CN112076793B - In-MOF material based on tricarboxylic acid ligand, preparation method and application - Google Patents

In-MOF material based on tricarboxylic acid ligand, preparation method and application Download PDF

Info

Publication number
CN112076793B
CN112076793B CN202010921095.6A CN202010921095A CN112076793B CN 112076793 B CN112076793 B CN 112076793B CN 202010921095 A CN202010921095 A CN 202010921095A CN 112076793 B CN112076793 B CN 112076793B
Authority
CN
China
Prior art keywords
mof material
dmf
mof
ligand
organic ligand
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
Application number
CN202010921095.6A
Other languages
Chinese (zh)
Other versions
CN112076793A (en
Inventor
李庆
蔡信彬
樊增禄
张洛红
武占省
王理明
朱炜
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.)
Xian Polytechnic University
Original Assignee
Xian Polytechnic 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 Xian Polytechnic University filed Critical Xian Polytechnic University
Priority to CN202010921095.6A priority Critical patent/CN112076793B/en
Publication of CN112076793A publication Critical patent/CN112076793A/en
Application granted granted Critical
Publication of CN112076793B publication Critical patent/CN112076793B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22Organic complexes
    • B01J31/2204Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208Oxygen, e.g. acetylacetonates
    • B01J31/2226Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33Electric or magnetic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/40Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00Preparation of carboxylic acid amides
    • C07C231/02Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008Supramolecular polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/33Indium
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/40Organic compounds containing sulfur
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

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)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Toxicology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses an In-MOF material based on a tricarboxylic acid ligand, which has a chemical formula of { [ (CH) 3 ) 2 NH 2 ] 2 (In 3 O 4 L 1 )} n ·(solvent) x Wherein H is 3 L is a triangular organic ligand 4,4' - [ benzene triacyl tri (carbonyl benzene)]-3,3',3 "-trimethyl-tribenzoic acid; the invention also discloses a preparation method of the material, which comprises the following steps: mixing indium nitrate trihydrate with an organic ligand H 3 Dissolving L and hexamethylenetetramine in N, N-dimethylformamide, dropwise adding a concentrated nitric acid solution to adjust the pH value, and reacting under the solvothermal condition to obtain the intermediate. The In-MOF material has the absorption wavelength range of 400-650nm for visible light, has excellent visible light response capability, and shows good photocatalysis when methyl orange In water is subjected to photocatalytic degradationDegradation efficiency, water stability, easy recovery and recyclable performance.

