Ag/NH2-MIL-125(Ti)的构建及可见光还原水中Cr(Ⅵ)

doi:10.11944/j.issn.1000-0518.2019.03.180220

摘要/Abstract

摘要：

开发高效、稳定的复合光催化材料是当前环境领域的迫切需求。本文采用溶剂热协同紫外光还原法成功制备了复合光催化材料Ag/NH₂-MIL-125(Ti),并通过X射线衍射(XRD)、扫描电子显微镜(SEM)、能谱(EDS)、紫外-可见漫反射光谱(UV-Vis DRS)及X射线光电子能谱(XPS)等技术手段对其形貌、结构及光学性质进行分析,考察了Ag/NH₂-MIL-125(Ti)可见光(λ≥420 nm)催化还原Cr(Ⅵ)的性能,并优化了催化剂用量、Cr(Ⅵ)浓度、空穴捕捉剂种类及用量等条件。结果表明,在最佳条件下,Ag/NH₂-MIL-125(Ti)具有良好的吸附及光催化还原Cr(Ⅵ)性能,其吸附及光催化还原率是NH₂-MIL-125(Ti)的3.11倍,Ag/NH₂-MIL-125(Ti)特殊的“芝麻饼”形貌以及Ag⁰与NH₂-MIL-125(Ti)之间形成的异质结有助于增强复合材料的光催化还原Cr(Ⅵ)的性能。同时,通过条件实验,提出了光催化还原过程中主要的活性物种以及Cr(Ⅵ) 的还原机理。本研究将为金属有机骨架(MOFs)复合材料在可见光催化环境修复领域的应用提供理论依据和实验参考。

关键词: 金属有机骨架, 银纳米颗粒, 可见光催化, 铬(Ⅵ)还原;

Abstract:

The development of efficient and stable photocatalysts is highly desired and significantly critical for the current environmental field. In this paper, a novel Ag/NH₂-MIL-125(Ti) was successfully prepared by solvothermal coupled with simple ultraviolet(UV) reduction method. The morphology, structure and optical properties of as-prepared samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS), UV-Vis diffuse reflectance spectra(DRS) and X-ray photoelectron spectroscopy(XPS). The photo-reduction performance of obtained catalysts were tested on Cr(Ⅵ) removal in various conditions. Under visible light irradiation(λ≥420 nm), the catalysts dosage, heavy metal concentration, pH and hole scavenger were fully investigated to optimize the best Cr(Ⅵ) reduction parameters. The results indicate that Ag/NH₂-MIL-125(Ti) exhibits excellent adsorption and photo-reduction activities on Cr(Ⅵ), which is 3.11 times higher than that of NH₂-MIL-125(Ti). This special “sesame cakes” and heterojunction formation of Ag/NH₂-MIL-125(Ti) are attributed to enhancing Cr(Ⅵ) catalytic reduction performance. Meanwhile, through the control experiments, the main active species during the photo-reduction route were suggested and the mechanism of the Cr(Ⅵ) reduction was proposed. This study will provide theoretical and experimental guidance for the application of novel metal-organic framework(MOF) composites in the field of environmental remediation.

Key words: metal-organic framework, Ag nanoparticle, visible light photocatalysis, Cr(Ⅵ) reduction;

孙雪娇, 王思琦, 董佳, 吴骑, 刘蕊, 李想, 于世钧, 张治广. Ag/NH₂-MIL-125(Ti)的构建及可见光还原水中Cr(Ⅵ)[J]. 应用化学, 2019, 36(3): 314-323.

SUN Xuejiao, WANG Siqi, DONG Jia, WU Qi, LIU Rui, LI Xiang, YU Shijun, ZHANG Zhiguang. Construction of Ag/NH₂-MIL-125(Ti) Catalyst for Photo-Driven Reduction of Aqueous Cr(Ⅵ) Pollutant[J]. Chinese Journal of Applied Chemistry, 2019, 36(3): 314-323.

