对甲基苯磺酸在Ti/PbO2电极上的电氧化反应信息

doi:10.11949/0438-1157.20201252

摘要/Abstract

摘要：

采用原位红外光谱法系统地研究了对甲基苯磺酸（p-TSA）在钛基二氧化铅（Ti/PbO₂）电极上的电氧化反应信息。循环伏安曲线显示，Ti/PbO₂对p-TSA有良好的电氧化活性，直接氧化电位区间为0.55~0.9 V。多步电位阶跃FTIRS（MSFTIRS）和时间分辨FTIRS（TRFTIRS）分析显示，电压小于1000 mV时，p-TSA主要发生了磺酸基的脱落和苯环侧链甲基的氧化；电压大于1000 mV时，p-TSA的苯环骨架被破坏，同时生成了酸、醇、酮。反应动力学研究结果表明，p-TSA电氧化表观速率常数K与电流密度j呈线性关系，化学需氧量（COD）去除量随比电荷增大而增加，平均电流效率则呈下降趋势。

关键词: 对甲基苯磺酸, 原位红外光谱, 钛基二氧化铅, 电化学氧化, 反应动力学

Abstract:

In situ infrared spectroscopy was used to systematically study the electro-oxidation reaction information of p-toluenesulfonic acid (p-TSA) on the titanium-based lead dioxide (Ti/PbO₂) electrode. The results of cyclic voltammentry curve indicated that Ti/PbO₂ electrode exhibited a high electrochemical activity for the oxidation of p-TSA, and the direct oxidation potential ranged from 0.55—0.9 V. When the voltage was less than 1000 mV (vs. SCE), the multi-step potential FTIRS (MSFTIRS) and time-resolved FTIRS (TRFTIRS) analysis showed that the p-TSA was in the process of breaking of sulfonic acid group and methyl group oxidation of side-chain of benzene ring . When the voltage was higher than 1000 mV (vs. SCE), the aromatic ring of p-TSA was degradated. Meanwhile, the compounds of acid, alcohol and ketone were generated. The results of the reaction kinetics study showed that the apparent rate constant K of p-TSA electrooxidation has a linear relationship with the current density j, the removal of chemical oxygen demand (COD) increased with the increase of specific charge, and the average current efficiency showed a downward trend.

Key words: p-toluene sulfonic acid, in situ FTIR, titanium-based lead dioxide, electrochemical oxidation, reaction kinetics

中图分类号:

O 646

叶志平, 周丹飞, 刘梓锋, 周青青, 王家德. 对甲基苯磺酸在Ti/PbO₂电极上的电氧化反应信息[J]. 化工学报, 2021, 72(5): 2810-2816.

YE Zhiping, ZHOU Danfei, LIU Zifeng, ZHOU Qingqing, WANG Jiade. Electro-oxidation information of p-toluene sulfonic acid on Ti/PbO₂electrode[J]. CIESC Journal, 2021, 72(5): 2810-2816.

图/表 7

图1 Ti/PbO2电极在p-TSA溶液和空白溶液的循环伏安图

Fig.1 Cyclic voltammogram for a Ti/PbO2 electrode in the presence and absence of p-TSA

图2 p-TSA在Ti/PbO2电极上的多步电位阶跃原位红外光谱图

Fig.2 MSFTIR spectra of p-TSA on Ti/PbO2electrode

图3 600 mV(a)和900 mV(b)时p-TSA的时间分辨原位红外光谱图

Fig.3 TRFTIR spectra of 600 mV(a) and 900 mV(b) of p-TSA

图4 p-TSA电氧化的主要中间产物

Fig.4 Main intermediates formed in the p-TSA degradation by electro-oxidation

图5 p-TSA在Ti/PbO2电极上降解路径

Fig.5 The pathway of p-TSA degradation on Ti/PbO2 electrode

图6 电流密度、pH对表观速率常数(K) 的影响

Fig.6 The influence of current indensity and pH on apparent rate constant(K)

图7 比电荷(Qsp)对p-TSA去除、能耗(EC)和电流效率(ACE)的影响

Fig.7 The influence of specific electric charge(Qsp) on p-TSA romoval, energy consumption, and average current efficiency

