CN108997441A - Polyacid Base Metal organic Hybrid Materials and its preparation method and application - Google Patents

Polyacid Base Metal organic Hybrid Materials and its preparation method and application Download PDF

Info

Publication number
CN108997441A
CN108997441A CN201810791035.XA CN201810791035A CN108997441A CN 108997441 A CN108997441 A CN 108997441A CN 201810791035 A CN201810791035 A CN 201810791035A CN 108997441 A CN108997441 A CN 108997441A
Authority
CN
China
Prior art keywords
tpma
hybrid materials
organic hybrid
base metal
metal organic
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.)
Granted
Application number
CN201810791035.XA
Other languages
Chinese (zh)
Other versions
CN108997441B (en
Inventor
谢景力
宫春华
徐昊
曾祥华
张俊勇
郭海洋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Weixiang New Material Co., Ltd
Jiaxing University
Original Assignee
Jiaxing University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiaxing University filed Critical Jiaxing University
Priority to CN201810791035.XA priority Critical patent/CN108997441B/en
Publication of CN108997441A publication Critical patent/CN108997441A/en
Application granted granted Critical
Publication of CN108997441B publication Critical patent/CN108997441B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/01—Organic compounds containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/016—Macromolecular compounds
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • 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
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Hydrology & Water Resources (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses polyacid Base Metal organic Hybrid Materials and its preparation method and application, synthesize the polyacid Base Metal organic Hybrid Materials using evaporation circumfluence method and/or hydrothermal synthesis method by metal salt, ammonium molybdate, organic ligand；Or, ammonium molybdate, organic ligand synthesize the polyacid Base Metal organic Hybrid Materials using evaporation circumfluence method；Wherein, the metal salt is mantoquita or cobalt salt, and the organic ligand is three pyridine methylene amine and/or 1- (tetrazole -5- base) -3- (triazole -1- base) benzene；Three pyridine methylene amine are referred to as TPMA, and 1- (tetrazole -5- base) -3- (triazole -1- base) benzene is referred to as 1,3-ttb.The present invention has the function of catalysis material degradating organic dye.

