CN108927220B - Synthesis method of meso-microporous Cr-MIL-101 carrier for synchronously immobilizing phosphotungstic acid - Google Patents

Synthesis method of meso-microporous Cr-MIL-101 carrier for synchronously immobilizing phosphotungstic acid Download PDF

Info

Publication number
CN108927220B
CN108927220B CN201810686099.3A CN201810686099A CN108927220B CN 108927220 B CN108927220 B CN 108927220B CN 201810686099 A CN201810686099 A CN 201810686099A CN 108927220 B CN108927220 B CN 108927220B
Authority
CN
China
Prior art keywords
mil
microporous
carrier
pta
synchronously
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201810686099.3A
Other languages
Chinese (zh)
Other versions
CN108927220A (en
Inventor
王艳
万金泉
郝金蕾
马邕文
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.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
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 South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201810686099.3A priority Critical patent/CN108927220B/en
Publication of CN108927220A publication Critical patent/CN108927220A/en
Application granted granted Critical
Publication of CN108927220B publication Critical patent/CN108927220B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/695—Pore distribution polymodal
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium

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)
  • Emergency Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a preparation method of a meso-microporous MIL-101 material synchronously immobilized with phosphotungstic acid. The preparation method comprises the following steps: distilled water, 2-amino terephthalic acid and Cr (NO) are stirred by magnetic force3)3∙9H2O, PTA and CTAB are uniformly mixed, the mixture is heated for 10-14 h at a preset constant temperature of 130-170 ℃, the mixture is naturally cooled to room temperature and then subjected to centrifugal separation, DMF and ethanol are repeatedly used for washing until the supernatant after centrifugal separation is clear and transparent, and the obtained solid is subjected to vacuum drying for 15.95-16.05 h at 78-82 ℃ to obtain the meso-microporous Cr-MIL-101 carrier synchronously immobilized with phosphotungstic acid. The preparation method has the advantages of simple preparation process, high yield and easy large-scale batch production, and the PTA @ MIL-101(Cr) -NH is obtained without adding organic or alkaline solution as a solvent in the synthesis process2Has good water and heat stability.

