金属纳米颗粒辅助木质纤维素暗发酵生物制氢的研究进展

doi:10.11949/0438-1157.S20211412

摘要/Abstract

摘要：

通过文献计量学分析表明暗发酵制氢是目前研究最热门的生物制氢方法，Fe、Ni、Co、Ag等金属纳米颗粒作为该领域研究热点可改善暗发酵制氢存在底物转化率与产氢效率均有待提高的难题。介绍了金属纳米颗粒的特点、生物相容性及其与酶、微生物细胞的作用机理，进一步从促进木质纤维素水解影响产氢、对水解酶的固定化影响产氢、提高氢化酶活性影响产氢、调控发酵微生物细胞代谢和促进细胞电子传递影响产氢、改善微生物群落结构影响多菌群协同产氢等几个方面对典型金属纳米颗粒辅助木质纤维素暗发酵产氢的研究现状进行综述，并对金属纳米颗粒应用于暗发酵产氢存在的难点及前景方向进行了展望。

关键词: 木质纤维素, 暗发酵, 生物制氢, 金属纳米颗粒, 酶, 微生物

Abstract:

Based on bibliometric analysis of bio-hydrogen published 2004 to 2020 indexed by web of science, dark fermentation as one of the four methods of bio-hydrogen, has received the highest attention for its assets such as high hydrogen-production rate without light, low energy consumption and comprehensively available microorganism and substrate. At the same time, some metal nanoparticles (Fe, Ni, Co, and Ag) that exhibit excellent promotion for dark fermentation has been spotlight in this research field. Nanoparticles equipped with the properties and characteristics of small volume, surface effect and quantum size effect can enhance the rate of electron transfer of cells and present good biocompatibility. The mechanism of metal nanoparticles (MNPs) interacting with enzymes and microoganisms has been illustrated. Particularly, impacts of MNPs are elaborated in details on different mechanisms of enhancing the hydrogen production process through dark fermentation by promoting hydrolysis of lignocellulose, immobilization of cellulase enzymes, and activity of hydrogenase, respectively. On one hand, MNPs assist pretreatment process of removing of lignin, and improve stability of enzymes by immobilizing them; on the other hand, MNPs enhance the rate of electron transfer, thus make a promotion of activity of hydrogenase, and finally lead the increase of hydrogen production. In addition to the impact of nanoparticles on enzymes, the role of nanoparticles on bacterial metabolism, interspecies electron transfer and synergistic hydrogen production of mixed culture are discussed. The difficulties and prospects of the application of metal nanoparticles in dark fermentation for hydrogen production are also prospected.

Key words: lignocellulose, dark fermentative, bio-hydrogen, metal nanoparticles, enzyme, microorganism

中图分类号:

TQ 929

童海航,石德智,刘嘉宇,蔡桦伊,罗丹,陈飞. 金属纳米颗粒辅助木质纤维素暗发酵生物制氢的研究进展[J]. 化工学报, DOI: 10.11949/0438-1157.S20211412.

Haihang TONG,Dezhi SHI,Jiayu LIU,Huayi CAI,Dan LUO,Fei CHEN. Research progress on dark fermentative bio-hydrogen production from lignocellulose assisted by metal nanoparticles[J]. CIESC Journal, DOI: 10.11949/0438-1157.S20211412.

