碳化金属-有机骨架强化种间电子传递产甲烷

doi:10.11949/0438-1157.20200650

摘要/Abstract

摘要：

为了解决厌氧发酵系统中氢分压限制种间氢扩散速率问题，利用金属-有机骨架ZIF-8衍生多孔碳材料促进乙醇厌氧发酵生产甲烷，探究其对微生物种间电子传递的增强机理。扫描电镜SEM表明ZIF-8衍生多孔碳起到菌群固定化作用，并且能促进纳米导线产生。实验结果表明，随着ZIF-8衍生多孔碳添加量的增加，甲烷产量和最大产甲烷速率逐渐提高。添加200 mg/L ZIF-8衍生多孔碳时，系统导电性提高了3.58倍，三维荧光光谱分析表明ZIF-8衍生多孔碳能够促进微生物胞外聚合物（EPS）中类富里酸的相对含量由18.0%提高到23.6%，对应的甲烷产量和最大产甲烷速率分别增加了18.81%和19.04%。

关键词: 衍生多孔碳, 厌氧, 发酵, 甲烷, 种间电子传递, 微生物胞外聚合物

Abstract:

To solve the problem that the hydrogen partial pressure in the anaerobic fermentation system limits the hydrogen diffusion rate among species, porous metal materials derived from the metal-organic framework ZIF-8 are used to promote the anaerobic fermentation of ethanol to produce methane, and the mechanism for enhancing the electron transfer between microorganism species is explored. Scanning electron microscopy (SEM) shows that ZIF-8 derived porous carbon plays immobilized role of microbial communities and promotes nanowires generation. The results show that the methane yield and the maximum methane production rate increase with an increase of ZIF-8 derived porous carbon addition. When 200 mg/L ZIF-8 derived porous carbon is added, the system conductivity increases by 3.58-fold. Moreover, three-dimensional fluorescence spectroscopy analysis (3D-EEM) showed that ZIF-8 derived porous carbon promotes the relative content of fulvic acid in extracellular polymeric substance (EPS) from 18.0% to 23.6%, corresponding to methane yield and maximum methane production rate increasing by 18.81% and 19.04% respectively.

Key words: derived porous carbon, anaerobic, fermentation, methane, interspecies electron transfer, extracellular polymer substance

中图分类号:

TK 6

张海华,董海泉,李慧,袁璐韫,方哲,程军. 碳化金属-有机骨架强化种间电子传递产甲烷[J]. 化工学报, 2020, 71(12): 5745-5754.

ZHANG Haihua,DONG Haiquan,LI Hui,YUAN Luyun,FANG Zhe,CHENG Jun. Metal-organic framework carbide enhances interspecies electron transfer to produce methane[J]. CIESC Journal, 2020, 71(12): 5745-5754.

图/表 11

图1 AMPTS Ⅱ厌氧发酵系统

Fig.1 AMPTS Ⅱ anaerobic digestion system

图2 添加不同浓度ZIF-8衍生多孔碳对甲烷产量及产率的影响

Fig.2 Methane yield and production rate with the addition of various concentrations of ZIF-8 derived porous carbon

表1 添加不同浓度ZIF-8衍生多孔碳时利用乙醇发酵产甲烷的动力学参数

Table 1 Kinetic parameters of fermentative methane production from ethanol with various concentrations of ZIF-8 derived porous carbon addition

底物	ZIF-8衍生多孔碳的添加浓度/(mg/L)	甲烷产量/(ml/g)	产甲烷峰值速率/(ml/(g·d))	动力学参数
底物	ZIF-8衍生多孔碳的添加浓度/(mg/L)	甲烷产量/(ml/g)	产甲烷峰值速率/(ml/(g·d))	H_m/(ml/g)	R_m/(ml/(g·d))	λ/h	T_m/h	R²
乙醇	0	479.03±12.07	28.61±3.06	526.89	29.18	2.34	8.98	0.995
	50	536.432±8.17	30.10±1.94	601.82	31.39	2.31	9.36	0.994
	100	548.903±12.35	29.95±0.90	600.99	33.26	2.14	8.78	0.996
	200	569.098±13.99	31.39±0.52	628.40	32.71	1.83	8.90	0.993

