Visible near-infrared amino phthalocyanine-titanium dioxide photocatalyst: preparation and performance

doi:10.11949/j.issn.0438-1157.20151401

Abstract

Abstract:

An α-TDMACuPc-TiO₂ photocatalyst was prepared through Sol-Gel method using 3,3',3",3"'-tetra-dimethylamino copper(Ⅱ) phthalocyanine (α-TDMACuPc) of a soluble amino phthalocyanine as a sensitizer. The photocatalyst was characterized by ultraviolet-visible spectroscopy (UV-Vis) and X-ray diffraction (XRD). Its photocatalytic performance for the degradation of methyl violet was evaluated. It showed that α-TDMACuPc sensitizer exhibited strong absorption in near-infrared region, and the absorption spectrum of sensitized TiO₂ could be extended to visible near-infrared light region. Besides, the sensitized TiO₂ features rutile structure. Its sensitization by α-TDMACuPc significantly improved the photocatalytic activity of TiO₂ in visible near-infrared light region. The α-TDMACuPc-TiO₂ photocatalyst with 1%(mass) α-TDMACuPc exhibited the highest catalytic activity as well as relatively good stability.

Key words: amino phthalocyanine, sensitization, titanium dioxide, visible near-infrared photocatalyst, absorption, catalysis, degradation

摘要：

以可溶性氨基酞菁3,3',3",3"'-四(二甲氨基)铜酞菁(α-TDMACuPc)为敏化剂,采用溶胶-凝胶法制备了氨基酞菁-二氧化钛(α-TDMACuPc-TiO₂)光催化剂,通过紫外-可见吸收光谱(UV-Vis)、X射线衍射(XRD)对其进行了表征,并通过对甲基紫的光催化降解考察了α-TDMACuPc-TiO₂光催化剂的催化性能。结果表明,α-TDMACuPc在近红外光区有较强的吸收,敏化后的二氧化钛吸收可被拓展至可见-近红外光区,而且二氧化钛呈金红石晶型。α-TDMACuPc敏化后的二氧化钛在可见-近红外光区的催化活性明显提高,在α-TDMACuPc质量分数为1%时催化活性达到最高,而且光催化剂具有较好的稳定性。

关键词: 氨基酞菁, 敏化, 二氧化钛, 可见-近红外光催化剂, 吸收, 催化, 降解

CLC Number:

O643

XU Yanming, ZHAO Ming, LI Jian, REN Qiang, WANG Chenyi. Visible near-infrared amino phthalocyanine-titanium dioxide photocatalyst: preparation and performance[J]. CIESC Journal, 2016, 67(5): 1915-1921.

徐延明, 赵明, 李坚, 任强, 汪称意. 氨基酞菁-二氧化钛可见-近红外光催化剂的制备及其性能[J]. 化工学报, 2016, 67(5): 1915-1921.