Description

Polyacid Base Metal organic Hybrid Materials and its preparation method and application
Technical field
The present invention relates to polyacid Base Metal organic Hybrid Materials fields.It is more particularly related to a kind of polyacid base Metal organic Hybrid Materials and its preparation method and application.
Background technique
Polyacid full name is polyoxometallate, is polynuclear complex, wherein the main metal element for constituting polyacid is molybdenum And tungsten.Polyoxometallic acid salt complex is developed so far in domain of inorganic chemistry, has there is more than 200 years history.From first Since polyacid is synthesized discovery, researchers find and have synthesized six kinds of common structures in succession, be respectively as follows: Keggin, Anderson、Silverton、Lindqvist、Dawson、Waugh。
As what polyacid was studied deepens continuously, the selectively high catalytic efficiency of good chemical in a mild condition by It fades in existing.In addition to this, polyacid is broken through in application aspect there are also very much, such as: nanotechnology, medical, biochemistry, material Expect chemistry, Surface Science etc..Polyoxometallate has benefited from its changeable structure, high porosity in the progress of above-mentioned aspect, than Surface area, pore size be adjustable, can after modify and synthesis facilitates.
Summary of the invention
The object of the present invention is to provide polyacid Base Metal organic Hybrid Materials and its preparation method and application.
In order to realize these purposes and other advantages according to the present invention, a kind of polyacid base of containing n-donor ligand induction is provided Metal organic Hybrid Materials,
The polyacid base is synthesized using evaporation circumfluence method and/or hydrothermal synthesis method by metal salt, ammonium molybdate, organic ligand Metal organic Hybrid Materials；Or, ammonium molybdate, organic ligand synthesize the polyacid Base Metal organic hybrid material using evaporation circumfluence method Material；
Wherein, the metal salt is mantoquita or cobalt salt, and the organic ligand is three pyridine methylene amine and/or 1- (four nitrogen Azoles -5- base) -3- (triazole -1- base) benzene；Three pyridine methylene amine are referred to as TPMA, 1- (tetrazole -5- base) -3- (three nitrogen Azoles -1- base) benzene is referred to as 1,3-ttb.
Preferably, the polyacid Base Metal organic Hybrid Materials are MoO3(TPMA)、2[Cu(TPMA)(H2O)]· (Mo8O26)·4H2O、[Co2(TPMA)2(β-Mo8O26)] or [Cu2(TPMA)2(1,3-ttb)(β-Mo8O26)]·2H2O。
Preferably, the MoO3(TPMA) synthetic method are as follows: by 0.1mmolTPMA, 0.1mmol ammonium molybdate, 0.45mmol hydrochloric acid, the mixing of 30mL water are put into container, and evaporation reflux 5 days, cooling at 110 DEG C, obtain yellowish-brown after filtering Turbid solution obtains faint yellow clear solution after filtering, obtain faint yellow cuboid after solution is placed in a beaker standing volatilization Shape crystal to get.
Preferably, 2 [Cu (TPMA) (H2O)]·(Mo8O26)·4H2The synthetic method of O are as follows: by 0.02mmol MoO3 (TPMA), 0.1mmol cupric sulfate pentahydrate and 10mL water are put into the high pressure stainless steel cauldron of polytetrafluoroethyllining lining, use nitric acid Solution adjusts pH to 2.35, and reaction kettle is placed in baking oven after sealing, and 160 DEG C are reacted 3 days, and it is molten that blue clarification is obtained after cooling Liquid, stand volatilization after with light blue rhomboidan to get.
Preferably, [Co2(TPMA)2(β-Mo8O26)] synthetic method are as follows: by 0.1mmol Cobalt(II) nitrate hexahydrate, 0.1mmol TPMA, 0.1mmol 1,3-ttb, 0.1mmol ammonium molybdate and 10mL water are put into the high pressure of polytetrafluoroethyllining lining not It becomes rusty in steel reaction kettle, adjusts pH to 2.52 with nitric acid solution, reaction kettle is placed in baking oven after sealing, 160 DEG C are reacted 3 days, journey Sequence cooling, obtain claret bulk crystals to get.
Preferably, [Cu2(TPMA)2(1,3-ttb)(β-Mo8O26)]·2H2The synthetic method of O are as follows: by 0.1mmol tri- Water copper nitrate, 0.1mmol TPMA, 0.1mmol 1,3-ttb, 0.1mmol ammonium molybdate and 10mL water are put into polytetrafluoroethyllining lining High pressure stainless steel cauldron in, adjust pH to 2.35 with hydrochloric acid solution, reaction kettle be placed in baking oven after sealing, 160 DEG C are anti- Answer 3 days, program cooling, obtain blue diamonds crystal to get.
The present invention also provides the polyacid Base Metal organic Hybrid Materials of containing n-donor ligand induction to degrade as catalysis material The application of organic dyestuff.
The present invention also provides the polyacid Base Metal organic Hybrid Materials of containing n-donor ligand induction to press down as bauxite desilication The application of preparation.
The present invention is include at least the following beneficial effects: utilize hydrothermal synthesis method when into reaction kettle be added metal salt, polyacid, Organic ligand and solvent, evaporation reflux rule are that metal salt, polyacid, organic ligand and solvent are added into round-bottomed flask to heat back Stream.Since polyoxoanion has end oxygen and bridging oxygen atom coordination site, so metal cation can be very good to be coordinated with polyacid. It recycles organic ligand (N in organic ligand, O atom have lone pair electrons) to be easy to metal bonding, obtains abundant knot to extend Structure and high-dimensional compound.