Description

In-MOF material based on tricarboxylic acid ligand, preparation method and application
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to an In-MOF material based on a tricarboxylic acid ligand, a preparation method of the In-MOF material, and application of the In-MOF material.
Background
About 2/3 of people around the world face the problem of water resource shortage, and water quality deterioration caused by water body pollution further aggravates water shortage. According to statistics, nearly tens of thousands tons of dyes are consumed in the world every year, about 15-20% of the dyes are lost in the production and use process, and then hundreds of millions of tons of high-concentration dyeing residues are generated, even if the concentration is diluted to be very low after the dyeing residues are discharged into a water body (<1mg L -1 ) Also can produce high chroma, shield sunlight and destroy aquatic ecosystems. From the molecular view, the dye has a multi-aromatic ring/heterocyclic ring conjugated system with a complex structure, and has the advantages of large molecular weight, high stability and incapability of natural degradation. This has led to a high level of attention from governments, industry and academia around the world. The research on how to solve the serious water pollution problem is a positive response to the national requirements for strengthening ecological environment protection and building ecological environment-friendly countries.
Physical flocculation/adsorption, chemical oxidation and microbial/enzymatic degradation have been used to remove organic contaminants such as dyes from water, but they have problems of time consumption, energy consumption, complicated treatment process and secondary pollution. Photocatalytic degradation has attracted attention because of its high economic efficiency, easy operation, thorough treatment, environment friendship, etc. and the capacity of utilizing solar energy effectively. However, metal oxides such as TiO 2 ZnO and the like are easy to run off and have poor reproducibility in the application process, and the existence energy of a single photocatalystWide band gap, difficult effective utilization of visible light, easy closing of photo-generated electron-hole pairs, low photocurrent quantum yield and degradation rate and the like. Metal sulfides such as CdS, in 2 S 3 The surface energy of the particles is high, and the particles are easy to agglomerate and lose efficacy. Metal-organic frameworks (MOFs) are crystalline porous hybrid materials formed by metal nodes and multidentate organic ligands through coordination bonds. The abundance of diverse metal ions, organic ligands, and the diversity and tunability of their compositions, allows MOFs to provide a way to integrate light trapping and photocatalytic components on a single solid platform; a new strategy is provided for integrating multiple components in a space-constrained manner, thereby enabling their cooperative functionality. The novel MOFs material is developed to be used as a photocatalyst for photocatalytic degradation of dye molecules in water, and a brand new way is provided for remediation of polluted water environments.
Disclosure of Invention
The invention aims to provide an In-MOF material based on a tricarboxylic acid ligand.
It is another object of the present invention to provide a method for preparing the above In-MOF materials based on tricarboxylic acid ligands.
The third purpose of the invention is to provide the application of the In-MOF material based on the tricarboxylic acid ligand In photocatalytic degradation of methyl orange In water.
The first technical scheme adopted by the invention is that the In-MOF material based on the tricarboxylic acid ligand has a chemical formula of { [ (CH) 3 ) 2 NH 2 ] 2 (In 3 O 4 L 1 )} n ·(solvent) x Wherein H is 3 L is a triangular organic ligand 4,4' - [ benzene triacyl tri (carbonyl benzene)]-3,3',3 "-trimethyl-tribenzoic acid, [ (CH) 3 ) 2 NH 2 ]Is protonated dimethylamine molecule, solvent is guest organic solvent molecule;
the crystal structure of the In-MOF material belongs to a monoclinic system, a C2/m space group, and unit cell parameters are as follows:
Figure BDA0002666763410000021
α=90°,β=121.55(3)°,γ=90°。
the second technical scheme adopted by the invention is a preparation method of an In-MOF material based on a tricarboxylic acid ligand, which specifically comprises the following steps:
under the closed condition, indium nitrate trihydrate and organic ligand H 3 L and a template agent hexamethylene tetramine are dissolved In N, N-dimethylformamide, a concentrated nitric acid solution is dripped to adjust the pH value of a reaction system to 4.0-6.0, and the In-MOF material is obtained through reaction under the solvothermal condition.
The present invention is also characterized in that,
the temperature of the solvothermal reaction is 100-120 ℃, and the required reaction time is 72-120 hours.
Indium nitrate trihydrate, organic ligand H 3 The mol ratio of L, hexamethylene tetramine and N, N-dimethylformamide is 2-4:1:0.2-0.5:300-500.
The mass fraction of the concentrated nitric acid solution is 65 percent.
Organic ligand H 3 The preparation method of L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dripping the trimesoyl chloride into the mixed solution obtained in the step a within 15min, dripping triethylamine into the mixed solution obtained in the step a within 10min, reacting in an ice water bath for 3h, and then reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine;
step c, adding distilled water into the reaction liquid under continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, washing and filtering the DMF and the distilled water by using distilled water and methanol in sequence, and drying the obtained white solid to obtain the organic ligand H 3 L;
In the step c, the drying temperature is 70 ℃, and the drying time is 8 hours.
