介孔二氧化钛/导电碳毡光电极的制备及光电催化性能

doi:10.7503/cjcu20150105

摘要/Abstract

摘要：

以四氯化钛为无机钛源, 十六烷基三甲基溴化铵为模板剂, 通过水热合成法制得无机物钛前驱体溶液. 以导电碳毡(CCF)为载体, 在超声波辅助下用浸渍提拉法负载钛前驱体, 通过高温煅烧得到介孔二氧化钛/导电碳毡(MPT/CCF)光电极材料, 对样品的结构进行了表征, 并以室内污染物气相苯甲醛为目标降解物, 通过评价不同煅烧温度和不同负载次数下MPT/CCF的光电催化性能优化了MPT/CCF的制备工艺条件, 探讨了催化降解条件(温度、湿度、偏电压)对协同增效机制的影响. 结果表明, 相对于纯介孔二氧化钛(MPT), MPT/CCF具有较小的粒径尺寸、更大的比表面积和较均匀的孔径分布, 这归功于CCF对晶粒生长的抑制作用. 其中负载2次MPT并在500 ℃下煅烧的2-MPT/CCF-500样品具有最高的光电催化活性, 主要是由于其具有完善的晶型、均匀的介孔分布和高浓度的羟基自由基, 并且在重复使用过程中也具有很高的光电催化活性. 最佳的催化条件为温度35 ℃、相对湿度55%、偏电压10 V.

关键词: 介孔二氧化钛, 导电碳毡, 光电催化, 苯甲醛

Abstract:

Based on employing the titanium tetrachloride and hexadecyl trimethyl ammonium bromide as inorganic titanium source and template agent, respectively, an inorganic titanium precursor solution was prepared by hydrothermal method. Mesoporous titania/conductive carbon felt electrode material(MPT/CCF) was obtained by the dip-coating method with the aid of ultrasonic system with CCF as a carrier. The material was characterized by X-ray diffraction(XRD), Raman spectrometry, X-ray photoelectron spectroscopy(XPS), scanning electron microscopy(SEM), transmission electronic microscopy(TEM), Fourier transform infrared spectroscopy(FTIR) and nitrogen adsorption-desorption. By using benzaldehyde gas as the target degradation product, the photoelectrocatalytic performance of MPT/CCF was discussed under ultraviolet light irradiation. And the effects of the catalytic degradation conditions(temperature, humidity, bias voltage) on synergies mechanism were discussed. The results show that the MPT/CCF have smaller particle size, larger specific surface area and uniform pore size distribution in comparsion to pure MPT, due to the inhibitory effect of CCF on grain growth. In addition, 2-MPT/CCF-500 have the highest photoelectrocatalytic activity due to perfect crystal shape, homogeneous mesoporous structure and high concentrations of hydroxyl radicals. Furthermore, it also has the very high photoelectric catalytic activity in the process of repeated use. The optimum catalytic condition is 55% of humidity and 10 V of bias voltage at 35 ℃.

Key words: Mesoporous titanium dioxide, Conductive carbon felt, Photoelectrocatalysis, Benzaldehyde

中图分类号:

O643

TrendMD:

李铭, 李佑稷, 徐鹏, 林晓, 韩文轩. 介孔二氧化钛/导电碳毡光电极的制备及光电催化性能. 高等学校化学学报, 2015, 36(8): 1596.

LI Ming, LI Youji, XU Peng, LIN Xiao, HAN Wenxuan. Preparation and Photoelectrocatalytic Performance of Mesoporous Titanium Dioxide/Conductive Carbon Felt Electrode^†. Chem. J. Chinese Universities, 2015, 36(8): 1596.

图/表 13

Fig.1 Schematic of photoelectrocatalytic degradation apparatus

Fig.2 XRD patterns of MPT/CCF and MPT calcined at different temperatures(A) and different load times(B) (A) a. MPT; b. MPT-200; c. MPT-300; d. 2-MPT/CCF-500; e. 2-MPT/CCF-600. (B) a. CCF; b. 1-MPT/CCF-500; c. 2-MPT/CCF-500; d. 3-MPT/CCF-500; e. 4-MPT/CCF-500.

Table 1 Grain size parameters(nm) of different samples

Sample	Calcination temperature/℃
Sample	400	500	600	700
MPT	16.9	19.1	20.9	27.7
1-MPT/CCF	12.5	13.8	18.7	22.4
2-MPT/CCF	9.9	18.5	20.2	27.1
3-MPT/CCF	12.7	22.3	16.1	27.4
4-MPT/CCF	10.4	19.4	20.5	22.2

Fig.3 Raman spectra of MPT/CCFA: Anatase; R: rutile; D and G: D-band and G-band of CCF. a. 2-MPT/CCF-400; b. 2-MPT/CCF-500; c. 2-MPT/CCF-600; d. 2-MPT/CCF-700.

