CN106902890B - 一种Cu-BTC/钒酸铋/SWCNTs三元异质结构光催化剂及制备方法和应用 - Google Patents
一种Cu-BTC/钒酸铋/SWCNTs三元异质结构光催化剂及制备方法和应用 Download PDFInfo
- Publication number
- CN106902890B CN106902890B CN201710244062.0A CN201710244062A CN106902890B CN 106902890 B CN106902890 B CN 106902890B CN 201710244062 A CN201710244062 A CN 201710244062A CN 106902890 B CN106902890 B CN 106902890B
- Authority
- CN
- China
- Prior art keywords
- btc
- solution
- bivo
- swcnts
- certain time
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000013148 Cu-BTC MOF Substances 0.000 title claims abstract description 99
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 title claims abstract description 99
- 239000002109 single walled nanotube Substances 0.000 title claims abstract description 74
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 11
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 75
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 7
- 239000000975 dye Substances 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 16
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 9
- 229940043267 rhodamine b Drugs 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
本发明属于复合材料制备的技术领域，特别涉及一种Cu‑BTC/钒酸铋/SWCNTs三元异质结构光催化剂、制备方法及其应用。制备方法是先用简单的水热法分别制备MOFs材料Cu‑BTC以及BiVO4，然后向分散好的BiVO4溶液中加入占其质量0.05~0.2%的PEG800，再将Cu‑BTC溶液逐滴加入到BiVO4溶液中，搅拌一定时间后，再逐滴加入分散好的SWCNTs溶液，再次搅拌一定时间。将得到的悬浊液离心分离，得到的产物在低于60℃的温度下干燥即可得到目标产物。本三元异质结构材料主要应用于选择性吸附、分离及光催化降解有机染料。本发明的制备过程简单易控、操作方便、重复性强，产品具有产率高、产品性能稳定的优点。
Description
技术领域
本发明属于复合材料制备的技术领域，特别涉及一种Cu-BTC/钒酸铋/SWCNTs三元异质结构光催化剂、制备方法及其应用。
背景技术
随着工业的不断发展，环境污染日益严重，而传统的处理工艺需要消耗大量的能源，这给日益枯竭的能源提出严峻的挑战。寻求一种新的具有高效处理污染物的方法是众多研究者共同追求的目标，随即光催化技术应运而生。光催化技术为彻底解决水污染问题提供了新的手段，它在环境污染治理中有广阔的应用新景。
金属有机框架（MOFs）材料可以通过改变中心金属离子与有机配体灵活有效地改变其结构，具有可修饰的孔道表面、可调控的孔径尺寸、超高比表面积（Y. Bai, Y. B.Dou, L. H. Xie, W. Rutledge, J. R. Li, H. C. Zhou, Chem. Soc. Rev. 2016, 45,2327-2367）、超低密度、不溶于常见溶剂的特点，在催化、气体吸附与分离、药物缓释、传感器（H. Wang, X. Z. Yuan, Y. Wu, G. M. Zeng, X. H. Chen, L. J. Leng, H. Li,Appl. Catal. B-Environ. 2015, 174, 445-454; J. J. Zhao, W. T. Nunn, P. C.Lemaire, Y. L. Lin, M. D. Dickey, H. J. Walls, G. W. Peterson, M. D. Losego,G. N. Parsons, J. Am.Chem. Soc. 2015, 137, 13756-13759）等方面都有较好的应用前景。作为MOFs材料家族中的一员，C18H6Cu3O12（Cu-BTC）的有机配体和金属离子或团簇的排列具有明显的方向性，可以形成不同的框架孔隙结构，从而表现出不同的吸附性能、光学性质、电磁学性质等，在吸附和光催化降解有机污染物等方面已有所研究。但是，Cu-BTC对可见光利用率不高且降解反应速率慢，限制了其实际应用。因此需要对Cu-BTC进行修饰，以期改进其光催化降解效果。