References 21

[1]	TONG H, OUYANG S, BI Y, et al. Nano-photocatalytic materials: possibilities and challenges [J]. Adv. Mater., 2012, 24(2): 229-251.
[2]	李晓佩, 陈锋, 张金龙. 酞菁改性的介孔TiO2的制备及其可见光光催化活性 [J]. 催化学报, 2007, 28(3): 229-233. DOI: 10.3321/j.issn:0253-9837.2007.03.010. LI X P, CHEN F, ZHANG J L. Preparation of phthalocyanine-modified mesoporous titania and its visible-light photocatalytic activity [J]. Chin. J. Catal., 2007, 28(3): 229-233. DOI: 10.3321/j.issn: 0253-9837.2007.03.010.
[3]	黄成, 常婷, 张越, 等. 卟啉锡敏化TiO2纳米管的光催化活性和光电性能 [J]. 无机化学学报, 2014, 30(2): 331-336. DOI: 10.11862/CJIC.2014.007. HUANG C, CHANG T, ZHANG Y, et al. Photocatalytic activity and optoelectronic property of porphyrin tin-sensitized TiO2 nanotubes [J]. Chinese J. Inorg. Chem., 2014, 30(2): 331-336. DOI: 10.11862/CJIC. 2014.007.
[4]	夏光志, 茆平, 李燕, 等. Pr3+:Y2SiO5/TiO2上转换复合膜光催化性能 [J]. 化工学报, 2015, 66(4): 1607-1614. DOI: 10.11949/j.issn. 0438-1157.20141606. XIA G Z, MAO P, LI Y, et al. Photocatalytic properties of upconversion composite film Pr3+:Y2SiO5/TiO2 [J]. CIESC Journal, 2015, 66(4): 1607-1614. DOI: 10.11949/j.issn.0438-1157.20141606.
[5]	高岳君, 许宜铭. 氟离子掺杂和吸附对二氧化钛光催化活性的影响 [J]. 物理化学学报, 2012, 28(3): 641-646. DOI: 10.3866/PKU. WHXB201201161. GAO Y J, XU Y M. Effect of fluoride doping and adsorption on the photocatalytic activity of TiO2 [J]. Acta. Phys.-Chim. Sin., 2012, 28(3): 641-646. DOI: 10.3866/PKU.WHXB201201161.
[6]	YIN S, AITA Y, KOMATSU M, et al. Synthesis of excellent visible-light responsive TiO2-xNy photocatalyst by a homogeneous precipitation-solvothermal process [J]. J. Mater. Chem., 2005, 15(6): 674-682.
[7]	水淼, 岳林海, 徐铸德. 几种制备方法的掺铁二氧化钛光催化特性 [J]. 物理化学学报, 2001, 17(3): 282-285. DOI: 10.3866/PKU. WHXB20010321. SHUI M, YUE L H, XU Z D. Photocatalytic activity of iron doping TiO2 prepared by several methods [J]. Acta. Phys. -Chim. Sin., 2001, 17(3): 282-285. DOI: 10.3866/PKU.WHXB20010321.
[8]	TADA H, SUZUKI F, YONEDA S, et al. The effect of nanometre-sized Au particle loading on TiO2 photocatalysed reduction of bis(2-dipyridyl) disulfide to 2-mercaptopyridine by H2O [J]. Phys. Chem. Chem. Phys., 2001, 3(7): 1376-1382.
[9]	LEE J S, CHOI W Y. Effect of platinum deposits on TiO2 on the anoxic photocatalytic degradation pathways of alkylamines in water: dealkylation and N-alkylation [J]. Environ. Sci. Technol., 2004, 38(14): 4026-4033.
[10]	TADA H, TERANISHI K, INUBUSHI Y-i, et al. TiO2 photocatalytic reduction of bis(2-dipyridyl) disulfide to 2-mercaptopyridine by H2O: incorporation effect of nanometer-sized Ag particles [J]. Chem. Commun., 1998, (21): 2345-2346.
[11]	CHERIAN S, WAMSER C C. Adsorption and photoactivity of tetra(4-carboxyphenyl)porphyrin (TCPP) on nanoparticulate TiO2 [J]. J. Phys. Chem. B, 2000, 104(15): 3624-3629.
[12]	BAE E Y, CHOI W Y, PARK J, et al. Effects of surface anchoring groups (carboxylate vs phosphonate) in ruthenium-complex-sensitized TiO2 on visible light reactivity in aqueous suspensions [J]. J. Phys. Chem. B, 2004, 108(37): 14093-14101.
[13]	MELE G, CICCARELLA G, VASAPOLLO G, et al. Photocatalytic degradation of 4-nitrophenol in aqueous suspension by using polycrystalline TiO2 samples impregnated with Cu(Ⅱ)-phthalocyanine [J]. Appl. Catal. B, 2002, 38(4): 309-319.
[14]	郭龙发, 潘海波, 沈水发, 等. CuTSPc/SnO2纳米介孔复合材料的合成及其可见光光催化活性 [J]. 催化学报, 2009, 30(1): 53-59. DOI: 10.3321/j.issn:0253-9837.2009.01.012. GUO L F, PAN H B, SHEN S F, et al. Preparation of nanosized mesoporous CuTSPc/SnO2 and its photocatalytic activity under visible light irradiation [J]. Chin. J. Catal., 2009, 30(1): 53-59. DOI: 10.3321/j.issn:0253-9837.2009.01.012.
[15]	WANG X C, YU J C. Nonaggregated zinc phthalocyanine in mesoporous nanocrystalline TiO2 thin films [J]. Macromol. Rapid Commun., 2004, 25(15): 1414-1418.
[16]	申乾宏, 杨辉, 高基伟. 具有稳定可见光催化活性TiO2薄膜的常温制备 [J]. 无机化学学报, 2007, 23(10): 1758-1762. DOI: 10.3321/j.issn:1001-4861.2007.10.015. SHEN Q H, YANG H, GAO J W. Ambient-temperature preparation of TiO2 films with stable visible-light photocatalytie activity [J]. Chinese J. Inorg. Chem., 2007, 23(10): 1758-1762. DOI: 10.3321/j.issn: 1001-4861.2007.10.015.
[17]	杨辉, 申乾宏, 高基伟. 酞菁敏化混晶TiO2薄膜的低温制备及其对罗丹明B的催化降解 [J]. 催化学报, 2007, 28(12): 1072-1076. DOI: 10.3321/j.issn:0253-9837.2007.12.012. YANG H, SHEN Q H, GAO J W. Low-temperature preparation of phthalocyanine-sensitized mischcrystal TiO2 film and its catalysis for degradation of rhodamine B [J]. Chin. J. Catal., 2007, 28(12): 1072-1076. DOI: 10.3321/j.issn:0253-9837.2007.12.012.
[18]	王智宇, 高春梅, 毛卫平, 等. 酞菁敏化纳米TiO2的水热法原位合成及其可见光催化性能 [J]. 稀有金属材料与工程, 2008, 37(Suppl.2): 468-472. DOI: 10.3321/j.issn:1002-185X.2008.z2.124. WANG Z Y, GAO C M, MAO W P, et al. Copper(Ⅱ) phthalocyanine tetrasulfonate sensitized nanocrystalline TiO2: in-situ hydrothermal synthesis and photocatalysis under visible light [J]. Rare Metal Mat. Eng., 2008, 37(Suppl.2): 468-472. DOI: 10.3321/j.issn: 1002-185X. 2008.z2.124.
[19]	赵明, 李坚, 纪俊玲, 等. 可溶性近红外吸收剂氨基酞菁的合成及应用 [J]. 化工学报, 2015, 66(4): 1577-1584. DOI: 10.11949/j.issn. 0438-1157.20141576. ZHAO M, LI J, JI J L, et al. Synthesis and application of soluble near-infrared absorption amino phthalocyanine dyes [J]. CIESC Journal, 2015, 66(4): 1577-1584. DOI: 10.11949/j.issn.0438-1157. 20141576.
[20]	KLUSON P, DROBEK M, STRASAK T, et al. Sulphonated phthalocyanines as effective oxidation photocatalysts for visible and UV light regions [J]. J. Mol. Catal. A, 2007, 272(1/2): 213-219.
[21]	AGBOOLA B, OZOEMENA K I, NYOKONG T. Comparative efficiency of immobilized non-transition metal phthalocyanine photosensitizers for the visible light transformation of chlorophenols [J]. J. Mol. Catal. A, 2006, 248(1/2): 84-92.