Since copper and cobalt have the chemical valence of flexible coordination mode and malleable, as transition metal ions.Institute For three pyridine methylene amine (TPMA) and 1- (tetrazole -5- base) -3- (triazole -1- base), (1,3-ttb matches benzene the ligand selected Body), select three pyridine methylene amine (TPMA) reasons are as follows: and there are four potential coordination sites by TPMA, there is bridging mode abundant, Possess to obtain the basis of various dimensions and high nuclear structure, and the report of polyacid Base Metal organic Hybrid Materials relevant to TPMA at present Road is fewer；1,3-ttb then has six potential coordination sites, this, which makes it possible to, is easily coordinated with metal, and obtains Geometric configuration abundant, while this ligand contains rigid backbone, so that the structure of the MOFs of synthesis is relatively stable, and 1,3- In ttb ligand there are two nitrogenous functional groups to make its coordination there are it is more a possibility that.For these reasons so TPMA and 1,3-ttb is selected to attempt the novel polyacid Base Metal organic Hybrid Materials of composite structure.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this The research and practice of invention and be understood by the person skilled in the art.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of compound 1；
Fig. 2 is the infrared spectrogram of compound 2；
Fig. 3 is the infrared spectrogram of compound 3；
Fig. 4 is the infrared spectrogram of compound 4；
Fig. 5 is the cyclic voltammetry curve figure of compound 1；
Fig. 6 is the cyclic voltammetry curve figure of compound 3；
Fig. 7 is the cyclic voltammetry curve figure of compound 4；
Fig. 8 is compound 4 to NaNO2Catalytic property；
Fig. 9 is compound 4 to H2O2Catalytic property；
Figure 10 is photocatalysis effect of the compound 1 to methylene blue solution；
Figure 11 is photocatalysis effect of the compound 3 to methylene blue solution；
Figure 12 is photocatalysis effect of the compound 4 to methylene blue solution；
Figure 13 is photocatalysis effect of the compound 1 to rhodamine b solution；
Figure 14 is photocatalysis effect of the compound 3 to rhodamine b solution；
Figure 15 is photocatalysis effect of the compound 4 to rhodamine b solution；
Figure 16 is the X-ray diffractogram of compound 1；
Figure 17 is the X-ray diffractogram of compound 2；
Figure 18 is the X-ray diffractogram of compound 3；
Figure 19 is the X-ray diffractogram of compound 4；
Figure 20 is the molecular structure of compound 1；
Figure 21 is the molecular structure of compound 2；
Figure 22 is the molecular structure of compound 3；
Figure 23 is the one-dimensional chain schematic diagram of compound 3；
Figure 24 is the molecular structure of compound 4；
Figure 25 is the two-dimensional structure figure of compound 2；
Figure 26 is the two-dimensional layer schematic diagram of compound 2.
Specific embodiment
The present invention will be further described in detail below with reference to the embodiments, to enable those skilled in the art referring to specification Text can be implemented accordingly.
TPMA synthetic method is that 2- methylamino pyridine, 2- chloromethyl pyridine hydrochloride, carbonic acid are added in round-bottomed flask Potassium, acetonitrile are heated to reflux three days under the conditions of 80 DEG C, cross column, obtain brown solid to get.
Embodiment 1
Compound 1:MoO3(TPMA) synthesis
MoO3(TPMA) synthetic method are as follows: by 0.1mmolTPMA, 0.1mmol ammonium molybdate, 0.45mmol hydrochloric acid, 30mL Water mixing is put into container, and evaporation reflux 5 days, cooling at 110 DEG C, and yellowish-brown turbid solution is obtained after filtering, after filtering To faint yellow clear solution, solution is placed in a beaker after standing volatilization obtain faint yellow rectangular-shape crystal to get.
Embodiment 2
Compound 2:2 [Cu (TPMA) (H2O)]·(Mo8O26)·4H2O
2[Cu(TPMA)(H2O)]·(Mo8O26)·4H2The synthetic method of O are as follows: by 0.02mmol MoO3(TPMA)、 0.1mmol cupric sulfate pentahydrate and 10mL water are put into the high pressure stainless steel cauldron of polytetrafluoroethyllining lining, with nitric acid solution tune PH to 2.35 is saved, reaction kettle is placed in baking oven after sealing, 160 DEG C are reacted 3 days, and blue clear solution is obtained after cooling, are stood After volatilization with light blue rhomboidan to get.
Embodiment 3
Compound 3:[Co2(TPMA)2(β-Mo8O26)]
[Co2(TPMA)2(β-Mo8O26)] synthetic method are as follows: by 0.1mmol Cobalt(II) nitrate hexahydrate, 0.1mmol TPMA, 0.1mmol 1,3-ttb, 0.1mmol ammonium molybdate and 10mL water are put into the high pressure stainless steel reaction of polytetrafluoroethyllining lining In kettle, pH to 2.52 is adjusted with nitric acid solution, reaction kettle is placed in baking oven after sealing, 160 DEG C are reacted 3 days, and program cooling obtains To claret bulk crystals to get.
Embodiment 4
Compound 4:[Cu2(TPMA)2(1,3-ttb)(β-Mo8O26)]·2H2O