The third technical scheme adopted by the invention is that the In-MOF material can be used for photocatalytic degradation of dye methyl orange In a water body.
The beneficial effect of the invention is that,
the invention adopts late transition metal indium (III) ions and a triangular organic ligand H 3 And L, constructing the In-MOF-based photocatalytic material through coordination self-assembly, wherein the material has an absorption wavelength range of 400-650nm for visible light and has excellent visible light response capability. The In-MOF material has good thermal stability, can keep the stability of the framework at the temperature of 245 ℃, and shows good photocatalytic degradation efficiency, water stability, easy recovery and recyclable performance when methyl orange In water is subjected to photocatalytic degradation. In addition, the preparation method is simple, the reaction condition for applying the photocatalyst degradation is mild, the recovery is easy, and no secondary pollution is caused.
Drawings
FIG. 1 shows [ In ] of the prepared In-organic framework material 33 -O)(O 2 C-) 6 (H 2 O) 3 ]Secondary structural units (central metal indium (III) and oxygen atoms are labeled in the figure, carbon atoms are not labeled);
FIG. 2 is a diagram showing the coordination environment of the prepared In-organic framework material (the central metal indium (III) and oxygen and nitrogen atoms are labeled In the figure, and carbon atoms are not labeled);
FIG. 3 is a three-dimensional block diagram of one of the mononets of the prepared In-MOF material;
FIG. 4 is a final three-dimensional structure diagram formed by mutually interpenetrating and nesting two identical three-dimensional monoweb structures of the prepared In-MOF material;
FIG. 5 is a graph of the thermal weight loss of the prepared In-MOF material;
FIG. 6 is an infrared spectrum of the prepared In-MOF material;
FIG. 7 is a simulated X-ray powder diffraction pattern of a single crystal and a real test X-ray powder diffraction pattern of a bulk crystal sample of the prepared In-MOF material;
FIG. 8 is a scanning electron micrograph of a prepared In-MOF material;
FIG. 9 is a UV-visible diffuse reflectance spectrum of the prepared In-MOF material;
FIG. 10 is a graph of UV-VIS absorption spectra of methyl orange liquid in water at various concentrations;
FIG. 11 is a standard curve of absorbance Y of the UV-VIS absorption spectrum of methyl orange liquid at different concentrations in water with corresponding concentration X;
FIG. 12 is a graph of UV-VIS absorption spectrum of an aqueous solution of methyl orange with an initial concentration of 47.54mg/L in water when the material is used for photocatalytic degradation;
FIG. 13 is a graph showing the concentration ratio C/C of the UV-VIS spectrum of the methyl orange liquid in FIG. 12 0 Graph (C) against time t 0 Initial concentration, C real-time concentration);
FIG. 14 is a graph showing the concentration ratio C/C of the UV-VIS spectrum of the methyl orange liquid in FIG. 12 0 A plot of the log value of (d) versus time t;
FIG. 15 is a graph of the photocatalytic degradation efficiency of the prepared material in 5 consecutive cycles of photocatalytic degradation of 47.54mg/L of methyl orange in water.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to an In-MOF material based on a tricarboxylic acid ligand, which has a chemical formula of { [ (CH) 3 ) 2 NH 2 ] 2 (In 3 O 4 L 1 )} n ·(solvent) x Wherein H is 3 L is a triangular organic ligand 4,4' - [ benzene triacyl tri (carbonyl benzene)]-3,3',3 "-trimethyl-tribenzoic acid, [ (CH) 3 ) 2 NH 2 ]The compound is a protonated dimethylamine molecule, solvent is a guest organic solvent molecule, n represents the infinite alternative arrangement of the internal components of the compound into the chemical simple formula, and x represents the number of disordered organic solvent molecules In-MOF pore channels/cavities; triangular organic ligand H 3 The molecular structural formula of L is as follows:
Figure BDA0002666763410000061
from the construction of a space framework structure, the crystal structure of the solid In-MOF material belongs to a monoclinic system, a C2/m space group, and unit cell parameters are as follows:
Figure BDA0002666763410000062
Figure BDA0002666763410000063
α=90°,β=121.55(3)°,γ=90°。
in the In-MOF material, 1 In 3+ Metal centre with 6H from deprotonation 3 L carboxyl groups of the organic ligand, 3 from H 2 O atom and 1. Mu. Of O molecule 3 Coordination of the-O/OH atoms to form a trimetallic-centered, hexa-linked [ In ] 33 -O)(O 2 C-) 6 (H 2 O) 3 ]Anionic secondary building blocks of deprotonated H 3 The L ligands are further connected to construct a three-dimensional space network structure, and two completely same three-dimensional network structures are further mutually interpenetrated and nested to form a final three-dimensional framework structure of the In-MOF.
The In-MOF material can be used for carrying out photocatalytic degradation on a dye methyl orange In a water body. The application of the In-MOF material as a photocatalyst In degrading methyl orange In water. The method comprises the following specific steps: pouring the dye solution containing methyl orange into a quartz tube reactor, adding In-MOF material, continuously stirring for 1-3h In a dark box under the condition of light isolation to ensure that the dye and the catalyst reach adsorption-desorption balance, and then continuously stirring for 20-120min under the irradiation of a 300W xenon lamp until the photocatalytic degradation is completed.
More preferably, the concentration of methyl orange In the dye aqueous solution is controlled to be 0.5-52mg/L, and 5-20mg of In-MOF-based photocatalyst is added into 60mL of dye aqueous solution with the concentration; and after the photocatalytic degradation is finished, centrifugally separating out the In-MOF material, and recycling according to the method.
