CN114805836B - 一种二重互穿结构的多酸基钴有机框架的制备及催化性能 - Google Patents
一种二重互穿结构的多酸基钴有机框架的制备及催化性能 Download PDFInfo
- Publication number
- CN114805836B CN114805836B CN202210478651.6A CN202210478651A CN114805836B CN 114805836 B CN114805836 B CN 114805836B CN 202210478651 A CN202210478651 A CN 202210478651A CN 114805836 B CN114805836 B CN 114805836B
- Authority
- CN
- China
- Prior art keywords
- polyacid
- organic framework
- metal organic
- framework material
- interpenetrating structure
- 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.)
- Active
Links
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 14
- 239000010941 cobalt Substances 0.000 title claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 title abstract description 15
- 239000013384 organic framework Substances 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 74
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 59
- 239000013078 crystal Substances 0.000 claims abstract description 22
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 11
- FBZJHKIVGBZUJB-UHFFFAOYSA-N N1(N=NC=C1)C=1C=NC=C(C=1)N1N=NC=C1 Chemical compound N1(N=NC=C1)C=1C=NC=C(C=1)N1N=NC=C1 FBZJHKIVGBZUJB-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N 4-aminoantipyrine Chemical compound CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 230000009977 dual effect Effects 0.000 description 9
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 238000002211 ultraviolet spectrum Methods 0.000 description 3
- AEEAZFQPYUMBPY-UHFFFAOYSA-N [I].[W] Chemical compound [I].[W] AEEAZFQPYUMBPY-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002678 macrocyclic compounds Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 150000004060 quinone imines Chemical class 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Toxicology (AREA)
- Thermal Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Plasma & Fusion (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种二重互穿结构的多酸基钴金属有机框架的制备及应用。本发明的目的是要解决一些多酸类材料作为催化剂材料在溶液中稳定性差，催化性能不高的问题，提供一种可以提高其催化性能作为比色传感催化剂材料和光催化降解材料的制备方法。本发明的一种二重互穿结构的多酸基金属有机框架材料的化学式为[Co2(btap)4(H2O)4][SiW12O40]，其中btap为3,5‑双(三唑‑1‑基)吡啶。合成方法为将硅钨酸、醋酸钴和btap加入到蒸馏水中搅拌均匀，调节pH值，在温度为160℃下反应4天。本发明可获得一种具有比色传感和可见光催化性能的多酸基二重互穿结构的钴金属有机框架晶体材料。
