还原染料在石墨毡电极上的直接电化学还原

doi:10.13475/j.fzxb.20201002808

摘要/Abstract

摘要：

针对还原染料的直接电化学还原存在不溶性染料和电极接触不充分而难以进行的难题,以石墨毡为工作电极,采用三电极体系,研究了还原黄3RT、还原绿FFB和还原橄榄绿B的电化学行为,并探讨了温度、电压、电流、电解质和染料浓度对直接电化学还原的影响,测试了电化学还原的电流效率和转化率。实验结果表明:还原染料可在石墨毡电极上直接进行电子得失;以石墨毡作为工作电极,可有效提高染料反应速度;提高温度可显著提高电化学反应速度;电流强度和电压过大,会增强析氢副反应,进而影响染料还原速度;在60 ℃,-1.0 V条件下恒压电解,染料可在10~40 min内完成还原,转化率可达90%以上,电流效率在50%~60%之间。

关键词: 直接电化学, 还原染料, 石墨毡, 电流效率

Abstract:

The direct electrochemical reduction of vat dyes is difficult to carry out due to poor contact between insoluble vat dyes and the electrodes. In order to solve this problem, using graphite felt as the electrode, under a three-electrode system, the electrochemical behaviors of Vat Yellow 3RT, Vat Green FFB and Vat Olive Green B were studied, and the effects of temperature, voltage, current, electrolyte and dye concentration on direct electrochemical reduction were explored, the current efficiency and conversion rate of electrochemical reduction were also tested. The results show that vat dyes could be directly reduced into leuco. Using carbon felt cathode as electrode direct electrochemical reduction rate could be effectively improved. Electrochemical reduction rate increases significantly with the increase of temperature. At excessive level of negative potential or current, hydrogen evolution begins to occur and becomes the main rection, which affects the rate of dye reduction. Under the conditions of 60 ℃ and -1.0 V, the vat dyes could be reduced within 10 min to 40 min, and the conversion rate could reach more than 90%, and the current efficiency is between 50% and 60%.

Key words: direct electrochemistry, vat dyes, carbon felt, current efficiency

中图分类号:

TS193.5

杨卓, 王炜. 还原染料在石墨毡电极上的直接电化学还原[J]. 纺织学报, 2021, 42(09): 104-111.

YANG Zhuo, WANG Wei. Direct electrochemical reduction of vat dyes on carbon felt electrodes[J]. Journal of Textile Research, 2021, 42(09): 104-111.

