Application of TiO2 nanotube arrays for bipolar photocatalytic fuel cells
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摘要: 光催化燃料电池技术(Photocatalytic Fuel Cell, PFC)结合了光催化技术与燃料电池技术, 可以同时进行降解废水与发电, 对污水处理具有重要意义. 探索了TiO2纳米管阵列(TiO2 Nanotubes Arrays, TNAs)光阳极制备工艺对其形貌结构的影响; 通过扫描电子显微镜(Field Emission Scanning Electron Microscope, FESEM)证实了电解时间与TNAs管长正相关; 与Cu2O光阴极组合得到的具有更强光催化活性系统证实了 PFC 协同效应的存在, 最佳的电解工艺为4 h, 该工艺制备的电极对双氯酚酸光催化降解率在 2 h内为79%; 对 3 种标准物的分析说明, 在较高的浓度范围内, 通过 PFC 外电路的净电荷量与化学需氧量(Chemical Oxygen Demand, COD)线性相关, 而随着降解进行, 传质过程减弱, 两者之间的相关性减弱.Abstract: Photocatalytic fuel cell (PFC) technology is a combination of photocatalytic technology and fuel cell technology, which can degrade wastewater and generate electricity at the same time. The influence of the preparation process for photoanodes of TiO2 Nanotube Arrays (TNAs) on its morphology and structure was explored; a positive correlation between the electrolysis time and the tube length of TNAs was confirmed by a Field Emission Scanning Electron Microscope (FESEM). We can combine TNAs with Cu2O photoelectrodes to obtain a system with stronger photocatalytic activity, confirming the existence of a PFC synergistic effect. The optimal electrolysis process was 4 h, and the photocatalytic degradation rate of the electrode prepared by this process was more than 79% within 2 h. Analysis of the three standards showed an excellent linear correlation between the photocurrent of PFC and the chemical oxygen demand (COD); as the degradation proceeds, the mass transfer process is reduced and the correlation between the two is weakened.
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图 1 PFC反应的原理示意图
Fig. 1 Schematic illustration of the PFC reaction mechanism for a semiconductor
图 2 不同电解时间TNAs的FESEM图像及TNAs-4的EDS图谱
Fig. 2 FESEM images of TNAs with different electrolysis time and EDS mapping of TNAs-4
图 3 样品TNAs-1的(a) 200 nm (b) 50 nm (c) 5 nm的TEM图和(d) TNAs-1的TEM衍射斑点
Fig. 3 TEM image of sample TNAs-1 at (a) 200nm (b) 50nm (c) 5nm and (d) TEM diffraction spot of TNAs-1
图 6 (a) TNAs电极、Cu2O电极与TNAs-Cu2O PFC光催化效果; (b) 不同电解时间的TNAs光阳级PFC的降解效率; (c) 不同DCF浓度对TNAs-Cu2O双极PFC的影响; (d)TNAs-Cu2O重复性
Fig. 6 (a) PFC performance of TNA anode, Cu2O cathode and TNA-Cu2O PFC; (b) PFC performance of TNA-Cu2O PFC with different electrolysis times; (c) PFC performance of TNA-Cu2O PFC with different fuel concentrations; and (d) repeatability of TNAs-Cu2O
图 7 (a)各浓度DCF的PFC净电荷对比; 各浓度DCF的PFC降解率与净电荷, (b)20 mg/L, (c)40 mg/L, (d) 60 mg/L, (e)80 mg/L, (f)100 mg/L
Fig. 7 (a) Net charge of PFC with different concentrations of DCF; (b-f) net charge and degradation rate with different concentrations of DCF
图 8 不同物质的实际COD变化量与理论COD变化量
Fig. 8 Actual and theoretical changes in COD of different substances
表 1 不同电解时间下管长、管直径、纳米管的比表面积以及光催化性能
Tab. 1 The length, diameter, specific surface area, and photocatalytic properties of the nanotubes studied under different electrolysis times
管长/μm 管内径/nm 比表面积/(m2·g–1) DCF降解率/% TNAs-1 0.59 77 178.7 41 TNAs-2 1.2 84 266.4 52 TNAs-3 1.6 90 304.8 57 TNAs-4 2.0 98 340.1 79 TNAs-5 坍塌 坍塌 21.2 25 
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[1] GRATZEL M. Photoelectrochemical cells [J]. Nature, 1983, 414(6861): 338-344. [2] ANTONIADOU M, KONDARIDES D I, LABOU D, et al. An efficient photoelectrochemical cell functioning in the presence of organic wastes [J]. Solar Energy Materials & Solar Cells, 2010, 94(3): 592-597. [3] ANTONIADOU M, KONDARIDES D I, DIONYSIOU D D, et al. Quantum dot sensitized titania applicable as photoanode in photoactivated fuel cells [J]. Journal of Physical Chemistry C, 2012, 116(32): 16901-16909. DOI: 10.1021/jp305098m. [4] LIU Y, LI J, ZHOU B, et al. Photoelectrocatalytic degradation of refractory organic compounds enhanced by a photocatalytic fuel cell [J]. Applied Catalysis B Environmental, 2012, 111(6): 485-491. [5] LIU Y, LI J, ZHOU B, et al. Efficient electricity production and simultaneously wastewater treatment via a high-performance photocatalytic fuel cell [J]. Water Research, 2011, 45(13): 3991-3998. DOI: 10.1016/j.watres.2011.05.004. [6] XIA L, JING B, LI J, et al. A highly efficient BiVO4/WO3/W heterojunction photoanode for visible-light responsive dual photoelectrode photocatalytic fuel cell [J]. Applied Catalysis B Environmental, 2016, 183: 224-230. DOI: 10.1016/j.apcatb.2015.10.050. [7] LIAO