Description
技术领域
本发明涉及一种二重互穿结构的多酸基钴金属有机框架材料的制备方法及催化性能。
背景技术
酚类化合物是一种常见的水污染物，其稳定性高，可生化性差，即使在很低的浓度下也具有严重的毒性，亟待检测和去除。在众多的酚类化合物检测方法中，比色传感是一种很有前途的方法。在H2O2和催化剂的辅助下，苯酚与无色的4-氨基安替比林(4-AAP)反应生成有色醌亚胺。因此，酚类的含量可以通过监测醌亚胺通过一个简单的比色分析来确定。光催化降解是利用辐射、光催化剂在反应体系中产生的活性极强的自由基，再通过自由基与有机污染物之间的加合、取代、电子转移等过程将污染物全部降解为无机物的过程。此外，光催化被广泛认为是一种环境友好的途径，可以将酚类污染物降解为无害的CO2和H2O产物。
多金属氧酸盐(Polyoxometalates,POMs)(又称多酸)，是具有可逆氧化活性的纳米氧化物团簇，具有结构可修饰、物理化学性质可调变等特点，可作为多种应用的基础材料。这些分子团簇非常稳定，并与各种晶体材料结合表现出强而稳定的相互作用，在比色传感和光催化降解领域有着广泛的应用前景。然而，由于POMs离散的分子团簇结构和高溶解度，POMs通常具有相对较小的表面积(<10m2·g-1)和较差的可循环利用性，使其严重限制了应用。多酸基金属有机框架材料是一类具有丰富的晶体结构并且长程有序的晶态材料，以多酸为预组装前驱体，引入金属有机复合物，构成多酸基金属有机框架材料，具有不溶于水，结构稳定，可循环利用等优点。更重要的是这类材料晶体结构具有可控性，并且结构变化具有多样性，这将为提高催化性能提供重要支持。基于多酸基金属有机框架材料良好的应用前景，我们研究制备出了一种未见文献报道的二重互穿结构的多酸基金属有机框架材料。
发明内容
本发明的目的是要解决多酸类聚合物作为催化材料在溶液中稳定性差，溶解度高的问题。为提高其催化性能，本发明提供一种具有双重互穿结构的多酸基金属有机框架材料的制备方法及性能研究。
为了解决上述技术问题，本发明是通过以下技术方案实现的：
一、制备pH值为2.5～3.0的反应液：将硅钨酸、醋酸钴、3,5-双(三唑-1-基)吡啶加入到蒸馏水中搅拌均匀，然后将该悬浊液的pH值调至2.5～3.0，得到pH值为2.5～3.0反应液；
二、制备一种具有双重互穿结构的多酸基金属有机框架材料：将步骤一中制备的反应液转移到聚四氟乙烯反应釜中，再在温度为160℃下反应4天，反应液温度降至室温后洗涤，得到粉色块状晶体，即一种具有双重互穿的金属有机框架的硅钨酸-钴聚合物，该聚合物的化学式为[Co2(btap)4(H2O)4][SiW12O40]，其中btap为3,5-双(三唑-1-基)吡啶；晶体外观呈粉色块状；晶系为斜方晶系；空间群为Pbca；晶胞参数为 α＝90°，β＝90°，γ＝90°，/>
三、一种具有双重互穿结构的多酸基金属有机框架材料作为比色检测催化剂，能够催化4-AAP和苯酚的显色反应，具有优异的催化性能。一种具有双重互穿结构的多酸基金属有机框架材料作为光催化降解催化剂，能够在可见光下催化降解酚类物质，并具有优异的催化效率。
与现有技术相比，本发明的有益效果是：
一、本发明首次利用3,5-双(三唑-1-基)吡啶有机配体、将其与醋酸钴、硅钨酸通过一步水热合成法成功制备出一种具有双重互穿结构的多酸基金属有机框架材料。单晶X-射线衍射结果表明，本发明制备的双重互穿结构的多酸基金属有机框架材料，其中金属与有机配体相互连接形成具有孔道的三维互穿结构，多酸作为客体分子插入到框架结构。这种独特的结构稳定，可重复利用，保持催化活性。
二、在H2O2，4-AAP和苯酚水溶液中，采用紫外光谱测试比色传感催化性能。在可见光下催化降解酚类物质，采用高效液相色谱测试光催化降解。表明本发明的一种具有双重互穿结构的多酸基金属有机框架材料具有优异的比色传感和光催化性能。其催化性能主要得益于其特殊的结构，这种独特结构能够促进电子转移，可以有效抑制光生电子/空穴对的复合，有效提高的比色传感和光催化降解性能。
附图说明
图1为实施例—一种二重互穿结构的多酸基金属有机框架材料的基本结构单元图。
图2为实施例—一种二重互穿结构的多酸基金属有机框架材料形成过程示意图
图3为实施例—一种二重互穿结构的多酸基金属有机框架材料的红外光谱图。
图4为实施例—一种二重互穿结构的多酸基金属有机框架材料的粉末X-射线衍射图。
图5为实施例—一种二重互穿结构的多酸基金属有机框架材料在H2O2，4-AAP和苯酚溶液中紫外光谱图。
图6为实施例—一种二重互穿结构的多酸基金属有机框架材料可见光催化降解图。
具体实施方式
本发明技术方案不局限于以下所列举具体实施方式，以下所列举具体实施方式仅用于说明本发明而并非受限于本发明实施例所描述的技术方案。本领域的普通技术人员应当理解，仍然可以对本发明进行修改或等同替换，以达到相同的技术效果。只要满足使用需要，都在本发明的保护范围内。