[Cu2(TPMA)2(1,3-ttb)(β-Mo8O26)]·2H2The synthetic method of O are as follows: by 0.1mmol nitrate trihydrate copper, 0.1mmol TPMA, 0.1mmol 1,3-ttb, 0.1mmol ammonium molybdate and 10mL water are put into the high pressure of polytetrafluoroethyllining lining not It becomes rusty in steel reaction kettle, adjusts pH to 2.35 with hydrochloric acid solution, reaction kettle is placed in baking oven after sealing, 160 DEG C are reacted 3 days, journey Sequence cooling, obtain blue diamonds crystal to get.
Related experiment
1, crystal structure determination
As shown in Figure 16~19, the single crystal X-ray diffraction data of compound 1~4 are by Xcalibur, Eos, Gemini Diffractometer measures, and selects size under the microscope and is properly measured with the preferable crystal of mass ratio.Room temperature is maintained at 296K, makes With graphite monochromatised MoK αRay radiation or Cu-K alpha rayCollect diffraction number According to having carried out empirical absorption correction to data using SADABS program.It is solved by direct method (SHELXS) and Olex2 program Out and obtain structured data.All non-hydrogen atom coordinates and anisotropic parameters all carry out complete matrix least square method amendment, It presses theoretical mode computation and determines that O-H atom finds according to difference Fourier first, then sits hydrogen atom in C-H atom position Mark and isotropism parameter carry out complete matrix least square method amendment, and participate in final structure refine.Crystallography diffraction point data It collects and is listed in table 1~3 with the partial parameters of structure refinement.
The crystallographic data and structural parameters of 1 compound 1-4 of table
The main bond distance of 2 compound of table 1,2With bond angle (o)
The main bond distance of 3 compound of table 3,4With bond angle (o)
2, the crystal structure analysis of compound 1-4
Compound 1:MoO3(TPMA) crystal structure
As shown in figure 20, a TPMA ligand, a MoO are contained in compound 13, crystallize in orthorhombic system Pbca, key Valence is calculation shows that all Mo atoms are all+VI oxidation state.In order to be more clear structure chart, all gap hydrones and hydrogen Atom has been omitted, and one hydrogen atom of hydrone is also omitted in compound 2-4 later, is no longer described in detail.
Three N atoms and Mo in compound 1, in Mo1 and TPMA8O26In three O atoms carry out 6 coordination, formed Double trigonal pyramidal structures.There is the N and exposed O atom not being coordinated in structure in TPMA ligand, so being with this crystal Raw material continues to introduce the second metal in the reaction system or ligand is attempted.Bond distance's range of Mo-O key and Mo-N key difference ?With
Compound 2:2 [Cu (TPMA) (H2O)]·(Mo8O26)·4H2O
As shown in figure 21, Cu (II) ion is contained in compound 2, a TPMA ligand, one free [Mo8O26]4-Polyoxoanion (abbreviation Mo8O26) and five hydrones.Belong to monoclinic system C2/2, bond valence sum shows all Mo atom be all+VI oxidation state, all Cu atoms are all+II oxidation state.
As shown in Figure 25,26, in compound 2, Cu1 ion and a TPMA ligand and a water carry out pentacoordinate, Mo8O26For free state, pentahedron structure is formd.Bond distance's range of Cu-O key and Cu-N key exists respectivelyWith
Compound 3:[Co2(TPMA)2(β-Mo8O26)]
As shown in figure 22, two Co (II) ions, two TPMA ligands, a β-[Mo are contained in compound 38O26]4- Polyoxoanion (abbreviation Mo8O26).Belong to monoclinic system P21/c, bond valence sum shows that all Mo atoms are all+VI oxidations State, all Co atoms are all+II oxidation state.
As shown in figure 23, the coordination environment of two Co ions is all identical and symmetrical in compound 3.Co and β-Mo8O26 Two O atoms (Mo-O) and TPMA carry out hexa-coordinate, form the octahedral structure of distortion.β-[Mo8O26]4-Unit passes through altogether It enjoys two shared vertex (O) condensations and forms unlimited [Mo8O27]n 4n-Chain, such eight molybdenums chain are more rare.Co-O key and Co-N Bond distance's range of key exists respectivelyWith
Compound 4:[Cu2(TPMA)2(1,3-ttb)(β-Mo8O26)]·2H2O
As shown in figure 24, two Cu (II) ions, two TPMA ligands are contained in compound 4,1 a, 3-ttb matches Body, a β-[Mo8O26]4-Polyoxoanion (abbreviation Mo8O26) and two hydrones.Belong to anorthic system P-1, bond valence sum table Bright all Mo atoms are all+VI oxidation state, and all Cu atoms are all+II oxidation state.
Cu1 and Cu1 in compound 4, in three Cu (II) ions#Be symmetrical, and coordination structure is identical.In structure Cu and two TPMA, two 1,3-ttb ligands, a β-[Mo8O26]4-Coordination, forms an irregular octahedral structure. Three Cu (II) ions are in same plane and cut on same chain in structure, and by Cu (II) ion and 1,3-ttb ligand is matched Position forms one-dimensional chain structure.Pass through β again-[Mo8O26]4-In oxygen linked with Cu (II) ion coordination and form two-dimensional surface knot Structure.Bond distance's range of Cu-O key and Cu-N key exists respectivelyWith
3, the infrared spectrum analysis of compound 1-4