参考文献

[1]	Das D P,Parida K M.Solar Light Induced Photocatalytic Degradation of Pollutants over Titania Pillared Zirconium Phosphate and Titanium Phosphate[J]. Catal Surveys Asia,2008,12(3):203-213.
[2]	Barrera-Diaz C E,Lugo-Lugo V,Bilyeu B. A Review of Chemical, Electrochemical and Biological Methods for Aqueous Cr(Ⅵ) Reduction[J] . J Hazard Mater,2012,223/224(2):1-12.
[3]	Xu X R,Li H B,Gu J D.Photocatalytic Reduction of Hexavalent Chromium and Degradation of Di-N-Butyl Phthalate in Aqueous TiO2 Suspensions under Ultraviolet Light Irradiation[J]. Environ Technol,2007,28(9):1055-1061.
[4]	WANG Xuejin, ZHU Xiaping,LAN Lumei.Efficient Removal of Cr(Ⅵ) in Wastewater by Mg/Al Layered Superamolecular Compounds[J]. Chinese J Appl Chem,2017,34(1):98-104(in Chinese). 王雪瑾,朱霞萍,蓝路梅. 镁铝层状超分子化合物去除废水中的六价铬[J]. 应用化学,2017,34(1):583-590.
[5]	Tian Y,Huang L,Zhou X,,et al. Electroreduction of Hexavalent Chromium Using a Polypyrrole-Modified Electrode under Potentiostatic and Potentiodynamic Conditions[J]. J Hazard Mater,2012,225/226(10):15-20.
[6]	Mo X,Yang Z H,Xu H Y,et al. Combination of Cathodic Reduction with Adsorption for Accelerated Removal of Cr(Ⅵ) Through Reticulated Vitreous Carbon Electrodes Modified with Sulfuric Acid-Glycine Co-doped Polyaniline[J]. J Hazard Mater,2015,286:493-502.
[7]	Brodie E L,Joyner D C,Faybishenko B,et al. Microbial Community Response to Addition of Polylactate Compounds to Stimulate Hexavalent Chromium Reduction in Groundwater[J]. Chemosphere,2011,85(4):660-665.
[8]	Daghio M,Espinoza Tofalos A,Leoni B,et al. Bioelectrochemical Btex Removal at Different Voltages:Assessment of the Degradation and Characterization of the Microbial Communities[J]. J Hazard Mater,2018,341:120-127.
[9]	Yoon J,Shim E,Bae S,et al. Application of Immobilized Nanotubular TiO2 Electrode for Photocatalytic Hydrogen Evolution:Reduction of Hexavalent Chromium(Cr(Ⅵ)) in Water[J]. J Hazard Mater,2009,161(2/3):1069-1074.
[10]	Maurin G,Serre C,Cooper A,et al. The New Age of MOFs and of Their Porous-Related Solids[J]. Chem Soc Rev,2017,46(11):3104-3107.
[11]	An Y,Xu B,Liu Y,et al. Photocatalytic Overall Water Splitting over MIL-125(Ti) upon CoPi and Pt Co-catalyst Deposition[J]. Chem Open,2017,6(6):701-705.
[12]	An Y,Liu Y,An P,et al. NiII Coordination to an Al-Based Metal-Organic Framework Made from 2-Aminoterephthalate for Photocatalytic Overall Water Splitting[J]. Angew Chem Int Ed,2017,129(11):3036-3040.
[13]	Shen L,Liang S,Wu W,et al. Multifunctional NH2-Mediated Zirconium Metal-Organic Framework as an Efficient Visible-Light-Driven Photocatalyst for Selective Oxidation of Alcohols and Reduction of Aqueous Cr(Ⅵ)[J]. Dalton Trans,2013,42(37):13649-13657.
[14]	An Y,Li H,Liu Y,et al. Photoelectrical, Photophysical and Photocatalytic Properties of Al-Based MOFs: MIL-53(Al) and MIL-53-NH2(Al)[J]. J Solid State Chem,2016,233:194-198.
[15]	Liang R,Jing F,Shen L,et al. MIL-53(Fe) as a Highly Efficient Bifunctional Photocatalyst for the Simultaneous Reduction of Cr(Ⅵ) and Oxidation of Dyes[J]. J Hazard Mater,2015,287:364-372.
[16]	Shi L,Wang T,Zhang H,et al. An Amine-Functionalized Iron(Ⅲ) Metal-Organic Framework as Efficient Visible-Light Photocatalyst for Cr(Ⅵ) Reduction[J]. Adv Sci,2015,2(3):1500006.
[17]	Murray W A,Barnes W L.Plasmonic Materials[J]. Adv Mater,2007,19(22):3771-3782.
[18]	Murray W A,Suckling J R,Barnes W L.Overlayers on Silver Nanotriangles:Field Confinement and Spectral Position of Localized Surface Plasmon Resonances[J]. Nano Lett,2006,6(8):1772-1777.
[19]	Li H Y,Sun Y J,Cai B,,et al. Hierarchically Z-Scheme Photocatalyst of Ag@AgCl Decorated on BiVO4. Hierarchically Z-Scheme Photocatalyst of Ag@AgCl Decorated on BiVO4(040) with Enhancing Photoelectrochemical and Photocatalytic Performance[J]. Appl Catal B,2015,170/171:206-214.