Description

Synthesis method of meso-microporous Cr-MIL-101 carrier for synchronously immobilizing phosphotungstic acid
Technical Field
The invention belongs to the field of materials, and particularly relates to a method for synthesizing a meso-microporous Cr-MIL-101 carrier for synchronously immobilizing phosphotungstic acid.
Background
The PTA is a solid acid catalyst with strong oxidability and strong electronegativity, has wide application prospect, and the key point for solving the difficulty of recycling and reusing the PTA is to realize immobilization. Under the condition of not influencing the catalytic efficiency of PTA, the pore channels of the solid-phase PTA formed by the existing solid-supported hydrogen type zeolite, MOFs and the like are all in a microporous structure with the pore channel less than 2 nm. Can only be applied to the catalytic conversion of small molecules such as hexanol, cyclopentene and the like, and macromolecular substances such as cellulose, starch and the like are difficult to enter the interior of MOFs pore channels to fully contact with PTA catalytic centers, so that the application of PTA is limited. The invention provides a meso-micro diplopore Cr-MIL-101 carrier for synchronously immobilizing phosphotungstic acidThe synthesis method of the body is characterized in that a template CTAB is added in the synthesis process of MOFs to form micelles in water, and the micelles are respectively placed in-NH through PTA2And CTAB to form Cr-MIL-101 around the micelle, and remove the micelle to form new pore channel to expand the pore of MOFs carrier, wherein PTA is synchronously immobilized on Cr-MIL-101. Meanwhile, CTAB can be used as a deprotonation reagent to promote coordination of an organic ligand and metal, and the addition of DMF, hydrofluoric acid or NaOH in the conventional synthesis method is replaced, so that MIL-101 green synthesis with water as a solvent is realized.
Disclosure of Invention
The invention provides a method for synthesizing a mesoporous-microporous Cr-MIL-101 carrier and synchronously immobilizing PTA (pure terephthalic acid) by using a metal organic framework green synthesis system taking water as a solvent.
The invention also aims to obtain the mesoporous-microporous Cr-MIL-101 material synchronously immobilized with phosphotungstic acid prepared by the method. According to the material, CTAB is added into a synthesis system taking water as a solvent to form micelles in water, metal and organic ligands are self-assembled around the micelles through electrostatic action to form Cr-MIL-101, a new pore channel structure is formed after the micelles are removed, and the ratio of meso-micropore of the obtained material can be regulated and controlled through the adding amount of CTAB.
The purpose of the invention is realized by the following technical scheme:
a synthesis method of a dielectric-microporous Cr-MIL-101 carrier for synchronously immobilizing phosphotungstic acid comprises the steps of forming micelles in a solution through a template CTAB, carrying out self-assembly on Cr-MIL-101 around the micelles, immobilizing PTA inside channels of the Cr-MIL-101 through electrostatic interaction between alkaline groups and PTA, and removing the micelles by adopting DMF and ethanol to form cavities on the Cr-MIL-101 carrier so as to expand the channels of the carrier.
In the above method, the solvent is distilled water, and the template reagent is CTAB.
The method specifically comprises the following steps: distilled water, basic group 2-amino terephthalic acid and Cr (NO) are stirred by magnetic force3)3∙9H2O, phosphotungstic acid (PTA) and template hexadecyltrimethyl bromideAmmonium (CTAB) is uniformly mixed, the mixture is heated for 10-14 hours at a preset constant temperature of 130-170 ℃, the mixture is naturally cooled to room temperature and then subjected to centrifugal separation, N-Dimethylformamide (DMF) and ethanol are repeatedly used for washing until the supernatant after centrifugal separation is clear and transparent, and the obtained solid is subjected to vacuum drying at 78-82 ℃ for 15.95-16.05 hours to obtain the dielectric-microporous Cr-MIL-101 carrier for synchronously immobilized phosphotungstic acid.
In the above method, the distilled water, 2-aminoterephthalic acid, PTA, CTAB, Cr (NO)3)3∙9H2The molar ratio of O is (370-480): (0.10-1): (0.05-0.2): 0.3-2.0): 1.
In the method, the aperture of the synthesized Cr-MIL-101 is 1.2-46.5 nm, and the ratio of meso-micro diplopore is (0.85-7): 1.
The preparation method and the obtained product have the following advantages:
(1) the method realizes the synthesis of the MIL-101 by taking water as a solvent for the first time, is green and environment-friendly, and replaces the existing MIL-101 synthesis system which takes water as a solvent and needs to add HF with high toxicity and strong corrosivity.
(2) The mesoporous-microporous Cr-MIL-101 material of the synchronously immobilized phosphotungstic acid prepared by the invention can regulate and control the ratio of mesoporous-microporous of the Cr-MIL-101 material by changing the addition of a template CTAB.
(3) The preparation method has the advantages of simple preparation process, high material yield and easy large-scale production.
Drawings
FIG. 1 is a pore size distribution diagram of a meso-microporous Cr-MIL-101 material of synchronously immobilized phosphotungstic acid obtained in example 1;
FIG. 2 is a pore size distribution diagram of the meso-microporous Cr-MIL-101 material of the synchronously immobilized phosphotungstic acid obtained in example 2.