The infrared infrared spectrogram of compound 1-4 is as shown in figures 1-4.When measuring infrared, with KBr and compound with Tabletting is measured by 640 model FT-IR spectrometer of Varian after the ratio mixing of 100:1.By spectrogram it can be seen that chemical combination Object 1,3343cm-1The characteristic peak at place is the O-H stretching vibration in hydroxyl.1159~1643cm-1The characteristic peak at place is C-N, C=C Stretching vibration.549~1058cm-1The characteristic peak at place can be attributed to [Mo8O26]4-In Mo-O and Mo-O-Mo flexible vibration It is dynamic.Compound 2,3340cm-1The characteristic peak at place can be attributed to the O-H stretching vibration in hydrone and hydroxyl.1153~ 1588cm-1The characteristic peak at place can be attributed to C-N, the stretching vibration of C=C.694~1042cm-1The characteristic peak at place can sum up In [Mo8O26]4-In Mo-O and Mo-O-Mo stretching vibration.Compound 3,3431cm-1The characteristic peak at place is the O-H in hydroxyl Stretching vibration.1152~1602cm-1The characteristic peak at place is the C-N in TPMA ligand, the stretching vibration of C=C.610~1056cm-1The characteristic peak at place can be attributed to [Mo8O26]4-In Mo-O and Mo-O-Mo stretching vibration.Compound 4,3488cm-1Place Characteristic peak can be attributed to the O-H stretching vibration in the hydrone and hydroxyl in compound.1164~1610cm-1The characteristic peak at place For TPMA ligand and 1, the stretching vibration of C-N, C=C and the N-N key in 3-ttb.528-1051cm-1The characteristic peak at place can return It ties in [Mo8O26]4-In Mo-O and Mo-O-Mo stretching vibration.
4, compound 1, the electrochemical property of compound 3 and compound 4
Since compound 2 is unstable in the electrolytic solution, so emphasis has probed into compound 1, compound 3 and compound 4 Electrochemical properties, as shown in Fig. 5~7.In agate mortar after being mixed after first respectively weighing compound 1-4 on a small quantity with graphite powder In be ground to uniformly mixed, be stirred for silicone oil to after sticky, be fitted into glass tube, it is to be measured to be inserted into copper wire after the completion.Detection Electrochemical workstation used is CHI660E electrochemical workstation, and reference electrode used is Ag/AgCl electrode, is to electrode Platinum electrode, electrolyte are sulfuric acid and sodium sulphate mixed solution, and the cyclic voltammetry curve finally measured is as shown in the figure.In 0-500mV Potential range in, there is a pair of of redox peaks (E at 200mV in compound 11/2=(Epa+Epc)/2) it is corresponding be Mo8O26 Reduction process.There are two couples of redox peaks (E at 200mV and at 350mV for compound 31/2=(Epa+Epc)/2) it is corresponding It is Mo8O26Reduction process.There is a pair of of redox peaks (E at 75mV in compound 41/2=(Epa+Epc)/2) corresponding be There is a pair of of redox peaks (E at 200mV in the electron redox process of Cu1/2=(Epa+Epc)/2) corresponding be Mo8O26Reduction process.
On the basis of based on above-mentioned, compound 4 is further studied to NaNO2And H2O2Catalytic Quality Research.As a result As shown in Fig. 8~9.It is analyzed according to the situation of change of figure redox peaks, it can be seen that its redox peaks is with NaNO2 And H2O2Increase constantly move up judge its have catalysis NaNO2And H2O2Property.
5, the photocatalysis performance of compound 1~4
Research for photocatalysis performance has selected methylene blue and rhodamine B as pollutant to study different crystal To the degradation property of dyestuff.Experimental procedure is to weigh a small amount of crystal in beaker, and methylene blue (6mg/L is added-1) or rhodamine B(10mg/L-1), then methylene blue (6mg/L is added into another beaker-1) or rhodamine B (10mg/L-1) it is used as blank pair According to.It places the beaker on the magnetic stirring apparatus under ultraviolet light irradiation, it is ultraviolet to take out a part of reaction solution progress every half an hour Measurement.
As shown in Figure 10~12, all has through ultraviolet determination post analysis figure 1~4 pair of methylene blue of available compound and urge Change degradation, in four compounds, the catalytic efficiency highest of compound 1, especially in preceding half an hour, compound 3 takes second place, The catalytic efficiency of compound 2 and compound 4 is very low.As shown in Figure 13~15, compound 1,3,4 has rhodamine B higher Catalytic efficiency, wherein compound 4 is very significant to the catalytic degradation effect of rhodamine B, and compound 3 takes second place, and compound 1 compares Difference.
6, application of the compound 1 as bauxite desilication inhibitor
Collecting agent uses enuatrol.
Inhibitor 1 uses waterglass.
Inhibitor 2 are made of 3000r/min stirring 15min after waterglass and the 100:3 in mass ratio of compound 1 mixing, Whipping temp is controlled at 20 DEG C.
Al in alumina green ore2O3Content is 40.13%, SiO2Content is 8.66%, the gangue mineral in alumina green ore For quartz, hydromica, chlorite, calcite etc..Alumina green ore is subjected to ore grinding with ball mill, grinding fineness is -0.074mm 70% is accounted for, pulp density 34% carries out one thick two and sweeps process, floating agent dosage: it is Na that regulator, which is added, in one roughing2CO3 1500g/t, inhibitor 600g/t, collecting agent 150g/t, scanning twice is that collecting agent 8g/t is added, and by rough concentrate and is scanned Obtained chats merges cleaning technological flowasheet twice, the results are shown in Table 1.
Table 1
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited In specific details and legend shown and described herein.