[20]	Xu H,Xie J,Jia W,et al. The Formation of Visible Light-Driven Ag/Ag2O Photocatalyst with Excellent Property of Photocatalytic Activity and Photocorrosion Inhibition[J]. J Colloid Interface Sci,2018,516:511-521.
[21]	Liu Q X,Zeng C M,Ai L H,et al. Boosting Visible Light Photoreactivity of Photoactive Metal-Organic Framework:Designed Plasmonic Z-Scheme Ag/AgCl@MIL-53-Fe[J]. Appl Catal,B,2018,224:8-45.
[22]	Gao S,Feng T,Feng C,et al. Novel Visible-Light-Responsive Ag/AgCl@MIL-101 Hybrid Materials with Synergistic Photocatalytic Activity[J]. J Colloid Interface Sci,2016,466:284-290.
[23]	Liu J X,Li R,Wang Y F,et al. The Active Roles of ZIF-8 on the Enhanced Visible Photocatalytic Activity of Ag/AgCl:Generation of Superoxide Radical and Adsorption[J]. J Alloys Compd,2017,693:543-549.
[24]	Fu Y H,Sun L,Yang H,et al. Visible-Light-Induced Aerobic Photocatalytic Oxidation of Aromatic Alcohols to Aldehydes over Ni-Doped NH2-MIL-125(Ti)[J]. Appl Catal B,2016,187:212-217.
[25]	Idris A,Hassan N,Rashid R,et al. Kinetic and Regeneration Studies of Photocatalytic Magnetic Separable Beads for Chromium(Ⅵ) Reduction under Sunlight[J]. J Hazard Mater,2011,186(1):629-635.
[26]	Zhou Y S,Chen G,Yu Y G,et al. A New Oxynitride-Based Solid State Z-Scheme Photocatalytic System for Efficient Cr(Ⅵ) Reduction and Water Oxidation[J]. Appl Catal B,2016,183:176-184.
[27]	Wang H,Yuan X,Wu Y,et al. Facile Synthesis of Amino-Functionalized Titanium Metal-Organic Frameworks and Their Superior Visible-Light Photocatalytic Activity for Cr(Ⅵ) Reduction[J]. J Hazard Mater,2015,286:187-194.
[28]	Zhu S R,Liu P F,Wu M K,et al. Enhanced Photocatalytic Performance of BiOBr/ NH2-MIL-125(Ti) Composite for Dye Degradation under Visible Light[J]. Royal Soc Chem,2016,45(43):17521.
[29]	Guo H X,Guo D,Zheng Z S,et al. Visible-Light Photocatalytic Activity of Ag@MIL-125(Ti) Microspheres[J]. Appl Organomet Chem,2015,29(9):18-623.
[30]	Wang A N,Zhou Y J,Wang Z L,et al. Titanium Incorporated with UIO-66(Zr)-Type Metal-Organic Framework(MOF) for Photocatalytic Application[J]. RSC Adv,2016,6(5):3671-3679.
[31]	Qin J N,Wang S B,Wang X C.Visible-Light Reduction CO2 with Dodecahedral Zeolitic Imidazolate Framework ZIF-67 as an Efficient Co-Catalyst[J]. Appl Catal B,2017,209:476-482.
[32]	Vignesh K,Priyanka R,Rajarajan M,et al. Photoreduction of Cr(Ⅵ) in Water Using Bi2O3-ZrO2 Nanocomposite under Visible Light Irradiation[J]. Mater Sci Eng B,2013,178(2):149-157.
[33]	Xu X R,Li H B,Gu J D.Simultaneous Decontamination of Hexavalent Chromium and Methyl Tert-Butyl Ether by UV/TiO2 Process[J]. Chemosphere,2006,63(2):254-260.
[34]	Liang R W,Shen L J,Jing F F,et al. NH2-Mediated Indium Metal-Organic Framework as a Novel Visible-Light-Driven Photocatalyst for Reduction of the Aqueous Cr(Ⅵ)[J]. Appl Catal B,2015,162:245-251.
[35]	Fu Y,Sun D,Chen Y,et al. An Amine-Functionalized Titanium Metal-Organic Framework Photocatalyst with Visible-Light-Induced Activity for CO2 Reduction[J]. Angew Chem Int Ed,2012,124(14):3420-3423.
[36]	Yang Z,Xu X,Liang X,et al. Construction of Heterostructured MIL-125/Ag/g-C3N4 Nanocomposite as an Efficient Bifunctional Visible Light Photocatalyst for the Organic Oxidation and Reduction Reactions[J]. Appl Catal B,2017,205:42-54.
[37]	Divya K S,Reethu V N,Mathew S.Enhanced Photocatalytic Performance of RGO/Ag Nanocomposites Produced via a Facile Microwave Irradiation for the Degradation of Rhodamine B in Aqueous Solution[J]. Appl Surf Sci,2018,444:811-818.

Ag/NH₂-MIL-125(Ti)的构建及可见光还原水中Cr(Ⅵ)

Construction of Ag/NH₂-MIL-125(Ti) Catalyst for Photo-Driven Reduction of Aqueous Cr(Ⅵ) Pollutant

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