图/表 12

参考文献 137

1	Ladole M R, Mevada J S, Pandit A B. Ultrasonic hyperactivation of cellulase immobilized on magnetic nanoparticles[J]. Bioresource Technology, 2017, 239: 117-126.
2	Taherdanak M, Zilouei H, Karimi K. The effects of Fe⁰ and Ni⁰ nanoparticles versus Fe²⁺ and Ni²⁺ ions on dark hydrogen fermentation[J]. International Journal of Hydrogen Energy, 2016, 41(1): 167-173.
3	Lang Y Z, Arnepalli R R, Tiwari A. A review on hydrogen production: methods, materials and nanotechnology[J]. Journal of Nanoscience and Nanotechnology, 2011, 11(5): 3719-3739.
4	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.
5	Srivastava N, Srivastava M, Gupta V K, et al. A novel strategy to enhance biohydrogen production using graphene oxide treated thermostable crude cellulase and sugarcane bagasse hydrolyzate under co-culture system[J]. Bioresource Technology, 2018, 270: 337-345.
6	Patel S K S, Lee J K, Kalia V C. Beyond the theoretical yields of dark-fermentative biohydrogen[J]. Indian Journal of Microbiology, 2018, 58(4): 529-530.
7	Sekoai P T, Ouma C N M, du Preez S P, et al. Application of nanoparticles in biofuels: an overview[J]. Fuel, 2019, 237: 380-397.
8	Srivastava N, Srivastava M, Malhotra B D, et al. Nanoengineered cellulosic biohydrogen production via dark fermentation: a novel approach[J]. Biotechnology Advances, 2019, 37(6): 107384.
9	Srivastava N, Srivastava M, Mishra P K, et al. Advances in nanomaterials induced biohydrogen production using waste biomass[J]. Bioresource Technology, 2020, 307: 123094.
10	Manish S, Banerjee R. Comparison of biohydrogen production processes[J]. International Journal of Hydrogen Energy, 2008, 33(1): 279-286.
11	Nikolaidis P, Poullikkas A. A comparative overview of hydrogen production processes[J]. Renewable and Sustainable Energy Reviews, 2017, 67: 597-611.
12	Azman N F, Abdeshahian P, Kadier A, et al. Biohydrogen production from de-oiled rice bran as sustainable feedstock in fermentative process[J]. International Journal of Hydrogen Energy, 2016, 41(1): 145-156.
13	Ding J, Wang X, Zhou X F, et al. CFD optimization of continuous stirred-tank (CSTR) reactor for biohydrogen production[J]. Bioresource Technology, 2010, 101(18): 7005-7013.
14	Venkata Mohan S. Harnessing of biohydrogen from wastewater treatment using mixed fermentative consortia: Process evaluation towards optimization[J]. International Journal of Hydrogen Energy, 2009, 34(17): 7460-7474.
15	Kim M, Day D F. Composition of sugar cane, energy cane, and sweet sorghum suitable for ethanol production at Louisiana sugar mills[J]. Journal of Industrial Microbiology & Biotechnology, 2011, 38(7): 803-807.
16	Hu F, Ragauskas A. Pretreatment and lignocellulosic chemistry[J]. Bioenergy Research, 2012, 5(4): 1043-1066.
17	Rocha G J M, Martín C, Da Silva V F N, et al. Mass balance of pilot-scale pretreatment of sugarcane bagasse by steam explosion followed by alkaline delignification[J]. Bioresource Technology, 2012, 111: 447-452.
18	Pandey A, Nigam P, Soccol C R, et al. Advances in microbial amylases[J]. Biotechnology and Applied Biochemistry, 2000, 31 (2): 135-152.
19	Furlan F F, Filho R T, Pinto F H, et al. Bioelectricity versus bioethanol from sugarcane bagasse: is it worth being flexible?[J]. Biotechnology for Biofuels, 2013, 6(1): 142.
20	Sharma M, Joshi M, Nigam S, et al. ZnO tetrapods and activated carbon based hybrid composite: Adsorbents for enhanced decontamination of hexavalent chromium from aqueous solution[J]. Chemical Engineering Journal, 2019, 358: 540-551.
21	Mishra P, Thakur S, Mahapatra D M, et al. Impacts of nano-metal oxides on hydrogen production in anaerobic digestion of palm oil mill effluent - A novel approach[J]. International Journal of Hydrogen Energy, 2018, 43(5): 2666-2676.
22	Grieger K D, Fjordbøge A, Hartmann N B, et al. Environmental benefits and risks of zero-valent iron nanoparticles (nZVI) for in situ remediation: Risk mitigation or trade-off?[J]. Journal of Contaminant Hydrology, 2010, 118(3-4): 165-183.
23	Lin H N, Hu B B, Zhu M J. Enhanced hydrogen production and sugar accumulation from spent mushroom compost by Clostridium thermocellum supplemented with PEG8000 and JFC-E[J]. International Journal of Hydrogen Energy, 2016, 41(4): 2383-2390.
24	Lin R C, Cheng J, Ding L K, et al. Enhanced dark hydrogen fermentation by addition of ferric oxide nanoparticles using Enterobacteraerogenes[J]. Bioresource Technology, 2016, 207: 213-219.
25	Pugazhendhi A, Shobana S, Nguyen D D, et al. Application of nanotechnology (nanoparticles) in dark fermentative hydrogen production[J]. International Journal of Hydrogen Energy, 2019, 44(3): 1431-1440.
26	Taherdanak M, Zilouei H, Karimi K. Investigating the effects of iron and nickel nanoparticles on dark hydrogen fermentation from starch using central composite design[J]. International Journal of Hydrogen Energy, 2015, 40(38): 12956-12963.
27	Hokkanen S, Bhatnagar A, Sillanpää M. A review on modification methods to cellulose-based adsorbents to improve adsorption capacity[J]. Water Research, 2016, 91: 156-173.
28	Srivastava N, Srivastava M, Kushwaha D, et al. Efficient dark fermentative hydrogen production from enzyme hydrolyzed rice straw by Clostridium pasteurianum (MTCC116)[J]. Bioresource Technology, 2017, 238: 552-558.
29	Sewwandi K A H S, Nitisoravut R. Nano zero valent iron embedded on chitosan for enhancement of biohydrogen production in dark fermentation[J]. Energy Reports, 2020, 6: 392-396.
30	Zhang J S, Zhao W Q, Yang J W, et al. Comparison of mesophilic and thermophilic dark fermentation with nickel ferrite nanoparticles supplementation for biohydrogen production[J]. Bioresource Technology, 2021, 329: 124853.
31	Wei Z, Zeng G M, Huang F, et al. Bioconversion of oxygen-pretreated Kraft lignin to microbial lipid with oleaginous Rhodococcus opacus DSM 1069[J]. Green Chemistry, 2015, 17(5): 2784-2789.
32	Bilal S, Ali L, Khan A L, et al. Endophytic fungus Paecilomyces formosus LHL10 produces sester-terpenoid YW3548 and cyclic peptide that inhibit urease and α-glucosidase enzyme activities[J]. Archives of Microbiology, 2018, 200(10): 1493-1502.
33	Srivastava N, Srivastava M, Manikanta A, et al. Nanomaterials for biofuel production using lignocellulosic waste[J]. Environmental Chemistry Letters, 2017, 15(2): 179-184.
34	Lynch I, Cedervall T, Lundqvist M, et al. The nanoparticle-protein complex as a biological entity; a complex fluids and surface science challenge for the 21st century[J]. Advances in Colloid and Interface Science, 2007, 134-135: 167-174.
35	Gao H, Shi W, Freund L B. Mechanics of receptor-mediated endocytosis[J]. Proceedings of the National Academy of Sciences of the United States of America, 2005, 102(27): 9469-9474.
36	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.
37	Wang J L, Wan W. Influence of Ni²⁺ concentration on biohydrogen production[J]. Bioresource Technology, 2008, 99(18): 8864-8868.
38	Zhang Y F, Shen J Q. Enhancement effect of gold nanoparticles on biohydrogen production from artificial wastewater[J]. International Journal of Hydrogen Energy, 2007, 32(1): 17-23.
39	Zheng X J, Yu H Q. Biological hydrogen production by enriched anaerobic cultures in the presence of copper and zinc[J]. Journal of Environmental Science and Health Part A-Toxic/Hazardous Substances and Environmental Engineering, 2004, 39(1): 89-101.
40	Thota S P, Badiya P K, Yerram S, et al. Macro-micro fungal cultures synergy for innovative cellulase enzymes production and biomass structural analyses[J]. Renewable Energy, 2017, 103: 766-773.
41	Lukowiak A, Kedziora A, Strek W. Antimicrobial graphene family materials: Progress, advances, hopes and fears[J]. Advances in Colloid and Interface Science, 2016, 236: 101-112.
42	Wang D, Ikenberry M, Peña L, et al. Acid-functionalized nanoparticles for pretreatment of wheat straw[J]. Journal of Biomaterials and Nanobiotechnolog, 2012, 3(3): 342-352.
43	Singh R K, Tiwari M K, Singh R, et al. From protein engineering to immobilization: promising strategies for the upgrade of industrial enzymes[J]. International Journal of Molecular Sciences, 2013, 14(1): 1232-1277.
44	Kumar A, Singh S, Nain L. Magnetic nanoparticle immobilized cellulase enzyme for saccharification of paddy straw[J]. International Journal of Current Microbiology and Applied Sciences, 2018, 7(4): 881-893.
45	Srivastava N, Singh J, Ramteke P W, et al. Improved production of reducing sugars from rice straw using crude cellulase activated with Fe₃O₄/Alginate nanocomposite[J]. Bioresource Technology, 2015, 183: 262-266.
46	Cherian E, Dharmendirakumar M, Baskar G. Immobilization of cellulase onto MnO₂ nanoparticles for bioethanol production by enhanced hydrolysis of agricultural waste[J]. Chinese Journal of Catalysis, 2015, 36(8): 1223-1229.