The In-MOF material provided by the invention has three important strips for efficiently catalyzing and degrading methyl orange In water by visible light under visible light irradiation simulated by a xenon lampA piece: firstly, an ultraviolet-visible diffuse reflection (UV-Vis DRS) spectrogram of the magnetic photocatalyst shows that the absorption wavelength range of the magnetic photocatalyst on visible light is 400-650nm, and most visible light regions are covered; secondly, the In-MOF framework has a three-dimensional structure with double insertion nesting, and the inside of the framework is deprotonated by aromatic H 3 The L ligands are highly orderly arranged, so that the light absorption and pi electron supply effects are enhanced, the generation and transfer of photoproduction electrons are promoted, the separation efficiency of photoproduction electrons and holes is improved, and the photocatalysis efficiency is improved.
Infrared spectroscopy tests related to the present invention: the In-MOF material was mixed uniformly with potassium bromide powder at a ratio of 1.
The invention relates to a test of a thermal weight loss curve: weighing 8-20 mg of naturally dried In-MOF material, putting the material into an alumina crucible, and testing on a thermal weight loss analyzer.
The photocatalytic degradation test related to the present invention: after the In-MOF material reaches adsorption-desorption equilibrium In a dye solution of methyl orange, taking out supernatant liquid at intervals under the irradiation of a 300W xenon lamp, placing the supernatant liquid In a cuvette, and testing the supernatant liquid on an ultraviolet-visible spectrophotometer.
A preparation method of an In-MOF material based on a tricarboxylic acid ligand specifically comprises the following steps:
under the closed condition, indium nitrate trihydrate In (NO) 3 ) 2 ·3H 2 O and organic ligand H 3 And L and a template agent hexamethylene tetramine are dissolved In N, N-dimethylformamide, a concentrated nitric acid solution is dripped to adjust the pH value of a reaction system to 4.0-6.0, and the In-MOF material with the crystal structure is obtained by reaction under the solvothermal condition.
The temperature of the solvothermal reaction is 100-120 ℃, and the required reaction time is 72-120 hours;
indium nitrate trihydrate, organic ligand H 3 The mol ratio of L, hexamethylene tetramine and N, N-dimethylformamide is 2-4:1:0.2-0.5:300-500; the mass fraction of the concentrated nitric acid solution is 65 percent;
more preferably, indium nitrate trihydrate, an organic ligandH 3 The mol ratio of L, template agent hexamethylene tetramine to N, N-dimethylformamide is 3:1:0.4:400, in particular 0.02mmol (12.22 mg) of organic ligand H per 0.06mmol (21.29 mg) of indium nitrate trihydrate 3 L and 0.008mmol (1.12 mg) of hexamethylenetetramine corresponded to 6.2mL of N, N-dimethylformamide. The temperature of the solvothermal reaction is 105 ℃, and the reaction time is 96h.
Organic ligand H 3 The preparation method of the L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dropwise adding the solution into the mixed solution in the step a within 15min, dropwise adding triethylamine within 10min, reacting in an ice water bath for 3h, and reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction liquid under continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, namely washing and vacuum filtration through distilled water and methanol in sequence, drying the obtained white solid to obtain the organic ligand H 3 L;
The drying temperature is 70 ℃, and the drying time is 8h;
the invention develops a method for preparing a novel organic ligand 4,4' - [ benzene triacyl tri (carbonyl benzene)]-3,3',3 "-trimethyl-tribenzoic acid In-MOF material. The In-MOF material is a solid crystalline porous material, and is a spatial three-dimensional framework structure. Specifically 1 In 3+ Metal centre with 6H from deprotonation 3 L carboxyl groups of the organic ligand, 3 from H 2 O atom and 1. Mu. Of O molecule 3 Coordinated by the-O/OH atoms to form a trimetallic-centered, hexa-linked [ In ] 33 -O)(O 2 C-) 6 (H 2 O) 3 ]Anionic secondary building blocks, deprotonatedH of (A) to (B) 3 The L ligands are further connected to construct a three-dimensional space network structure, and two completely same three-dimensional network structures are further mutually interpenetrated and nested to form a final three-dimensional framework structure of the In-MOF.
Example 1
Organic ligand H 3 L(0.02mmol,12.22mg)、In(NO 3 ) 2 ·3H 2 O (0.04mmol, 12.75mg) and hexamethylenetetramine (0.004mmol, 0.56mg) were mixed in 6.5mL of N, N-dimethylformamide, and a 65% by mass concentrated nitric acid solution was added dropwise thereto to adjust the pH of the reaction system to 5.0, and the mixture was sealed in a 25mL glass vial. And carrying out solvothermal reaction at 115 ℃ for 72 hours, and naturally cooling to room temperature to obtain a colorless and transparent long-strip In-MOF material.
The crystal structure of the In-MOF material obtained In the above example is tested by the same method and structure, specifically the following:
determination of crystal structure:
single crystals of clear, non-fractured In-MOF material were selected, single crystal structure testing and diffraction data collection were performed at room temperature (about 296K) using a Bruker Aper II CCD type single crystal X-ray diffractometer from Bruker, germany, monochromator monochromated Mo-Ka
Figure BDA0002666763410000102
Figure BDA0002666763410000103
The crystal cell parameters obtained by least square correction are analyzed by adopting SHELXS-97 software package, and the absorption correction of the collected data is completed by adopting SADABS program. The crystallographic data are shown in table 1, and the crystal structures are shown in fig. 1 to 4.
