Mechanism of phenol electro-oxidation in aqueous solution based on in situ infrared spectroscopy

doi:10.11949/0438-1157.20190689

Abstract

Abstract:

The electrochemical oxidation mechanism of phenol on the surface of Pt electrode was studied by electrochemical in situ spectroscopy. In 0.1 mol/L Na₂SO₄ solution, the reaction potential of electrochemical oxidation of phenol on Pt electrode is +0.9—1.0 V (vs SCE), and the oxygen evolution potential is +1.3 V. In situ infrared spectroscopy showed that electrode potential had a great influence on oxidation behavior of phenol. When the potential was lower than 0.9 V, the main intermediates of phenol oxidation were dihydroxyhenzene, quinone and a few alcohols. When the potential was controlled between 0.9 V and 1.1 V, the structure of benzene ring was destroyed, and the main intermediates were ketones, acids, alcohols and CO₂. According to the changes in absorption peak of functional group, phenol oxidation on the platinum electrode surface was as follows: phenol, dihydroxyhenzene, quinone, ketone, alcohol, acid and CO₂. The potential of ammonia oxidation on the platinum electrode surface was + 0.5 V, which indicated that ammonia in competition with phenol oxidation in the low potential region (< 0.9 V).

Key words: phenol, in situ FTIR, electrochemical oxidation, interface, mechanism

摘要：

采用电化学原位红外光谱技术，研究了苯酚在Pt电极表面的电化学氧化机理。在0.1 mol/L Na₂SO₄溶液中，Pt电极上电化学氧化苯酚的反应电位为+0.9~1.0 V（vs SCE）、析氧电位为+1.3 V；电化学原位红外光谱结果表明，当电位<0.9 V时，苯酚氧化产物主要为苯二酚、醌及少量醇类物质；电位0.9~1.1 V时，苯环结构被破坏，氧化产物主要为酮、酸、醇和CO₂；根据官能团吸收峰的变化，苯酚在Pt电极表面氧化经历如下途径：苯酚→苯二酚→苯醌→酮、醇、酸→CO₂。同时研究了NH₄⁺对苯酚在Pt电极表面的电氧化的影响，结果表明在低电位区（<0.9 V）对苯酚氧化构成竞争。

关键词: 苯酚, 原位红外光谱, 电化学氧化, 界面, 机理

CLC Number:

O 646

Jiade WANG, Tongbin YUAN, Danfei ZHOU, Xule ZHOU, Yongping GAN. Mechanism of phenol electro-oxidation in aqueous solution based on in situ infrared spectroscopy[J]. CIESC Journal, 2019, 70(12): 4821-4827.

王家德, 袁通斌, 周丹飞, 周栩乐, 甘永平. 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.

Figures/Tables 7

Fig.1 Reflective in situ infrared electrolytic cell

Fig.2 Cyclic voltammetry curve of phenol on Pt surfaceA—0.1 mol/L sodium sulfate solution and 100 mg/L phenol solution;B—0.1 mol/L sodium sulfate solution

Fig.3 In situ infrared reflectance spectrum of phenol on Pt electrode surface

Fig.4 In situ infrared spectra of 300 mV(a) and 900 mV(b) aqueous phenol at Pt electrode surface

Fig.5 (NH4)2SO4 cyclic voltammetry curves and in frared spectra on the surface of Pt electrode