47	Ingle A P, Chandel A K, Antunes F A F, et al. New trends in application of nanotechnology for the pretreatment of lignocellulosic biomass[J]. Biofuels Bioproducts and Biorefining, 2019, 13(3): 776-788.
48	Guo F, Fang Z, Xu C C, et al. Solid acid mediated hydrolysis of biomass for producing biofuels[J]. Progress in Energy and Combustion Science, 2012, 38(5): 672-690.
49	Gill C S, Price B A, Jones C W. Sulfonic acid-functionalized silica-coated magnetic nanoparticle catalysts[J]. Journal of Catalysis, 2007, 251(1): 145-152.
50	Peña L, Ikenberry M, Ware B, et al. Cellobiose hydrolysis using acid-functionalized nanoparticles[J]. Biotechnology and Bioprocess Engineering, 2011, 16(6): 1214-1222.
51	Su T C, Fang Z, Zhang F, et al. Hydrolysis of selected tropical plant wastes catalyzed by a magnetic carbonaceous acid with microwave[J]. Scientific Reports, 2015, 5: 17538.
52	Ingle A P, Philippini R R, Souza Melo Y C, et al. Acid-functionalized magnetic nanocatalysts mediated pretreatment of sugarcane straw: an eco-friendly and cost-effective approach[J]. Cellulose, 2020, 27(12): 7067-7078.
53	Antunes F A F, Chandel A K, Terán-Hilares R, et al. Overcoming challenges in lignocellulosic biomass pretreatment for second-generation (2G) sugar production: emerging role of nano, biotechnological and promising approaches[J]. 3 Biotech, 2019, 9(6): 1-17.
54	Amin R, Khorshidi A, Shojaei A F, et al. Immobilization of laccase on modified Fe₃O₄@SiO₂@Kit-6 magnetite nanoparticles for enhanced delignification of olive pomace bio-waste[J]. International Journal of Biological Macromolecules, 2018, 114: 106-113.
55	Ibarra-Gonzalez P, Rong B G. A review of the current state of biofuels production from lignocellulosic biomass using thermochemical conversion routes[J]. Chinese Journal of Chemical Engineering, 2019, 27(7): 1523-1535.
56	Riva S. Laccases: blue enzymes for green chemistry[J]. Trends in Biotechnology, 2006, 24(5): 219-226.
57	Sukumaran R K, Singhania R R, Mathew G M, et al. Cellulase production using biomass feed stock and its application in lignocellulose saccharification for bio-ethanol production[J]. Renewable Energy, 2009, 34(2): 421-424.
58	Khoshnevisan K, Poorakbar E, Baharifar H, et al. Recent advances of cellulase immobilization onto magnetic nanoparticles: an update review[J]. Magnetochemistry, 2019, 5(2): 36.
59	Rajnish K N, Samuel M S, John J A, et al. Immobilization of cellulase enzymes on nano and micro-materials for breakdown of cellulose for biofuel production-a narrative review[J]. International Journal of Biological Macromolecules, 2021, 182: 1793-1802.
60	Han H L, Cui M J, Wei L L, et al. Enhancement effect of hematite nanoparticles on fermentative hydrogen production[J]. Bioresource Technology, 2011, 102(17): 7903-7909.
61	Ramrez W G. Plaza Central de Mercado de Bogotá: Las variaciones de un paradigma 1849-1953[M]. Plaza Central de Mercado de Bogotá: Las variaciones de un paradigma1849-1953, 2017.
62	Cao X H, Tan C L, Zhang X, et al. Solution-processed two-dimensional metal dichalcogenide-based nanomaterials for energy storage and conversion[J]. Advanced Materials, 2016, 28(29): 6167-6196.
63	Vaghari H, Jafarizadeh-Malmiri H, Mohammadlou M, et al. Application of magnetic nanoparticles in smart enzyme immobilization[J]. Biotechnology Letters, 2016, 38(2): 223-233.
64	Chen F, Fan G Q, Zhang Z P, et al. Encapsulation of omega-3 fatty acids in nanoemulsions and microgels: Impact of delivery system type and protein addition on gastrointestinal fate[J]. Food Research International, 2017, 100: 387-395.
65	Lynch I, Dawson K A. Protein-nanoparticle interactions[J]. Nano Today, 2008, 3(1-2): 40-47.
66	Brady D, Jordaan J. Advances in enzyme immobilisation[J]. Biotechnology Letters, 2009, 31(11): 1639-1650.
67	Poorakbar E, Saboury A A, Laame Rad B, et al. Immobilization of cellulase onto core-shell magnetic gold nanoparticles functionalized by aspartic acid and determination of its activity[J]. The Protein Journal, 2020, 39(4): 328-336.
68	Xu J L, Huo S H, Yuan Z H, et al. Characterization of direct cellulase immobilization with superparamagnetic nanoparticles[J]. Biocatalysis and Biotransformation, 2011, 29(2-3):71-76.
69	Srivastava N, Rawat R, Sharma R, et al. Effect of nickel-cobaltite nanoparticles on production and thermostability of cellulases from newly isolated thermotolerant aspergillus fumigatus NS (class: eurotiomycetes)[J]. Applied Biochemistry and Biotechnology, 2014, 174(3): 1092-1103.
70	Salem A H, Mietzel T, Brunstermann R, et al. Effect of cell immobilization, hematite nanoparticles and formation of hydrogen-producing granules on biohydrogen production from sucrose wastewater[J]. International Journal of Hydrogen Energy, 2017, 42(40): 25225-25233.
71	Gou Z C, Ma N L, Zhang W Q, et al. Innovative hydrolysis of corn stover biowaste by modified magnetite laccase immobilized nanoparticles[J]. Environmental Research, 2020, 188: 109829.
72	Han J, Rong J H, Wang Y, et al. Immobilization of cellulase on thermo-sensitive magnetic microspheres: improved stability and reproducibility[J]. Bioprocess and Biosystems Engineering, 2018, 41(7): 1051-1060.
73	Li Y, Wang X Y, Zhang R Z, et al. Molecular imprinting and immobilization of cellulase onto magnetic Fe₃O₄@SiO₂ nanoparticles[J]. Journal of Nanoscience and Nanotechnology, 2014, 14(4): 2931-2936.
74	Hu J P, Yuan B N, Zhang Y M, et al. Immobilization of laccase on magnetic silica nanoparticles and its application in the oxidation of guaiacol, a phenolic lignin model compound[J]. RSC Advances, 2015, 5(120): 99439-99447.
75	Tao Q L, Li Y, Shi Y, et al. Application of molecular imprinted magnetic Fe₃O₄@SiO₂ nanoparticles for selective immobilization of cellulase[J]. Journal of Nanoscience and Nanotechnology, 2016, 16(6): 6055-6060.
76	Sánchez-Ramírez J, Martínez-Hernández J L, Segura-Ceniceros P, et al. Cellulases immobilization on chitosan-coated magnetic nanoparticles: application for agave atrovirens lignocellulosic biomass hydrolysis[J]. Bioprocess and Biosystems Engineering, 2017, 40(1): 9-22.
77	Zang L M, Qiu J H, Wu X L, et al. Preparation of magnetic chitosan nanoparticles as support for cellulase immobilization[J]. Industrial & Engineering Chemistry Research, 2014, 53(9): 3448-3454.
78	Abbaszadeh M, Hejazi P. Metal affinity immobilization of cellulase on Fe₃O₄ nanoparticles with copper as ligand for biocatalytic applications[J]. Food Chemistry, 2019, 290: 47-55.
79	Alahakoon T, Koh J W, Chong X W C, et al. Immobilization of cellulases on amine and aldehyde functionalized Fe₂O₃ magnetic nanoparticles[J]. Preparative Biochemistry and Biotechnology, 2012, 42(3): 234-248.
80	Bohara R A, Thorat N D, Pawar S H. Immobilization of cellulase on functionalized cobalt ferrite nanoparticles[J]. Korean Journal of Chemical Engineering, 2016, 33(1): 216-222.
81	Poorakbar E, Shafiee A, Saboury A A, et al. Synthesis of magnetic gold mesoporous silica nanoparticles core shell for cellulase enzyme immobilization: Improvement of enzymatic activity and thermal stability[J]. Process Biochemistry, 2018, 71: 92-100.
82	Manasa P, Saroj P, Korrapati N, et al. Immobilization of cellulase enzyme on zinc ferrite nanoparticles in increasing enzymatic hydrolysis on ultrasound-assisted alkaline pretreated crotalaria juncea biomass[J]. Indian Journal of Science and Technology, 2017, 10(24): 1-7.
83	Logan, B E. Peer Reviewed: extracting hydrogen and electricity from renewable resources[J]. Environmental Science & Technology, 2004, 38(9): 160A-167A.
84	Kapdan I K, Kargi F. Bio-hydrogen production from waste materials[J]. Enzyme and Microbial Technology, 2006, 38(5): 569-582.
85	Akhtar M K, Jones P R. Construction of a synthetic YdbK-dependent pyruvate: H₂ pathway in Escherichia coli BL21(DE3)[J]. Metabolic Engineering, 2009, 11(3): 139-147.
86	Adams M W, Stiefel E I. Organometallic iron: the key to biological hydrogen metabolism[J]. Current Opinion in Chemical Biology, 2000, 4(2): 214-220.
87	Latifi A, Avilan L, Brugna M. Clostridial whole cell and enzyme systems for hydrogen production: current state and perspectives[J]. Applied Microbiology and Biotechnology, 2019, 103(2): 567-575.
88	Broderick J B, Byer A S, Duschene K S, et al. H-Cluster assembly during maturation of the [FeFe]-hydrogenase[J]. Journal of Biological Inorganic Chemistry, 2014, 19(6): 747-757.
89	Lee D Y, Li Y Y, Oh Y K, et al. Effect of iron concentration on continuous H₂ production using membrane bioreactor[J]. International Journal of Hydrogen Energy, 2009, 34(3): 1244-1252.
90	Van Ginkel S W, Oh S E, Logan B E. Biohydrogen gas production from food processing and domestic wastewaters[J]. International Journal of Hydrogen Energy, 2005, 30(15): 1535-1542.
91	Yang G, Wang J L. Improving mechanisms of biohydrogen production from grass using zero-valent iron nanoparticles[J]. Bioresource Technology, 2018, 266: 413-420.
