Ti(100-δ)Cuδ(δ=0.02, 0.28, 1.39, 5.65)阴极的制备及电催化还原NO3-机理

doi:10.7503/cjcu20170229

摘要/Abstract

摘要：

以Ti板为基体, 采用异位电沉积法通过调控电镀时间制备了质量分数(δ)分别为0.02, 0.28, 1.39和5.65的Ti_(100-_δ₎Cu_δ阴极; 利用扫描电子显微镜(SEM)、 X射线衍射(XRD)、电化学测试及N $O 3 -$ 处理实验等手段对其微观形貌、物相组成、电催化活性、抗腐蚀性能和产物选择性等进行了表征. 结果表明, δ≥0.28时Ti_(100-_δ₎Cu_δ电极表面的Cu镀层呈现(111)晶面择优取向, 可有效提高电极稳定性; Cu活性层的形成为N $O 3 -$ 的吸附提供了活性点位, 增强了电极的电催化性能, 但Cu的加入会降低电极抗腐蚀性能; 在一定的载铜量范围内, 单质Cu对N $O 3 -$ 降解产物N $O 2 -$ 的吸附有一定的抑制作用, 但会增强N $O 2 -$ 的还原反应活性, 提高N₂选择系数. 应用Ti_(100-_δ₎Cu_δ(δ=5.65)阴极在电流密度为20 mA/cm²、电解时间6 h条件下对N $O 3 -$ 进行处理, 结果表明, N $O 3 -$ 去除率和N₂选择系数分别高达75.47%和32.65%, 与Ti电极的N $O 3 -$ 去除率(39.89%)和N₂选择系数(2.19%)相比有显著提高.

关键词: Ti(100-δ)Cuδ阴极, 电催化还原, 硝态氮, 机理, 选择系数

Abstract:

The ectopic electro-deposition method was used to prepare Ti_(100-_δ₎Cu_δ cathodes with various mass fraction(δ) of 0.02, 0.28, 1.39 and 5.65, respectively, over titanium plates under different electro-deposition time. The scanning electron microscope(SEM), X-ray diffraction(XRD), electrochemical tests including cyclic voltammetry, linear sweep voltammetry and Tafel plots on an electrochemical workstation and nitrate ion reduction experiments were performed to characterize and investigate the microstructure, physical composition, electro-catalytic reduction performance, corrosion resistance and the products selectivity. The experimental results indicate that the active layer existing on the surface of Ti_(100-_δ₎Cu_δ cathodes presents as lattice pattern (111) if the value of δ is no less than 0.28, which can effectively improve the stability of the active layer. The existence of the active layer provides additional active sites for adsorption of nitrate ion(N $O 3 -$ ), which enhances the electro-catalytic performance of cathodes; however, the involvement of copper element would reduce the corrosion resistance of cathodes compared with that of Ti electrode. Besides, Cu exhibits a certain negative effect on the adsorption of nitrite ion while enhances the reduction activity of nitrite ion thus improving selectivity of nitrogen gas. The results of nitrate treatment experiments using Ti_(100-_δ₎Cu_δ(δ=5.65) cathodes at current density of 20 mA/cm² and reaction time of 6 h illustrate that nitrate removal and the selectivity of N₂ were 75.47% and 32.65%, respectively, but as a comparison only 39.89% and 2.19% of those variables were obtained on a titanium electrode at the same experimental conditions.

Key words: Ti(100-δ)Cuδ cathode, Electro-catalytic reduction, Nitrate ion(N $O 3 -$ ), Mechanism, Selectivity coefficient

中图分类号:

O646

TrendMD:

孔艳, 王立章, 杨胜翔, 赵鹏. Ti_(100-_δ₎Cu_δ(δ=0.02, 0.28, 1.39, 5.65)阴极的制备及电催化还原NO₃^-机理. 高等学校化学学报, 2018, 39(1): 132.

KONG Yan, WANG Lizhang, YANG Shengxiang, ZHAO Peng. Preparation and Electro-catalytic Mechanisms for Nitrate Ion Reduction of Ti_(100-_δ₎Cu_δ(δ=0.02, 0.09, 0.28, 1.39, 5.65) Cathodes^†. Chem. J. Chinese Universities, 2018, 39(1): 132.

图/表 11

Fig.1 SEM images of the prepared Ti(100-δ)Cuδ cathodes under different electro-deposition time(A) t=0 min(δ=0); (B) t=0.5 min(δ=0.02); (C) t=6 min(δ=0.28); (D) t=30 min(δ=1.39).

Fig.2 XRD patterns of the prepared Ti(100-δ)Cuδ cathodes under different electro-deposition timea. t=0(δ=0); b. t=0.5 min(δ=0.02); c. t=6 min(δ=0.28); d. t=30 min(δ=1.39); e. t=120 min(δ=5.65).