Fig. 3 is a glucose yield graph of a medium-micro double-pore Cr-MIL-101 material of synchronous immobilized phosphotungstic acid obtained in examples 1 to 3, which is subjected to three-time catalytic hydrolysis of microcrystalline cellulose, and a pure PTA catalytic hydrolysis microcrystalline cellulose having the same PTA immobilization amount as that in the material, wherein 1, 2, and 3 are glucose yield graphs of medium-micro double-pore Cr-MIL-101 materials of synchronous immobilized phosphotungstic acid synthesized in examples 1, 2, and 3, respectively.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
The mesoporous-microporous Cr-MIL-101 material synchronously immobilized with phosphotungstic acid is prepared by the following method: 45 mL of distilled water and 6.0 mmol of Cr (NO)3)3∙9H2O, 0.3 mmol PTA, 6.0 mmol 2-amino terephthalic acid and 1.8 mmol CTAB are stirred uniformly at room temperature, added into a 100 mL polytetrafluoroethylene reaction kettle, heated at the constant temperature of 150 ℃ for 12 h, cooled to room temperature, repeatedly washed with DMF and ethanol, centrifuged to obtain a solid, and dried in vacuum at 80 ℃ for 16 h to obtain the solid, namely the dielectric-microporous Cr-MIL-101 material of the synchronously immobilized phosphotungstic acid.
Example 2
The mesoporous-microporous Cr-MIL-101 material synchronously immobilized with phosphotungstic acid is prepared by the following method: 45 mL of distilled water and 6.0 mmol of Cr (NO)3)3∙9H2O, 0.3 mmol PTA, 6.0 mmol 2-amino terephthalic acid and 3.6 mmol CTAB are stirred uniformly at room temperature, added into a 100 mL polytetrafluoroethylene reaction kettle, heated at the constant temperature of 150 ℃ for 12 h, cooled to room temperature, repeatedly washed with DMF and ethanol, centrifuged to obtain a solid, and dried in vacuum at 80 ℃ for 16 h to obtain the solid, namely the dielectric-microporous Cr-MIL-101 material of the synchronously immobilized phosphotungstic acid.
The pore size distribution diagrams of the materials obtained in the examples 1-2 are shown in fig. 1 and fig. 2, and it can be seen that the products added with CTAB all have a meso-micro double-pore structure, wherein the pore size distribution of the materials obtained in the examples 1-2 is 1.1-46 nm, the meso-micro double-pore ratio of the example 1 is 0.85:1, the meso-micro double-pore ratio of the example 2 is 1.46:1, and the increase of the adding amount of the template CTAB is beneficial to promoting the increase of the meso-pore ratio of the Cr-MIL-101 material.
The acidity tables of the materials obtained in examples 1 to 2 are shown in Table 1, and it can be seen that Cr3+CTAB is increased from 1:0.3 to 1:0.6, PTA solid loading of Cr-MIL-101 is increased from 13.3 wt% to 14.8 wt%, initial potential and acid density are correspondingly increased, and increasing the adding amount of template CTAB is beneficial to promotingAnd (4) immobilization of PTA.
Table 1 shows the acidity table of the meso-microporous Cr-MIL-101 material of the synchronously immobilized phosphotungstic acid obtained in examples 1-3.
TABLE 1
Sample (I) Cr3+:CTAB Initial potential (mV) Acid Density (mmol ∙ g-1) PTA content (wt%)
1 1:0.3 198 0.33 13.3
2 1:0.6 201 0.39 14.8
Example 3
The application of the mesoporous-microporous Cr-MIL-101 material synchronously immobilized with phosphotungstic acid comprises the following steps: 0.12 g of meso-microporous Cr-MIL-101 material synchronously immobilized with phosphotungstic acid or pure PTAx g with the same PTA immobilization amount as that in 0.12 g of meso-microporous Cr-MIL-101 material synchronously immobilized with phosphotungstic acid is added into 10 mL of distilled water, 0.04 g of microcrystalline cellulose is added at the same time, the mixture is heated at a constant temperature of 180 ℃ and continuously stirred for 11 hours, and centrifugal separation is carried out after the reaction is finished. And solid residues precipitated at the bottom of the centrifugal tube after centrifugal separation are reacted large-pore metal organic framework materials of the immobilized PTA for catalyzing and hydrolyzing the microcrystalline cellulose, washed by distilled water and dried for 16 h at 80 ℃ and then can be recycled.
Cr3+CTAB is increased from 1:0.3 to 1:0.6, the glucose yield of the first catalytic hydrolysis microcrystalline cellulose of the Cr-MIL-101 material is increased from 23.7% to 26.8%, the glucose yield of the pure PTA catalytic hydrolysis microcrystalline cellulose with the same PTA solid load in the material is increased from 34.4% to 35.1%, namely, the glucose yield of the Cr-MIL-101 material is increased from 68.9% to 76.4% of the pure PTA glucose yield along with the increase of the adding amount of CTAB, the mesoporous proportion of the material is increased to facilitate more microcrystalline cellulose to enter the interior of the material to be fully contacted with PTA acid catalytic centers, more PTA solid load can provide more acid catalytic active centers, and the combination of the two results in the improvement of the glucose yield. The yield reduction of the tertiary glucose of the Cr-MIL-101 material is less than 5%, and the material well solves the problems of difficult PTA recovery and difficult reutilization.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which are made without departing from the spirit and principle of the present invention should be construed as equivalents and all fall within the protection scope of the present invention.

