Synthesis of NiY zeolite and hydrogen evolution performance in cathode of a microbial electrolysis cell
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摘要: 在Na2O-Al2O3-SiO2-H2O体系中添加硝酸镍，采用导向剂法合成了NiY分子筛。利用XRD、SEM、TEM、N2吸附-脱附等手段对合成的NiY分子筛进行了表征。结果表明，随着镍添加量的增加，结晶度和zeta电位呈先增大后减小的趋势。当Si/Ni（mol ratio）大于5时，硝酸镍对分子筛的形成具有促进作用，当Si/Ni（mol ratio）小于5时，则具有抑制作用。晶粒粒径为1.5-3 μm，形貌为凹槽结构的六方或四方柱型，且具有微孔-介孔多级孔道结构特征。通过循环伏安曲线和极化曲线测试，在Si/Ni（mol ratio）=5时，样品的氧化还原性能最强，过电势最小，电催化活性最高。在12 h内，每4 mg的Si/Ni（mol ratio）=5样品，产气总量为10.1 mL，氢气纯度达81.69%，与Pt电极相比其氢气产量提高了28%。NiY分子筛表现出良好的析氢催化活性，有望取代Pt成为MEC新型阴极材料。Abstract: NiY zeolites were synthesized in the system of Na2O-Al2O3-SiO2-H2O with the addition of nickel nitrate by crystallization directing agent and characterized by XRD, SEM, TEM, N2 adsorption-desorption, etc. The results show that the crystallinity and zeta potential decrease after an increase at first with the increasing of nickel added. It means that nickel nitrate can promote the formation of molecular sieve when Si/Ni(mol ratio) is greater than 5, while it has an inhibitory effect when Si/Ni(mol ratio) is less than 5. The NiY zeolites with 1.5-3 μm of size not only possess special morphology, six or four square columns with grooved structure, but also have a multiple porous structure including microporous and mesoporous. The sample test by cyclic voltammetry (CV) and polarization curve(LSV) in microbial electrolysis cell (MEC) indicates that the NiY zeolites with Si/Ni(mol ratio)=5 present the best electrochemical characteristics with an outstanding redox performance, a minimum overvoltage and the highest electrocatalytic activity. Moreover, the hydrogen production yield reaches 10.1 mL/4 mg in 12 h with the hydrogen purity of 81.69%, surpassing that with Pt electrodes by about 28%. It suggests that the NiY zeolites have a better hydrogen evolution activity and it is possible to replace Pt as a novel cathode catalyst in microbial electrolysis cell.
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Key words:
- NiY zeolite /
- morphology /
- microbial electrolysis cell /
- catalytic hydrogen evolution
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图 1 分子筛的XRD谱图
Figure 1 XRD patterns of zeolites
Si/Ni(mol ratio): a: 200; b: 60; c: 20; d: 10; e: 5; f: 4; g: 3
图 2 NiY分子筛的zeta电位和相对结晶度
Figure 2 Zeta potential curve of NiY zeolites Si/Ni(mol ratio): a: 200; b: 60; c: 20; d: 10; e: 5; f: 4; g: 3
图 3 分子筛的SEM照片
Figure 3 SEM photos of zeolites Si/Ni(mol ratio): (a): pure Y; (b): 60; (c): 10; (d): 5
图 5 NiY的Ni 2p、O 1s和Si 2p电子结合能XPS谱图
Figure 5 XPS pattern of Ni 2p, O 1s and Si 2p of NiY zeolites with different Si/Ni ratios Si/Ni(mol ratio): a=60; b=10; c=5
图 6 NiY分子筛N2吸附-脱附等温线及孔径分布
Figure 6 Nitrogen adsorption-desorption isotherms and pore size distribution of NiY zeolite
图 7 不同样品的循环伏安曲线和极化曲线
Figure 7 Cyclic voltammetry curves and polarization curves of different samples
图 8 电流密度和产气速率随时间的变化
Figure 8 Current density and gas production yield versus time Si/Ni(mol ratio): a: 5; b: 10; c: 20; d: 60; e: 200
图 9 MEC的气体总量和气体组分
Figure 9 Gas volume and Gas composition of MEC with different zeolites
Si/Ni(mol ratio): a: 5; b: 10; c: 20; d: 60; e: 200 : H2; : CH4; : CO; : CO2
表 1 测定区域的元素组成
Table 1 Elemental composition of selective region
Sample Si/Ni(mol ratio) Elemental composition of selective region watomic /% Si/Al (atomic ratio) O Na Al Si Ni a 60 65.48 9.59 9.93 14.96 0.04 1.51 b 10 65.81 8.49 9.40 14.52 0.18 1.54 c 5 65.91 8.61 8.08 15.93 1.02 1.97 
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表 2 分子筛的孔结构参数
