基于Fe<sub>2</sub>O<sub>3</sub>的微生物杂化体增强暗发酵产氢性能与机理研究

弓俊莎; 宋敬雯; 侯雅男; 刘志华; 李海波; 吴丽萍; 黄聪

doi:10.13205/j.hjgc.202605003

基于Fe₂O₃的微生物杂化体增强暗发酵产氢性能与机理研究

doi: 10.13205/j.hjgc.202605003

1. 天津城建大学水质科学与技术重点实验室, 天津 300384;
2. 中国科学院天津工业生物技术研究所, 天津 300308

基金项目:

国家自然科学基金项目“基于数字细胞模型的人工极简产氢微生物菌群构建与优化”（52470168），“微生物自组装钯金双金属强化氯代污染物还原脱氯及作用机制”（52000134）；天津城建大学低碳比市政污水节能低碳治理中波联合研究中心建设（24PTLYHZ00310）

详细信息

作者简介:
弓俊莎(2000—),女,硕士研究生,主要研究方向为污水生物处理技术。gongjsh@tib.cas.cn

通讯作者:
侯雅男(1989—),女,副教授,主要研究方向为污水生物处理技术。houyn2013@163.com

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出版历程
- 收稿日期: 2025-03-25
- 网络出版日期: 2026-06-06

Fe₂O₃-based microbial hybrids for enhancing dark fermentation hydrogen production: performance and mechanistic insights

1. Tianjin Key Laboratory of Aquatic Science and Technology, Tianjin Chengjian University, Tianjin 300384, China;
2. Tianjin Institute of Industrial Biotechnology, Chinese Academy of Sciences, Tianjin 300308, China

摘要

摘要: 研究构建了一种基于Fe₂O₃纳米颗粒的混菌生物杂化体，通过增强产氢菌的氢化酶活性、微生物代谢活性及电子传递效率，实现了暗发酵制氢效率的显著提升。其中，当Fe₂O₃浓度为300 mg/L（S₃₀₀）时，氢气产量达到2.94 mol/mol（葡萄糖），相当于暗发酵理论氢气产率的73.5%，较未添加Fe₂O₃纳米颗粒的对照组（S₀）高出1.59倍。S₃₀₀杂化体中ATP含量和总蛋白质含量分别提高了4.09，1.30倍，氢化酶和脱氢酶活性分别提升24.62%和63.11%，电子传递系统活性增加了3.44倍，传荷电阻值显著降低。此外，研究发现在S₅₀—S₃₀₀杂化体中，Fe²⁺浓度逐渐增加，是刺激氢化酶活性和增强电子传递效率的重要因素。微生物群落分析显示，S₃₀₀杂化体中产氢菌属Clostridium的相对丰度比对照组增加9.75百分点，达到42.60%，在增强氢气生成中发挥了关键作用。研究不仅提出了一种高效的Fe₂O₃纳米颗粒生物杂化体策略，还深入揭示了纳米材料与微生物之间的协同机制，为未来提升暗发酵制氢技术提供理论和实践基础。
- Fe₂O₃ /
- 暗发酵 /
- 产氢 /
- 电子传递 /
- 酶活性 /
- 微生物群落
Abstract: This study developed a mixed microbial biohybrid system based on Fe₂O₃ nanoparticles to significantly enhance dark fermentation hydrogen production by improving hydrogenase activity， microbial metabolic activity， and electron transfer efficiency. At a Fe₂O₃ concentration of 300 mg/L （denoted as S₃₀₀）， the hydrogen yield attained 2.94 mol H₂ per mole of glucose， which was equivalent to 73.5% of the theoretical hydrogen production rate in dark fermentation. This yield was 1.59 times higher than that of the control group （S₀） without the addition of Fe₂O₃ nanoparticles. In the S₃₀₀ biohybrid， the ATP content and total protein concentration increased by 4.09- and 1.30-fold， respectively； hydrogenase and dehydrogenase activities were enhanced by 24.62% and 63.11%， respectively； and the electron transfer system activity increased by 3.44-fold， accompanied by a significant reduction in charge transfer resistance. Additionally， a gradual increase in Fe²⁺ concentration from S₅₀ to S₃₀₀ was identified as a key factor in stimulating hydrogenase activity and enhancing electron transfer efficiency. Microbial community analysis revealed that the relative abundance of the hydrogen-producing genus Clostridium in S₃₀₀ increased by 9.75 percentage points to 42.60%， playing a pivotal role in enhancing hydrogen production. This study not only proposes an efficient Fe₂O₃ nanoparticle-based biohybrid strategy but also provides in-depth insights into the synergistic mechanisms between nanomaterials and microorganisms， thereby offering a theoretical and practical foundation for advancing dark fermentation hydrogen production technologies.
- Fe₂O₃ /
- dark fermentation /
- hydrogen production /
- electron transfer /
- enzyme activity /
- microbial community