TABLE 1 crystallographic data Table
Figure BDA0002666763410000101
FIG. 1 shows [ In ] of the prepared In-organic framework material 33 -O)(O 2 C-) 6 (H 2 O) 3 ]Secondary building blocks, the structure of FIG. 1 shows, in 3+ Metal centre with 6H from deprotonation 3 L carboxyl groups of the organic ligand, 3 from H 2 O atom and 1. Mu. Of O molecule 3 Coordination of the-O/OH atoms to form a trimetallic-centered, hexa-linked [ In ] 33 -O)(O 2 C-) 6 (H 2 O) 3 ]An anionic secondary building block.
FIG. 2 is a diagram showing coordination environments of the prepared In-organic framework material, and the structure of FIG. 2 shows that one deprotonated coordinated H is contained In the asymmetric structural unit of In-MOF 3 L ligand, 1 [ In ] 33 -O)(O 2 C-) 6 (H 2 O) 3 ]A secondary building block.
FIG. 3 is a three-dimensional structure diagram of one of the mononets of the In-MOF prepared. The structure of FIG. 3 shows that the three metal centers are six connected [ In ] 33 -O)(O 2 C-) 6 (H 2 O) 3 ]Secondary building block, deprotonated H of triangular form 3 The L ligands are further connected to form a three-dimensional space single-net framework structure.
FIG. 4 is a final three-dimensional structure diagram formed by mutually interpenetrating and nesting two identical three-dimensional mononetwork structures of the prepared In-MOF. The structure of fig. 4 shows that 2 identical spatial single-net framework junctions are further interpenetrated and nested with each other, and a final three-dimensional double-interpenetration framework structure of In-MOF is formed.
FIG. 5 is a graph of the thermal weight loss of the prepared In-MOF material, and the thermal weight loss curve of FIG. 5 shows that the In-MOF material undergoes 3 major weight loss stages at a temperature of 10 ℃/min and within a temperature range of 30-800 ℃ under flowing nitrogen. The weight loss rate of about 11.44% between 30 ℃ and 105 ℃ should come from the leaving of the water molecules and air adsorbed In the pore channels/cavities, and the weight loss rate of about 37.50% between 106 ℃ and 246 ℃ comes from the leaving of the guest DMF solvent molecules In the cavities of the In-MOF material; between 247 and 550 ℃, the weight loss rate of 34.63 percent is from collapse of In-MOF framework and decomposition of part of organic ligands; the remaining 16.43% by mass are non-decomposed ligand, ash and In oxides. The result of thermogravimetric analysis shows that the In-MOF material has good thermal stability.
FIG. 6 is an infrared spectrum of the prepared In-MOF material. The spectrum of FIG. 6 shows 3260cm -1 The characteristic peaks In the vicinity are caused by stretching vibration of amide groups on organic ligands of the In-MOF material; 1392cm -1 The nearby stretching vibration peak is attributed to the asymmetric stretching vibration peak of the carbonyl group on the aromatic ring of the In-MOF framework.
Fig. 7 is a simulated X-ray powder diffraction pattern (theoretical value) of a single crystal of the prepared In-MOF material and an actual X-ray powder diffraction pattern (actual value) of a large number of crystal samples, and the spectra In fig. 7 show that the actual values (i.e. 2 theta angle values) of the diffraction peaks of the X-ray powder diffraction patterns of the large number of In-MOF samples are basically consistent with the theoretical values obtained by the In-MOF single crystal diffraction test, which shows that the spatial structure of the large number of synthesized In-MOFs is consistent with the spatial structure of the single crystal used for single crystal test, and the difference of the intensities of the individual diffraction peaks is related to the preferred orientation of the samples.
FIG. 8 is a scanning electron micrograph of the In-MOF material prepared. The spectrum of FIG. 8 shows that the In-MOF crystals have polygonal long stripes In appearance and the size of single crystals is about 80X 40X 20 μm 3
Fig. 9 is a uv-vis diffuse reflectance spectrum of the prepared In-MOF material. The uv-vis diffuse reflectance curve of fig. 9 shows that the In-MOF material has an absorption wavelength range of 400-650nm for visible light covering the entire visible region within the range of 200-800 nm, using a white barium sulfate white plate as a blank control.
When the In-MOF material prepared In example 1 is used for degrading methyl orange under visible light catalysis, the concentration range of the dye aqueous solution is 0.5 mg/L-80 mg/L. Preparing 10 methyl orange aqueous solutions with concentrations of 0.5, 1.0, 2.0, 4.0, 8.0, 10, 20, 40, 60 and 80mg/L respectively by using distilled water as an experimental group, and testing the absorbance values of the methyl orange aqueous solutions with different concentrations at the maximum absorption wavelength of 465nm respectively by using an ultraviolet-visible spectrophotometer by using the distilled water as a blank control, wherein the absorbance values at the maximum absorption wavelength of 465nm are gradually increased along with the concentration of prepared dye methyl orange as shown in FIG. 10And then also increases; and drawing a standard curve by taking the concentration of the methyl orange aqueous solution as an X axis and the corresponding absorbance value as a Y axis, as shown in FIG. 11, the absorbance value Y of the dye and the concentration X thereof present a standard linear function relation curve, R 2 Is 0.9999.