作为一类新型无毒、稳定及对可见光具有较强吸收的光催化剂，铋基复合氧化物半导体材料具有独特的电子结构，价带由Bi-6s和O-2p轨道杂化而成。这种结构使其在可见光范围内有较陡峭的吸收边，阴阳离子间的反键作用更有利于空穴的形成与流动，使得光催化反应更容易进行。经文献调研，铋基复合氧化物中的单斜相BiVO4的禁带宽度为2.4eV，它足够高的价带可以实现空穴对有机物的降解，同时其导带位置也有利于光生电子的还原，具有较高的氧化能力，且其价带氧化电位位于2.4eV附近，为其在可见光下降解有机物提供了理论依据。
此外，单壁碳纳米管（缩写为SWCNTs）具有良好的机械性和导电性、高化学稳定性、大表面积以及独特的一维结构（Z. R. Hesabi, N. K. Allam, K. Dahmen, H.Garmestani, M. A. E. Sayed, ACS Appl. Mater. Inter. 2011, 3, 952-955）。
因此，人们期望将Cu-BTC、BiVO4、SWCNTs结合在一起，形成一种吸咐能力强、催化效率高的Cu-BTC/BiVO4/SWCNTs三元异质结构光催化剂，以解决有机染料污染问题。
发明内容
本发明要解决的技术问题是公开一种Cu-BTC/BiVO4/SWCNTs三元异质结构光催化剂及制备方法和应用。该光催化剂吸附能力增强、提高光催化效率、扩展光响应范围，而且有利于回收催化剂，极大地提高了半导体光催化剂的综合性能。该发明的制备过程简单易控、操作方便、重复性强，产品具有产率高、产品性能稳定的优点。
本发明的技术方案是：
先用简单的水热法分别制备MOFs材料Cu-BTC以及BiVO4，然后向分散好的BiVO4溶液中加入占其质量0.05~0.2%的PEG800，再将Cu-BTC溶液逐滴加入到BiVO4溶液中，搅拌一定时间后，再逐滴加入分散好的SWCNTs溶液，再次搅拌一定时间。将得到的悬浊液离心分离，得到的产物在低于60℃的温度下干燥即可得到目标产物。
本发明的有益效果是：
1 、SWCNTs与MOFs及半导体光催化剂BiVO4结合能够增强催化剂的吸附能力、提高光催化效率、扩展光响应范围，而且有利于回收催化剂，极大地提高了半导体光催化剂的综合性能。
2、本发明三元异质结构光催化剂Cu-BTC/BiVO4/SWCNTs，主要应用于选择性吸附、分离及光催化降解有机染料。
3.本发明的制备过程简单易控、操作方便、重复性强，产品具有产率高、产品性能稳定的优点。
附图说明
图1为Cu-BTC、BiVO4、SWCNTs、Cu-BTC/BiVO4、Cu-BTC/BiVO4/5%SW
CNTs、Cu-BTC/BiVO4/10%SWCNTs和Cu-BTC/BiVO4/15%SWCNTs的XRD图。
图2为Cu-BTC、BiVO4、SWCNTs、Cu-BTC/BiVO4、Cu-BTC/BiVO4/5%SW
CNTs、Cu-BTC/BiVO4/10%SWCNTs和Cu-BTC/BiVO4/15%SWCNTs的FT-IR图。
图3为Cu-BTC和Cu-BTC/BiVO4/SWCNTs的PL图。
图4为Cu-BTC、BiVO4、SWCNTs、Cu-BTC/BiVO4、Cu-BTC/BiVO4/5%SW
CNTs、Cu-BTC/BiVO4/10%SWCNTs和Cu-BTC/BiVO4/15%SWCNTs的UV-vis DRS图。
图5为三元异质结构Cu-BTC/BiVO4/15%SWCNTs的SEM图。
图6为三元异质结构Cu-BTC/BiVO4/15%SWCNTs的TEM图。
图7为Cu-BTC、BiVO4、Cu-BTC/BiVO4、Cu-BTC/BiVO4/5%SWCNTs、Cu-BTC/BiVO4/10%SWCNTs、Cu-BTC/BiVO4/15%SWCNTs和Cu-BTC/BiVO4/20%SWCNTs光催化剂降解罗丹明B的光催化降解性能示意图。
具体实施方式
实施例1
（一）Cu-BTC的制备
（1）将6.28 g的三水硝酸铜溶解于45 mL的去离子水中；
（2）将3.0 g的均苯三甲酸溶解于90 mL的乙醇/N,N-二甲基甲酰胺(体积比1:1)的混合溶液中；
（3）将上述两种溶液混合后在室温下搅拌10 min,然后转移到内衬聚四氟乙烯不锈钢反应釜中，在100℃下保温10 h，然后冷却，产物用去离子水和乙醇洗涤数次，再将产物在60℃下干燥10 h，即可得到Cu-BTC晶体粉末。
产物Cu-BTC的XRD、FT-IR、PL和UV-vis DRS谱图分别如图1-4所示。
（二）BiVO4的制备
（1）将2mmol的五水合硝酸铋溶解在3ml 的2mol/L的硝酸溶液中，搅拌3h。