92	Chen K F, Li S L, Zhang W X. Renewable hydrogen generation by bimetallic zero valent iron nanoparticles[J]. Chemical Engineering Journal, 2011, 170(2-3): 562-567.
93	Reardon E J. Anaerobic corrosion of granular iron: measurement and interpretation of hydrogen evolution rates[J]. Environmental Science &Technology, 1995, 29(12): 2936-2945.
94	Beckers L, Hiligsmann S, Lambert S D, et al. Improving effect of metal and oxide nanoparticles encapsulated in porous silica on fermentative biohydrogen production by Clostridium butyricum[J]. Bioresource Technology, 2013, 133: 109-117.
95	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.
96	Soni D, Bafana A, Gandhi D, et al. Stress response of pseudomonas species to silver nanoparticles at the molecular level[J]. Environmental Toxicology and Chemistry, 2014, 33(9): 2126-2132.
97	Zhang J S, Fan C F, Zhang H W, et al. Ferric oxide/carbon nanoparticles enhanced bio-hydrogen production from glucose[J]. International Journal of Hydrogen Energy, 2018, 43(18): 8729-8738.
98	Rambabu K, Bharath G, Banat F, et al. Ferric oxide/date seed activated carbon nanocomposites mediated dark fermentation of date fruit wastes for enriched biohydrogen production[J]. International Journal of Hydrogen Energy, 2021, 46(31): 16631-16643.
99	Rambabu K, Show P L, Bharath G, et al. Enhanced biohydrogen production from date seeds by Clostridium thermocellum ATCC 27405[J]. International Journal of Hydrogen Energy, 2020, 45(42): 22271-22280.
100	Kumar G, Mathimani T, Rene E R, et al. Application of nanotechnology in dark fermentation for enhanced biohydrogen production using inorganic nanoparticles[J]. International Journal of Hydrogen Energy, 2019, 44(26): 13106-13113.
101	Nath D, Manhar A K, Gupta K, et al. Phytosynthesized iron nanoparticles: effects on fermentative hydrogen production by Enterobactercloacae DH-89[J]. Bulletin of Materials Science, 2015, 38(6): 1533-1538.
102	Malik S N, Pugalenthi V, Vaidya A N, et al. Kinetics of nano-catalysed dark fermentative hydrogen production from distillery wastewater[J]. Energy Procedia, 2014, 54: 417-430.
103	Reddy K, Nasr M, Kumari S, et al. Biohydrogen production from sugarcane bagasse hydrolysate: Effects of pH, S/X, Fe²⁺, and magnetite nanoparticles[J]. Environmental Science and Pollution Research, 2017, 24(9): 8790-8804.
104	Nasr M, Tawfik A, Awad H M, et al. Dual production of hydrogen and biochar from industrial effluent containing phenolic compounds[J]. Fuel, 2021, 301: 121087.
105	Singhvi M, Maharjan A, Thapa A, et al. Nanoparticle-associated single step hydrogen fermentation for the conversion of starch potato waste biomass by thermophilic Parageobacillus thermoglucosidasius[J]. Bioresource Technology, 2021, 337: 125490.
106	Yang G, Wang J L. Synergistic enhancement of biohydrogen production from grass fermentation using biochar combined with zero-valent iron nanoparticles[J]. Fuel, 2019, 251: 420-427.
107	Zhang L, Zhang L X, Li D P. Enhanced dark fermentative hydrogen production by zero-valent iron activated carbon micro-electrolysis[J]. International Journal of Hydrogen Energy, 2015, 40(36): 12201-12208.
108	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.
109	Mostafa A, El-Dissouky A, Fawzy A, et al. Magnetite/graphene oxide nano-composite for enhancement of hydrogen production from gelatinaceous wastewater[J]. Bioresource Technology, 2016, 216: 520-528.
110	Sarma S J, Brar S K, Reigner J, et al. Enriched hydrogen production by bioconversion of biodiesel waste supplemented with ferric citrate and its nano-spray dried particles[J]. RSC Advances, 2014, 4(91): 49588-49594.
111	Moura A G L, Rabelo C A B S, Okino C H, et al. Enhancement of Clostridium butyricum hydrogen production by iron and nickel nanoparticles: Effects on hydA expression[J]. International Journal of Hydrogen Energy, 2020, 45(53): 28447-28461.
112	Mullai P, Yogeswari M K, Sridevi K. Optimisation and enhancement of biohydrogen production using nickel nanoparticles - A novel approach[J]. Bioresource Technology, 2013, 141: 212-219.
113	Rambabu K, Bharath G, Thanigaivelan A, et al. Augmented biohydrogen production from rice mill wastewater through nano-metal oxides assisted dark fermentation[J]. Bioresource Technology, 2021, 319: 124243.
114	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: 349-361.
115	Mohanraj S, Anbalagan K, Kodhaiyolii S, et al. Comparative evaluation of fermentative hydrogen production using Enterobacter cloacae and mixed culture: Effect of Pd (II) ion and phytogenic palladium nanoparticles[J]. Journal of Biotechnology, 2014, 192: 87-95.
116	Zhao W, Zhang Y F, Du B, et al. Enhancement effect of silver nanoparticles on fermentative biohydrogen production using mixed bacteria[J]. Bioresource Technology, 2013, 142: 240-245.
117	Li Y M, Zhang Z P, Lee D J, et al. Role of L-cysteine and iron oxide nanoparticle in affecting hydrogen yield potential and electronic distribution in biohydrogen production from dark fermentation effluents by photo-fermentation[J]. Journal of Cleaner Production, 2020, 276: 123193.
118	Cao X Y, Zhao L, Dong W F, et al. Revealing the mechanisms of alkali-based magnetic nanosheets enhanced hydrogen production from dark fermentation: Comparison between mesophilic and thermophilic conditions[J]. Bioresource Technology, 2022, 343: 126141.
119	Cheng J, Li H, Ding L K, 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.
120	Elsamadony M, Elreedy A, Mostafa A, et al. Perspectives on potential applications of nanometal derivatives in gaseous bioenergy pathways: mechanisms, life cycle, and toxicity[J]. ACS Sustainable Chemistry and Engineering, 2021, 9(29): 9563-9589.
121	Nozhevnikova A N, Russkova Y I, Litti Y V, et al. Syntrophy and interspecies electron transfer in methanogenic microbial communities[J]. Microbiology, 2020, 89(2): 129-147.
122	Saha S, Basak B, Hwang J H, et al. Microbial symbiosis: a network towards biomethanation[J]. Trends in Microbiology, 2020, 28(12): 968-984.
123	Rotaru A E, Shrestha P M, Liu F H, et al. A new model for electron flow during anaerobic digestion: direct interspecies electron transfer to Methanosaeta for the reduction of carbon dioxide to methane[J]. Energy and Environmental Science, 2014, 7(1): 408-415.
124	Kato S, Hashimoto K, Watanabe K. Methanogenesis facilitated by electric syntrophy via (semi)conductive iron-oxide minerals[J]. Environmental Microbiology, 2012, 14(7): 1646-1654.
125	Liu F H, Rotaru A E, Shrestha P M, et al. Magnetite compensates for the lack of a pilin-associated c-type cytochrome in extracellular electron exchange[J]. Environmental Microbiology, 2015, 17(3): 648-655.
126	El-Naggar M Y, Wanger G, Leung K M, et al. Electrical transport along bacterial nanowires from Shewanella oneidensis MR-1[J]. Proceedings of the National Academy of Sciences, 2010, 107(42): 18127-18131.
127	Zhao J, Wang Z Y, Dai Y H, et al. Mitigation of CuO nanoparticle-induced bacterial membrane damage by dissolved organic matter[J]. Water Research, 2013, 47(12): 4169-4178.
128	Gagliano M C, Ismail S B, Stams A J M, et al. Biofilm formation and granule properties in anaerobic digestion at high salinity[J]. Water Research, 2017, 121: 61-71.
129	Fang H H P, Zhang T, Liu H. Microbial diversity of a mesophilic hydrogen-producing sludge[J]. Applied Microbiology and Biotechnology, 2002, 58(1): 112-118.
130	Castelló E, Ferraz A D N, Andreani C, et al. Stability problems in the hydrogen production by dark fermentation: Possible causes and solutions[J]. Renewable and Sustainable Energy Reviews, 2020, 119: 109602.
131	Whiteley M, Diggle S P, Greenberg E P. Progress in and promise of bacterial quorum sensing research[J]. Nature, 2017, 551(7680): 313-320.
132	Kalia V C. Quorum sensing inhibitors: an overview[J]. Biotechnology Advances, 2013, 31(2): 224-245.
133	Kalia V C, Purohit H J. Quenching the quorum sensing system: potential antibacterial drug targets[J]. Critical Reviews in Microbiology, 2011, 37(2): 121-140.
134	Kumar P, Patel S K S, Lee J K, et al. Extending the limits of Bacillus for novel biotechnological applications[J]. Biotechnology Advances, 2013, 31(8): 1543-1561.
135	Wang L H, Weng L X, Dong Y H, et al. Specificity and enzyme kinetics of the quorum-quenching N-Acyl homoserine lactone lactonase (AHL-lactonase)[J]. Journal of Biological Chemistry, 2004, 279(14): 13645-13651.
136	Chen R D, Zhou Z G, Cao Y N, et al. High yield expression of an AHL-lactonase from bacillus sp. B546 in Pichia pastoris and its application to reduce Aeromonas hydrophila mortality in aquaculture[J]. Microb Cell Factories, 2010, 9(1): 1-10.
137	Song J X, An D, Ren N Q, et al. Effects of pH and ORP on microbial ecology and kinetics for hydrogen production in continuously dark fermentation[J]. Bioresource Technology, 2011, 102(23): 10875-10880.