图3 厌氧发酵液相代谢产物分析

Fig.3 Analysis of liquid metabolites in anaerobic digestion

图4 厌氧发酵结束后的产甲烷污泥SEM图

Fig.4 SEM images of methanogenic sludge after anaerobic digestion

图5 厌氧发酵结束后产甲烷污泥电导率

Fig.5 Conductivity of methanogenic sludge after anaerobic digestion

图6 乙醇发酵结束后厌氧产甲烷污泥中总蛋白质浓度和细胞色素c 浓度变化

Fig.6 Changes of total protein and c-Cyts’ concentration in methanogenic sludge after anaerobic digestion

图7 微生物胞外聚合物三维荧光光谱分析区域(1)—酪氨酸类蛋白；区域(2) —色氨酸类蛋白；区域(3) —类富里酸；区域(4) —可溶性微生物副产物；区域(5) —类胡敏酸

Fig.7 3D-EEM analysis of microbial extracellular polymeric substance

表2 基于三维荧光光谱图的各荧光区域百分比参数

Table 2 Parameters of five fluorescent regions based on the 3D-EEM spectrogram

区域	波长(E_x/E_m)/nm	荧光响应百分比/%
区域	波长(E_x/E_m)/nm	0 mg/L ZIF-8衍生多孔碳	200 mg/L ZIF-8衍生多孔碳
（1）	220~250/200~300	14.5	10.6
（2）	200~250/330~380	28.9	34.2
（3）	200~250/380~500	18.0	23.6
（4）	250~280/200~380	10.9	9.3
（5）	250~400/380~500	27.7	22.3

图8 ZIF-8衍生多孔碳材料强化生物甲烷化过程机制示意图

Fig.8 The enhanced mechanism of bio-methanation with ZIF-8 derived porous carbon materials

图A1 碳化及清洗后ZIF-8材料SEM（左）和EDS（右）图

Fig.A1 SEM (left) and EDS (right) images of ZIF-8 after carbonization and dezincification