Claims (3)

1. A synthetic method of a dielectric-microporous Cr-MIL-101 carrier for synchronously immobilizing phosphotungstic acid is characterized in that a template CTAB forms micelles in a solution, Cr-MIL-101 is self-assembled around the micelles, PTA is immobilized in a pore channel of the Cr-MIL-101 through the electrostatic action between a basic group and PTA, and a cavity is formed in the Cr-MIL-101 carrier after the micelles are removed by adopting DMF and ethanol, so that the pore channel of the carrier is enlarged;
the method specifically comprises the following steps: distilled water and 2-amino are stirred by magnetic forceTerephthalic acid, Cr (NO)3)3∙9H2O, PTA and CTAB are mixed uniformly, the mixture is heated for 10-14 h at a preset constant temperature of 130-170 ℃, the mixture is naturally cooled to room temperature and then is centrifugally separated, DMF and ethanol are used for washing repeatedly until the supernatant after centrifugal separation is clear and transparent, and the obtained solid is dried for 15.95-16.05 h in vacuum at 78-82 ℃ to obtain the dielectric-microporous Cr-MIL-101 carrier synchronously immobilized with phosphotungstic acid.
2. The method for synthesizing the meso-microporous Cr-MIL-101 carrier synchronously immobilized with phosphotungstic acid as claimed in claim 1, wherein the carrier comprises distilled water, 2-amino terephthalic acid, PTA, CTAB, Cr (NO)3)3∙9H2The molar ratio of O is (370-480): (0.10-1): (0.05-0.2): 0.3-2.0): 1.
3. The synthesis method of the meso-microporous Cr-MIL-101 carrier for synchronously immobilized phosphotungstic acid according to claim 2, wherein the pore diameter of the synthesized Cr-MIL-101 is 1.2-46.5 nm, and the ratio of meso-microporous to microporous is (0.85-7): 1.
CN201810686099.3A 2018-06-28 2018-06-28 Synthesis method of meso-microporous Cr-MIL-101 carrier for synchronously immobilizing phosphotungstic acid Expired - Fee Related CN108927220B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810686099.3A CN108927220B (en) 2018-06-28 2018-06-28 Synthesis method of meso-microporous Cr-MIL-101 carrier for synchronously immobilizing phosphotungstic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810686099.3A CN108927220B (en) 2018-06-28 2018-06-28 Synthesis method of meso-microporous Cr-MIL-101 carrier for synchronously immobilizing phosphotungstic acid

Publications (2)

Publication Number Publication Date
CN108927220A CN108927220A (en) 2018-12-04
CN108927220B true CN108927220B (en) 2021-06-08

Family

ID=64446492

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810686099.3A Expired - Fee Related CN108927220B (en) 2018-06-28 2018-06-28 Synthesis method of meso-microporous Cr-MIL-101 carrier for synchronously immobilizing phosphotungstic acid

Country Status (1)

Country Link
CN (1) CN108927220B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110560171A (en) * 2019-09-09 2019-12-13 沈阳师范大学 Composite nanofiber with desulfurization performance and preparation method and application thereof
CN110724276B (en) * 2019-10-28 2021-10-08 中国科学院青岛生物能源与过程研究所 Preparation method of acid-alkali difunctional MOFs material and method for synthesizing 3, 4-dimethylfurazan by using acid-alkali difunctional MOFs material as catalyst

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104211580A (en) * 2014-08-04 2014-12-17 湘潭大学 Method for catalytically synthesizing bisphenol F with phosphotungstic acid modified metal organic frame
CN104549508A (en) * 2014-12-17 2015-04-29 天津大学 Phosphotungstic acid-metal organic framework compound composite material for catalyzing thiophenic sulfur and application of phosphotungstic acid-metal organic framework compound composite material
CN104857988A (en) * 2015-05-07 2015-08-26 盐城工学院 Heteropolyacid-modified Zr-MOF catalyst as well as preparation method and application thereof
CN105344378A (en) * 2015-10-13 2016-02-24 华南理工大学 Phosphotungstic acid-metal organic skeleton used for catalyzing hydrolysis of cellulose, and preparation method and application thereof
CN105566069A (en) * 2015-12-09 2016-05-11 湘潭大学 Method for synthesizing bisphenol-F with catalysis of phosphotungstic acid modified short channel HPW-Zr/SBA-15 catalyst
CN107694611A (en) * 2017-09-29 2018-02-16 中国石油大学(华东) A kind of preparation and application of grade mesoporous metal organic backbone carried heteropoly acid catalyst

