V, Bartlett S G, Samuelsson G. Carbonic anhydrases in plants and algae[J]. Plant，Cell and Environment, 2001, 24(2):141-153.

[62] Badger M. The roles of carbonic anhydrases in photosynthetic CO₂ concentrating mechanisms [J]. Photosynthesis Research, 2003, 77(2/3):83.

[63] Takemura K, Kato J, Kato S, et al. Autotrophic growth and ethanol production enabled by diverting acetate flux in the metabolically engineered Moorella thermoacetica[J]. Journal of Bioscience and Bioengineering, 2021, 132(6):569-574.

[64] Baltar F, Lundin D, Palovaara J, et al. Prokaryotic responses to ammonium and organic carbon reveal alternative CO₂ fixation pathways and importance of alkaline phosphatase in the Mesopelagic North Atlantic [J]. Frontiers in Microbiology, 2016, 7:1670.

[65] Schuchmann K, Müller V. Autotrophy at the thermodynamic limit of life：A model for energy conservation in acetogenic bacteria[J]. Nature Reviews Microbiology, 2014, 12(12):809-821.

[66] Yin M D, Lemaire O N, Rosas Jiménez J G, et al. Snapshots of acetyl—CoA synthesis，the final step of CO₂ fixation in the Wood—Ljungdahl pathway[J]. bioRxiv, 2024, 8(5):606187.

[67] Jin S, Bae J, Song Y, et al. Synthetic biology on acetogenic bacteria for highly efficient conversion of C₁ gases to biochemicals [J]. International Journal of Molecular Sciences, 2020, 21(20):7639.

[68] Liew F, Henstra A M, Köpke M, et al. Metabolic engineering of Clostridium autoethanogenum for selective alcohol production[J]. Metabolic Engineering, 2017, 40:104-114.

[69] Wei H, Wang W, Chou Y C, et al. Prospects for engineering Ralstonia eutropha and Zymomonas mobilis for the autotrophic production of 2，3—butanediol from CO₂ and H₂[J]. Engineering Microbiology, 2023, 3(2):100074.

[70] Garrigues L, Maignien L, Lombard E, et al. Isopropanol production from carbon dioxide in Cupriavidus necator in a pressurized bioreactor[J]. New Biotechnology, 2020, 56:16-20.

[71] Marc J, Grousseau E, Lombard E, et al. Over expression of groesl in Cupriavidus necator for heterotrophic and autotrophic isopropanol production[J]. Metabolic Engineering, 2017, 42:74-84.

[72] Wang L, Yao J H, Tu T, et al. Heterotrophic and autotrophic production of L—isoleucine and L—valine by engineered Cupriavidus necator H16[J]. Bioresource Technology, 2024, 398:130538.

[73] Li Z K, Xin X Q, Xiong B, et al. Engineering the calvin—benson—bassham cycle and hydrogen utilization pathway of Ralstonia eutropha for improved autotrophic growth and polyhydroxybutyrate production[J]. Microbial Cell Factories, 2020, 19(1):1-9.

[74] Kim S, Jang Y J, Gong G, et al. Engineering Cupriavidus necator H16 for enhanced lithoautotrophic poly(3—hydroxybutyrate)production from CO₂ [J]. Microbial Cell Factories, 2022, 21(1):231.

[75] Zhang Y W, Zhou J, Zhang Y C, et al. Auxiliary module promotes the synthesis of carboxysomes Ine. Coli to achieve high—efficiency CO₂ assimilation [J]. ACS Synthetic Biology, 2021, 10(4):707-715.

[76] Dowaidar M. Synthetic biology of metabolic cycles for enhanced CO₂ capture and sequestration [J]. Bioorganic Chemistry, 2024, 153:107774.

[77] Yang Q Y, Guo X X, Liu Y W, et al. Biocatalytic C—C bond formation for one carbon resource utilization[J]. International Journal of Molecular Sciences, 2021, 22(4):1890.