Fig.4 SEM(A—E) and TEM(F) images of CCF(A) and MPT/CCF(B—F)(B) 1-MPT/CCF-500; (C, F) 2-MPT/CCF-500; (D) 3-MPT/CCF-500; (E) 4-MPT/CCF-500. Inset of (F) is HRTEM image of 2-MPT/CCF-500.

Fig.5 N2 adsorption-desorption isotherms(A) and pore size distributions(B) of the samples

Table 2 Structural parameters of the samples

Sample	TiO₂ content^a(%)	$S BET b$ /(m²·g^-1)	Average pore size^c/nm	O₁_s content^d(%)
Sample	TiO₂ content^a(%)	$S BET b$ /(m²·g^-1)	Average pore size^c/nm	Ti—O	C—O	O—H
MPT	100	103.377	16.628	86.3	13.6	0.1
2-MPT/CCF-400	9.73	139.137	18.153	83.7	16.1	0.2
2-MPT/CCF-500	9.25	144.015	19.360	77.9	10.0	12.1
2-MPT/CCF-600	9.14	119.120	24.843	73.7	19.8	6.5
2-MPT/CCF-700	9.03	72.618	15.656	78.4	18.7	2.9
1-MPT/CCF-500	7.67	39.530	19.134	77.5	22.4	0.1
3-MPT/CCF-500	11.26	41.173	19.107	68.9	26.5	4.6
4-MPT/CCF-500	12.89	66.709	19.152	78.1	20.0	1.9
CCF	0	58.786	15.430

Table 2 Structural parameters of the samples

Sample	TiO₂ content^a(%)	$S BET b$ /(m²·g^-1)	Average pore size^c/nm	O₁_s content^d(%)
Sample	TiO₂ content^a(%)	$S BET b$ /(m²·g^-1)	Average pore size^c/nm	Ti—O	C—O	O—H
MPT	100	103.377	16.628	86.3	13.6	0.1
2-MPT/CCF-400	9.73	139.137	18.153	83.7	16.1	0.2
2-MPT/CCF-500	9.25	144.015	19.360	77.9	10.0	12.1
2-MPT/CCF-600	9.14	119.120	24.843	73.7	19.8	6.5
2-MPT/CCF-700	9.03	72.618	15.656	78.4	18.7	2.9
1-MPT/CCF-500	7.67	39.530	19.134	77.5	22.4	0.1
3-MPT/CCF-500	11.26	41.173	19.107	68.9	26.5	4.6
4-MPT/CCF-500	12.89	66.709	19.152	78.1	20.0	1.9
CCF	0	58.786	15.430

Fig.6 XPS spectra of MPT and MPT/CCF(A,B) Full spectra; (C,D) Ti2p; (E, F) O1s. (A) a. 2-MPT/CCF-400; b. 2-MPT/CCF-500; c. 2-MPT/CCF-600; d. 2-MPT/CCF-700. (B) a. 1-MPT/CCF-500; b. 2-MPT/CCF-500; c. 3-MPT/CCF-500; d. 4-MPT/CCF-500. (C), (E) a. MPT; b. 2-MPT/CCF-400; c. 2-MPT/CCF-500; d. 2-MPT/CCF-600; e. 2-MPT/CCF-700. (D), (F) a. MPT; b. 1-MPT/CCF-500; c. 2-MPT/CCF-500; d. 3-MPT/CCF-500; e. 4-MPT/CCF-500.

Fig.7 FTIR spectra of the samplesa. MPT-500; b. CCF; c. 1-MPT/CCF-500; d. 2-MPT/CCF-500; e. 3-MPT/CCF-500; f. 4-MPT/CCF-500.

Fig.8 Effects of degradation time on degradation rate(A) and ln(c0/c)(B) with different catalysts(A, B) a. CCF; b. 1-MPT/CCF-500; c. 2-MPT/CCF-500; d. 3-MPT/CCF-500; e. 4-MPT/CCF-500.(B) a. y=0.0017x, R2=0.94, t1/2=407.73 min; b. y=0.0067x, R2=0.98, t1/2=103.45 min; c. y=0.0176x, R2=0.98, t1/2=39.38 min; d. y=0.0107x, R2=0.97, t1/2=64.78 min; e. y=0.0086x, R2=0.99, t1/2=80.69 min.

Fig.9 Effects of calcination temperature of the catalyst on degradation rate constantDegradation conditions: 35 ℃; relative humidity:55%; bias voltage: 10 V.

Fig.10 Effect of temperature(A), relative humidity(B) and bias voltage(C) on degradation rate constant

Fig.11 2-MPT/CCF-500 recycling performance

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