（2）2mmol的NH4VO3固体加入到12ml的去离子水中，在剧烈的搅拌下得到均匀的悬浊液。
（3）将（1）和（2）两种溶液混合，然后在室温下搅拌0.5h，进而用25wt%的氨水调节pH=3，最后将其混合溶液转移到内衬聚四氟乙烯不锈钢反应釜中，150℃下加热24h。将得到的悬浊液用去离子水和无水乙醇洗涤数次，然后在100℃下烘干即可得到BiVO4粉末。
产物BiVO4的XRD、FT-IR、UV-vis DRS谱图分别如图1、2、4所示。
（三）Cu-BTC/BiVO4/5%SWCNTs的制备
（1）将0.015g的SWCNTs分散在无水乙醇中超声分散0.5h。
（2）将0.15g的Cu-BTC放入100ml的去离子水中，搅拌0.5h，将其混合均匀。
（3）将0.15g的BiVO4放入100ml的去离子水中，先搅拌0.5h，然后超声分散0.5h，将其混合均匀。
（4）向分散好的BiVO4溶液中加入0.1g PEG800，再将Cu-BTC溶液逐滴加入到BiVO4溶液中，然后搅拌1h，再逐滴加入分散好的SWCNTs溶液，再次搅拌1h。
（5）将得到的悬浊液离心分离，得到的产物在60℃下干燥即可得到目标产物Cu-BTC/BiVO4/5%SWCNTs。
多种比例的Cu-BTC/BiVO4/SWCNTs的XRD、FT-IR、PL、UV-vis DRS、SEM和TEM谱图分别如图1-6所示。
实施例2
（一）Cu-BTC的制备
（1）将6.28 g的三水硝酸铜溶解于50mL的去离子水中；
（2）将3.0 g的均苯三甲酸溶解于 90mL的乙醇/N,N-二甲基甲酰胺(体积比1:2)的混合溶液中；
（3）将上述两种溶液混合后在室温下搅拌20min,然后转移到内衬聚四氟乙烯不锈钢反应釜中，在80 ℃下保温8 h，然后冷却，产物用去离子水和乙醇洗涤数次，再将产物在55℃下干燥8 h，即可得到Cu-BTC晶体粉末。
（二）BiVO4的制备
（1）将2mmol的五水合硝酸铋溶解在2ml 的2mol/L的硝酸溶液中，搅拌0.5h。
（2）2mmol的NH4VO3固体加入到14ml的去离子水中，在剧烈的搅拌下得到均匀的悬浊液。
（3）将（1）和（2）两种溶液混合，然后在室温下搅拌3h，进而用25wt%的氨水调节pH=2，最后将其混合溶液转移到内衬聚四氟乙烯不锈钢反应釜中，130℃下加热20h。将得到的悬浊液用去离子水和无水乙醇洗涤数次，然后在80℃下烘干即可得到BiVO4粉末。
（三）Cu-BTC/BiVO4/15%SWCNTs的制备
（1）将0.045g的SWCNTs分散在无水乙醇中超声分散1h。
（2）将0.15g的Cu-BTC放入80ml的去离子水中，搅拌0.5h，将其混合均匀。
（3）将0.15g的BiVO4放入80ml的去离子水中，先搅拌0.5h，然后超声分散0.5h，将其混合均匀。
（4）向分散好的BiVO4溶液中加入0.08g PEG800，再将Cu-BTC溶液逐滴加入到BiVO4溶液中，然后搅拌1h，再逐滴加入分散好的SWCNTs溶液，再次搅拌1h。
（5）将得到的悬浊液离心分离，得到的产物在50℃下干燥即可得到目标产物Cu-BTC/BiVO4/15%SWCNTs。
实施例3
在光化学反应仪中进行光催化实验，将20mg的光催化剂放入100ml 浓度为0.0015mmol/L的罗丹明B溶液中，在磁力搅拌的情况下，首先暗反应5分钟，使罗丹明B在光催化剂表面达到吸附平衡状态。然后用300W的氙灯照射用来提供可见光，在氙灯和反应容器之间使用滤光片去除紫外光，每隔10分钟取出4ml的悬浊液，将其离心取上层清液用紫外-可见分光光度计测试罗丹明B溶液的浓度。
不同的光催化剂对罗丹明B的降解性能如图7所示。
实施例4
在光化学反应仪中进行光催化实验，将50mg的光催化剂放入100ml 浓度为0.005mmol/L的罗丹明B溶液中，在磁力搅拌的情况下，首先暗反应5分钟，使罗丹明B在光催化剂表面达到吸附平衡状态。然后用300W的氙灯照射用来提供可见光，在氙灯和反应容器之间使用滤光片去除紫外光，每隔10分钟取出4ml的悬浊液，将其离心取上层清液用紫外-可见分光光度计测试罗丹明B溶液的浓度。
附图详细说明
图1为所制备样品的XRD图。从Cu-BTC/BiVO4、Cu-BTC/BiVO4/5%SWCNTs、Cu-BTC/BiVO4/10%SWCNTs和Cu-BTC/BiVO4/15%SWCNTs的XRD图可以看出，基本符合Cu-BTC和BiVO4的衍射峰，但是从图中观察不到SWCNTs的衍射峰，因为SWCNTs的含量较低，衍射峰太弱，所以观测不到其衍射峰。
图2为所制备样品Cu-BTC、BiVO4、SWCNTs、Cu-BTC/BiVO4、Cu-BTC/BiVO4/5%SWCNTs、Cu-BTC/BiVO4/10%SWCNTs和Cu-BTC/BiVO4/15%SWCNTs的FT-IR图。从图中可以看出，SWCNTs的特征峰（3450 cm-1、1634 cm-1、1375 cm-1、1100 cm-1）在Cu-BTC/BiVO4/5%SWCNTs、Cu-BTC/BiVO4/10%SWCNTs、Cu-BTC/BiVO4/15%SWCNTs的红外谱图中都可以找到，说明SWCNTs负载成功。