具体实施方式一：本实施方式的一种二重互穿结构的多酸基金属有机框架材料的制备方法是按以下步骤完成的：
一、制备pH值为2.5～3.0的反应液：将0.15g硅钨酸、0.16g醋酸钴和0.04g 3,5-双(三唑-1-基)吡啶加入到蒸馏水中搅拌均匀，然后将该悬浊液的pH值调至2.5～3.0，得到pH值为2.5～3.0反应液；
二、制备一种二重互穿结构的多酸基金属有机框架材料：将步骤一中制备的反应液转移到聚四氟乙烯反应釜中，再在温度为160℃下反应4天，反应液温度降至室温后洗涤，得到绿色块状晶体，即一种二重互穿结构的多酸基金属有机框架材料，该聚合物的化学式为[Co2(btap)4(H2O)4][SiW12O40]，其中btap为3,5-双(三唑-1-基)吡啶；晶体外观分别呈粉色块状；晶系为斜方晶系；空间群为Pbca；晶胞参数为 α＝90°，β＝90°，γ＝90°，/>
三、一种二重互穿结构的多酸基金属有机框架材料的比色传感性能：在离心管中加入4-AAP、苯酚、H2O2和多酸基金属有机框架材料。将混合溶液的体积设定为3mL，室温反应30min后，用紫外-可见分光光度计记录反应溶液在505nm处的吸光度。
四、一种二重互穿结构的多酸基金属有机框架材料的光催化降解性能：取多酸基金属有机框架材料添加到10mg L-1的4-氯苯酚(4-CP)水溶液(50mL)中。然后将催化剂和4-CP悬浮液在黑暗条件下混合60min，以确保吸附-解吸平衡。然后，用500W的碘钨灯照射悬浮液。每隔一定时间收集一小部分悬浮液，用0.22μm滤膜过滤分析。采用高效液相色谱(HPLC)(配有紫外检测器(UV)和C18柱)，记录4-CP的浓度。
具体实施方式二：具体实施方式一步骤一所述的一种二重互穿结构的多酸基金属有机框架材料，所述3,5-双(三唑-1-基)吡啶、醋酸钴、硅钨酸的摩尔比为1:(3.2-3.5):(0.26-0.5)。
具体实施方式三：本实施方式与具体实施方式一的不同点是：步骤一中所述的金属铜盐为氯化钴、硝酸钴或硫酸钴。其他与具体实施方式一至二相同。
具体实施方式四：具体实施方式一步骤一所述的一种二重互穿结构的多酸基金属有机框架材料的制备方法，所述硅钨酸的摩尔数与蒸馏水的体积比为0.62mmol:15mL。
具体实施方式五：本实施方式与具体实施方式一的不同点是：步骤一中将反应液的pH值调至2.5～3.0是使用摩尔浓度均为1mol/L的HCl溶液和NaOH溶液调节的。其它步骤与具体实施方式一至四相同。
具体实施方式六：本实施方式与具体实施方式一的不同点是：步骤二中所述的反应温度为120～160℃，时间为3～5天。其它步骤与具体实施方式一至五相同。
采用以下实施例验证本发明的有益效果：
实施例一：一种二重互穿结构的多酸基金属有机框架材料的制备方法，按以下步骤实现：
一、制备pH值为2.5的反应液：将0.05mmol的硅钨酸、0.62mmol醋酸钴和0.19mmol3,5-双(三唑-1-基)吡啶，均匀分散到15mL蒸馏水中，然后使用1mol/L的HCl溶液和1mol/L的NaOH溶液将反应液的pH值调至2.5，得到pH值为2.5的反应液。
二、将上述制备好的pH值为2.5的反应液转移到25mL聚四氟乙烯反应釜中，再在温度为160℃下反应4天，反应液降至室温后洗涤，得到绿色块状晶体，即为一种二重互穿结构的多酸基金属有机框架材料。
(一)对实施例一制备的一种二重互穿结构的多酸基金属有机框架材料进行结构测定：
结论①X–射线晶体学参数：见表1。
表1材料晶体学参数
aR1＝∑║Fo│─│Fc║/∑│Fo│.b wR2＝{∑[w(Fo 2─Fc 2)2]/∑[w(Fo 2)2]}1/2
结论②X-射线晶体结构描述：X-射线单晶衍射分析表明，
一种二重互穿结构的多酸基金属有机框架材料为斜方晶系，Pbca空间群。该聚合物存在一个独立Co离子,它提供一个六配位模式，由四个btap配体分子中的四个氮原子和两个水分子中的两个氧原子组成。6个钴离子与6个桥接btap分子连接，形成两种扭曲的分子大环。通过将每个Co离子转换为四个连接的节点，并将每个btap收缩为一个臂/弦，从而形成一个具有4个臂/弦并指向4个方向的节点。随后，两种扭曲的分子大环通过共享相邻的钴离子和btap分子融合在一起，形成一个具有66dia拓扑网络的3D框架。更重要的是，即使有这种相互渗透，整个3D网络仍然拥有许多空隙空间，可以容纳纳米大小的聚氧阴离子[SiW12O40]4-作为客体。因此，生成了一种新型的封装POM的三维多孔二重互穿的金属-有机框架材料。
图1为实施例—一种二重互穿结构的多酸基金属有机框架材料的基本结构单元图。
图2为实施例—一种二重互穿结构的多酸基金属有机框架材料形成过程示意图。
(二)对实施例一制备的一种二重互穿结构的多酸基金属有机框架材料[Co2(btap)4(H2O)4][SiW12O40]进行红外光谱表征，得到该硅钨酸金属有机超分子聚合物的红外光谱图，如图3所示。该红外光谱图表明，材料中既含有硅钨酸特征峰又含有有机配体特征峰。