序号	纳米材料	固定/结合模式	条件参数
1	Fe₃O₄ NPs ^[68]	戊二醛表面修饰共价结合	T=60℃, pH=4.5
2	Fe₃O₄NPs^[72]	通过半胱氨酸基团的表面功能化卵清蛋白结合	T=80℃, pH=4.5
3	Fe₃O₄@SiO₂^[73]	物理吸附	T=70℃, pH=4.0
4	Fe₃O₄ NPs @SiO₂^[74]	APTES共价结合	T=25℃, pH=4
5	Fe₃O₄ NPs @SiO₂^[75]	甲基丙烯酸缩水甘油酯表面功能化共价结合	T=50℃, pH=5.0
6	Fe₃O₄@SiO₂@KIT-6NPs^[54]	APTES共价结合	T=35℃, pH=4.5
7	Fe₃O₄ NPs /壳聚糖^[76]	戊二醛表面修饰共价结合	T=60℃, pH=5.5
8	Fe₃O₄ NPs/壳聚糖^[77]	戊二醛表面修饰共价结合	T=60℃, pH=5.0
9	Cu/Fe₃O₄ NPs^[78]	APTES共价结合	T=80℃, pH=5
10	Cu²⁺ modified Fe₃O₄-NH₂NPs^[71]	亲和吸附	T=35℃, pH=4.5
11	Fe₃O₄@Au NPs^[67]	通过聚乙二醇和L-天门冬氨酸共价结合	T=50℃, pH=4.8
12	Fe₂O₃ NPs^[79]	戊二醛表面修饰共价结合	T=50℃, pH=4.8
13	CoFe₂O₄NPs^[80]	基于EDS & NHS的戊二醛结合	T=50℃, pH=5.0
14	MnO₂NPs^[46]	戊二醛表面改性卵圆结合	T=70℃, pH=5.0

