Promoting Effect of Nonmetal Ion Doping and Hierarchically 3D Dendrimeric Architecture for Visible-light-active Mesoporous TiO2 Photocatalyst†

doi:10.7503/cjcu20160573

Abstract

Abstract:

This study aimed at getting insight into the promoting effect of nonmetal ion(N and C) doping and hierarchically 3D dendrimeric architecture on mesoporous TiO₂ based photocatalysts for efficient visible light activated photocatalysis. A comparison of the photocatalytic efficiencies of bare and nonmetal ion doped mesoporous TiO₂ with/without-hierarchically 3D dendrimeric architectures was studied. The resultant photocatalytic performance of TiO₂ based samples was improved greatly by nonmetal doping treatment. Meanwhile, the mesoporous TiO₂ based materials with hierarchically 3D dendrimeric architecture present superior photocatalytic activity compared to the one without hierarchical structure.

Key words: Titania, 3D dendrimental nanostructure, Nonmetal doping, Visible light photocatalyst

CLC Number:

O643
O611

TrendMD:

ZHANG Chunlei, HUANG Danya, SUN Minghui, OUYANG Yiting, WANG Chao, LI Xiaoyun, CHEN Lihua, SU Baolian. Promoting Effect of Nonmetal Ion Doping and Hierarchically 3D Dendrimeric Architecture for Visible-light-active Mesoporous TiO₂ Photocatalyst^†[J]. Chem. J. Chinese Universities, 2017, 38(3): 471.

Figures/Tables 12

Fig.1 High magnification SEM images of the nanoribbons in MT550(A), MTN350(B) and MTC550(C) The insets are corresponding low magnification SEM images of mesoporous TiO2 with hierarchically 3D dendrimeric architecture.

Fig.2 Low magnification TEM images of MT550(A), MTN350(B) and MTC550(C) The insets are corresponding HRTEM images.

Fig.3 XRD patterns of MTs(A), MTNs(B) and MTCs(C) a. MTRT; b. MT350; c. MT450; d. MT550.

Table 1 Textural properties of the synthesized samples

Sample	Crystalline size^a/nm	$S BET b$ /(m²·g^-1)	$D des c$ /nm	$V pore d$ /(cm³·g^-1)	Band-gap energy/eV
Sample	Crystalline size^a/nm	$S BET b$ /(m²·g^-1)	$D des c$ /nm	$V pore d$ /(cm³·g^-1)	E_g1	E_g2
MT350	13.6	76	76	0.20	3.24
MT450	18.2	44	44	0.17	3.23
MT550	27.3	33	33	0.14	3.22
MTN350	10.9	83	83	0.22	3.18	2.40
MTN450	16.6	55	55	0.16	3.19	2.41
MTN550	23.4	35	35	0.12	3.22
MTC350	10.2	197	197	0.25	3.23
MTC450	14.4	87	87	0.26	3.19
MTC550	20.5	64	64	0.23	3.17

Table 1 Textural properties of the synthesized samples

Sample	Crystalline size^a/nm	$S BET b$ /(m²·g^-1)	$D des c$ /nm	$V pore d$ /(cm³·g^-1)	Band-gap energy/eV
Sample	Crystalline size^a/nm	$S BET b$ /(m²·g^-1)	$D des c$ /nm	$V pore d$ /(cm³·g^-1)	E_g1	E_g2
MT350	13.6	76	76	0.20	3.24
MT450	18.2	44	44	0.17	3.23
MT550	27.3	33	33	0.14	3.22
MTN350	10.9	83	83	0.22	3.18	2.40
MTN450	16.6	55	55	0.16	3.19	2.41
MTN550	23.4	35	35	0.12	3.22
MTC350	10.2	197	197	0.25	3.23
MTC450	14.4	87	87	0.26	3.19
MTC550	20.5	64	64	0.23	3.17

Fig.4 N2 adsorption-desorption isotherms(A—C) and pore size distribution(A‘—C‘) of MTs(A, A‘), MTNs(B, B‘) and MTCs(C, C‘)

Fig.5 Ti2p(A) and O1s(B)XPS spectra of MT550(a), MTN350(b) and MTC550(c), N1s XPS spectra of MTN350(C) and C1s XPS spectra of MTC550(D)

Fig.6 Raman spectra of samples in the full length spectra(A) and expanded spectra for the Eg mode at 140.7 cm-1(B)

Fig.7 FTIR spectra of MTN350(a), MTC550(b) and MT550(c) in the range of 4000—500 cm-1(A) and 2500—1000 cm-1(B)

Fig.8 UV-Vis diffuse reflectance spectra of MT550, MTN550, MTC550(A) and MT550, MTN350, MTC550(B) in the range of 350—800 nm

Table 2 Summary of UV-Visible light photocatalytic activity of samples*

Sample	Calcination temperature/℃	Degradation efficiency(%)			Degradation rate, k/min^-1
Sample	Calcination temperature/℃	MT	MTN	MTC	MT	MTN	MTC
With 3D dendrimeric architecture	350	89	91	93	0.055	0.058	0.072
	450	92	95	97	0.061	0.072	0.087
	550	98	99	100	0.120	0.140	0.190
With broken 3D dendrimeric architecture
	550	61	77	86	0.024	0.037	0.049

Fig.9 SEM images of samples with broken 3D dendrimeric architecture (A) MT550; (B) MTN550; (C) MTC550.

Table 3 Summary of visible light photocatalytic activity of samples*

Sample	Calcination temperature/℃	Degradation efficiency(%)		Degradation rate, k/min^-1
Sample	Calcination temperature/℃	MTN	MTC	MTN	MTC
With 3D dendrimeric architecture	350	100	84.7	5.45×10^-2	1.80×10^-2
	450	87.56	88.30	2.00×10^-2	2.12×10^-2
	550	86.63	97.60	1.95×10^-2	3.24×10^-2
Without 3D dendrimeric architecturea	350	45.5		6.1×10^-3
	550		42.5		5.7×10^-3

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Promoting Effect of Nonmetal Ion Doping and Hierarchically 3D Dendrimeric Architecture for Visible-light-active Mesoporous TiO₂ Photocatalyst^†

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