Fig.6 Electrooxidation of phenol on Pt electrode surface

Fig.7 GC-MS analysis of phenol degradation intermediates

References 30

1	Zinola C F, Rodríguez J L, Arévalo M C, et al. Electrochemical and FTIR spectroscopic studies of tyrosine oxidation at polycrystalline platinum surfaces in alkaline solutions[J]. Journal of Solid State Electrochemistry, 2008, 12(5): 523-528.
2	Jin B, Liu P, Wang Y, et al. Rapid-scan time-resolved FT-IR spectroelectrochemistry studies on the electrochemical redox process[J]. The Journal of Physical Chemistry B, 2007, 111(7): 1517-1522.
3	Trettenhahn G, Koberl A. Anodic decomposition of citric acid on gold and stainless steel electrodes: an in situ-FTIR-spectroscopic investigation[J]. Electrochimica Acta, 2007, 52(7): 2716-2722.
4	毛信表, 何峰强, 张寅旭, 等. 二元离子液体OMImBF₄/HMImPF₆中硝基苯的电化学还原[J]. 化工学报, 2016, 67(5): 1998-2004.
	Mao X B, He F Q, Zhang Y X, et al. Electrochemical reduction of nitrobenzene in binary ionic liquid OMImBF₄/HMImPF₆[J]. CIESC Journal, 2016, 67(5): 1998-2004.
5	Mousset E, Frunzo L, Esposito G, et al. A complete phenol oxidation pathway obtained during electro-Fenton treatment and validated by a kinetic model study[J]. Applied Catalysis B Environmental, 2016, 180(180): 189-198.
6	焦庆周, 柴多里, 鲍远志. 高级氧化技术与含酚废水处理[J]. 现代化工, 2013, 33(1): 40-44.
	Jiao Q Z, Chai D L, Bao Y Z. Advanced oxidation technology and treatment of phenolic wastewater[J]. Modern Chemical Industry, 2013, 33(1): 40-44.
7	丛燕青, 伏芳霞, 马香娟, 等. 吸附-电催化联合处理苯酚废水及动力学[J]. 化工学报, 2010, 61(11): 2971-2977.
	Cong Y Q, Fu F X, Ma X J, et al. Adsorption-electrocatalysis combined treatment of phenol wastewater and kinetics[J]. CIESC Journal, 2010, 61(11): 2971-2977.
8	Czaplicka M. Sources and transformations of chlorophenols in the natural environment[J]. Science of the Total Environment, 2003, 322(1/2/3): 21-39.
9	Siddiqui M, Al-Malack M H. Phenol degradation mechanism by electrooxidation using stainless steel electrodes[J]. Journal of Water Chemistry & Technology, 2016, 38(1): 28-33.
10	丁海洋, 冯玉杰, 刘峻峰. 多晶铂电极电催化氧化苯酚的电化学过程[J]. 哈尔滨工业大学学报, 2007, 39(10): 1580-1582.
	Ding H Y, Feng Y J, Liu J F. Electrochemical process of phenol oxidation with polycrystalline platinum electrode[J]. Journal of Harbin Institute of Technology, 2007, 39(10): 1580-1582.
11	Jarrah N, Mu azu D N, Nuhu D. Simultaneous electro-oxidation of phenol, CN^-, S^2- and NH₄⁺ in synthetic wastewater using boron doped diamond anode[J]. Journal of Environmental Chemical Engineering, 2016, 4(3): 2656-2664.
12	李天成, 朱慎林. 电催化氧化技术处理苯酚废水研究[J]. 电化学, 2005, 11(1): 101-104.
	Li T C, Zhu S L. Study on treatment of phenol wastewater by electrocatalytic oxidation technology[J]. Journal of Electrochemistry, 2005, 11(1): 101-104.
13	Feng Y, Li X. Electro-catalytic oxidation of phenol on several metal-oxide electrodes in aqueous solution[J]. Water Research, 2003, 37(10): 2399-2407.
14	王辉, 于秀娟, 孙德智. 一种新型电化学体系降解苯酚的机理研究[J]. 环境科学学报, 2005, 25(7): 901-907.
	Wang H, Yu X J, Sun D Z. Mechanism of degradation of phenol by a new electrochemical system[J]. Acta Scientiae Circumstantiae, 2005, 25(7): 901-907.
15	楚鑫鹏. 三维PbO₂电极制备及电催化降解含酚废水研究[D]. 武汉: 华中科技大学, 2018.
	Chu X P. Preparation of 3D PbO₂ electrode and electrocatalytic degradation of phenol-containing wastewater[D]. Wuhan: Huazhong University of Science and Technology, 2018.