Claims (8)

1. the polyacid Base Metal organic Hybrid Materials of containing n-donor ligand induction, which is characterized in that
The polyacid Base Metal is synthesized using evaporation circumfluence method and/or hydrothermal synthesis method by metal salt, ammonium molybdate, organic ligand Organic Hybrid Materials；Or, ammonium molybdate, organic ligand synthesize the polyacid Base Metal organic Hybrid Materials using evaporation circumfluence method；
Wherein, the metal salt is mantoquita or cobalt salt, and the organic ligand is three pyridine methylene amine and/or 1- (tetrazole -5- Base) -3- (triazole -1- base) benzene；Three pyridine methylene amine are referred to as TPMA, 1- (tetrazole -5- base) -3- (triazole -1- Base) benzene is referred to as 1,3-ttb.
2. the polyacid Base Metal organic Hybrid Materials of containing n-donor ligand induction as described in claim 1, which is characterized in that described more Acidic group metal organic Hybrid Materials are MoO3(TPMA)、2[Cu(TPMA)(H2O)]·(Mo8O26)·4H2O、[Co2(TPMA)2(β- Mo8O26)] or [Cu2(TPMA)2(1,3-ttb)(β-Mo8O26)]·2H2O。
3. the polyacid Base Metal organic Hybrid Materials of containing n-donor ligand induction as claimed in claim 2, which is characterized in that described MoO3(TPMA) synthetic method are as follows: 0.1mmol TPMA, 0.1mmol ammonium molybdate, 0.45mmol hydrochloric acid, 30mL water are mixed and put Enter in container, evaporation reflux 5 days, cooling at 110 DEG C, and yellowish-brown turbid solution is obtained after filtering, is obtained after filtering faint yellow Clear solution, by solution be placed in a beaker standing volatilization after obtain faint yellow rectangular-shape crystal to get.
4. the polyacid Base Metal organic Hybrid Materials of containing n-donor ligand induction as claimed in claim 3, which is characterized in that 2 [Cu (TPMA)(H2O)]·(Mo8O26)·4H2The synthetic method of O are as follows: by 0.02mmol MoO3(TPMA), five water sulfuric acid of 0.1mmol Copper and 10mL water are put into the high pressure stainless steel cauldron of polytetrafluoroethyllining lining, adjust pH to 2.35, sealing with nitric acid solution Reaction kettle is placed in baking oven afterwards, 160 DEG C are reacted 3 days, and blue clear solution is obtained after cooling, are obtained after standing volatilization with light blue Rhomboidan to get.
5. the polyacid Base Metal organic Hybrid Materials of containing n-donor ligand induction as claimed in claim 2, which is characterized in that [Co2 (TPMA)2(β-Mo8O26)] synthetic method are as follows: by 0.1mmol Cobalt(II) nitrate hexahydrate, 0.1mmol TPMA, 1 0.1mmol, 3-ttb, 0.1mmol ammonium molybdate and 10mL water are put into the high pressure stainless steel cauldron of polytetrafluoroethyllining lining, use nitric acid solution PH to 2.52 is adjusted, reaction kettle is placed in baking oven after sealing, 160 DEG C are reacted 3 days, and it is blocky brilliant to obtain claret for program cooling Body to get.
6. the polyacid Base Metal organic Hybrid Materials of containing n-donor ligand induction as claimed in claim 2, which is characterized in that [Cu2 (TPMA)2(1,3-ttb)(β-Mo8O26)]·2H2The synthetic method of O are as follows: by 0.1mmol nitrate trihydrate copper, 0.1mmol TPMA, 0.1mmol 1,3-ttb, 0.1mmol ammonium molybdate and 10mL water are put into the high pressure stainless steel cauldron of polytetrafluoroethyllining lining, PH to 2.35 is adjusted with hydrochloric acid solution, reaction kettle is placed in baking oven after sealing, 160 DEG C are reacted 3 days, and program cooling obtains indigo plant Color rhomboidan to get.
7. the polyacid Base Metal organic Hybrid Materials that the containing n-donor ligand as described in claim 3~6 is any induces are as photocatalysis The application of material degradation organic dyestuff.
8. the polyacid Base Metal organic Hybrid Materials of containing n-donor ligand induction as claimed in claim 3 press down as bauxite desilication The application of preparation.
CN201810791035.XA 2018-07-18 2018-07-18 Polyacid-based metal organic hybrid material and preparation method and application thereof Active CN108997441B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810791035.XA CN108997441B (en) 2018-07-18 2018-07-18 Polyacid-based metal organic hybrid material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810791035.XA CN108997441B (en) 2018-07-18 2018-07-18 Polyacid-based metal organic hybrid material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN108997441A true CN108997441A (en) 2018-12-14
CN108997441B CN108997441B (en) 2020-09-22