Table 2 Pore structure parameters of zeolite
Sample ABET /(m2·g-1) Amicro /(m2·g-1) Ameso /(m2·g-1) vtotal /(cm3·g-1) vmicro /(cm3·g-1) vmeso /(cm3·g-1) dmicro /nm dmeso /nm NiY 341.0 320.6 20.38 0.3719 0.3189 0.0530 0.9400 2.673
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[1] 代红艳, 杨慧敏, 刘宪, 简选, 郭敏敏, 曹乐乐, 梁镇海. MoS2/石墨烯复合阴极材料的制备及微生物电解池催化产氢性能[J].高等学校化学学报, 2018, 39(2):351-358. doi: 10.7503/cjcu20170255DAI Hong-yan, YANG Hui-min, LIU Xian, JIAN Xuan, GUO Min-min, CAO Le-le, LIANG Zhen-hai. Preparation and electrochemical evaluation of MoS2/graphene as a catalyst for hydrogen evolution in microbial electrolysis cell[J]. Chem J Chin Univ, 2018, 39(2):351-358. doi: 10.7503/cjcu20170255 [2] 谢淼, 徐龙君, 胡金凤, 徐艳昭.阴极催化剂对微生物燃料电池性能的影响[J].燃料化学学报, 2017, 45(10):1275-1280. doi: 10.3969/j.issn.0253-2409.2017.10.016XIE Miao, XU Long-jun, HU Jin-feng, XU Yan-zhao. Effects of cathode catalyst modification on the performance of microbial fuel cells[J]. J Fuel Chem Technol, 2017, 45(10):1275-1280. doi: 10.3969/j.issn.0253-2409.2017.10.016 [3] 贾羽洁, 蒋剑春, 孙康, 陆天虹. Pt/Au原子比对活性炭负载Au-Pt直接甲酸燃料电池阴极催化剂性能的影响[J].燃料化学学报, 2011, 39(10):792-795. doi: 10.3969/j.issn.0253-2409.2011.10.013JIA Yu-jie, JIANG Jian-chun, SUN Kang, LU Tian-hong. Effect of Pt/Au atomic ratio in active carbonsupported Au-Pt catalyst on its cathodic performance in direct formic acid fuel cell[J]. J Fuel Chem Technol, 2011, 39(10):792-795. doi: 10.3969/j.issn.0253-2409.2011.10.013 [4] JEREMIASSEA W, HAMELERS H V, KLEIJN J M, BUISMAN C J N. Use of biocompatible buffers to reduce the concentration overpotential for hydrogen evolution[J]. Environ Sci Technol, 2009, 43(17):6882-6887. doi: 10.1021/es9008823 [5] CONWAY B E, JERKIEWICZ G. Relation of energy and coverages of underpotential and over potential deposited H at Pt and other metals to the 'vocano curve' for cathodic H2evolution kinetics[J]. Electro chim Acta, 2000, 45(25/26):4075-4083. doi: 10.1021/jp960130n [6] HU H, FAN Y, LIU H. Hydrogen production in single-chamber tubular microbial electrolysis cells using non-precious-metal catalysts[J]. Int J Hydrogen Energy, 2009, 34(20):8535-8542. doi: 10.1016/j.ijhydene.2009.08.011 [7] ZHANG Y M, MERRILL M D, LOGEN B E. The use and optimization of stainless steel mesh cathodes in microbial electrolysis cells[J]. Int J Hydrogen Energy, 2010, 35:12020-12028. doi: 10.1016/j.ijhydene.2010.08.064 [8] MARIO M, ELITSA C, RASHKO R, HUBENOVA Y. Novel nanostructured electrocatalysts for hydrogen evolution reaction in neutral and weak acidic solutions[J]. Int J Hydrogen Energy, 2012, 37:16522-16526. doi: 10.1016/j.ijhydene.2012.02.102 [9] 周继红, 罗一斌, 宗保宁. Y型分子筛复合材料的成孔机理[J].石油炼制与化工, 2012, 43(1):26-31. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=sylzyhg201201006ZHOU Ji-Hong, LUO Yi-bin, ZONG Bao-ning. Formation mechanism ofporous molecular sieve Y composite[J]. Pet Process Petrochem, 2012, 43(1):26-31. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=sylzyhg201201006 [10] KUMAR R, MUKHERJEE P, PANDEY P K, RAJMOHANAN P, BHAMMIK A. Role of oxyanions as promoter for enhancing nucleation and crystallization in the sythesis of MFI-type microporous mateials[J]. Micproporous Mesoporous Mater, 1998, 22(1/3):23-31. [11] RAJIV K, ASIM B, RANJEET K AHEDI, GANAPATHY S. Promoter-induced enhancement of the crystallization rate of zeolites and related molecular sieves[J]. Nature, 1996, 381(6580):298-300. doi: 10.1038/381298a0 [12] 陈松.金属原位改性ZSM-5分子筛的合成及其形貌特征[J].石油学报(石油加工), 2009, 25(s2):116-119. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=syxb-syjg2009z2028CHEN Song. Metal-incorpprated ZSM-5 by in-situ synthesis and its morphology characteristics[J]. Acta Pet Sin, 2009, 25(s2):116-119. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=syxb-syjg2009z2028 [13] 初筠. 甲烷无氧芳构化Mo/HMCM-22催化剂制备及成型研究[D]. 大连: 大连理工大学, 2013: 25-28.CHU Jun. Synthesis and Extruded Molding of Mo/HMCM-22 Catalyst in Methane Dehydroaromatization[D]. Dalian: Dalian University of Technology, 2013: 25-28. [14] 申宝剑, 覃正兴, 林枫, 周淑歌, 沈文, 王宝杰, 赵红娟, 刘宏海.碱处理脱硅与提高Y型分子筛硅铝比-矛盾的对立与统一[J].催化学报, 2012, 33(1):152-163. http://d.wanfangdata.com.cn/Periodical_cuihuaxb201201016.aspxSHEN Bao-jian, QIN Zheng-xing, LIN Feng, ZHOU Shu-ge, SHEN Wen, WANG Bao-jie, ZHAO Hong-juan, LIU Hong-hai. Desilication by alkaline treatment and increasing the silica to alumina ratio of zeolite Y[J]. Chin J Catal, 2012, 33(1):152-163. http://d.wanfangdata.com.cn/Periodical_cuihuaxb201201016.aspx [15] 查全性.物理化学, 电极过程动力学导论[M].北京:科学出版社, 2002.CHA Quan-xing. Physical Chemistry, Dynamics Introduction of Electrode Process[M]. Beijing:Science Press, 2002. [16] LIU H, GUO R X, LIU Y, THOMPSON G E, LIU Z. The effect of processing gas on corrosion performance of electroless Ni-W-P coatings treated by laser[J]. Surf Coat Technol, 2012, 206(15):3350-3359. doi: 10.1016/j.surfcoat.2012.01.039 [17] PRIETO P, NISTOR V, NOUNEH K, QYAMA A, ABD-LEFDIL M, DIAZ R. XPS study of silver, nickel and bimetallic silver-nickel nanoparticles prepared by seed-mediated growth[J]. Appl Surf Sci, 2012, 258(22):8807-8813. doi: 10.1016/j.apsusc.2012.05.095 [18] 范春晖, 马宏瑞, 花莉, 王家宏, 王海军. FT-IR和XPS对沸石合成特性及Cr(Ⅲ)去除机制的谱学表征[J].光谱学与光谱学分析, 2012, 32(2):324-329. http://d.wanfangdata.com.cn/Periodical_gpxygpfx201202009.aspxFAN Chun-hui, MA Hong-rui, HUA Li, WANG Jia-hong, WANG Hai-jun. FT-IR and XPS analysis of characteristics of synthesized zeolite and removal mechanisms for Cr(Ⅲ)[J]. Spectrosc Spect Anal, 2012, 32(2):324-329. http://d.wanfangdata.com.cn/Periodical_gpxygpfx201202009.aspx [19] KIM K S, WINOGRAD N. X-ray photoelectron spectroscopic studies of palladium oxides and the palladium-oxygen electrode[J]. Surf Sci, 1974, 43:625. doi: 10.1016/0039-6028(74)90281-7 [20] KIM K S, DAVIS R E. Electron spectroscopy of the nickel-oxygen system[J]. J Electron Spectrosc Relat Phenom, 1972/73, 1(3):251. doi: 10.1016/0368-2048(72)85014-X [21] KRESGE C T, LEONOWICZ M E, ROTH W J, VARTULI J C, BECK J C. Ordered mesoporous melocular sievers synthesized by a liquid template mechanism[J]. Nature, 1992, 35:710-712. http://cn.bing.com/academic/profile?id=f79f873424e8c64c6f7eadd0470a9dc6&encoded=0&v=paper_preview&mkt=zh-cn [22] 曹寅亮. 高活性镍基析氢电极的制备及其在碱性条件下析氢行为研究[D]. 北京: 北京化工大学, 2013: 99-112.CAO Yin-liang. Synthesis of highly active nickel-bsced hydrogen evolution electrodes and their hydrogen evolution bebavior in the alkaline medium[D]. Beijing: Beijing University of Chemical Technology, 2013: 99-112. [20] FREGUIA S, RABAEY K, YUAN Z, KELLER J. Non-catalyzed cathodic oxygen reduction at graphite granules in microbial fuel cells[J]. Electrochim Acta, 2007, 53(2):598-603. doi: 10.1016/j.electacta.2007.07.037 [23] LIU M Y, HE Y Q, MAO Z Q, XIE X F. CO-poisoning mechanism of anodic electrocatalyst in proton-exchange membrane fuel cell[J]. Chin J Power Sources, 2002, 26(z1):247-249. https://www.researchgate.net/publication/309697610_CO-poisoning_mechanism_of_anodic_electrocatalyst_in_proton-exchange_membrane_fuel_cell [24] 贾梦秋, 杨文胜.应用电化学[M].北京:高等教育出版社, 2004:124.JIA Meng-qiu, YANG Wen-sheng. Applied Electrochemistry[M]. Beijing:Higher Education Press, 2004:124. -
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