The In-MOF material prepared In example 1 was used to photocatalytically degrade methyl orange at a concentration of 50.70 mg/L. 10mg of the In-MOF material prepared In example 1 was weighed, placed In a 100mL quartz tube reactor, 60mL of methyl orange aqueous solution with a certain concentration was poured into the reactor, transferred to a dark box at room temperature, and placed for about 2h under magnetic stirring until the adsorption-desorption equilibrium between the dye molecules and the photocatalyst was reached. Taking out 4mL of methyl orange supernatant to test the absorbance value, determining the concentration of the methyl orange to be 50.70mg/L through a standard curve, then starting a 300W xenon lamp under magnetic stirring for irradiation, setting a 50.70mg/L methyl orange aqueous solution without adding other photocatalysts as a blank reference sample, taking out 4mL of supernatant at regular intervals (quickly pouring the supernatant into a quartz tube after the test is finished), and testing an ultraviolet-visible absorption spectrogram of the methyl orange by using an ultraviolet-visible spectrophotometer, wherein as shown in FIG. 12, the absorbance value of the methyl orange at 465nm is quickly reduced along with the extension of the illumination time, and a characteristic absorption peak of the methyl orange almost completely disappears after 120 min. The change of methyl orange concentration with time was read from the standard curve of FIG. 11, and the concentration C at that time was compared with the initial concentration C 0 Ratio of (C)/(C) 0 The photocatalytic degradation efficiency of the In-MOF material on methyl orange is obtained by taking time as an X axis and a Y axis, as shown In FIG. 13, within 120min, the visible photocatalytic degradation efficiency of the In-MOF material on methyl orange is 93.25%; in the blank control without photocatalyst, the concentration of the dye only undergoes a slight negligible change, which indicates that the In-MOF material has a significant visible photocatalytic degradation efficiency for methyl orange. Further, as shown in FIG. 14, ln (C/C) is used 0 ) Plotted as Y-axis and time as X-axis, the resulting photocatalytic degradation rate constant (i.e., the slope of the line in FIG. 14) was 1.286h -1 (R 2 =0.995)。
Continuously circulating visible light photocatalytic degradation is carried out on methyl orange by recycling In-MOF materials;
after the degradation experiment was completed, the photocatalyst was centrifugally separated and the photocatalytic degradation experiment was repeated again. As shown In fig. 15, in the next 4 consecutive photocatalytic degradation cycle experiments, the photocatalytic degradation efficiency of the recycled In-MOF material on methyl orange is 92.13%, 89.34%, 84.57% and 82.36%, respectively, and the experimental results show that the In-MOF material is stable In the process of visible light photocatalytic degradation of methyl orange, and has a good catalytic degradation effect.
Example 2
A preparation method of an In-MOF material based on a tricarboxylic acid ligand specifically comprises the following steps:
under the closed condition, indium nitrate trihydrate In (NO) 3 ) 2 ·3H 2 O and organic ligand H 3 And L and a template agent hexamethylene tetramine are dissolved In N, N-dimethylformamide, a concentrated nitric acid solution is dropwise added to adjust the pH value of a reaction system to 4.0, and the In-MOF material with the crystal structure is obtained through reaction under the solvothermal condition.
The temperature of the solvothermal reaction is 100 ℃, and the required reaction time is 72 hours;
indium nitrate trihydrate, organic ligand H 3 The mol ratio of L, hexamethylene tetramine and N, N-dimethylformamide is 2:1:0.2:300, and (c) a step of cutting; the mass fraction of the concentrated nitric acid solution is 65 percent;
organic ligand H 3 The preparation method of the L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
step b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dropwise adding the solution into the mixed solution obtained in the step 1.1 within 15min, dropwise adding triethylamine within 10min, reacting in an ice water bath for 3h, and reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction solution under continuous magnetic stirringAnd after 30min, removing DMF and distilled water by vacuum filtration with a Buchner funnel, namely washing with distilled water and methanol in sequence and carrying out vacuum filtration, and drying the obtained white solid to obtain the organic ligand H 3 L;
The drying temperature is 70 ℃, and the drying time is 8 hours;
example 3
A preparation method of an In-MOF material based on a tricarboxylic acid ligand specifically comprises the following steps:
under the closed condition, indium nitrate trihydrate In (NO) 3 ) 2 ·3H 2 O and organic ligand H 3 And L and a template agent hexamethylene tetramine are dissolved In N, N-dimethylformamide, a concentrated nitric acid solution is dripped to adjust the pH value of a reaction system to 4.0-6.0, and the In-MOF material with the crystal structure is obtained by reaction under the solvothermal condition.
The temperature of the solvothermal reaction is 120 ℃, and the required reaction time is 120 hours;
indium nitrate trihydrate, organic ligand H 3 The mol ratio of L, hexamethylene tetramine and N, N-dimethylformamide is 4:1:0.5:500; the mass fraction of the concentrated nitric acid solution is 65 percent;
organic ligand H 3 The preparation method of L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF (dimethyl formamide), and continuously magnetically stirring under the condition of ice-water bath until the 4-amino-2-methylbenzoic acid is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
step b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dropwise adding the solution into the mixed solution obtained in the step 1.1 within 15min, dropwise adding triethylamine within 10min, reacting in an ice water bath for 3h, and reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction solution under continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, namely washing with distilled water and methanol in sequence and carrying out suction filtration, and obtaining whiteDrying the solid to obtain the organic ligand H 3 L;
The drying temperature is 70 ℃, and the drying time is 8h.