16	Comninellis C, Pulgarin C. Anodic oxidation of phenol for waste water treatment[J]. Journal of Applied Electrochemistry, 1991, 21(8): 703-708.
17	周明华, 吴祖成. 含酚模拟废水的电催化降解[J]. 化工学报, 2002, 53(1): 40-44.
	Zhou M H, Wu Z C. The electrocatalytic degradation of wastewater containing phenol is simulated[J]. Journal of Chemical Industry and Engineering(China), 2002, 53(1): 40-44.
18	田中群, 孙世刚, 罗瑾, 等. 现场光谱电化学研究的新进展[J].物理化学学报, 1994, 10(9): 860-866.
	Tian Z Q, Sun S G, Luo J, et al. New progress in on-site spectroelectrochemical research[J]. Acta Physico-Chimica Sinica, 1994, 10(9): 860-866.
19	鲁弘懿, 王栋, 马长宝, 等. 苯酚环境模拟水相的铂电极电解特征研究[J]. 化工环保, 2004, 24(S1): 40-45.
	Lu H Y, Wang D, Ma C B, et al. Study on electrolysis characteristics of platinum electrode simulating aqueous phase in phenol environment[J]. Environmental Protection of Chemical Industry, 2004, 24(S1): 40-45.
20	谢晶曦, 常俊标. 红外光谱在有机化学和药物化学中的应用[M]. 北京: 科学出版社, 2002: 282.
	Xie J X, Chang J B. Application of Infrared Spectroscopy in Organic Chemistry and Drug Chemistry[M]. Beijing: Science Press, 2002: 282.
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: 332-333.
	Weng S F. Fourier Transform Infrared Spectroscopy[M]. 3rd ed. Beijing: Chemical Industry Press, 2017: 332-333.
22	刘俊逸, 张宇, 张蕾, 等. 含酚工业废水处理技术的研究进展[J]. 工业水处理, 2018, 38(10): 12-16.
	Liu J Y, Zhang Y, Zhang L, et al. Research progress on treatment technology of industrial wastewater containing phenol[J]. Industrial Water Treatment, 2018, 38(10): 12-16.
23	闫俊娟, 高璟, 刘有智, 等. RuO₂-IrO₂-SnO₂/Ti电极电催化氧化降解苯酚废水[J]. 含能材料, 2017, 25(9): 780-785.
	Yan J J, Gao J, Liu Y Z, et al. Electrocatalytic oxidation degradation of phenol wastewater by RuO₂-IrO₂-SnO₂/Ti electrode[J]. Chinese Journal of Energetic Materials, 2017, 25(9): 780-785.
24	马一玫. 电化学-生物膜耦合技术处理废水中的苯酚与NH₄⁺-N及NO₃^--N 的研究[D]. 苏州: 苏州大学, 2016.
	Ma Y M. Study on treatment of phenol and NH₄⁺-N and NO₃^--N in wastewater by electrochemical-biological membrane coupling technology[D]. Suzhou: Soochow University, 2016.
25	刘咏, 刘丹, 赵仕林, 等. 苯酚在含氯体系中的电化学氧化[J]. 电化学, 2007, 13(1): 30-34.
	Liu Y, Liu D, Zhao S L, et al. Electrochemical oxidation of phenol in chlorine-containing system[J]. Journal of Electrochemistry, 2007, 13(1): 30-34.
26	Andreescu S, Andreescu D, Sadik O A. A new electrocatalytic mechanism for the oxidation of phenols at platinum electrodes[J]. Electrochemistry Communications, 2003, 5(8): 681-688.
27	Loloi M, Rezaee A, Aliofkhazraei M, et al. Electrocatalytic oxidation of phenol from wastewater using Ti/SnO₂-Sb₂O₄ electrode: chemical reaction pathway study[J]. Environmental Science and Pollution Research International, 2016, 23(19): 19735-19743.
28	Pastor E, González S, Arvia A J. Electroreactivity of isopropanol on platinum in acids studied by DEMS and FTIRS[J]. Journal of Electroanalytical Chemistry, 1995, 395(1): 233-242.
29	Mahoney E G, Sheng W C, Cheng M, et al. Analyzing the electrooxidation of ethylene glycol and glucose over platinum-modified gold electrocatalysts in alkaline electrolyte using in-situ infrared spectroscopy[J]. Journal of Power Sources, 2016, 305(305): 89-96.
30	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.

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