图3为所制备样品Cu-BTC和Cu-BTC/BiVO4/SWCNTs的PL谱图。Cu-BTC/BiVO4/SWCNTs的峰值明显低于Cu-BTC的峰值，说明三组分光催化剂的光生电子空穴对的复合几率较低，将具有较好的光催化性能。
图4为所制备样品Cu-BTC、BiVO4、SWCNTs、Cu-BTC/BiVO4、Cu-BTC/BiVO4/5%SWCNTs、Cu-BTC/BiVO4/10%SWCNTs和Cu-BTC/BiVO4/15%SWCNTs的UV-vis DRS谱图。从图中可以看出三组分光催化剂对可见光有较强的吸收，说明可以作为可见光催化剂。
图5为所制备样品Cu-BTC/BiVO4/15%SWCNTs的SEM图，从图中可以看到BiVO4、SWCNTs纳米粒子沉积在不规则形状的Cu-BTC表面，从而形成三元异质结构。
图6为所制备样品Cu-BTC/BiVO4/15%SWCNTs的TEM图,从图中可以看出Cu-BTC、BiVO4、SWCNTs形成了三元异质结构。
图7为所制备的多种光催化剂Cu-BTC、BiVO4、Cu-BTC/BiVO4、Cu-BTC/BiVO4/5%SWCNTs、Cu-BTC/BiVO4/10%SWCNTs、Cu-BTC/BiVO4/15%SWCNTs和Cu-BTC/BiVO4/20%SWCNTs光催化降解罗丹明B的性能示意图，从图中可以观察到单一相光催化剂和两组分光催化剂的光催化降解性能远远低于三元异质结构Cu-BTC/BiVO4/SWCNTs。
Claims (5)
1.一种Cu-BTC/钒酸铋/SWCNTs三元异质结构光催化剂的制备方法，其特征在于：先用简单的水热法分别制备MOFs材料Cu-BTC以及BiVO4，然后向分散好的BiVO4溶液中加入占其质量0.05~0.2%的PEG800，再将Cu-BTC溶液逐滴加入到BiVO4溶液中，搅拌一定时间后，再逐滴加入分散好的SWCNTs溶液，再次搅拌一定时间，将得到的悬浊液离心分离，得到的产物在低于60℃的温度下干燥即可得到目标产物。
2.根据权利要求1所述的一种Cu-BTC/钒酸铋/SWCNTs三元异质结构光催化剂的制备方法，其特征在于:将三水硝酸铜和去离子水以质量比为1:6~9的比例混合均匀，再将均苯三甲酸与体积比为1:1~3的乙醇和N,N-二甲基甲酰胺的混合溶液以质量比为1:25~30的比例混合，然后将两种溶液混合之后在室温下搅拌一定时间至混合均匀，然后转移到内衬聚四氟乙烯不锈钢反应釜中，在80~120 ℃下维持8~12 h，然后冷却，产物用去离子水和无水乙醇洗涤数次，再将产物在低于60 ℃的条件下干燥一定时间，即可得到Cu-BTC晶体粉末。
3.根据权利要求1所述的一种Cu-BTC/钒酸铋/SWCNTs三元异质结构光催化剂的制备方法，其特征在于:
（1）将五水合硝酸铋与2mol/L的HNO3以质量比为2~4:1的比例混合，然后搅拌一定时间至混合均匀；
（2）将NH4VO3固体与去离子水以质量比为1:40~60的比例混合，在剧烈的搅拌下得到均匀的悬浊液；
（3）将上述两种溶液混合，然后室温搅拌一定时间至混合均匀，进而用25wt%的氨水调节pH=2~3，最后将其混合溶液转移到内衬聚四氟乙烯不锈钢反应釜中，120~150℃的条件下加热18~24h；将得到的悬浊液用去离子水和无水乙醇洗涤数次，然后在低于100℃的温度下烘干即可得到BiVO4粉末。
4.根据权利要求1所述的一种Cu-BTC/钒酸铋/SWCNTs三元异质结构光催化剂的制备方法，其特征在于:
（1）将一定量的SWCNTs分散在无水乙醇中，然后超声分散一定时间至分散均匀；
（2）将Cu-BTC粉末与去离子水以质量比为1:400-700的比例混合，搅拌一定时间，将其混合均匀；
（3）将BiVO4粉末与去离子水以质量比为1:400~700的比例混合，先搅拌一定时间至混合均匀，进而再超声分散一定时间至分散均匀；
（4）向分散好的BiVO4溶液中加入占其质量0.05~0.2%的PEG800，再将Cu-BTC溶液逐滴加入到BiVO4溶液中，搅拌一定时间至混合均匀，再逐滴加入分散好的SWCNTs溶液，再次搅拌一定时间至混合均匀；
（5）将得到的悬浊液离心分离，得到的产物在低于60℃的温度下干燥即可得到目标产物Cu-BTC/BiVO4/SWCNTs。
5.根据权利要求1所述的一种Cu-BTC/钒酸铋/SWCNTs三元异质结构光催化剂的制备方法制备的催化剂应用于选性吸附、分离及光催化降解有机染料。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710244062.0A CN106902890B (zh) | 2017-04-14 | 2017-04-14 | 一种Cu-BTC/钒酸铋/SWCNTs三元异质结构光催化剂及制备方法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710244062.0A CN106902890B (zh) | 2017-04-14 | 2017-04-14 | 一种Cu-BTC/钒酸铋/SWCNTs三元异质结构光催化剂及制备方法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106902890A CN106902890A (zh) | 2017-06-30 |