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参考文献(48)

[1]	CHU S，MAJUMDAR A. Opportunities and challenges for a sustainable energy future［J］. Nature，2012，488（7411）：294- 303.
[2]	ZHANG Q，JIAO Y，HE C，et al. Biological fermentation pilot-scale systems and evaluation for commercial viability towards sustainable biohydrogen production［J］. Nature Communications，2024，15（1）：4539.
[3]	YANG G，WANG J. Enhancing biohydrogen production from waste activated sludge disintegrated by sodium citrate［J］. Fuel，2019，258：116177.
[4]	BOLATKHAN K，KOSSALBAYEV B D，ZAYADAN B K，et al. Hydrogen production from phototrophic microorganisms:Reality and perspectives［J］. International Journal of Hydrogen Energy，2019，44（12）：5799- 5811.
[5]	RAMPRAKASH B，LINDBLAD P，EATON-RYE J J，et al. Current strategies and future perspectives in biological hydrogen production：A review［J］. Renewable and Sustainable Energy Reviews，2022，168：112773.
[6]	YIN T，WANG W，GUO W，et al. Enhanced thermophilic hydrogen production by an enriched novel acetic-acid-type fermentative bacterium from inoculum sludge with nonheat pretreatment［J］. Energy & Fuels，2024，38（10）：8749- 8761.
[7]	DE VRIJE T，CLAASSEN P. Dark hydrogen fermentations［J］. Bio-methane & Bio-hydrogen，2003：103- 123.
[8]	NARESH KUMAR A，BANDARAPU A K，VENKATA MOHAN S. Microbial electro-hydrolysis of sewage sludge for acidogenic production of biohydrogen and volatile fatty acids along with struvite［J］. Chemical Engineering Journal，2019，374：1264- 1274.
[9]	LI Z，WANG J，TIAN K，et al. Nickel-cobalt oxide nanoparticle-induced biohydrogen production［J］. ACS Omega，2022，7（45）：41594- 41605.
[10]	YILDIRIM O，TUNAY D，OZKAYA B，et al. Effect of green synthesized silver oxide nanoparticle on biological hydrogen production［J］. International Journal of Hydrogen Energy，2022，47（45）：19517- 19525.
[11]	LIN R，CHENG J，DING L，et al. Enhanced dark hydrogen fermentation by addition of ferric oxide nanoparticles using Enterobacter aerogenes［J］. Bioresource Technology，2016，207：213- 219.
[12]	GADHE A，SONAWANE S S，VARMA M N. Enhancement effect of hematite and nickel nanoparticles on biohydrogen production from dairy wastewater［J］. International Journal of Hydrogen Energy，2015，40（13）：4502- 4511.
[13]	GADHE A，SONAWANE S S，VARMA M N. Influence of nickel and hematite nanoparticle powder on the production of biohydrogen from complex distillery wastewater in batch fermentation［J］. International Journal of Hydrogen Energy，2015，40（34）：10734- 10743.
[14]	LEE S H，CHOI D S，KUK S K，et al. Photobiocatalysis:activating redox enzymes by direct or indirect transfer of photoinduced electrons［J］. Angewandte Chemie International Edition，2018，57（27）：7958- 7985.
[15]	ZHAO X，XING D，LIU B，et al. The effects of metal ions and l-cysteine on hydA gene expression and hydrogen production by Clostridium beijerinckii RZF-1108［J］. International Journal of Hydrogen Energy，2012，37（18）：13711- 13717.
[16]	ZHONG D，LI J，MA W，et al. Magnetite nanoparticles enhanced glucose anaerobic fermentation for bio-hydrogen production using an expanded granular sludge bed（EGSB）reactor［J］. International Journal of Hydrogen Energy，2020，45（18）：10664- 10672.
[17]	FANG J Y，ZHENG Q Z，LOU Y Y，et al. Ampere-level current density ammonia electrochemical synthesis using CuCo nanosheets simulating nitrite reductase bifunctional nature［J］. Nature Communications，2022，13（1）：7899.