Table 1 Effects of electro-deposition time(t) on the mass fraction(δ), crystallinity and grain size(D) of Cu on Ti(100-δ)Cuδ cathodes

t/min	δ	Crystallinity(%)	D/nm	t/min	δ	Crystallinity(%)	D/nm
0	0			30	1.39	74.71	>100
0.5	0.02	3.03	35.7	120	5.65	15.93	>100
6	0.28	41.69	73.1

Table 2 Calculated results of the texture coefficient(TC) of Cu coating on Ti(100-δ)Cuδ cathodes from XRD patterns

δ	TC(%)				δ	TC(%)
δ	(111)		(200)	(220)	(311)	(111)	(200)	(220)	(311)
0.02	20.8	19.9	41.7	17.5	1.39	34.9	23.5	23.5	18.1
0.28	32.0	24.8	24.5	18.7	5.65	38.0	27.3	22.4	12.3

Fig.3 CV curves of the prepared Ti(100-δ)Cuδ cathodes in hybrid of NaNO3(0.01 mol/L) and Na2SO4(3%, mass fraction) at a scanning rate of 10 mV/sδ: (A) 0; (B) 0.02; (C) 0.28; (D) 1.39; (E) 5.65.

Fig.4 Tafel plots of the prepared Ti(100-δ)Cuδ cathodes and copper in hybrid of NaNO3(0.01 mol/L) and Na2SO4(3%) at a scanning rate of 5 mV/sδ: a. 0; b. 0.02; c. 0.28; d. 1.39; e. 5.65; f. 100.

Table 3 Tafel constants(a,b) of Ti(100-δ)Cuδ cathodes in NaNO3(0.01 mol/L) solution

δ	a/mV	b/mV	δ	a/mV	b/mV
0	81.82	75.99	1.39	61.93	108.29
0.02	66.29	97.14	5.65	91.54	69.17
0.28	60.15	114.20	100	105.66	62.83

Fig.5 NO3- removal efficiency and product selectivity during electro-catalytic reduction on the prepared Ti(100-δ)Cuδ cathodesCurrent density: 20 mA/cm2; electrolysis time: 6 h.

Fig.6 pH values during electro-catalytic reduction of N O 3 - on the prepared Ti(100-δ)Cuδ cathodesCurrent density: 20 mA/cm2; electrolysis time: 6 h.

Fig.7 LSV curves of the prepared Ti(100-δ)Cuδ cathodes in 0.01 mol/L NaNO3(a) and 0.01 mol/L NaNO2(b) solutionsScanning rate: 10 mV/s. δ: (A) 0; (B) 0.02; (C) 0.28; (D) 1.39; (E) 5.65; (F) the enlarged panel in NaNO3 solution. P1 and P2 represent the reduction peaks of the nitrate and nitrite ions, respectively; the subscripts of A, B, C, D and E denote the peaks at δ values of 0, 0.02, 0.28, 1.39, 5.65, respectively.

Fig.8 Linear relationship between concentration and peak currents obtained by recorded LSV data in NaNO3(0.01 mol/L) solutionScanning rate: 10 mV/s. δ: a. 0; b. 0.02; c. 0.28; d. 1.39; e. 5.65.