Claims (4)

1. An In-MOF material based on a tricarboxylic acid ligand, characterized by the formula { [ (CH) 3 ) 2 NH 2 ] 2 (In 3 O 4 L 1 )} n ·(solvent) x Wherein H is 3 L is a triangular organic ligand 4, 4'' - [ benzene triacyl tris (carbonyl benzene)]-3, 3'' -trimethyl-tribenzoic acid, [ (CH) 3 ) 2 NH 2 ]Is a protonated dimethylamine molecule and solvent is a guest organic solvent molecule;
the crystal structure of the In-MOF material belongs to a monoclinic system,C2/mspace group, cell parameters are: a = 31.01 (6) a, b = 34.11 (6) a, c = 18.57 (3) a; α = 90 °, β = 121.55 (3) °, γ = 90 °.
2. The preparation method of the In-MOF material based on the tricarboxylic acid ligand is characterized by comprising the following steps:
under the closed condition, indium nitrate trihydrate and organic ligand H 3 L and a template agent hexamethylene tetramine are dissolved In N, N-dimethylformamide, a concentrated nitric acid solution is dripped to adjust the pH value of a reaction system to 4.0-6.0, and the In-MOF material is obtained through reaction under the solvothermal condition;
the temperature of the solvothermal reaction is 100-120 ℃, and the required reaction time is 72-120 hours; the indium nitrate trihydrate and the organic ligand H 3 The mol ratio of L, hexamethylene tetramine and N, N-dimethylformamide is 2-4:1:0.2-0.5:300-500;
the organic ligand H 3 The preparation method of L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF (dimethyl formamide), and continuously magnetically stirring under the condition of ice-water bath until the 4-amino-2-methylbenzoic acid is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dropwise adding the solution into the mixed solution in the step a within 15min, dropwise adding triethylamine within 10min, reacting in an ice water bath for 3h, and reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine;
step c, adding distilled water into the reaction liquid under continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, washing and filtering the DMF and the distilled water by using distilled water and methanol in sequence, and drying the obtained white solid to obtain the organic ligand H 3 L。
3. The method of preparing an In-MOF material based on a tricarboxylic acid ligand according to claim 2, wherein the mass fraction of the concentrated nitric acid solution is 65%.
4. The method for preparing In-MOF materials based on tricarboxylic acid ligands according to claim 2, wherein In the step c, the drying temperature is 70 ℃ and the drying time is 8h.
CN202010921095.6A 2020-09-04 2020-09-04 In-MOF material based on tricarboxylic acid ligand, preparation method and application Active CN112076793B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010921095.6A CN112076793B (en) 2020-09-04 2020-09-04 In-MOF material based on tricarboxylic acid ligand, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010921095.6A CN112076793B (en) 2020-09-04 2020-09-04 In-MOF material based on tricarboxylic acid ligand, preparation method and application