参考文献 32

1	杨倩. 对甲基苯磺酸高效降解菌的筛选、代谢机制及其在废水生物强化处理中的应用[D].南京: 南京农业大学, 2017.
	Yang Q. Screening and metabolic mechanism of p-toluenesulfonic acid degrading straino and ITS application in bioaugmentation of wastewater[D]. Nanjing: Nanjing Agricultural University, 2017.
2	唐加翠. 对甲苯磺酸废水强化预处理研究[D]. 上海: 华东理工大学, 2011.
	Tang J C. Research on pretreatment of p-toluene sulfonic acid wastewater[D]. Shanghai: East China University of Science and Technology, 2011.
3	Sun Y, Li X, Zheng W, et al. Effect of functional group density of anion exchange resins on removal of p-toluene sulfonic acid from aqueous solution[J]. Applied Sciences, 2019, 10(1): 1-14.
4	Borthakur S, Srivastava R C. Kinetics of removal of p-toluene sulphonic acid from concentrated solution by granular activated carbon[J]. Journal of Chemical Technology & Biotechnology, 1991, 51(4): 497-506.
5	张凌, 陶莹, 常志显, 等. 臭氧法降解水中对甲基苯磺酸的动力学研究[J].环境科学学报, 2011, 31(10): 2185-2191.
	Zhang L, Tao Y, Chang Z X, et al. Kinetics of p-toluene sulfonic acid degradation by ozone in aqueous solutions[J]. Acta Scientiae Circumstantiae, 2011, 31(10): 2185-2191.
6	Cao H, Feng Q. Kinetics of photocatalytic degradation of p-toluene sulfonic acid on TiO₂ surface[J]. Asian Journal of Chemistry, 2013, 25(18): 10195-10198.
7	Dai Q Z, Shen H, Xia Y J, et al. Typical rare earth doped lead dioxide electrode: preparation and application[J]. International Journal of Electrochemical Science, 2012, 7(10): 10054-10062.
8	余丽娜, 宋玉栋, 周岳溪, 等. 三维电极法处理丙烯酸丁酯生产废水的研究[J].环境工程学报, 2011, 5(5): 1025-1028.
	Yu L N, Song Y D, Zhou Y X, et al. Treatment of butyl acrylate production wastewater by three-dimensional electrode process[J]. Chinese Journal of Environmental Engineering, 2011, 5(5): 1025-1028.
9	Taleb Z, Montilla F, Quijada C, et al. Electrochemical and in situ FTIR study of o-cresol on platinum electrode in acid medium[J]. Electrocatalysis, 2014, 5(2): 186-192.
10	Ye J Y, Jiang Y X, Sheng T, et al. In-situ FTIR spectroscopic studies of electrocatalytic reactions and processes[J]. Nano Energy, 2016, 29(SI): 414-427.
11	Gomes J F, Garcia A C, Gasparotto L H S, et al. Influence of silver on the glycerol electro-oxidation over AuAg/C catalysts in alkaline medium: a cyclic voltammetry and in situ FTIR spectroscopy study[J]. Electrochimica Acta, 2014, 144: 361-368.
12	Borrás C, Laredo T, Mostany J, et al. Study of the oxidation of solutions of p-chlorophenol and p-nitrophenol on Bi-doped PbO₂ electrodes by UV-Vis and FTIR in situ spectroscopy[J]. Electrochimica Acta, 2004, 49(4): 641-648.
13	Labiadh L, Barbucci A, Carpanese M P, et al. Comparative depollution of methyl orange aqueous solutions by electrochemical incineration using TiRuSnO₂, BDD and PbO₂ as high oxidation power anodes[J]. Journal of Electroanalytical Chemistry, 2016, 766: 94-99.
14	Feng Y J, Li X Y. Electro-catalytic oxidation of phenol on several metal-oxide electrodes in aqueous solution[J]. Water Research, 2003, 37(10): 2399-2407.
15	He Y P, Huang W M, Chen R L, et al. Anodic oxidation of aspirin on PbO₂, BDD and porous Ti/BDD electrodes: mechanism, kinetics and utilization rate[J]. Separation & Purification Technology, 2015, 156: 124-131.
16	甘永平, 马淳安. 疏水性二氧化铅电极的镀制及强化寿命研究[J]. 化学世界, 2002, 43(11): 584-586.
	Gan Y P, Ma C A. Eelctroplating and strengthening lifetime of PbO₂ hydrophobic electrode[J]. Chemical World, 2002, 43(11): 584-586.
17	王家德, 袁通斌, 周丹飞, 等. 基于原位红外光谱的水相苯酚电氧化机理研究[J].化工学报, 2019, 70(12): 4821-4827.