序号	纳米材料	固定/结合模式	条件参数
1	Fe₃O₄ NPs ^[68]	戊二醛表面修饰共价结合	T=60℃, pH=4.5
2	Fe₃O₄NPs^[72]	通过半胱氨酸基团的表面功能化卵清蛋白结合	T=80℃, pH=4.5
3	Fe₃O₄@SiO₂^[73]	物理吸附	T=70℃, pH=4.0
4	Fe₃O₄ NPs @SiO₂^[74]	APTES共价结合	T=25℃, pH=4
5	Fe₃O₄ NPs @SiO₂^[75]	甲基丙烯酸缩水甘油酯表面功能化共价结合	T=50℃, pH=5.0
6	Fe₃O₄@SiO₂@KIT-6NPs^[54]	APTES共价结合	T=35℃, pH=4.5
7	Fe₃O₄ NPs /壳聚糖^[76]	戊二醛表面修饰共价结合	T=60℃, pH=5.5
8	Fe₃O₄ NPs/壳聚糖^[77]	戊二醛表面修饰共价结合	T=60℃, pH=5.0
9	Cu/Fe₃O₄ NPs^[78]	APTES共价结合	T=80℃, pH=5
10	Cu²⁺ modified Fe₃O₄-NH₂NPs^[71]	亲和吸附	T=35℃, pH=4.5
11	Fe₃O₄@Au NPs^[67]	通过聚乙二醇和L-天门冬氨酸共价结合	T=50℃, pH=4.8
12	Fe₂O₃ NPs^[79]	戊二醛表面修饰共价结合	T=50℃, pH=4.8
13	CoFe₂O₄NPs^[80]	基于EDS & NHS的戊二醛结合	T=50℃, pH=5.0
14	MnO₂NPs^[46]	戊二醛表面改性卵圆结合	T=70℃, pH=5.0