Publications (2)

Publication Number Publication Date
CN112076793A CN112076793A (en) 2020-12-15
CN112076793B true CN112076793B (en) 2022-12-09

Family

ID=73732581

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010921095.6A Active CN112076793B (en) 2020-09-04 2020-09-04 In-MOF material based on tricarboxylic acid ligand, preparation method and application

Country Status (1)

Country Link
CN (1) CN112076793B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113461958B (en) * 2021-06-18 2022-06-07 北京工业大学 In-based metal organic framework material of two tridentate carboxylic acid ligands and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669773A (en) * 2015-12-31 2016-06-15 郑州大学 Co-MOF material, preparation method and application thereof
CN106955742A (en) * 2017-03-29 2017-07-18 华南理工大学 A kind of Ce MOF catalysis materials and preparation method and application

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104324756B (en) * 2014-10-09 2016-06-22 济南大学 A kind of preparation method and application of mesoporous metal organic coordination compound based composites
EP3599239A1 (en) * 2018-07-24 2020-01-29 Ecole Polytechnique Federale De Lausanne (EPFL) EPFL-TTO Metal organic frameworks and methods for using thereof
CN111205470B (en) * 2020-02-11 2021-08-10 河北大学 Azole functionalized divalent copper frame coordination material, preparation method and application thereof, and p-nitrophenol detection method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105669773A (en) * 2015-12-31 2016-06-15 郑州大学 Co-MOF material, preparation method and application thereof
CN106955742A (en) * 2017-03-29 2017-07-18 华南理工大学 A kind of Ce MOF catalysis materials and preparation method and application

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
A two-fold interpenetrated (3,6)-connected metal–organic framework;Xiaokai Song et al.;《New Journal of Chemistry》;20100726;第34卷;第2398页实验部分 *
Conformational control of ligands to create a finite metal–organic cluster and an extended metal–organic framework;Lalit Rajput et al.;《CrystEngComm》;20121004;第15卷;摘要、第260页试验部分 *
李庆.水稳定型In/Zr-有机骨架材料的设计、合成与光催化降解有机染料.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2019,(第4期), *
水稳定型In/Zr-有机骨架材料的设计、合成与光催化降解有机染料;李庆;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20190415(第4期);第49页第2-3段、第2.1.2节 *

Also Published As

Publication number Publication date
CN112076793A (en) 2020-12-15

Similar Documents

Publication Publication Date Title
Gu et al. Morphology modulation of hollow-shell ZnSn (OH) 6 for enhanced photodegradation of methylene blue
CN104402914B (en) The zinc metal-organic framework materials of catalyzed degradation organic dye under a kind of visible ray
CN112076796B (en) Preparation method and application of magnetic Cu-MOF-based photocatalyst
CN109395761B (en) Nitrogen-doped BiOIO3Preparation method and application of photocatalyst
Liu et al. Facile synthesis of ternary AgBr/BiOI/Bi2O2CO3 heterostructures via BiOI self-sacrifice for efficient photocatalytic removal of gaseous mercury
Khajeh et al. Ternary NiCuZr layered double hydroxide@ MIL-101 (Fe)-NH2 metal-organic framework for photocatalytic degradation of methylene blue
CN109701497A (en) Metal-organic framework materials, synthetic method, application
CN106693996B (en) Preparation method and application of bismuth sulfide-bismuth ferrite composite visible-light-driven photocatalyst
Yang et al. An acid–base resistant paddle-wheel Cu (II) coordination polymer for visible-light-driven photodegradation of organic dyes
CN111004397B (en) Metal organic framework molecular material of electron-rich system and application thereof in photocatalytic reduction of heavy metal ions
CN112076794B (en) Cu-MOF material based on triangular organic ligand, and preparation method and application thereof
CN112076793B (en) In-MOF material based on tricarboxylic acid ligand, preparation method and application
Lan et al. Heterojunction of UiO-66 and porous g-C3N4 for boosted photocatalytic removal of organic dye
Zhang et al. Structure determines performance: isomeric Ti-MOFs for photocatalytic synthesis of hydrogen peroxide
CN111848654A (en) Zinc complex with property of catalyzing photo-degradation of methyl orange dye and preparation method thereof
CN110639616A (en) Preparation of amino modified MIL-68(Ga) novel photocatalyst and method for reducing Cr (VI) by using same
CN103212405B (en) Cadmium-doped bismuth molybdate visible-light-induced photocatalyst and preparation method and application of cadmium-doped bismuth molybdate visible-light-induced photocatalyst
CN112958158A (en) Double-ligand rare earth complex photocatalyst and preparation method and application thereof
Huang et al. Construction of the Z-scheme heterogeneous HKUST-1/BiVO4 nanorod composite for enhanced piezo-photocatalytic reduction performance of Cr (VI)
CN111097386B (en) Two-dimensional layered water-stable dye adsorbent and preparation method thereof
CN113856766A (en) Preparation method and application of copper Schiff base chelate intercalation zinc-chromium hydrotalcite
CN117258846A (en) Floating catalyst, preparation method and application thereof
CN112076795B (en) Preparation method and application of magnetic In-MOF-based photocatalyst
CN111171055A (en) Copper complex with dye catalytic photodegradation property and preparation method thereof
CN110105584B (en) Porous cadmium/copper-doped complex and preparation method and application thereof

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
CB03 Change of inventor or designer information

Inventor after: Li Qing

Inventor after: Cai Xinbin

Inventor after: Fan Zenglu

Inventor after: Zhang Luohong

Inventor after: Wu Zhansheng

Inventor after: Wang Liming

Inventor after: Zhu Wei

Inventor before: Li Qing

Inventor before: Fan Zenglu

Inventor before: Zhang Luohong

Inventor before: Wu Zhansheng

Inventor before: Wang Liming

Inventor before: Zhu Wei

CB03 Change of inventor or designer information
GR01 Patent grant
GR01 Patent grant