Photocatalytic Activity of Tetrabutyl Ammonium Hydroxide Modified TiO2 Under Visible Light Irradiation†

doi:10.7503/cjcu20140952

Abstract

Abstract:

Tetrabutyl ammonium hydroxide modified TiO₂ photocatalyst(TBAH-TiO₂) was prepared by a sol-gel method and surface modification method with tetrabutyl ammonium hydroxide(TBAH). The structure, crystallite size and energy levels of the photocatalysts were studied by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), transmission electron microscopy(TEM), Fourier transform infrared(FTIR) spectroscopy and surface photovoltaic spectroscopy(SPS). The experimental results of 4-chlorophenol photocatalytic degradation showed that TBAH-TiO₂ exhibited a better photocatalytic activity than TiO₂. Its photocatalytic efficiency is 2.6 and 1.7 times as high as that of pure TiO₂ under visible light and ultraviolet light, respectively. The results reveal that NO_x(x=1, 2 and 3) species that exist on the surface of the TBAH-TiO₂ catalyst introduce the energy level of surface states 0.20 eV above the valence band. This energy level not only makes the catalyst responsible to visible light but also promotes the separation of photogenerated carriers. Thus, the activities under ultraiolet light and visible light irradiations are increased.

Key words: TiO2, Tetrabutyl ammonium hydroxide(TBAH), Photocatalytic activity

CLC Number:

O643
O644

TrendMD:

KUANG Yuanjiang, GU Yao, GUO Limei, WANG Haitao, WANG Enjun, CAO Yaan. Photocatalytic Activity of Tetrabutyl Ammonium Hydroxide Modified TiO₂ Under Visible Light Irradiation^†[J]. Chem. J. Chinese Universities, 2015, 36(6): 1174.

Figures/Tables 11

Fig.1 XRD patterns of TiO2(a) and TBAH-TiO2(b) samples

Table 1 Cell parameters, cell volume, crystallite size and specific surface area of TiO2 and TBAH-TiO2 samples

Sample	Cell parameter/nm		Cell volume/nm³	Crystallite size/nm	S_BET/(m²·g^-1)
Sample	a=b		Cell volume/nm³	Crystallite size/nm	c
TiO₂	0.378474	0.951324	0.1363	10.6	63.84
TBAH-TiO₂	0.378554	0.950304	0.1362	13.4	58.89

Fig.2 TEM(A, B) and HRTEM(C, D) images of TiO2(A, C) and TBAH-TiO2(B, D) samplesInsets of (C) and (D) are fast Fourier transformation(FFT) analysis of square area selected in the corresponding image.

Fig.3 FTIR spectra of TiO2(a) and TBAH-TiO2(b) samplesInset: FTIR spectra in the region of 792—1996 cm-1 of TiO2(a) and TBAH-TiO2(b) samples.

Fig.4 N1s XPS peaks of TBAH-TiO2

Fig.5 SPS spectra(A, B) and UV-Vis absorption spectra(C) of TiO2(A, a) and TBAH-TiO2(B, b) samples

Fig.6 Valence band XPS spectra of TiO2(a) and TBAH-TiO2(b) samples

Fig.7 Comparison of photocatalytic degradation of 4-chlorophenol in the presence of TiO2 and TBAH-TiO2 samples under visible light irradiation(A), ultraviolet light irradiation(B) and photo-degradation of methylene blue under UV light irradiationInset in (C): UV-Vis absorption spectral changes of methylene blue aqueous solution over TBAH-TiO2 at 0, 3, 6, 9, 12 min(from up to down).

Table 2 Photodegradation of 4-chlorophenol under visible light irradiation

Sample	Δc/ $c 0 a$ (%)	10⁵k^b/min^-1	t_1/2/min	Specific photocatalytic activity/(μmol·g^-1·h^-1)
Adsorption^c	2.0
Blank	3.6	7.6	9120.4
TiO₂	15.7	36.0	1946.2	4.3
TBAH-TiO₂	48.1	137.0	505.9	13.5

Table 2 Photodegradation of 4-chlorophenol under visible light irradiation

Sample	Δc/ $c 0 a$ (%)	10⁵k^b/min^-1	t_1/2/min	Specific photocatalytic activity/(μmol·g^-1·h^-1)
Adsorption^c	2.0
Blank	3.6	7.6	9120.4
TiO₂	15.7	36.0	1946.2	4.3
TBAH-TiO₂	48.1	137.0	505.9	13.5

Table 3 Photodegradation of 4-chlorophenol under ultraviolet light irradiation

Sample	Δc/ $c 0 a$ (%)	10⁴k^b/min^-1	t_1/2/min	Specific photocatalytic activity/(μmol·g^-1·h^-1)
Adsorption^c	0
Blank	5.4	9.2	753.4
TiO₂	31.9	64.1	108.2	143
TBAH-TiO₂	55.8	135.9	51.0	250

Table 3 Photodegradation of 4-chlorophenol under ultraviolet light irradiation

Sample	Δc/ $c 0 a$ (%)	10⁴k^b/min^-1	t_1/2/min	Specific photocatalytic activity/(μmol·g^-1·h^-1)
Adsorption^c	0
Blank	5.4	9.2	753.4
TiO₂	31.9	64.1	108.2	143
TBAH-TiO₂	55.8	135.9	51.0	250

Fig.8 Schematic diagram for the alignment of energy levels of TBAH-TiO2A: O2, A-: O2-, D: 4-chlorophenol, D+: CO2 and H2O.

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Photocatalytic Activity of Tetrabutyl Ammonium Hydroxide Modified TiO₂ Under Visible Light Irradiation^†

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