图3为实施例—一种二重互穿结构的多酸基金属有机框架材料的红外光谱图。
(三)对实施例一制备的一种一种二重互穿结构的多酸基金属有机框架材料[Co2(btap)4(H2O)4][SiW12O40]进行粉末X-射线衍射测定，得到一种硅钨酸金属有机框架材料的粉末X-射线衍射谱图，如图4所示。由粉末X-射线衍射谱图知，实验测得的谱图与晶体模拟得到的谱图的峰位置一致，表明该材料的纯度较高。
图4为实施例—一种二重互穿结构的多酸基金属有机框架材料的粉末X-射线衍射图。
(四)对实施例一制备的一种二重互穿结构的多酸基金属有机框架材料[Co2(btap)4(H2O)4][SiW12O40]进行比色传感性能测试。在H2O2的参与下，通过催化4-AAP和苯酚的显色反应，研究了多酸基金属有机框架材料的比色传感性能。在离心管中加入4-AAP(2mgmL-1)、多酸基金属有机框架材料(0.5mg mL-1)、苯酚(6mM)和H2O2(5mM)。将混合溶液的体积设定为3mL，室温反应30min后，用紫外-可见分光光度计记录反应溶液在505nm处的吸光度。
图5为实施例—一种二重互穿结构的多酸基金属有机框架材料在H2O2，4-AAP和苯酚溶液中紫外光谱图。
(五)对实施例一制备的一种二重互穿结构的多酸基金属有机框架材料[Co2(btap)4(H2O)4][SiW12O40]进行光催化降解性能测试。取多酸基金属有机框架材料(30mg)添加到10mg L-1的4-氯苯酚(4-CP)水溶液(50mL)中。然后将催化剂和4-CP悬浮液在黑暗条件下混合60min，以确保吸附-解吸平衡。然后，用500W的碘钨灯照射悬浮液。每隔一定时间收集一小部分悬浮液，用0.22μm滤膜过滤分析。采用高效液相色谱(HPLC)(配有紫外检测器(UV)和C18柱)，记录4-CP的浓度。
图6为实施例—一种二重互穿结构的多酸基金属有机框架材料可见光催化降解图。
综上所述：对实施例一的一种二重互穿结构的多酸基金属有机框架材料是采用水热合成方法成功制备，并将其成功制备比色传感和光催化降解材料，该材料具有良好稳定性导和较高的氧化还原活性，是一种性能优异的催化材料，同时为设计多功能多酸基金属有机框架材料开辟了一条新途径。
Claims (5)
1.一种二重互穿结构的多酸基钴金属有机框架材料，其特征在于：化学式为[Co2(btap)4(H2O)4][SiW12O40]，其中btap为3,5-双(三唑-1-基)吡啶；晶体外观呈粉色块状；晶系为斜方晶系；空间群为Pbca；晶胞参数为 α＝90°，β＝90°，γ＝90°，/>
2.如权利要求1所述的一种二重互穿结构的多酸基钴金属有机框架材料的制备方法，其特征在于：该制备方法是按以下步骤完成的：
一、制备pH值为2.5～3.0的反应液：将0.15g硅钨酸、0.16g醋酸钴和0.04g 3,5-双(三唑-1-基)吡啶加入到蒸馏水中搅拌均匀，然后将所得悬浊液的pH值调至2.5～3.0，得到pH值为2.5～3.0反应液；
二、制备一种二重互穿结构的多酸基钴金属有机框架材料：将步骤一中制备的反应液转移到聚四氟乙烯反应釜中，再在温度为160℃下反应4天，反应液温度降至室温后洗涤，得到粉色块状晶体，即一种二重互穿结构的多酸基钴金属有机框架材料。
3.根据权利要求2所述的一种二重互穿结构的多酸基钴金属有机框架材料的制备方法，其特征在于：步骤一中所述的硅钨酸的摩尔数与蒸馏水的体积比为0.62mmol:15mL。
4.根据权利要求2所述的一种二重互穿结构的多酸基钴金属有机框架材料的制备方法，其特征在于：步骤一中将反应液的pH值调节至2.5～3.0的过程，使用物质的量浓度为1mol/L的HCl溶液和物质的量浓度为1mol/L的NaOH溶液调节。
5.如权利要求1所述的一种二重互穿结构的多酸基钴金属有机框架材料的应用，其特征在于：所述多酸基钴金属有机框架材料在比色传感和光催化降解酚类化合物中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210478651.6A CN114805836B (zh) | 2022-05-05 | 2022-05-05 | 一种二重互穿结构的多酸基钴有机框架的制备及催化性能 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210478651.6A CN114805836B (zh) | 2022-05-05 | 2022-05-05 | 一种二重互穿结构的多酸基钴有机框架的制备及催化性能 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114805836A CN114805836A (zh) | 2022-07-29 |
| CN114805836B true CN114805836B (zh) | 2023-09-08 |