Family

ID=64600485

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810791035.XA Active CN108997441B (en) 2018-07-18 2018-07-18 Polyacid-based metal organic hybrid material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN108997441B (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109776578A (en) * 2019-03-19 2019-05-21 嘉兴学院 Polyacid base copper complex based on 2- pyridine carboxylic acid and its preparation method and application
CN109833889A (en) * 2019-03-19 2019-06-04 嘉兴学院 The vacant polyacid and its application that transition metal, noble metal connect
CN110078773A (en) * 2019-05-30 2019-08-02 嘉兴学院 A kind of Ge-V-O compound based on aromatic series organic ligand
CN110511395A (en) * 2019-09-04 2019-11-29 吉林化工学院 The Inorganic-Organic Hybrid Material and preparation method and application of polyacid base silver complex
CN111057016A (en) * 2019-12-11 2020-04-24 嘉兴学院 Polyacid compound modified by multidentate bridging organic ligand
CN111450890A (en) * 2020-04-09 2020-07-28 通化师范学院 Mixed isopolymolybdate organic-inorganic hybrid material and preparation method and application thereof
CN112778536A (en) * 2021-01-18 2021-05-11 太原科技大学 Dawson type polyacid-based metal-BBPTZ organic framework material and preparation method and application thereof
CN112900098A (en) * 2021-01-22 2021-06-04 南通大学 Photocatalytic self-cleaning functional cotton fabric and preparation method thereof
CN113929924A (en) * 2021-11-30 2022-01-14 常州大学 Isopolymolybdic acid metal organic framework material for preparing polylactic acid and preparation method
CN114989440A (en) * 2022-01-24 2022-09-02 渤海大学 Polyacid-based supramolecular complex for normal-temperature catalytic oxidation desulfurization of thioether compounds and application thereof
US20230173469A1 (en) * 2021-12-03 2023-06-08 Changzhou University Isopoly-molybdic acid coordination polymer catalyst, method of manufacturing the same and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105153203A (en) * 2015-08-28 2015-12-16 太原科技大学 Isopolymolybdate organic-inorganic hybrid compound and preparation method thereof
CN105237587A (en) * 2015-11-20 2016-01-13 天津工业大学 Mixed metal complex constructed by tris(2-picoline) amine and preparing method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105153203A (en) * 2015-08-28 2015-12-16 太原科技大学 Isopolymolybdate organic-inorganic hybrid compound and preparation method thereof
CN105237587A (en) * 2015-11-20 2016-01-13 天津工业大学 Mixed metal complex constructed by tris(2-picoline) amine and preparing method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHUNHUA GONG等: "A series of organic–inorganic hybrid materials consisting of flexible organic amine modified polyoxomolybdates: synthesis, structures and properties", 《RSC ADV.》 *
LI XU等: "Synthesis, structures, and fluxional behavior of tricarbonylmolybdenum and trioxomolybdenum complexes of tris(2-pyridylmethyl)amine with one free arm", 《CHEMISTRY LETTERS》 *
WEN ZHANG等: "Synthesis, characterization, and photoresponsive properties of a series of Mo(IV)–Cu(II) complexes", 《DALTON TRANSACTIONS》 *
王志芳: "基于钼八异构体的无机有机杂化物的合成及其光降解活性的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109833889A (en) * 2019-03-19 2019-06-04 嘉兴学院 The vacant polyacid and its application that transition metal, noble metal connect
CN109776578A (en) * 2019-03-19 2019-05-21 嘉兴学院 Polyacid base copper complex based on 2- pyridine carboxylic acid and its preparation method and application
CN110078773A (en) * 2019-05-30 2019-08-02 嘉兴学院 A kind of Ge-V-O compound based on aromatic series organic ligand
CN110511395A (en) * 2019-09-04 2019-11-29 吉林化工学院 The Inorganic-Organic Hybrid Material and preparation method and application of polyacid base silver complex
CN111057016B (en) * 2019-12-11 2021-06-25 嘉兴学院 Polyacid compound modified by multidentate bridging organic ligand
CN111057016A (en) * 2019-12-11 2020-04-24 嘉兴学院 Polyacid compound modified by multidentate bridging organic ligand
CN111450890A (en) * 2020-04-09 2020-07-28 通化师范学院 Mixed isopolymolybdate organic-inorganic hybrid material and preparation method and application thereof
CN112778536A (en) * 2021-01-18 2021-05-11 太原科技大学 Dawson type polyacid-based metal-BBPTZ organic framework material and preparation method and application thereof
CN112778536B (en) * 2021-01-18 2022-09-27 太原科技大学 Dawson type polyacid-based metal-BBPTZ organic framework material and preparation method and application thereof
CN112900098A (en) * 2021-01-22 2021-06-04 南通大学 Photocatalytic self-cleaning functional cotton fabric and preparation method thereof
CN113929924A (en) * 2021-11-30 2022-01-14 常州大学 Isopolymolybdic acid metal organic framework material for preparing polylactic acid and preparation method
CN113929924B (en) * 2021-11-30 2022-04-22 常州大学 Isopolymolybdic acid metal organic framework material for preparing polylactic acid and preparation method
US20230173469A1 (en) * 2021-12-03 2023-06-08 Changzhou University Isopoly-molybdic acid coordination polymer catalyst, method of manufacturing the same and application thereof
CN114989440A (en) * 2022-01-24 2022-09-02 渤海大学 Polyacid-based supramolecular complex for normal-temperature catalytic oxidation desulfurization of thioether compounds and application thereof
CN114989440B (en) * 2022-01-24 2022-12-06 渤海大学 Polyacid-based supramolecular complex for normal-temperature catalytic oxidation desulfurization of thioether compounds and application thereof