Q, LI L, CHEN R, et al. Respective electrode potential characteristics of photocatalytic fuel cell with visible-light responsive photoanode and air-breathing cathode [J]. International Journal of Hydrogen Energy, 2015, 40(46): 16547-16555. [8] JENNY S, MASAYA M, MASATO T, et al. Understanding TiO2 photocatalysis: mechanisms and materials [J]. Chemical Reviews, 2014, 114(19): 9919-9986. DOI: 10.1021/cr5001892. [9] TANG X H, LI D Y. Evaluation of asphaltene degradation on highly ordered TiO2 nanotubular arrays via variations in wettability [J]. Langmuir : the ACS Journal of Surfaces and Colloids, 2011, 27(3): 1218-1223. [10] CARNEIRO J T, SAVENIJE T J, MOULIJN J A, et al. Toward a physically sound structure−activity relationship of TiO2-based photocatalysts [J]. Journal of Physical Chemistry C, 2010, 114(1): 327-332. DOI: 10.1021/jp906395w. [11] KUANG D, BRILLET J, CHEN P, et al. Application of highly ordered TiO2 nanotube arrays in flexible dye-sensitized solar cells [J]. ACS Nano, 2008, 2(6): 1113-1116. DOI: 10.1021/nn800174y. [12] ALBU S P, GHICOV A, MACAK J M, et al. Self-organized, free-standing TiO2 nanotube membrane for flow-through photocatalytic applications [J]. Nano Letters, 2007, 7(5): 1286-1289. DOI: 10.1021/nl070264k. [13] HISATOMI T, KUBOTA J, DOMEN K. Cheminform abstract: Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting [J]. Cheminform, 2014, 43(22): 7520-7535. [14] LI B, CAO H, GUI Y, et al. Cu2O@reduced graphene oxide composite for removal of contaminants from water and supercapacitors [J]. Journal of Materials Chemistry, 2011, 21(29): 10645-10648. DOI: 10.1039/c1jm12135a. [15] MCSHANE C M, CHOI K S. Photocurrent enhancement of n-type Cu2O electrodes achieved by controlling dendritic branching growth [J]. Journal of the American Chemical Society, 2013, 131(7): 2561-2569. [16] DOMINI C E, HIDALGO M, MARKEN F,et al. Comparison of three optimized digestion methods for rapid determination of chemical oxygen demand: Closed microwaves, open microwaves and ultrasound irradiation [J]. Analytica Chimica Acta, 2006, 569(1): 275-276. [17] ZHAO H, JIANG D, ZHANG S, et al. Development of a direct photoelectrochemical method for determination of chemical oxygen demand [J]. Analytical Chemistry, 2004, 76(1): 155-160. [18] LIU Z, ZHANG X, NISHIMOTO S, et al. Highly Ordered TiO2 Nanotube Arrays with Controllable Length for Photoelectrocatalytic Degradation of Phenol [J]. The Journal of Physical Chemistry C, 2008, 112(1): 253-259. DOI: 10.1021/jp0772732. [19] HOU X, WANG C W, ZHU W D,et al. Preparation of nitrogen-doped anatase TiO2 nanoworm/nanotube hierarchical structures and its photocatalytic effect [J]. Solid State Sciences, 2014, 29(3): 27-33. [20] ZHOU Z Y, WU Z Y, XU Q J, et al. A solar-charged photoelectrochemical wastewater fuel cell for efficient and sustainable hydrogen production [J]. Journal of Materials Chemistry A, 2017, 5:25450-25459. [21] LIU L, CHEN X. Titanium Dioxide Nanomaterials: Self-Structural Modifications [J]. Chemical Reviews, 2014, 114(19): 9890-9918. DOI: 10.1021/cr400624r. [22] KUMAR S G, RAO K S R K. Comparison of modification strategies towards enhanced charge carrier separation and photocatalytic degradation activity of metal oxide semiconductors (TiO2, WO3 and ZnO) [J]. Applied Surface Science, 2017, 391: 124-148. DOI: 10.1016/j.apsusc.2016.07.081. [23] FUJISHIMA A, ZHANG X, TRYK D A. TiO photocatalysis and related surface phenomena [J]. Surface Science Reports, 2008, 63(12): 515-582. DOI: 10.1016/j.surfrep.2008.10.001. [24] YING D W, CAO R Q, LI C J, et al. Study of the photocurrent in a photocatalytic fuel cell for wastewater treatment and the effects of TiO2 surface morphology to the apportionment of the photocurrent [J]. Electrochimica Acta, 2016, 192: 319-327. DOI: 10.1016/j.electacta.2016.01.210. [25] LIAO Q, LI L, CHEN R, et al. Respective electrode potential characteristics of photocatalytic fuel cell with visible-light responsive photoanode and air-breathing cathode [J]. International Journal of Hydrogen Energy, 2015, 40(46): 16547-16555. DOI: 10.1016/j.ijhydene.2015.10.002. [26] PROIETTI E, JAOUEN F, LEFÈVRE M, et al. Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells [J]. Nature Communications, 2011, 2: Article number 416. DOI: 10.1038/ncomms1427. -
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