[18]	JONES J R，KNOWLTON M F. Suspended solids in Missouri reservoirs in relation to catchment features and internal processes［J］. Water Research，2005，39（15）：3629- 3635.
[19]	VLYSSIDES A，BARAMPOUTI E，MAI S. Influence of ferrous iron on the granularity of a UASB reactor［J］. Chemical Engineering Journal，2009，146（1）：49- 56.
[20]	HE Y，GUO J，SONG Y，et al. Acceleration mechanism of bioavailable Fe（Ⅲ）on Te（Ⅳ）bioreduction of Shewanella oneidensis MR-1：Promotion of electron generation，electron transfer and energy level［J］. Journal of Hazardous Materials，2021，403：123728.
[21]	HAN H，CUI M，WEI L，et al. Enhancement effect of hematite nanoparticles on fermentative hydrogen production［J］. Bioresource Technology，2011，102（17）：7903- 7909.
[22]	ZHANG J，FAN C，ZHANG H，et al. Ferric oxide/carbon nanoparticles enhanced bio-hydrogen production from glucose［J］. International Journal of Hydrogen Energy，2018，43（18）：8729- 8738.
[23]	ENGLIMAN N S，ABDUL P M，WU S Y，et al. Influence of iron（Ⅱ）oxide nanoparticle on biohydrogen production in thermophilic mixed fermentation［J］. International Journal of Hydrogen Energy，2017，42（45）：27482- 27493.
[24]	NASR M，TAWFIK A，OOKAWARA S，et al. Continuous biohydrogen production from starch wastewater via sequential dark-photo fermentation with emphasize on maghemite nanoparticles［J］. Journal of Industrial and Engineering Chemistry，2015，21：500- 506.
[25]	LI Y，ZHU Q，DING P，et al. Effects of Fe⁰ and Ni⁰ nanoparticles on hydrogen production from cotton stalk hydrolysate using Klebsiella sp. WL1316：Evaluation of size and concentration of the nanoparticles［J］. International Journal of Hydrogen Energy，2020，45（11）：6243- 6253.
[26]	NATH D，MANHAR A K，GUPTA K，et al. Phytosynthesized iron nanoparticles:effects on fermentative hydrogen production by Enterobacter cloacae DH-89［J］. Bulletin of Materials Science，2015，38（6）：1533- 1538.
[27]	HSIEH P H，LAI Y C，CHEN K Y，et al. Explore the possible effect of TiO₂ and magnetic hematite nanoparticle addition on biohydrogen production by Clostridium pasteurianum based on gene expression measurements［J］. International Journal of Hydrogen Energy，2016，41（46）：21685- 21691.
[28]	SIVAGURUNATHAN P，SAHOO P C，KUMAR M，et al. Unrevealing the role of metal oxide nanoparticles on biohydrogen production by Lactobacillus delbrueckii［J］. Bioresource Technology，2023，367：128260.
[29]	RAMPRAKASH B，INCHAROENSAKDI A. Supplementation of magnetic nanoparticles for enhancement of dark fermentative hydrogen production from pretreated garden wastes using Enterobacter aerogenes［J］. Fuel，2023，342：127857.
[30]	CHENG J，LI H，DING L，et al. Improving hydrogen and methane co-generation in cascading dark fermentation and anaerobic digestion：The effect of magnetite nanoparticles on microbial electron transfer and syntrophism［J］. Chemical Engineering Journal，2020，397：125394.
[31]	ELREEDY A，FUJII M，KOYAMA M，et al. Enhanced fermentative hydrogen production from industrial wastewater using mixed culture bacteria incorporated with iron，nickel，and zinc-based nanoparticles［J］. Water Research，2019，151：349- 61.
[32]	YIN Y，WANG J. Enhanced sewage sludge disintegration and hydrogen production by ionizing radiation pretreatment in the presence of Fe²⁺［J］. ACS Sustainable Chemistry & Engineering，2019，7（18）：15548- 15557.
[33]	CAI G，JIN B，MONIS P，et al. Metabolic flux network and analysis of fermentative hydrogen production［J］. Biotechnology Advances，2011，29（4）：375- 387.