| CN106902890B true CN106902890B (zh) | 2020-05-08 |
Family
ID=59210836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710244062.0A Expired - Fee Related CN106902890B (zh) | 2017-04-14 | 2017-04-14 | 一种Cu-BTC/钒酸铋/SWCNTs三元异质结构光催化剂及制备方法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106902890B (zh) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107597134A (zh) * | 2017-10-19 | 2018-01-19 | 浙江师范大学 | 一种Cu掺杂BiVO4多孔纳米管光催化剂的制备方法 |
| CN109569726B (zh) * | 2018-11-30 | 2021-09-07 | 华纺股份有限公司 | 一种MOFs/CNT光催化剂及制备方法 |
| CN109622062B (zh) * | 2019-01-16 | 2021-06-04 | 南京工程学院 | 一种改性钒酸铋光催化剂及其制备方法 |
| CN109876867A (zh) * | 2019-03-05 | 2019-06-14 | 西北师范大学 | 一种双金属-有机骨架/钒酸铋复合光电阳极材料的制备方法 |
| CN112337510B (zh) * | 2019-08-06 | 2022-04-15 | 吉林师范大学 | 功能化聚噻吩敏化二氧化钛复合光催化剂的制备方法及其在光催化降解有机污染物中的应用 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500356A (zh) * | 2011-11-11 | 2012-06-20 | 东华大学 | 一种碳纳米管-纳米钒酸铋复合光催化剂的制备方法 |
| CN104437466A (zh) * | 2014-12-25 | 2015-03-25 | 东华大学 | 一种碳纳米管复合钒酸铋绿色深度水处理剂的制备方法 |
-
2017
- 2017-04-14 CN CN201710244062.0A patent/CN106902890B/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500356A (zh) * | 2011-11-11 | 2012-06-20 | 东华大学 | 一种碳纳米管-纳米钒酸铋复合光催化剂的制备方法 |
| CN104437466A (zh) * | 2014-12-25 | 2015-03-25 | 东华大学 | 一种碳纳米管复合钒酸铋绿色深度水处理剂的制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| Enhancement in the photo-to-current efficiency by fabrication of CNT-BiVO4 composites;ZHOU Xiaochen等;《RARE METALS》;20110331;第30卷;摘要 * |
| HKUST-1-MOF–BiVO4 hybrid as a new sonophotocatalyst for simultaneous degradation of disulfine blue and rose bengal dyes optimization and statistical modeling;S. Mosleh等;《RSC Advances》;20160608;第6卷;摘要，第2.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106902890A (zh) | 2017-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106902890B (zh) | 一种Cu-BTC/钒酸铋/SWCNTs三元异质结构光催化剂及制备方法和应用 | |
| Wang et al. | Preparation of p–n junction Cu2O/BiVO4 heterogeneous nanostructures with enhanced visible-light photocatalytic activity | |