[78] Kim S R, Kim S J, Kim S K, et al. Yeast metabolic engineering for carbon dioxide fixation and its application[J]. Bioresource Technology, 2022, 346:126349.

[79] Guadalupe—Medina V, Wisselink H W, Luttik M A, et al. Carbon dioxide fixation by Calvin—cycle enzymes improves ethanol yield in Yeast[J]. Biotechnology for Biofuels, 2013, 6(1):125.

[80] Malubhoy Z, Bahia F M, de Valk S C, et al. Carbon dioxide fixation via production of succinic acid from glycerol in engineered Saccharomyces cerevisiae[J]. Microbial Cell Factories, 2022, 21(1):102.

[81] Luo S S, Diehl C, He H, et al. Construction and modular implementation of the theta cycle for synthetic CO₂ fixation[J]. Nature Catalysis, 2023, 6(12):1228-1240.

[82] Gleizer S, Ben—Nissan R, Bar—On Y M, et al. Conversion of Escherichia coli to generate all biomass carbon from CO₂ [J]. Cell, 2019, 179(6):1255-1263.

[83] Fast A G, Papoutsakis E T. Functional expression of the Clostridium ljungdahlii acetyl—coenzyme A synthase in Clostridium acetobutylicum as demonstrated by a novel in vivo CO exchange activity en route to heterologous installation of a functional Wood—Ljungdahl pathway[J]. Applied and Environmental Microbiology, 2018, 84(7):e2307-e2317.

[84] Gassler T, Sauer M, Gasser B, et al. The industrial yeast Pichia pastoris is converted from a heterotroph into an autotroph capable of growth on CO₂ [J]. Nature Biotechnology, 2020, 38(2):210-216.

[85] Xiao S, Fu Q, Li Z, et al. Solar—driven biological inorganic hybrid systems for the production of solar fuels and chemicals from carbon dioxide[J]. Renewable and Sustainable Energy Reviews, 2021, 150:111375.

[86] Li T, Huang H W, Wang S B, et al. Recent advances in 2D semiconductor nanomaterials for photocatalytic CO₂ reduction [J]. Nano Research, 2023, 16(7):8542-8569.

[87] Gan Y M, Chai T T, Zhang J, et al. Light—driven CO₂ utilization for chemical production in bacterium biohybrids [J]. Chinese Journal of Catalysis, 2024, 60:294-303.

[88] Nichols E M, Gallagher J J, Liu C, et al. Hybrid bioinorganic approach to solar—to—chemical conversion[J]. Proceedings of the National Academy of Sciences, 2015, 112(37):11461-11466.

[89] Kornienko N, Zhang J Z, Sakimoto K K, et al. Interfacing nature’s catalytic machinery with synthetic materials for semi—artificial photosynthesis[J]. Nature Nanotechnology, 2018, 13(10):890-899.

[90] Song J, Lin H C, Zhao G Z, et al. Photocatalytic material—microorganism hybrid system and its application—A review[J]. Micromachines, 2022, 13(6):861.

[91] Wu N, Xing M Y, Li Y F, et al. Recent advances in microbe—photocatalyst hybrid systems for production of bulk chemicals：A review[J]. Applied Biochemistry and Biotechnology, 2023, 195(2):1574-1588.

[92] Liang J, Xiao K M, Wang X Y, et al. Revisiting solar energy flow in nanomaterial—microorganism hybrid systems[J]. Chemical Reviews, 2024, 124(15):9081-9112.

[93] Yang Y, Liu L N, Tian H N, et al. Making the connections：Physical and electric interactions in biohybrid photosynthetic systems[J]. Energy & Environmental Science, 2023, 16(1):435-439.

[94] Kumar S, Tripathi A, Chakraborty I, et al. Engineered nanomaterials for carbon capture and bioenergy production in microbial electrochemical technologies：A review[J]. Bioresource Technology, 2023, 389:129809.

[95] Zeng Y, Zhou X, Qi R L, et al. Photoactive conjugated polymer based hybrid biosystems for enhancing Cyanobacterial photosynthesis and regulating redox state of protein[J]. Advanced Functional Materials, 2021, 31(8):2007814.