序号	微生物种类	基质	条件参数	纳米材料	H₂产量提高效果^a
1	Enterobacter	Straw	pH 7,37℃	Fe⁰NPs	提高73.1%^[91]
2	Enterobacter cloacae DH-89	Glucose	pH 7,37℃	FeNPs	提高230%^[101]
3	Clostridium pasteurianum	Glucose	35℃	Fe₂O₃ NPs	提高52.5%^[70]
4	Clostridium butyricum	Sucrose	pH 7,35℃	α-Fe₂O₃ NPs	提高32.64%^[60]
5	Enterobacter aerogenes	Glucose	pH 6.0,37℃	γ- Fe₂O₃ NPs	提高17%^[24]
6	Mixed culture bacteria	Inorganic salt	pH 6,37℃	Iron oxide NPs	提高81.4%^[102]
7	Heat pretreated sludge	Sugarcane bagasse	pH 5.0,30℃	Fe₃O₄ NPs	提高69.6%^[103]
8	Anaerobic sludge	Paper mill waste water	pH 7.5	Fe₃O₄ NPs	提高127.4%^[104]
9	Parageobacillus thermoglucosidasius KCTC 33548	Glucose, Starch	pH 6.5,55℃	Fe₃O₄ NPs	提高315%^[105]
10	Heat pretreated sludge	Grass	pH 7,37℃	Fe⁰ NPs / biochar	提高89.8%^[106]
11	Anaerobic bacteria	Glucose	pH 7,30℃	Fe⁰ NPs / activated carbon	提高50.2%^[107]
12	Enterobacter aerogenes	Glucose	pH 6.8,37℃	Fe⁰ NPs /chitosan	提高30%^[29]
13	Clostridium pasteurianum	Glucose	pH 7,35℃	α-Fe₂O₃&TiO₂ NPs	提高24.9%^[108]
14	Anaerobic mixed bacteria	Glucose	pH 7,37℃	Fe₂O₃-Fe₃O₄ NPs /carbon	提高33.7%^[97]
15	Enterobacter aerogenes	Fruit waste	pH 6.5,37℃	Fe₃O₄ NPs /DSAC	提高204.5%^[98]
16	Mixed culture bacteria	Gelatinaceous wastewater	pH 6,35℃	Fe₃O₄/graphene oxide	提高41.9%^[109]
17	Enterobacter aerogenes	Glucose	pH 6,37℃	Ferric citrate NPs	提高50.45%^[110]
18	Mesophilic bacteria	Starch	pH 5.0-6.0,37℃	Fe⁰ NPs, Ni⁰ NPs	提高37%^[2]
19	Clostridium butyricum	Glucose, Starch	pH 6.8,37℃	Fe⁰ NPs&Ni⁰ NPs	提高28%^[111]
20	Hydrogen-producing bacteria	Anaerobic sludge	pH 5.0,37℃	Fe₂O₃ NPs, NiO Nps	分别提高24%和16%^[95]
21	Thermophilic mixed bacteria	Glucose	pH 5.5,60℃	α-Fe₂O₃ NPs, NiO NPs	分别提高34.38%和5.47%^[4]
22	Mixed consortia	Glucose	pH 5.6,35℃	Ni NPs	提高22.71%^[112]
23	Clostridium butyricum	Glucose	pH6.9,37℃,55℃	NiFe₂O₄ NPs	分别提高38.6%(37℃),28.3%(55℃)^[30]
24	Bacillus anthracis	Palm oil	pH 7,37℃	NiO NPs, CoO NPs	分别提高151%和167%^[21]
25	Clostridium beijerinckii	Rice mill wastewater	pH 7,37℃	NiO NPs, CoO NPs	分别提高109%和90.4%^[113]
26	Clostridiumbutyricum	Glucose	pH 7.6,30℃	Fe NPs@SiO₂, Pd NPs@SiO₂, Ag NPs@SiO₂, Cu NPs/SiO₂	提高38%^[94]
27	Mixed consortia	Glucose	pH 5.5,50℃	ZnO NPs	提高29%^[114]
28	Clostridiumbutyricum	Sucrose	pH 7.2,35℃	Au NPs	提高61.7%^[38]
29	Enterobacter cloacae	Glucose	pH 7,37℃	Pd(II) NPs	在单一菌种和混合菌种培养条件下分别提高1.5%和9%^[115]
30	Mixed culture dominated by Clostridium species	Glucose	pH 8.0-9.4,35℃	Ag NPs	提高67.3%^[116]