Family
ID=82511092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210478651.6A Active CN114805836B (zh) | 2022-05-05 | 2022-05-05 | 一种二重互穿结构的多酸基钴有机框架的制备及催化性能 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114805836B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116173989B (zh) * | 2023-01-30 | 2024-06-11 | 哈尔滨理工大学 | 一种高1T-MoS2相异金属比色传感器材料的制备及性能研究 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107243361A (zh) * | 2017-07-11 | 2017-10-13 | 东北师范大学 | 一种多酸基金属有机骨架纳米晶催化剂的制备方法和应用 |
| CN109970986A (zh) * | 2019-03-22 | 2019-07-05 | 河南大学 | 一种多酸基CoII配位聚合物及其制备方法和应用 |
| CN110026241A (zh) * | 2019-04-25 | 2019-07-19 | 哈尔滨理工大学 | 一种三维多酸基镍金属-有机晶态催化材料及其制备方法 |
| CN110227555A (zh) * | 2019-07-08 | 2019-09-13 | 哈尔滨理工大学 | 一种多酸基钴金属有机杂化材料制备及光催化应用 |
-
2022
- 2022-05-05 CN CN202210478651.6A patent/CN114805836B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107243361A (zh) * | 2017-07-11 | 2017-10-13 | 东北师范大学 | 一种多酸基金属有机骨架纳米晶催化剂的制备方法和应用 |
| CN109970986A (zh) * | 2019-03-22 | 2019-07-05 | 河南大学 | 一种多酸基CoII配位聚合物及其制备方法和应用 |
| CN110026241A (zh) * | 2019-04-25 | 2019-07-19 | 哈尔滨理工大学 | 一种三维多酸基镍金属-有机晶态催化材料及其制备方法 |
| CN110227555A (zh) * | 2019-07-08 | 2019-09-13 | 哈尔滨理工大学 | 一种多酸基钴金属有机杂化材料制备及光催化应用 |
Non-Patent Citations (1)
| Title |
|---|
| Five isomorphous polyoxometalate-based inorganic-organic hybrid materials comprising 2D metal-organic layers;Yingying Wu等;《Journal of Solid State Chemistry》;第286卷;文献号121302（1-10） * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114805836A (zh) | 2022-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114790298B (zh) | 一种具有互穿结构的多酸基镍金属有机框架比色传感材料 | |
| Meng et al. | Construction of g-C3N4/ZIF-67 photocatalyst with enhanced photocatalytic CO2 reduction activity | |
| Zou et al. | Understanding the modifications and applications of highly stable porous frameworks via UiO-66 | |
| Yu et al. | Enhanced adsorption and visible-light photocatalytic degradation of toluene by CQDs/UiO-66 MOG with hierarchical pores | |
| Abe et al. | A new type of water splitting system composed of two different TiO2 photocatalysts (anatase, rutile) and a IO3−/I− shuttle redox mediator | |