参考文献 34

1	Xu F, Li Y, Ge X, et al. Anaerobic digestion of food waste — challenges and opportunities[J]. Bioresource Technology, 2018, 247: 1047-1058.
2	Kougias P G, Angelidaki I. Biogas and its opportunities—a review[J]. Frontiers of Environmental Science & Engineering, 2018, 12(3): 14.
3	Weiland P. Biogas production: current state and perspectives[J]. Applied Microbiology and Biotechnology, 2010, 85(4): 849-860.
4	Park J H, Kang H J, Park K H, et al. Direct interspecies electron transfer via conductive materials: a perspective for anaerobic digestion applications[J]. Bioresource Technology, 2018, 254: 300-311.
5	Stams A J, Plugge C M. Electron transfer in syntrophic communities of anaerobic bacteria and archaea[J]. Nat. Rev. Microbiol., 2009, 7(8): 568-577.
6	Zhao Z, Zhang Y, Li Y, et al. Potentially shifting from interspecies hydrogen transfer to direct interspecies electron transfer for syntrophic metabolism to resist acidic impact with conductive carbon cloth[J]. Chemical Engineering Journal, 2017, 313: 10-18.
7	Ishii S I, Kosaka T, Hori K, et al. Coaggregation facilitates interspecies hydrogen transfer between Pelotomaculum thermopropionicum and Methanothermobacter thermautotrophicus[J]. Appl. Environ. Microbiol., 2005, 71(12): 7838-7845.
8	Yuan H Y, Ding L J, Zama E F, et al. Biochar modulates methanogenesis through electron syntrophy of microorganisms with ethanol as a substrate[J]. Environmental Science & Technology, 2018, 52(21): 12198-12207.
9	Zhang S, Chang J, Lin C, et al. Enhancement of methanogenesis via direct interspecies electron transfer between Geobacteraceae and Methanosaetaceae conducted by granular activated carbon[J]. Bioresource Technology, 2017, 245: 132-137.
10	Liu F, Rotaru A E, Shrestha P M, et al. Promoting direct interspecies electron transfer with activated carbon[J]. Energy & Environmental Science, 2012, 5(10): 8982-8989.
11	Zhang J, Zhao W, Zhang H, et al. Recent achievements in enhancing anaerobic digestion with carbon-based functional materials[J]. Bioresource Technology, 2018, 266: 555-567.
12	Salvador A F, Martins G, Melle‐Franco M, et al. Carbon nanotubes accelerate methane production in pure cultures of methanogens and in a syntrophic coculture[J]. Environmental Microbiology, 2017, 19(7): 2727-2739.
13	Yan W, Sun F, Liu J, et al. Enhanced anaerobic phenol degradation by conductive materials via EPS and microbial community alteration[J]. Chemical Engineering Journal, 2018, 352: 1-9.
14	Chen S, Rotaru A E, Shrestha P M, et al. Promoting interspecies electron transfer with biochar[J]. Scientific Reports, 2014, 4: 5019.
15	Wang X, Cheng S, Feng Y, et al. Use of carbon mesh anodes and the effect of different pretreatment methods on power production in microbial fuel cells[J]. Environmental Science & Technology, 2009, 43(17): 6870-6874.
16	Kato S, Hashimoto K, Watanabe K. Microbial interspecies electron transfer via electric currents through conductive minerals[J]. Proceedings of the National Academy of Sciences, 2012, 109(25): 10042-10046.
17	Reguera G, McCarthy K D, Mehta T, et al. Extracellular electron transfer via microbial nanowires[J]. Nature, 2005, 435(7045): 1098-1101.
18	Wang M, Zhao Z, Niu J, et al. Potential of crystalline and amorphous ferric oxides for biostimulation of anaerobic digestion[J]. ACS Sustainable Chemistry & Engineering, 2018, 7(1): 697-708.
19	Cheng Q, Call D F. Hardwiring microbes via direct interspecies electron transfer: mechanisms and applications[J]. Environmental Science: Processes & Impacts, 2016, 18(8): 968-980.
20	Liu Y, Li G, Guo Y, et al. Flexible and binder-free hierarchical porous carbon film for supercapacitor electrodes derived from MOFs/CNT[J]. ACS Applied Materials & Interfaces, 2017, 9(16): 14043-14050.
21	Salunkhe R R, Kaneti Y V, Kim J, et al. Nanoarchitectures for metal–organic framework-derived nanoporous carbons toward supercapacitor applications[J]. Accounts of Chemical Research, 2016, 49(12): 2796-2806.
22	Gargiulo N, Peluso A, Aprea P, et al. Chromium-based MIL-101 metal organic framework as a fully regenerable D4 adsorbent for biogas purification[J]. Renewable Energy, 2019, 138: 230-235.
23	Xu, Y X, Li Q, Xue H G, et al. Metal-organic frameworks for direct electrochemical applications[J]. Coordination Chemistry Reviews, 2018, 376: 292-318.
24	Cheng J, Xie B, Zhou J, et al. Cogeneration of H2 and CH4 from water hyacinth by two-step anaerobic fermentation[J]. International Journal of Hydrogen Energy, 2010, 35(7): 3029-3035.
25	Xia A, Cheng J, Song W, et al. Fermentative hydrogen production using algal biomass as feedstock[J]. Renewable and Sustainable Energy Reviews, 2015, 51: 209-230.
26	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.
27	Yang G, Lin J, Zeng E Y, et al. Extraction and characterization of stratified extracellular polymeric substances in Geobacter biofilms[J]. Bioresource Technology, 2019, 276: 119-126.
28	Wang D, Huang Y, Xu Q, et al. Free ammonia aids ultrasound pretreatment to enhance short-chain fatty acids production from waste activated sludge[J]. Bioresource Technology, 2019, 275: 163-171.
29	Chen W, Westerhoff P, Leenheer J A, et al. Fluorescence excitation- emission matrix regional integration to quantify spectra for dissolved organic matter[J]. Environmental Science & Technology, 2003, 37(24): 5701-5710.
30	Reguera G. Harnessing the power of microbial nanowires[J]. Microbial Biotechnology, 2018, 11(6): 979-994.
31	Xu H, Chang J, Wang H, et al. Enhancing direct interspecies electron transfer in syntrophic-methanogenic associations with (semi)conductive iron oxides: effects and mechanisms[J]. Sci. Total Environ., 2019, 695: 133876.
32	Liu X, Shi L, Gu J D. Microbial electrocatalysis: redox mediators responsible for extracellular electron transfer[J]. Biotechnol. Adv., 2018, 36(7): 1815-1827.
33	Dang Y, Lei Y, Liu Z, et al. Impact of fulvic acids on bio-methanogenic treatment of municipal solid waste incineration leachate[J]. Water Research, 2016, 106: 71-78.
34	Liang Z, Tu Q, Su X, et al. Formation, extracellular polymeric substances, and structural stability of aerobic granules enhanced by granular activated carbon[J]. Environmental Science and Pollution Research, 2019, 26(6): 6123-6132.

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