序号	微生物种类	基质	条件参数	纳米材料	H₂产量提高效果^a
1	Enterobacter	Straw	pH 7,37℃	Fe⁰NPs	提高73.1%^[91]
2	Enterobacter cloacae DH-89	Glucose	pH 7,37℃	FeNPs	提高230%^[101]
3	Clostridium pasteurianum	Glucose	35℃	Fe₂O₃ NPs	提高52.5%^[70]
4	Clostridium butyricum	Sucrose	pH 7,35℃	α-Fe₂O₃ NPs	提高32.64%^[60]
5	Enterobacter aerogenes	Glucose	pH 6.0,37℃	γ- Fe₂O₃ NPs	提高17%^[24]
6	Mixed culture bacteria	Inorganic salt	pH 6,37℃	Iron oxide NPs	提高81.4%^[102]
7	Heat pretreated sludge	Sugarcane bagasse	pH 5.0,30℃	Fe₃O₄ NPs	提高69.6%^[103]
8	Anaerobic sludge	Paper mill waste water	pH 7.5	Fe₃O₄ NPs	提高127.4%^[104]
9	Parageobacillus thermoglucosidasius KCTC 33548	Glucose, Starch	pH 6.5,55℃	Fe₃O₄ NPs	提高315%^[105]
10	Heat pretreated sludge	Grass	pH 7,37℃	Fe⁰ NPs / biochar	提高89.8%^[106]
11	Anaerobic bacteria	Glucose	pH 7,30℃	Fe⁰ NPs / activated carbon	提高50.2%^[107]
12	Enterobacter aerogenes	Glucose	pH 6.8,37℃	Fe⁰ NPs /chitosan	提高30%^[29]
13	Clostridium pasteurianum	Glucose	pH 7,35℃	α-Fe₂O₃&TiO₂ NPs	提高24.9%^[108]
14	Anaerobic mixed bacteria	Glucose	pH 7,37℃	Fe₂O₃-Fe₃O₄ NPs /carbon	提高33.7%^[97]
15	Enterobacter aerogenes	Fruit waste	pH 6.5,37℃	Fe₃O₄ NPs /DSAC	提高204.5%^[98]
16	Mixed culture bacteria	Gelatinaceous wastewater	pH 6,35℃	Fe₃O₄/graphene oxide	提高41.9%^[109]
17	Enterobacter aerogenes	Glucose	pH 6,37℃	Ferric citrate NPs	提高50.45%^[110]
18	Mesophilic bacteria	Starch	pH 5.0-6.0,37℃	Fe⁰ NPs, Ni⁰ NPs	提高37%^[2]
19	Clostridium butyricum	Glucose, Starch	pH 6.8,37℃	Fe⁰ NPs&Ni⁰ NPs	提高28%^[111]
20	Hydrogen-producing bacteria	Anaerobic sludge	pH 5.0,37℃	Fe₂O₃ NPs, NiO Nps	分别提高24%和16%^[95]
21	Thermophilic mixed bacteria	Glucose	pH 5.5,60℃	α-Fe₂O₃ NPs, NiO NPs	分别提高34.38%和5.47%^[4]
22	Mixed consortia	Glucose	pH 5.6,35℃	Ni NPs	提高22.71%^[112]
23	Clostridium butyricum	Glucose	pH6.9,37℃,55℃	NiFe₂O₄ NPs	分别提高38.6%(37℃),28.3%(55℃)^[30]
24	Bacillus anthracis	Palm oil	pH 7,37℃	NiO NPs, CoO NPs	分别提高151%和167%^[21]
25	Clostridium beijerinckii	Rice mill wastewater	pH 7,37℃	NiO NPs, CoO NPs	分别提高109%和90.4%^[113]
26	Clostridiumbutyricum	Glucose	pH 7.6,30℃	Fe NPs@SiO₂, Pd NPs@SiO₂, Ag NPs@SiO₂, Cu NPs/SiO₂	提高38%^[94]
27	Mixed consortia	Glucose	pH 5.5,50℃	ZnO NPs	提高29%^[114]
28	Clostridiumbutyricum	Sucrose	pH 7.2,35℃	Au NPs	提高61.7%^[38]
29	Enterobacter cloacae	Glucose	pH 7,37℃	Pd(II) NPs	在单一菌种和混合菌种培养条件下分别提高1.5%和9%^[115]
30	Mixed culture dominated by Clostridium species	Glucose	pH 8.0-9.4,35℃	Ag NPs	提高67.3%^[116]

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[2]	段重达, 姚小伟, 朱家华, 孙静, 胡南, 李广悦. 环境因素对克雷白氏杆菌诱导碳酸钙沉淀的影响[J]. 化工学报, 2023, 74(8): 3543-3553.
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