| Liang et al. | The improvement of photocatalytic performance for hydrogen evolution over mesoporous gC 3 N 4 modified with nitrogen defects | |
| CN108997594B (zh) | 一种多酸为模板的多酸基金属有机框架晶体材料 | |
| CN114805836B (zh) | 一种二重互穿结构的多酸基钴有机框架的制备及催化性能 | |
| CN109092365B (zh) | 一种具有三维插层结构的多酸基晶体材料及其制备方法 | |
| CN114316291B (zh) | 一种基于三吡唑配体的金属-有机框架、制备方法及其在有机染料降解的应用 | |
| CN115536860B (zh) | 一种用于电催化和光催化的生物mof材料及其制备方法和应用 | |
| He et al. | UiO-66 with confined dyes for adsorption and visible-light photocatalytic reduction of aqueous Cr (VI) | |
| CN111001400B (zh) | 一种二氧化钛材料及其制备方法 | |
| Ma et al. | Hydrogen bonded metal–organic supramolecule functionalized BiVO4 photoanode for enhanced water oxidation efficiency | |
| Xiao et al. | In-situ regulation of hollow TiO2 with tunable anatase/rutile heterophase homojunction for promoting excellent photocatalytic degradation of pesticides | |
| Lu et al. | Sulfur-doped carbon nitride functionalized PVDF membrane with S⋯ HN bridge induced fast carrier transfer for bifunctional H2O2 and H2 production | |
| Hutchings et al. | Facile synthesis of a porous 3D g-C3N4 photocatalyst for the degradation of organics in shale gas brines | |
| Liu et al. | Antibiotics photodegradation over recycling Z-scheme Bi2Ti2O7@ Bi2S3/PU with super-efficiency: DFT calculation, toxicity of oxytetracycline intermediates and photoactivation mechanism | |
| Li et al. | Understanding the effect of multiple configurations in polymeric carbon nitride for efficient solar-driven hydrogen peroxide photosynthesis | |
| CN114621453B (zh) | 一种双功能吡啶羧酸卟啉配体的锆的金属有机框架材料的制备及应用 | |
| Sun et al. | Sulfur atom-directed metal–ligand synergistic catalysis in zirconium/hafnium-oxo clusters for highly efficient amine oxidation | |
| Sun et al. | Synthesis of a novel Ce-Pr-Fe-O@ C photocatalyst and its photocatalytic activity | |
| CN105562094A (zh) | 微孔过渡金属卤化物可见光催化材料及其制备方法和应用 | |
| CN117258846A (zh) | 漂浮型催化剂和漂浮型催化剂的制备方法及应用 | |
| Ren et al. | Defective UiO-66-NH 2 design with enhanced photocatalytic reduction of Cr (vi) |
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 |