Also Published As

Publication number Publication date
CN108997441B (en) 2020-09-22

Similar Documents

Publication Publication Date Title
CN108997441A (en) Polyacid Base Metal organic Hybrid Materials and its preparation method and application
Fouad et al. Effects of sono-assisted modified precipitation on the crystallinity, size, morphology, and catalytic applications of hematite (α-Fe2O3) nanoparticles: A comparative study
Casan-Pastor et al. Crystal structures of. alpha.-[CoIIW12O40] 6-and its heteropoly blue 2e reduction product,. alpha.-[CoIIW12O40] 8-. Structural, electronic, and chemical consequences of electron delocalization in a multiatom mixed-valence system
Wang et al. Preparation and optical properties of Eu3+-doped tin oxide nanoparticles
Akhbari et al. Two-dimensional thallium (I) supramolecular polymer constructed from Tl⋯ π interactions: a new precursor for the preparation of thallium (III) oxide with a nano-structural surface
Chen et al. The first purely inorganic polyoxotungstates constructed from dimeric tungstoantimonate-based iron–rare-earth heterometallic fragments
Puzan et al. Structure transformations in nickel oxalate dihydrate NiC2O4· 2H2O and nickel formate dihydrate Ni (HCO2) 2· 2H2O during thermal decomposition
Oestreicher et al. One-pot epoxide-driven synthesis of M2Al (OH) 6Cl· 1.5 H2O layered double hydroxides: Precipitation mechanism and relative stabilities
CN105668589B (en) A kind of preparation method of high-crystallinity SAPO-11 molecular sieves
CN108502897A (en) A kind of photochemistry green synthesis method of Zr doping SBA-15 meso-porous molecular sieve materials
Hwang et al. Eu (III)–BaTiO3 nanoparticles and BaTiO3/TiO2/Ti sheets; photocatalytic and electrocatalytic CO2 reduction
Dyer et al. Insights into the crystal and aggregate structure of Fe3+ oxide/silica co-precipitates
Peng et al. Hydrothermal formation of controllable hexagonal holes and Er2O3/Er2O3-RGO particles on silicon wafers toward superhydrophobic surfaces
Zhou et al. In Situ X‐ray Absorption Spectroscopy/Energy‐Dispersive X‐ray Diffraction Studies on the Hydrothermal Formation of Bi2W1–xMoxO6 Nanomaterials
CN105727922B (en) A kind of Li adulterates SrTiO3The preparation method and product of ten octahedron nanometer particles
Guru et al. Influence of nature of surfactant and precursor salt anion on the microwave assisted synthesis of barium carbonate nanoparticles
Gómez-Morales et al. Bioinspired crystallization, sensitized luminescence and cytocompatibility of citrate-functionalized Ca-substituted europium phosphate monohydrate nanophosphors
Zhang et al. Syntheses, structures, spectroscopic and electrochemical properties of two 1D organic–inorganic CuII–LnIII heterometallic germanotungstates
CN114933710B (en) Aluminum metal organic framework material with MIL-101 structure and preparation method thereof
CN109574526A (en) Method for preparing high-strength gypsum by desulfurization gypsum normal-pressure salt solution method
CN103977758B (en) A kind of preparation method of tantalum doping hydrous antimony pentoxide (HAP) sorbing material
Butuzova et al. Processes of Formation of Iron—Manganese Oxyhydroxides in the Atlantis‐II and Thetis Deeps of the Red Sea
CN109776578A (en) Polyacid base copper complex based on 2- pyridine carboxylic acid and its preparation method and application
Wang et al. Ceramic montmorillonite nanocomposites by electrochemical synthesis
CN102745728A (en) Preparation method of ultrafine alumina

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
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20200622

Address after: 314000 No.2 Building of Photovoltaic Science Park, 1288 Kanghe Road, Xiuzhou District, Jiaxing City, Zhejiang Province

Applicant after: JIAXING University

Applicant after: Anhui Weixiang New Material Co., Ltd

Address before: 314001 Yuexiu South Road, Zhejiang, No. 56, No.

Applicant before: JIAXING University

GR01 Patent grant
GR01 Patent grant