[96] Wang B, Jiang Z F, Yu J C, et al. Enhanced CO₂ reduction and valuable C₂₊ chemical production by a CdS—photosynthetic hybrid system [J]. Nanoscale, 2019, 11(19):9296-9301.

[97] Zhang L, Lovinger G J, Edelstein E K, et al. Catalytic conjunctive cross—coupling enabled by metal—induced metallate rearrangement[J]. Science, 2016, 351(6268):70-74.

[98] Xu M Y, Tremblay P, Jiang L L, et al. Stimulating bioplastic production with light energy by coupling Ralstonia eutropha with the photocatalyst graphitic carbon nitride[J]. Green Chemistry：An International Journal and Green Chemistry Resource, 2019, 21(9):2392-2400.

[99] Zhang H J, Casadevall C, van Wonderen J H, et al. Rational design of covalent multiheme cytochrome carbon dot biohybrids for photoinduced electron transfer[J]. Advanced Functional Materials, 2023, 33(40):2302204.

[100] Kees E D, Pendleton A R, Paquete C M, et al. Secreted flavin cofactors for anaerobic respiration of fumarate and urocanate by Shewanella oneidensis：Cost and role[J]. Applied and Environmental Microbiology, 2019, 85(16)：e00852—19.

[101] Chen J J, Chen W, He H, et al. Manipulation of microbial extracellular electron transfer by changing molecular structure of phenazine—type redox mediators[J]. Environmental Science & Technology, 2013, 47(2):1033-1039.

[102] Mevers E, Su L, Pishchany G, et al. An elusive electron shuttle from a facultative anaerobe[J]. Elife, 2019, 8:e48054.

[103] Ma J Y, Yan Z, Sun X D, et al. A hybrid photocatalytic system enables direct glucose utilization for methanogenesis[J]. Proceedings of the National Academy of Sciences, 2024, 121(4):e2317058121.

[104] Liu X, Huang L Y, Rensing C, et al. Syntrophic interspecies electron transfer drives carbon fixation and growth by Rhodopseudomonas palustris under dark，anoxic conditions[J]. Science Advances, 2021, 7(27):eabh1852.

[105] Zhang K J, Li R J, Chen J X, et al. Biohybrids of twinning Cd_0.8Zn_0.2S nanoparticles and Sporomusa ovata for efficient solar—driven reduction of CO₂ to acetate [J]. Applied Catalysis B：Environmental, 2024, 342:123375.

[106] Liu C, Gallagher J J, Sakimoto K K, et al. Nanowire bacteria hybrids for unassisted solar carbon dioxide fixation to value—added chemicals[J]. Nano Letters, 2015, 15(5):3634-3639.

[107] Dai Y, Li H, Wang Y, et al. Zn—doped CaFeO₃ perovskite—derived high performed catalyst on oxygen reduction reaction in microbial fuel cells [J]. Journal of Power Sources, 2021, 489:229498.

[108] Thatikayala D, Min B. Copper ferrite supported reduced graphene oxide as cathode materials to enhance microbial electrosynthesis of volatile fatty acids from CO₂[J]. Science of the Total Environment, 2021, 768:144477.

[109] Ding Y C, Bertram J R, Nagpal P. Utilizing atmospheric carbon dioxide and sunlight in graphene quantum dot—based nano—biohybrid organisms for making carbon—negative and carbon—neutral products[J]. ACS Applied Materials & Interfaces, 2023, 15(46):53464-53475.

[110] Ding Y C, Bertram J R, Eckert C, et al. Nanorg microbial factories：Light—driven renewable biochemical synthesis using quantum dot—bacteria nanobiohybrids[J]. Journal of the American Chemical Society, 2019, 141(26):10272-10282.

[111] Chen F Q, Yang N, Huang X M, et al. Carbon dots alleviate photoinhibition and enhance photosynthesis in Chlorella pyrenoidosa[J]. Chemical Engineering Journal, 2025, 507:160429.