	Wang J D, Yuan T B, Zhou D F, et al. Mechanism of phenol electro-oxidation in aqueous solution based on in situ infrared spectroscopy[J]. CIESC Journal, 2019, 70(12): 4821-4827.
18	蔡少卿, 何月峰, 戴启洲, 等. 臭氧氧化对甲基苯磺酸的动力学模型[J].化工学报, 2011, 62(5): 1414-1420.
	Cai S Q, He Y F, Dai Q Z, et al. Kinetic model on ozonation of p-toluene sulfonic acid[J]. CIESC Journal, 2011, 62(5): 1414-1420.
19	Wang L Z, Yang S X, Wu B, et al. The influence of anode materials on the kinetics toward electrochemical oxidation of phenol[J]. Electrochimica Acta, 2016, 206: 270-277.
20	Song S, Fan J, He Z, et al. Electrochemical degradation of azo dye CI Reactive Red 195 by anodic oxidation on Ti, SnO₂-Sb, PbO₂ electrodes[J]. Electrochimica Acta, 2010, 55(11): 3606-3613.
21	翁诗甫.傅里叶变换红外光谱分析[M]. 3版. 北京: 化学工业出版社, 2017.
	Weng S F. Fourier Transform Infrared Spectroscopy[M]. 3rd ed. Beijing: Chemical Industry Press, 2017.
22	张凌, 楚红英, 常志显, 等. 超声波光催化协同降解对甲基苯磺酸水溶液的机理研究[J].环境工程学报, 2011, 5(4): 819-824.
	Zhang L, Chu H Y, Chang Z X, et al. Study on mechanism of degradation 4-toluene sulfonic acid by sonophotocatalysis [J]. Chinese Journal of Environmental Engineering, 2011, 5(4): 819-824.
23	Li M C, Bao D D, Ma C A. Studies on electrochemical hydrodebromination mechanism of 2, 5-dibromobenzoic acid on Ag electrode by in situ FTIR spectroscopy[J]. Electrochimica Acta, 2011, 56(11): 4100-4104.
24	叶咏薇, 王希, 郑万芳, 等. 间溴苯甲酸在Pt电极上的电氧化反应[J].物理化学学报, 2013, 29(3): 553-558.
	Ye Y W, Wang X, Zheng W F, et al. Electrooxidation reaction of 3-bromobenzoic acid on Pt electrode[J]. Acta Phys. -Chim. Sin., 2013, 29 (3): 553-558.
25	Chumillas S, Palomaki T, Zhang M, et al. Analysis of catechol, 4-methylcatechol and dopamine electrochemical reactions on different substrate materials and pH conditions[J]. Electrochimica Acta, 2018, 292: 309-321.
26	Vigier F, Coutanceau C, Hahn F, et al. On the mechanism of ethanol electro-oxidation on Pt and PtSn catalysts: electrochemical and in situ IR reflectance spectroscopy studies[J]. Journal of Electroanalytical Chemistry, 2004, 563(1): 81-89.
27	You L X, Fang Y M, Guo J W, et al. Mechanism of electro-catalytic oxidation of shikimic acid on Cu electrode based on in situ FTIRS and theoretical calculations[J]. Electrochimica Acta, 2011, 58: 165-171.
28	Chen L C, Uchida T, Chang H C, et al. Adsorption and oxidation of glycine on Au electrode: an in situ surface-enhanced infrared study[J]. Electrochemistry Communications, 2013, 34: 56-59.
29	Salavagione H J, Joaquín A P, Pedro G T, et al. Spectroelectrochemical study of the oxidation of aminophenols on platinum electrode in acid medium[J]. Journal of Electroanalytical Chemistry, 2004, 565(2): 375-383.
30	Planes G A, Moran E, Rodriguez J L, et al. Electrochemical behavior of benzaldehyde on polycrystalline platinum: an in situ FTIR and DEMS study[J]. Langmuir, 2003, 19(21): 8899-8906.
31	Clémence L, Frédéric M, Martin V, et al. Degradation of carbon-supported platinum-group-metal electrocatalysts in alkaline media studied by in situ Fourier transform infrared spectroscopy and identical-location transmission electron microscopy[J]. ACS Catalysis, 2019, 9(6): 5613-5622.
32	Zheng J, Yan K, Wu Z, et al. Effective removal of sulfanilic acid from water using a low-pressure electrochemical RuO₂-TiO₂@Ti/PVDF composite membrane[J]. Frontiers in Chemistry, 2018, 6: 395.

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对甲基苯磺酸在Ti/PbO₂电极上的电氧化反应信息

Electro-oxidation information of p-toluene sulfonic acid on Ti/PbO₂electrode

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