Advances in electro-microbial synergistic systems for value-added conversion of carbon dioxide

doi:10.12211/2096-8280.2025-070

Synthetic Biology Journal

Advances in electro-microbial synergistic systems for value-added conversion of carbon dioxide

HAN Lin¹, GUO Yuman², LI Yan², CAO Hengheng², LI Jiajing², YANG Minghao², WANG Mengmeng², LI Jinping¹, LV Yongqin¹^,²

^1.State Key Laboratory of Organic-Inorganic Composites，Beijing Advanced Innovation Center for Soft Matter Science and Engineering，Beijing University of Chemical Technology，Beijing，100029，China
^2.National Energy R&D Center for Biorefinery，Beijing Key Laboratory of Green Chemicals Biomanufacturing，Beijing Synthetic Bio-manufacturing Technology Innovation Center，College of Life Science and Technology，Beijing University of Chemical Technology，Beijing 100029，China

Received:2025-07-01 Revised:2025-10-01 Published:2025-10-10
Contact: HAN Lin, LV Yongqin

电-微生物协同系统用于CO₂高值转化的研究进展

韩林¹, 郭禹曼², 李燕², 曹珩珩², 李嘉婧², 杨明浩², 汪萌萌², 李晋萍¹, 吕永琴¹^,²

^1.有机无机复合材料全国重点实验室，北京软物质科学与工程高精尖创新中心，北京化工大学，北京 100029
^2.国家能源生物炼制研发中心，教育部生物能源国际合作联合实验室，绿色化学品生物制造北京市重点实验室，生命科学与技术学院，北京化工大学，北京 100029

通讯作者: 韩林,吕永琴
作者简介:韩林（1995—），男，博士研究生。研究方向为异位耦合电生物固碳。E-mail：mzkd1314@qq.com
郭禹曼（1999—），女，博士研究生。研究方向为光/电驱动生物固碳。E-mail：2023400321@buct.edu.cn
吕永琴（1983—），女，博士，教授，博士生导师。研究方向为光电驱动生物固碳，酶的分子改造和固定化，仿生抗体工程。国家重点研发计划首席科学家，国家优秀青年基金获得者。相关研究成果在PNAS、J. Am. Chem. Soc.、Matter、Adv. Energy Mater.、Adv. Sci.、Prog. Energ. Combust.等期刊发表SCI论文80余篇，申请发明专利三十余项。获侯德榜化工科学技术奖青年奖、教育部自然科学奖二等奖、石油化工联合会技术发明奖一等奖等奖项。先后主持了国家重点研发计划项目/课题、国家自然科学基金优秀青年基金项目、联合基金重点项目、国际合作项目等10余项。担任中国生物工程学会一碳生物技术专委会委员、中国化工学会青年工作委员会委员、中国生物工程学会生物催化专业委员会委员、中国化工学会女科技工作者委员会委员、中国微生物学会微生物代谢与生物制造专业委员会委员。担任5本SCI期刊的客座编辑和编委。E-mail：lvyq@mail.buct.edu.cn
基金资助:
国家重点研发计划(2024YFB4206300);国家自然科学基金(U22A20426);国家自然科学基金(22408017);国家自然科学基金(22122801);北京市自然科学基金(2244075)

Abstract

Abstract:

With the escalating challenge of global climate change, the development of efficient and sustainable carbon dioxide (CO₂) conversion technologies has become a forefront priority in energy and environmental research. Among the diverse strategies, the upgrading of CO₂ into high-value, long-chain hydrocarbons (C₃₊) not only alleviates the greenhouse effect but also provides a transformative pathway toward carbon neutrality and a circular carbon economy. Electrocatalysis and biocatalysis have each demonstrated unique advantages, including mild operating conditions, tunable selectivity, and modular integration capacity. Nevertheless, when deployed independently, both approaches suffer from intrinsic bottlenecks, such as limited carbon fixation efficiency, suboptimal product selectivity, and long-term instability. In recent years, electro-microbial hybrid systems have emerged as a promising solution by synergistically coupling electrochemical reduction with microbial metabolism. In such systems, electrical energy can directly fuel microbial CO₂ fixation, or electrocatalysts can reduce CO₂ into C₁/C₂ intermediates (e.g., CO, formate, acetate) that subsequently serve as versatile carbon feedstocks for microbial pathways. Through rationally engineered metabolic networks, these intermediates are further upgraded into multicarbon products, such as butanol, hexanoic acid, and olefins, thereby bridging the gap between simple reduction chemistry and complex biochemical synthesis. Depending on the degree of spatial, temporal, and energetic coupling, these systems can be broadly classified into in situ electro-microbe interfaces and ex situ cascade configurations, each offering distinct advantages and challenges. This review provides a comprehensive overview of recent advances in electro-microbial CO₂ conversion, with emphasis on key scientific and technological frontiers: (i) control of product selectivity through pathway engineering and catalyst design, (ii) elucidation of direct versus mediated electron transfer mechanisms, (iii) strategies for designing robust and conductive bio-electrode interfaces, and (iv) approaches to enhance system durability and scalability. Finally, by highlighting the convergence of synthetic biology, materials science, and systems engineering, we outline future research opportunities, including precision genetic regulation, high-throughput catalyst-microbe screening, and integrated device architectures. This review aims to deliver mechanistic insights and design principles that will guide the next generation of electro-microbial technologies for carbon-neutral chemical manufacturing.

Key words: electrocatalysis, microorganism, hybrid system, CO₂ fixation

摘要：

随着全球气候变化问题的日益加剧，开发高效、可持续的CO₂转化技术已成为国际研究的前沿课题。特别是将CO₂升级转化为具有高附加值的长链碳氢化合物（C₃及以上）不仅有助于缓解温室效应，还为实现碳中和和构建循环经济体系提供了新路径。在众多技术路线中，电催化与生物催化因其温和的反应条件、良好的可控性和可模块化集成特性，展现出广阔的发展前景。然而，两者在独立应用中分别存在产物选择性差、固碳效率低或系统稳定性不足等瓶颈问题。近年来，电催化与微生物催化的协同耦合策略逐渐成为研究热点。该策略利用电能为微生物固碳过程提供能量和还原力，或通过电催化将CO₂还原为C₁/C₂中间产物（如CO、甲酸、乙酸等），进一步作为碳源被特定微生物利用，通过代谢途径高选择性合成丁醇、己酸、烯烃等多碳产物，实现对CO₂的深度转化和资源化利用。根据电化学系统与生物系统在时间、空间及能量耦合方式的不同，该类系统可划分为电-菌原位耦合系统与电-菌异位耦合系统两大类。本文系统梳理了当前电-微生物细胞协同固碳转化合成化学品领域的研究进展，重点分析了不同耦合模式在产物分布调控、电子传递机制、界面构建策略及系统稳定性等方面的技术关键与科学挑战。进一步结合合成生物学、材料科学与反应工程的交叉融合趋势，提出了未来该领域在精准调控、高通量筛选与系统集成等方向的发展前景。本综述为推动电-微生物协同固碳转化技术的深入研究与实际应用提供了重要参考与理论支撑。

关键词: 电催化, 微生物, 耦合系统, CO₂固定

CLC Number:

Q819

HAN Lin, GUO Yuman, LI Yan, CAO Hengheng, LI Jiajing, YANG Minghao, WANG Mengmeng, LI Jinping, LV Yongqin. Advances in electro-microbial synergistic systems for value-added conversion of carbon dioxide[J]. Synthetic Biology Journal, DOI: 10.12211/2096-8280.2025-070.

韩林, 郭禹曼, 李燕, 曹珩珩, 李嘉婧, 杨明浩, 汪萌萌, 李晋萍, 吕永琴. 电-微生物协同系统用于CO₂高值转化的研究进展[J]. 合成生物学, DOI: 10.12211/2096-8280.2025-070.