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参考文献 16

[1]	ROESSLERA, JIN X. State of the art technologies and new electrochemical methods for the reduction of vat dyes[J]. Dyes and Pigments, 2003, 59:223-235. doi: 10.1016/S0143-7208(03)00108-6
[2]	KULANDAINATHAN M A, PATIL K, MUTHUKUMARANA A, et al. Review of the process development aspects of electrochemical dyeing: its impact and commercial applications[J]. Coloration Technology, 2007, 123(3):143-151. doi: 10.1111/cte.2007.123.issue-3
[3]	BOZIC M, KOKOL V. Ecological alternatives to the reduction and oxidation processes in dyeing with vat and sulphur dyes[J]. Dyes and Pigments, 2008, 76(2):299-309. doi: 10.1016/j.dyepig.2006.05.041
[4]	彭勇刚, 陈大俊, 纪俊玲, 等. 还原染料电化学还原技术研究进展[J]. 染整技术, 2011, 33(2):7-10, 25.
	PENG Yonggang, CHEN Dajun, JI Junling, et al. Research progress of electrochemical reduction technology of vat dyes[J]. Textile Dyeing and Finishing Journal, 2011, 33(2):7-10, 25.
[5]	BECHTOLD T, TURCANU A. Fe³⁺-D-gluconate and Ca²⁺-Fe³⁺-D-gluconate complexes as mediators for indirect cathodic reduction of vat dyes: cyclic voltammetry and batch electrolysis experiments[J]. J Appl Electrochem, 2004, 34(12):1221-1227. doi: 10.1007/s10800-004-1707-z
[6]	汪康康, 李晓燕, 姚继明. 铁盐媒介对靛蓝电化学还原体系的影响[J]. 纺织学报, 2020, 40(1):75-79, 87.
	WANG Kangkang, LI Xiaoyan, YAO Jiming. Effect of different iron salt media on indigo electrochemical reduction system[J]. Journal of Textile Research, 2020, 40(1):75-79, 87. doi: 10.1177/004051757004000111
[7]	YI C, TAN X, BIE B, et al. Practical and environment-friendlyindirect electrochemical reduction of indigo and dyeing[J]. Scientific Reports, 2020, 10:4927. doi: 10.1038/s41598-020-61795-5
[8]	BECHTOLD T, TURCANU A. Electrochemical reduction in vat dyeing: greener chemistry replaces traditional processes[J]. J Clean Prod, 2009, 17(18):1669-1679. doi: 10.1016/j.jclepro.2009.08.004
[9]	ROESSLER A, CRETTENAND D, DOSSENBACH O, et al. Direct electrochemical reduction of indigo[J]. Electrochim Acta, 2002, 47(12):1989-1995. doi: 10.1016/S0013-4686(02)00028-2
[10]	ROESSLER A, CRETTENAND D. Direct electrochemical reduction of vat dyes in a fixed bed of graphite granules[J]. Dyes and Pigments, 2004, 63:29-37. doi: 10.1016/j.dyepig.2004.01.005
[11]	ROESSLERA, CRETTENAND D, DOSSENBACH O, et al. Electrochemical reduction of indigo in fixed and fluidized beds of graphite granules[J]. Journal of Applied Electrochemistry, 2003, 33:901-908. doi: 10.1023/A:1025876114390
[12]	YANG Z, SHEN W, WANG W, et al. Direct electrochemical reduction and dyeing properties of CI Vat Yellow 1 using carbon felt electrode[J]. Dyes and Pigments, 2021, 184:1-9.
[13]	APUL O G, WANG Q L, ZHOU Y, et al. Adsorption of aromatic organic contaminants by graphene nanosheets: comparison with carbon nanotubes and activated carbon[J]. Water Res, 2013, 47(4):1648-1654. doi: 10.1016/j.watres.2012.12.031
[14]	GUIN P S, DAS S, MANDAL P C. Electrochemical reduction of sodium 1,4-dihydroxy-9,10-anthraquinone-2-sulphonate in aqueous and aqueous aimethyl formamide mixed solvent: a cyclic voltammetric study[J]. Int J Electrochem Sci, 2008, 3(9):1016-1028.
[15]	GUIN P S, DAS S, MANDAL P C. Sodium 1, 4-dihydroxy-9, 10-anthraquinone-2-sulphonate interacts with calf thymus DNA in a way that mimics anthracycline antibiotics: an electrochemical and spectroscopic study[J]. J Phys Org Chem, 2010, 23(6):477-482. doi: 10.1002/poc.1624
[16]	SIMON P, GOGOTSI Y. Materials for electrochemical capacitors[J]. Nature Materials, 2008, 7(11):845-854. doi: 10.1038/nmat2297

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电压/V	还原黄3RT			还原橄榄绿B			还原绿FFB
电压/V	还原时间/min	转化率/%	电流效率/%	还原时间/min	转化率/%	电流效率/%	还原时间/min	转化率/%	电流效率/%
-0.8	18	88.7	66.1	30	95.6	51.3	80	87.5	44.6
-1.0	12	87.5	58.5	10	99.1	53.7	35	91.3	50.8
-1.2	12	87.3	35.6	10	98.0	35.5	100	90.6	3.9
-1.4	12	87.5	6.8	—	—	—	180	80.6	0.1

电流强度/mA	还原黄3RT			还原橄榄绿B			还原绿FFB
电流强度/mA	还原时间/min	转化率/%	电流效率/%	还原时间/min	转化率/%	电流效率/%	还原时间/min	转化率/%	电流效率/%
10	15	93.5	33.8	10	94.2	25.2	100	82.4	2.2
5	20	94.4	51.2	15	96.1	34.4	60	87.7	8.0
3	40	95.0	49.2	25	98.0	35.0	60	87.7	13.3
1	110	94.5	47.0	60	95.9	42.9	70	91.5	35.7