[112] Ding Y, Xu H, Xu C, et al. A nanomedicine fabricated from gold nanoparticles decorated metal organic framework for cascade chemo/chemodynamic cancer therapy[J]. Advanced Science, 2020, 7(17):2001060.

[113] Qiu J F, Ahmad F, Ma J X, et al. From synthesis to applications of biomolecule—protected luminescent gold nanoclusters[J]. Analytical and Bioanalytical Chemistry, 2024, 416(17):3923-3944.

[114] Zhang H, Liu H, Tian Z Q, et al. Bacteria photosensitized by intracellular gold nanoclusters for solar fuel production[J]. Nature Nanotechnology, 2018, 13(10):900-905.

[115] Tremblay P L, Xu M Y, Chen Y M, et al. Nonmetallic abiotic—biological hybrid photocatalyst for visible water splitting and carbon dioxide reduction[J]. iScience, 2020, 23(1):100784.

[116] Li H, Opgenorth P H, Wernick D G, et al. Integrated electromicrobial conversion of CO₂ to higher alcohols [J]. Science, 2012, 335(6076):1596.

[117] Jin S, Jeon Y, Jeon M S, et al. Acetogenic bacteria utilize light—driven electrons as an energy source for autotrophic growth[J]. Proceedings of the National Academy of Sciences, 2021, 118(9):e2020552118.

[118] Yu Y J, Pi S S, Ke T, et al. Artificial soil—like material enhances CO₂ bio—valorization into chemicals in gas fermentation [J]. ACS Applied Materials & Interfaces, 2023, 15(46):53488-53497.

[119] Li H, Opgenorth P H, Wernick D G, et al. Integrated electromicrobial conversion of CO₂ to higher alcohols [J]. Science, 2012, 335(6076):1596.

[120] He Y, Wang S R, Han X Y, et al. Photosynthesis of acetate by Sporomusa ovata—CdS biohybrid system[J]. ACS Applied Materials & Interfaces, 2022, 14(20):23364-23374.

[121] Lim J, Choi S Y, Lee J W, et al. Biohybrid CO₂ electrolysis for the direct synthesis of polyesters from CO₂ [J]. Proceedings of the National Academy of Sciences, 2023, 120(14):e2221438120.

[122] Liu Q J, Xu W L, Ding Q R, et al. Engineering Shewanella oneidensis carbon felt biohybrid electrode decorated with bacterial cellulose aerogel electropolymerized anthraquinone to boost energy and chemicals production[J]. Advanced Science, 2024, 11(39):2407599.

[123] Yu W, Pavliuk M V, Liu A J, et al. Photosynthetic polymer dots — bacteria biohybrid system based on transmembrane electron transport for fixing CO₂ into poly—3—hydroxybutyrate[J]. ACS Applied Materials & Interfaces, 2023, 15(1):2183-2191.

[124] Zhang Z Y, Li F, Cao Y X, et al. Electricity—driven 7α—hydroxylation of a steroid catalyzed by a cytochrome p450 monooxygenase in engineered Yeast[J]. Catalysis Science & Technology, 2019, 9(18):4877-4887.

[125] Honda Y, Hagiwara H, Ida S, et al. Application to photocatalytic H₂ production of a whole—cell reaction by Recombinantescherichia coli cells expressing [FeFe]—hydrogenase and maturases genes[J]. Angewandte Chemie International Edition, 2016, 55(28):8045-8048.

[126] Honda Y, Watanabe M, Hagiwara H, et al. Inorganic/whole—cell biohybrid photocatalyst for highly efficient hydrogen production from water[J]. Applied Catalysis B：Environmental, 2017, 210:400-406.

[127] Wang X Y, Zhang J C, Li K, et al. Photocatalyst—mineralized biofilms as living bio—abiotic interfaces for single enzyme to whole—cell photocatalytic applications[J]. Science Advances, 2022, 8(18):eabm7665.

基金资助

国家自然科学基金资助项目(22378305)