| CN104399516B (zh) | 一种处理硝基苯酚废水的光催化剂的制备方法、一种硝基苯酚废水的处理方法 | |
| CN104128184B (zh) | 一种漂浮型CoFe2O4/TiO2/漂珠复合光催化剂及其制备方法 | |
| CN104383910B (zh) | 一种颗粒大小可控的钒酸铋/石墨烯复合光催化剂的制法 | |
| Li et al. | Facile synthesis of ZnO/g-C3N4 composites with honeycomb-like structure by H2 bubble templates and their enhanced visible light photocatalytic performance | |
| Lai et al. | Photocatalytic toluene degradation over Bi-decorated TiO2: Promoted O2 supply to catalyst’s surface by metallic Bi | |
| CN103007944A (zh) | 石墨烯基磁性复合可见光催化材料Fe3O4-G-TiO2的制备方法 | |
| CN104941662A (zh) | 一种Ag/BFeO3复合光催化剂的制备方法 | |
| CN105540640A (zh) | 一种花状纳米氧化锌的制备方法 | |
| Wang et al. | One-step synthesis of Bi4Ti3O12/Bi2O3/Bi12TiO20 spherical ternary heterojunctions with enhanced photocatalytic properties via sol-gel method | |
| CN104383909B (zh) | 一种碳包覆的钒酸铋颗粒/石墨烯复合物的可控制备方法 | |
| CN113663732A (zh) | 一种ZIF-67(Co)/空心微球状β-Bi2O3/g-C3N4可见光催化剂 | |
| Zhang et al. | Raspberry-like TiO 2 hollow spheres consisting of small nanocrystals towards efficient NO removal | |
| Zhang et al. | Rhombic TiO2 grown on g-C3N4 nanosheets towards fast charge transfer and enhanced Cr (VI) and NO removal | |
| Quan et al. | Superior performance in visible-light-driven hydrogen evolution reaction of three-dimensionally ordered macroporous SrTiO 3 decorated with Zn x Cd 1− x S | |
| Zhang et al. | Fabrication of metal/semiconductor hybrid Ag/AgInO 2 nanocomposites with enhanced visible-light-driven photocatalytic properties | |
| CN103962160B (zh) | 一种碳基固体酸的芬顿载体及其制备方法和应用 | |
| Deng et al. | Fabrication of In-rich AgInS2 nanoplates and nanotubes by a facile low-temperature co-precipitation strategy and their excellent visible-light photocatalytic mineralization performance | |
| CN110368979B (zh) | 一种管状g-C3N4/CuS/Cu2S纳米复合材料及其制备方法和应用 | |
| CN108745405B (zh) | 氮化碳/氮掺中空介孔碳/三氧化二铋三元z型光催化剂及其制备方法 | |
| CN111939957A (zh) | 一种光催化固氮材料多孔氮化碳纳米纤维/石墨烯的制备方法 | |
| CN111266114A (zh) | 一种金属铁/氧化锌/碳三元纳米复合可见光催化剂及其制备方法和应用 | |
| CN108940343B (zh) | Fe-TiO2纳米管/g-C3N4复合材料及其制备方法和应用 | |
| CN109078644B (zh) | 石墨烯负载Bi-BiOCl-TiO2光催化剂及制法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200508 Termination date: 20210414 |