Figures/Tables 19

Fig.1 Classifications of electrocatalytic-microbial in situ coupling systems

Fig.2 Design of different electrode materials and schematic diagram of the MES systems

Fig.3 Design of artificially regulated MES systems

Fig. 4 MES for C2+ product synthesis

Fig. 5 H2-mediated enhancement strategies for MES-1

Fig. 6 H2-mediated enhancement strategies for MES-2

Fig. 7 Schematic of enhanced CO2-to-CH4 energy efficiency via redox-mediated cathode functionalization in MES[80]

Fig. 8 Construction of an artificial photosynthesis system by integrating a photoelectrochemical system with genetically engineered cells expressing rhodopsin and an outer-membrane conduit MtrCAB[95]

Fig. 9 Three integrated modes of electrocatalytic-microbial ex situ coupling systems for CO2 conversion[9]

Fig. 10 An integrated electromicrobial process for converting CO2 into higher alcohols[90]

Fig. 11 Schematic illustration of the integrated EMC2 system[96]

Fig. 12 Schematic of the continuous-flow biohybrid CO2 electrolysis-fermentation system[102]

Fig. 13 Schematic illustration of the electromicrobial cascade system for artificial glucose synthesis[103]

Fig. 14 Schematic of the spatially separated electrochemical CO2 reduction reaction (CO2RR) and microbial fermentation process for efficient β-farnesene synthesis from CO2[98]

Fig. 15 Schematic of the sequential CO2 electrolysis and microbial fermentation system for artificial synthesis of PHB[104]

Fig. 16 Schematic illustration of L-tyrosine synthesis from CO2 using a blended nexus molecular system based on an abiotic/biotic cascade catalysis[105]

Fig. 17 Schematic diagram of the carbon dioxide electrocatalytic platform and microbial conversion for long-chain compound synthesis. a) Schematic illustration of the integrated electrocatalytic/biocatalytic platform system for the synthesis of long-chain compounds from CO2. b) Schematic depiction of the fabrication process of the MPN@deCOP@Ag-Cu2O electrocatalytic platform. c) Construction of the ethanol utilization pathway[106].

Table 1 Representative work: in situ vs ex situ coupling

	产物种类	电极材料或者催化剂种类	细菌种类	产量	生成速率	参考文献
原位耦合体系	甲烷	Co-N₄@Co-NP	电活性产甲烷混菌	——	3860 mmol/(m²·day)	[22]
	C₂₊	CNTs增强的中空纤维膜	活性污泥中的微生物种群（Macellibacteroides为）	乙酸产量达230 mg/L，乙醇最高浓度达7.05 mg/L	——	[32]
	PHB	亲水导电聚合物络合物涂敷的碳毡	Acetobacterium, Clostridium, Pseudomonas, Rhodobacter, Caulobacter	——	43.518 ± 0.931 mg/L	[41]
	异丙醇	钴基催化剂	R. eutropha	216 ± 17 mg/L	43.2 ± 3.4 mg/(L·day)	[49]
	乙酸	大孔网状玻璃碳电极	Acetoanaerobium, Hydrogenophaga, Methanobrevibacter, one New Reference_OTU	——	1330 g/(m²·d)	[67]
	番茄红素	——	C. necator	1.73 mg/L	——	[74]
	α-石竹烯	——	R. eutropha	10.8 ± 2.5 mg/L	0.08 ± 0.01 mg/(L·h)	[75]
	甲酸	——	S. oneidensis	——	3.50 mmol/(L·μg protein)	[94]
异位耦合体系	高级醇（异丁醇和3-甲基-1-丁醇）	Pt阴极	R. eutropha	846 mg/L异丁醇和570 mg/L 3-甲基-1-丁醇	——	[90]
	PHA	Cu/PTFE	P. putida	556.2 mg/L	2.75 g/L DCW	[96]
	PHB	Sn	Cupriavidus	1.38 g	11.5 mg/h	[102]
	β-法尼烯	Ni-N-C	Y. lipolytica	——	14.8±0.23 g/L	[98]
	PHB	Bi₂O₃纳米片	R. eutropha	——	99.6 mg/（L·d）	[104]

Table 2 Comparative analysis of in situ and ex situ coupling systems

	原位耦合系统	异位耦合系统
固碳位点	微生物胞内	人工电极表面
生物-非生物偶联方式	直接/间接电子转移	通过含碳中间体转移
产物选择性	较高	较高
运行稳定性	较差	较好
放大可行性	较难	较易

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Advances in electro-microbial synergistic systems for value-added conversion of carbon dioxide

电-微生物协同系统用于CO₂高值转化的研究进展

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Advances in electro-microbial synergistic systems for value-added conversion of carbon dioxide

电-微生物协同系统用于CO2高值转化的研究进展

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电-微生物协同系统用于CO₂高值转化的研究进展