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1838437A1 (en) * 2005-01-18 2007-10-03 Showa Denko Kabushiki Kaisha Production and use of supported catalysts

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104211580A (en) * 2014-08-04 2014-12-17 湘潭大学 Method for catalytically synthesizing bisphenol F with phosphotungstic acid modified metal organic frame
CN104549508A (en) * 2014-12-17 2015-04-29 天津大学 Phosphotungstic acid-metal organic framework compound composite material for catalyzing thiophenic sulfur and application of phosphotungstic acid-metal organic framework compound composite material
CN104857988A (en) * 2015-05-07 2015-08-26 盐城工学院 Heteropolyacid-modified Zr-MOF catalyst as well as preparation method and application thereof
CN105344378A (en) * 2015-10-13 2016-02-24 华南理工大学 Phosphotungstic acid-metal organic skeleton used for catalyzing hydrolysis of cellulose, and preparation method and application thereof
CN105566069A (en) * 2015-12-09 2016-05-11 湘潭大学 Method for synthesizing bisphenol-F with catalysis of phosphotungstic acid modified short channel HPW-Zr/SBA-15 catalyst
CN107694611A (en) * 2017-09-29 2018-02-16 中国石油大学(华东) A kind of preparation and application of grade mesoporous metal organic backbone carried heteropoly acid catalyst

Also Published As

Publication number Publication date
CN108927220A (en) 2018-12-04

Similar Documents

Publication Publication Date Title
CN108927220B (en) Synthesis method of meso-microporous Cr-MIL-101 carrier for synchronously immobilizing phosphotungstic acid
CN109485063B (en) Method for preparing Y molecular sieve from waste MTP catalyst and application of waste MTP catalyst
CN109265704B (en) Method for efficiently preparing ZIF-8 material
CN108569950B (en) Method for preparing n-butanol by poly 3-hydroxybutyrate industrial crude product one-pot method
CN108940366B (en) Preparation method of pore-adjustable Fe-based metal organic framework-phosphotungstic acid
CN113318788A (en) Cu-NH2Preparation of-MIL-125/TpPa-2 composite material and hydrogen production by photolysis of water
CN106905271A (en) A kind of preparation and application containing the mesoporous material heterogeneous catalysis of MCM 41
CN112961053A (en) Method for preparing branched fatty acid methyl ester by using modified ZSM-5 molecular sieve catalyst
CN102974370B (en) Solid acid catalyst and use thereof
CN113198538A (en) Preparation method of superstrong fiber-loaded Schiff base palladium catalyst
CN113908882B (en) Heterogeneous catalyst, preparation method and application of heterogeneous catalyst in catalyzing isomerization of glucose to fructose
CN108250049B (en) Synthesis method of bisphenol fluorene
CN109734722B (en) Method for preparing isosorbide by dehydrating sorbitol
CN107051589A (en) A kind of method of the short mesoporous molecular sieve catalytic biodiesel synthesis of DCNH Zr SBA 15
CN112495438B (en) Preparation method of super-strong fiber loaded acid-base bifunctional catalyst
CN112299952B (en) Method for producing 3-chloro-1, 2-propanediol by using acetic anhydride modified graphene oxide
CN108525664A (en) A kind of preparation and its application of magnetic Nano nucleocapsid catalyst
CN103709010A (en) Method for synthesizing cyclohexanol by reacting cyclohexene, carboxylic acid and water
CN103923683A (en) Novel method for catalytically cracking waste polyolefin to recycle liquid fuel oil by adopting ionothermally synthesized mesoporous molecular sieve
CN111085266B (en) Method for synthesizing dimethyl silicone oil by catalysis of immobilized type bi-acid ionic liquid
CN110294672B (en) Method for directly preparing lactate from 1, 2-propylene glycol and short-chain alkyl alcohol
CN114478611A (en) Synthesis method of tetraethylene silane
CN113578386A (en) Preparation of Fe2 Co-based metal organic framework CO2 reduction photocatalyst
CN110479377B (en) Catalyst for reaction of 4-iodonitrobenzene and phenylacetylene
CN111841548A (en) Method for preparing basic nickel silicate catalyst from silicon-containing industrial solid waste

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20210608

CF01 Termination of patent right due to non-payment of annual fee