参考文献 28

[1]	Li R., Song C. Z., Zhao X., Mao R., Chin. J. Environ. Eng., 2016, 10(2), 648—654
	(李熔, 宋长忠, 赵旭, 冒冉.环境工程学报, 2016, 10(2), 648—654)
[2]	Ding J., Li W., Zhao Q. L., Wang K., Zheng Z., Gao Y. Z., Chem. Eng. J., 2015, 271, 252—259
[3]	Gao M. C., Wang S., Ren Y., Jin C. J., She Z. L., Zhao Y. G., Yang S. Y., Guo L., Zhang J., Li Z. W., Chem. Eng. J., 2016, 284, 1008—1016
[4]	Ye S. F., Hu X. M., Zhang Y., Dong J., Environ. Sci., 2010, 31(8), 1827—1833
	(叶舒帆, 胡筱敏, 张杨, 董俊.环境科学, 2010, 31(8), 1827—1833)
[5]	Ye S. F., Hu X. M., Dong J., Zhang Y., He Y. D., China Environ. Sci., 2011, 31(1), 44—49
	(叶舒帆, 胡筱敏, 董俊, 张杨, 和英滇.中国环境科学, 2011, 31(1), 44—49)
[6]	Hasnat M. A., Islam M. A., Aoun S.B., Safwan J. A., Rahman M. M., Asiri A. M., ChemPlusChem, 2015, 80(11), 1634—1641
[7]	Molodkina E. B., Botryakova I. G., Danilov A. I., Souza-Garcia J., Feliu J. M., Russ. J. Electrochem., 2012, 48(3), 302—315
[8]	Comisso N., Cattarin S., Stefania F., Luca M., Marco M., Lourdes V., Enrico V., Electrochem. Commun., 2012, 25, 91—93
[9]	Zhou L., Deng H. P., Sang S. B., Environ. Chem., 2008, 27(2), 172—176
	(周丽, 邓慧萍, 桑松表.环境化学, 2008, 27(2), 172—176)
[10]	González P. O., Bisang J. M., Electrochim. Acta, 2016, 194, 448—453
[11]	David R., Daniel B., Lionel R., Electrochim. Acta, 2008, 53(20), 5977—5984
[12]	Ma X. J., Li M., Feng C. P., Hu W. W., Wang L. L., Liu X. J., Electroanal. Chem., 2016, 782, 270—277
[13]	Yang S. X., Wang L. Z., Jiao X. M., Li P., Int. J. Electrochem. Sci., 2017, 12(5), 4370—4383
[14]	Du N., Shu W. F., Zhao Q., Chen Q. L., Wang S. X., Nonferr. Metal. Soc., 2013, 23(2), 426—433
	(杜楠, 舒伟发, 赵晴, 陈庆龙, 王帅星.中国有色金属学报, 2013, 23(2), 426—433)
[15]	Guo X. H., Li S. P., Hou W. G., Han S. H., Hu J. F., Li D. Q., Chem. Res. Chinese Universities, 2003, 19(2), 211—215
[16]	Wong K. N., Khiew P. S., Isa D., Chiu W. S., Mater. Lett., 2014, 128, 97—100
[17]	Editorial Committee of “Determination Methods for Examination of Water and Wastewater” of State Environmental Protection Administration, Determination Methods for Examination of Water and Wastewater, China Environmental Science Press, Beijing, 2002, 258—281
	(国家环境保护总局《水和废水监测分析方法》编委会. 水和废水监测分析方法,北京: 中国环境科学出版社, 2002, 258—281)
[18]	Jung J., Bae S., Lee W., Appl. Catal. B: Environ., 2012, 127, 148—158
[19]	Fan N. W., Li Z. K., Zhao L., Wu N. M., Zhou T., Chem. Eng. J., 2013, 214, 83—90
[20]	David R., Daniel B., Lionel R., J. Hazard. Mater., 2011, 192(2), 507—513
[21]	Fan G.N., Zheng H. B., Han P., Zhao J. L.,Chem. Eng., 2015, (8), 22—24, 30
	(范国宁, 郑红兵, 韩萍, 赵家琳. 化学工程师, 2015, (8), 22—24, 30)
[22]	Gu M., Yang F. Z., Huang L., Yao S. B., Zhou S. M., Acta Phys. Chim. Sin., 2002, 18(11), 973—978
	(辜敏, 杨防祖, 黄令, 姚士冰, 周绍民.物理化学学报, 2002, 18(11), 973—978)
[23]	Ding X. C., Zhang Z., Nonferr. Metal. Soc., 2015, 25(3), 815—823
	(丁辛城, 张震.中国有色金属学报, 2015, 25(3), 815—823)
[24]	Jafari Y., Ghoreishi S. M., Shabani-Nooshabadi M., Synthetic Met., 2016, 217, 220—230
[25]	Huang J. Z., Xu Z., Li H. L., Kang G. H., Wang W. J., Chem. J. Chinese Universities, 2006, 27(5), 909—913
	(黄金昭, 徐征, 李海玲, 亢国虎, 王文静.高等学校化学学报, 2006, 27(5), 909—913)
[26]	Shin H., Jung S., Bae S., Lee W., Kim H., Environ. Sci. Technol., 2014, 48(21), 12768—12774
[27]	Szpyrkowicz L., Daniele S., Radaelli M., Specchia S., Appl. Catal. B: Environ., 2006, 66(1/2), 40—50
[28]	Fernandes A., Santos D., Pacheco M. J., Ciríaco L., Lopes A., Santos D., Pacheco M. J., Ciríaco L., Lopes A., Appl. Catal. B: Environ., 2014, 148/149, 288—294

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Ti_(100-_δ₎Cu_δ(δ=0.02, 0.28, 1.39, 5.65)阴极的制备及电催化还原NO₃^-机理

Preparation and Electro-catalytic Mechanisms for Nitrate Ion Reduction of Ti_(100-_δ₎Cu_δ(δ=0.02, 0.09, 0.28, 1.39, 5.65) Cathodes^†

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