[34]	WEN X，HOU Y N，GUO J，et al. Mechanistic insight into enhanced methyl orange degradation by Raoultella planticola/MoS₂ biohybrid：Implication for electron transfer and microbial metabolism［J］. Journal of Cleaner Production，2024，469：143201.
[35]	ELBESHBISHY E，DHAR B R，NAKHLA G，et al. A critical review on inhibition of dark biohydrogen fermentation［J］. Renewable and Sustainable Energy Reviews，2017，79：656- 668.
[36]	NICOLET Y，FONTECILLA-CAMPS J C，FONTECAVE M. Maturation of［FeFe］-hydrogenases:Structures and mechanisms［J］. International Journal of Hydrogen Energy，2010，35（19）：10750- 10760.
[37]	YöRüKLü H C，FILIZ B C，FIGEN A K，et al. Screening of biohydrogen production based on dark fermentation in the presence of nano-sized Fe₂O₃ doped metal oxide additives［J］. International Journal of Hydrogen Energy，2022，47（34）：15383- 15396.
[38]	XU N，LI H，GUO T，et al. Effect of ibuprofen on the sulfur autotrophic denitrification process and microbial toxic response mechanism［J］. Bioresource Technology，2023，384：129261.
[39]	BROBERG A. Effects of heavy metals on electron transport system activity（ETSA）in freshwater sediments［J］. Ecological Bulletins，1983：403- 418.
[40]	TU J，GUO J，LU C，et al. Effect and mechanism of cyclodextrins on nitrate reduction and bio-activity by S. oneidensis. MR-1［J］. Bioresource Technology，2020，317：124002.
[41]	YIN Q，YANG S，WANG Z，et al. Clarifying electron transfer and metagenomic analysis of microbial community in the methane production process with the addition of ferroferric oxide［J］. Chemical Engineering Journal，2018，333：216- 225.
[42]	YANG G，WANG J. Changes in microbial community structure during dark fermentative hydrogen production［J］. International Journal of Hydrogen Energy，2019，44（47）：25542- 25550.
[43]	RATTI R P，DELFORNO T P，SAKAMOTO I K，et al. Thermophilic hydrogen production from sugarcane bagasse pretreated by steam explosion and alkaline delignification［J］. International Journal of Hydrogen Energy，2015，40（19）：6296- 6306.
[44]	JYOTHSNA T S，TUSHAR L，SASIKALA C，et al. Paraclostridium benzoelyticum gen. nov.，sp. nov.，isolated from marine sediment and reclassification of Clostridium bifermentans as Paraclostridium bifermentans comb. nov. Proposal of a new genus Paeniclostridium gen. nov. to accommodate Clostridium sordellii and Clostridium ghonii［J］. International Journal of Systematic and Evolutionary Microbiology，2016，66（3）：1268- 1274.
[45]	KURIBAYASHI K，KOBAYASHI Y，YOKOYAMA K，et al. Digested sludge-degrading and hydrogen-producing bacterial floras and their potential for biohydrogen production［J］. International Biodeterioration & Biodegradation，2017，120：58- 65.
[46]	YANG G，YIN Y，WANG J. Microbial community diversity during fermentative hydrogen production inoculating various pretreated cultures［J］. International Journal of Hydrogen Energy，2019，44（26）：13147- 13156.
[47]	BAEK G，KIM J，CHO K，et al. The biostimulation of anaerobic digestion with（semi）conductive ferric oxides:their potential for enhanced biomethanation［J］. Applied Microbiology and Biotechnology，2015，99（23）：10355- 10366.
[48]	KANCHANASUTA S，PROMMEENATE P，BOONAPATCHARONE N，et al. Stability of Clostridium butyricum in biohydrogen production from non-sterile food waste［J］. International Journal of Hydrogen Energy，2017，42（5）：3454- 3465.