水杨酸和精氨酸改性二氧化钛颗粒的制备及其在油-水界面的光催化反应

doi:10.15541/jim20150423

无机材料学报 ›› 2016, Vol. 31 ›› Issue (4): 413-420.DOI: 10.15541/jim20150423

水杨酸和精氨酸改性二氧化钛颗粒的制备及其在油-水界面的光催化反应

李磊¹, 张巧玲¹, 范红蕾¹, 刘有智¹, 魏冰¹, 冯玉杰²

(1. 中北大学超重力化工过程山西省重点实验室, 太原 030051; 2. 哈尔滨工业大学城市水资源与水环境国家重点实验室, 哈尔滨150090)

收稿日期:2015-09-09 修回日期:2015-11-17 出版日期:2016-04-20 网络出版日期:2016-03-25
作者简介:李磊(1991–), 男, 硕士研究生. E-mail: flytolilei@126.com.cn
基金资助:
城市水资源与水环境国家重点实验室开放基金(QA201401);山西省研究生优秀创新项目(2014301)

Titanium Dioxide Particles Modified by Salicylic Acid and Arginine and Their Photocatalytic Reaction on Oil-Water Interface

LI Lei¹, ZHANG Qiao-Ling¹, FAN Hong-Lei¹, LIU You-Zhi¹, WEI Bing¹, FENG Yu-Jie²

(1. Shanxi Province Key Laboratory of Higee-Oriented Chemical Engineering, North University of China, Taiyuan 030051, China; 2. State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090, China)

Received:2015-09-09 Revised:2015-11-17 Published:2016-04-20 Online:2016-03-25
About author:LI Lei. E-mail: flytolilei@126.com.cn
Supported by:
Open Project of State Key Laboratory of Urban Water Resource and Environment (QA201401);Outstanding Graduate Innovation Project of Shanxi Province(2014301)

摘要/Abstract

摘要：

采用浸渍改性法将水杨酸与精氨酸同时接枝到纳米TiO₂表面制备了水杨酸和精氨酸共改性二氧化钛颗粒(TiO₂-SA/Arg), 并采用傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)、热失重分析(TGA)、紫外-可见光漫反射光谱(UV-Vis DRS)、扫描电子显微镜(SEM)、高倍透射电子显微(HRTEM)、表面接触角测试及粒度分布分析等技术对材料的形貌、结构及性能进行表征, 同时研究了催化剂对硝基苯的吸附性能及在油-水界面的吸附能力。结果表明: 水杨酸和精氨酸分别以螯合和桥连结构稳定修饰到TiO₂表面, 与未改性TiO₂相比, 水杨酸和精氨酸共改性TiO₂疏水性及分散性更好, 对硝基苯的吸附能力更强, 并可在油-水界面稳定吸附形成O/W型Pickering乳液。研究了Pickeing乳液光催化体系对硝基苯的去除能力, 与悬浮体系相比, 改性颗粒稳定的Pickering乳液体系对高浓度硝基苯去除效率较高。

关键词: 表面改性, 表面结构, 光催化, Pickering乳液

Abstract:

Salicylate acid and arginine-modified TiO₂particles (TiO₂-SA/Arg) were successfully fabricated by impregnation approach using salicylate acid and arginine grafted onto the surface of nano-TiO₂. The morphology, structure and properties of modified samples were characterized by means of Fourier-transform infrared spectroscope (FT-IR), X-ray photoelectron spectroscope (XPS), thermogravimetry ansysis (TGA), ultraviolet-visible diffuse reflectance spectroscope (UV-Vis DRS), scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), surface contact angle analysis, and particle size distribution analysis. The nitrobenzene adsorption capacity and the ability to be attracted to the oil-water interface of the modified samples were also confirmed. Results revealed that salicylate acid and arginine were modified to TiO₂ surface by chelation and bridging structure, respectively. The modified TiO₂ had better hydrophobicity, dispersion properties and adsorption capacity of nitrobenzene than the unmodified TiO₂. A stable O/W Pickering emulsion was successfully fabricated via the photocatalyst stably adsorbed to oil-water interface. Nitrobenzene in Pickeing emulsion-based photocatalytic reaction system, stabilized by modified photocatalyst, showed a higher removal rate of high concentrations of nitrobenzene than the suspension system.

Key words: surface modification, surface structure, photocatalysis, Pickering emulsion

中图分类号:

TQ174

李磊, 张巧玲, 范红蕾, 刘有智, 魏冰, 冯玉杰. 水杨酸和精氨酸改性二氧化钛颗粒的制备及其在油-水界面的光催化反应[J]. 无机材料学报, 2016, 31(4): 413-420.

LI Lei, ZHANG Qiao-Ling, FAN Hong-Lei, LIU You-Zhi, WEI Bing, FENG Yu-Jie. Titanium Dioxide Particles Modified by Salicylic Acid and Arginine and Their Photocatalytic Reaction on Oil-Water Interface[J]. Journal of Inorganic Materials, 2016, 31(4): 413-420.

图/表 10

图1 改性前后各物质的傅里叶变换红外光谱

Fig. 1 FT-IR spectra of different samples (a) Arg; (b) SA; (c) TiO2; (d) TiO2-SA/Arg before irradiation; (e) TiO2- SA/Arg after1h irradiation; (f) TiO2-SA/Arg after 3h irradiation; (f) TiO2-SA/Arg after 24 h irradiation

图2 改性后样品的C1s (a)、N1s (b)和O1s (c)的XPS谱图

Fig. 2 C1s (a), N1s (b) and O1s (c) XPS spectra of modified samples

图3 改性后样品的TG曲线

Fig. 3 TG curve of samples after modification

图4 光催化剂的接触角

Fig. 4 Contact angles of photocatalyst (a) TiO2; (b) TiO2-SA/Arg; (c) TiO2-SA/Arg after irradiation

图5 光催化剂的扫描和高倍透射电子显微镜照片

Fig. 5 SEM and HRTEM images of photocatalysts (a,d,g) TiO2; (b,e,h) TiO2-SA/Arg; (c,f,i) TiO2-SA/Arg after irradiation

图6 样品的紫外-可见光漫反射光谱

Fig. 6 UV-Vis diffuse reflectance spectra of samples

图7 水溶液中硝基苯的吸附曲线

Fig. 7 Adsorption isotherms of NB measured in aqueous solutions

图8 TiO2-SA/Arg稳定的Pickeing乳液的稳定性

Fig. 8 Stability of Pickeing emulsion stabilized by TiO2- SA/Arg

图9 光催化降解NB曲线图

Fig. 9 Curves of photocatalytic degradation of NB (a) Blank; (b) TiO2 in suspension; (c) TiO2-SA/Arg in suspension; (d) 2.66wt% TiO2-SA/Arg in emulsion; (e) 9.85wt% TiO2-SA/Arg in emulsion; (f) 5.18wt% TiO2-SA/Arg in emulsion. Inset is the HPLC curves of emulsion

图10 水杨酸和精氨酸共改性TiO2颗粒在水/油界面自组装形成的高效皮克林乳液光催化体系

Fig.10 Schematic of a highly efficient Pickering emulsion- based photocatalytic system formed by self-assembling TiO2 particles co-modified by salicylic acid and arginine at water/oil interface

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水杨酸和精氨酸改性二氧化钛颗粒的制备及其在油-水界面的光催化反应

Titanium Dioxide Particles Modified by Salicylic Acid and Arginine and Their Photocatalytic Reaction on Oil-Water Interface

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