CN112206829A - MOF catalyst UiO-66-SO3Preparation method of H - Google Patents
MOF catalyst UiO-66-SO3Preparation method of H Download PDFInfo
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- 239000012918 MOF catalyst Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 150000003754 zirconium Chemical class 0.000 claims abstract description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 11
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 6
- DJYPJBAHKUBLSS-UHFFFAOYSA-M sodium;hydron;terephthalate Chemical compound [Na+].OC(=O)C1=CC=C(C([O-])=O)C=C1 DJYPJBAHKUBLSS-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 229910003130 ZrOCl2·8H2O Inorganic materials 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- JARIJYUQOKFVAJ-UHFFFAOYSA-M sodium;4-carboxy-2-sulfobenzoate Chemical compound [Na+].OC(=O)C1=CC=C(C([O-])=O)C(S(O)(=O)=O)=C1 JARIJYUQOKFVAJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 17
- 239000013207 UiO-66 Substances 0.000 description 12
- 239000011734 sodium Substances 0.000 description 10
- 229910006069 SO3H Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000013208 UiO-67 Substances 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011469 building brick Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000007734 materials engineering Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000012987 post-synthetic modification Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- 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]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
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- 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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Zirconium MOF catalyst UiO-66-SO is rapidly prepared by taking zirconium salt, 2-sulfonic monosodium terephthalate and terephthalic acid as raw materials and performing ultrasonic-assisted dissolution3H, a process for producing the same. The method comprises the following steps: adding zirconium salt, 2-sulfonic acid group monosodium terephthalate and terephthalic acid into a monocarboxylic acid solution, dissolving for 3-10 min by ultrasonic wave assistance, and reacting for 10-24 h at 40-60 ℃. After the reaction is finished, cooling the materials to room temperature, carrying out centrifugal separation, washing the obtained white powder with a solvent for 3-6 times, and then carrying out vacuum drying at 10-20 kPa and 200-300 ℃ to constant weight to obtain UiO-66-SO3And H, powder. Compared with the prior art, the preparation method has the advantages that: simple synthesis steps, high reaction speed, high yield, larger particle size of particles, complete crystal form and good thermal stability.
Description
Technical Field
The invention relates toAnd a zirconium MOF catalyst UiO-66-SO3A preparation method of H, in particular to a method for quickly preparing a zirconium MOF catalyst UiO-66-SO by taking zirconium salt, 2-sulfonic acid group monosodium terephthalate and terephthalic acid as raw materials and carrying out ultrasonic-assisted dissolution3H, belonging to the field of catalytic materials and chemical engineering.
Background
As a new class of porous organic materials, MOFs materials mainly have the following characteristics: the adjustability of the aperture; high density and uniform distribution of catalytically active sites; unsaturation of metal center ions in MOFs materials; the diversity of the functional groups of MOFs materials. These characteristics allow MOFs materials to have both the high efficiency of homogeneous catalysis and the renewable recovery of heterogeneous catalysis. Therefore, MOFs have great potential for catalytic reaction and have been developed rapidly. However, most MOFs have poor chemical and thermal stability, which greatly limits their application in high temperature catalytic reactions.
Yaghi and the like systematically research the thermal stability of MOFs materials, and discover that the thermal stability of the MOFs materials is related to metal central ions, the MOFs materials taking Al, Fe, Cr, Cu and the like as the metal central ions have generally poor heat resistance, while the MOFs materials taking Zr as the metal central ions have higher thermal stability, and the heat resistance temperature of UiO-66, UiO-67 and the like can reach more than 540 ℃ [ ZHou H C, Long J R, Yaghi O M. integral to metal-organic frameworks [ J ]].Chemical Reviews,2012,112(2):673-674；Sherry B D,Fürstner,Alois.The Promise and Challenge of Iron-Catalyzed Cross Coupling[J].Accounts of Chemical Research,2008,41(11):1500-1511；Cavka J H,Jakobsen S,Olsbye U,et al.A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability[J].Journal of the American Chemical Society,2008,130(42):13850-13851]. UiO-66 is an inorganic metal unit Zr6O4(OH)4Coordinated with 12 terephthalic acids to form a three-dimensional structure material with octahedron and cubic hole cages. Because the node of the UiO-66 has larger link number and the Zr-O bond is stronger, the UiO-66 has very high chemical stability and thermal stability and has high temperature of 500 DEG CThe lower skeleton structure can still remain intact.
The structure and the synthesis method of UiO-66 are researched by Valenzano, which shows that Zr in the UiO-664+The Lewis acid is provided by the metal ion site, and the sulfonic group is introduced by the modification of the organic ligand, and the Lewis acid can also be provided
Acid sites, which through the synergistic effect of L-and B-acid double sites can increase the catalytic activity of UO-66 [ Valenzano L, Civalleri B, Chavan S, et al, purifying the Complex Structure of UO-66 Metal Organic Framework: asynchronous communication of Experiment and therapy [ J].Chemistry of Materials,2011,23(7):1700-1718；Torbina V V,Nedoseykina N S,Ivanchikova I D,et al.Propylene glycol oxidation with hydrogen peroxide over Zr-containing metal-organic framework UiO-66[J].Catalysis Today,2019,333:47-53]. Some documents report the preparation of UiO-66 containing sulfonic acid groups. Luan Y et al with ZrCl4Taking 2-amino-terephthalic acid as an organic ligand as a raw material, and firstly synthesizing UiO-66-NH2Then reacting with 1, 3-propane sultone to synthesize MOFs (UiO-66-NH-RSO) containing both amino and sulfonic acid groups3H) And as a catalyst for the condensation of benzaldehyde and ethanol. The process is as follows: respectively reacting ZrCl4(1.6g,6.8mmol) in a mixed solvent of N, N-dimethylformamide (DMF, 150mL) and acetic acid (11.4mL,3.4mol), 2-amino-terephthalic acid (1.2g,6.8mmol) in 50mL DMF, then mixing the two, and adding 0.5mL water, then reacting at 120 ℃ for 24h, washing the resulting product with DMF (20mL x 2), ethanol (20mL x 3), then vacuum drying at 80 ℃ for 3h to obtain UiO-66-NH2. Then, 1.5g (0.85mmol) of UiO-66-NH was added2Dispersed in 20mL CHCl3To the reaction solution, 1, 3-propanesultone (207mg,1.7mmol) was added in a 2-fold molar amount, the mixture was stirred at 25 ℃ for 12h, soaked with DMF (10mL) for three days, replaced with fresh DMF once a day, and then treated with CHCl once a day3Washing once for 2 days, and vacuum drying at 40 deg.C to obtain UiO-66-NH-RSO3H. The method has multiple synthesis steps, long reaction time and low product yield [ Luan Y, Zheng N, Qi Y, et alpment of a SO3H-Functionalized UiO-66Metal–Organic Framework by Postsynthetic Modification and Studies of Its Catalytic Activities[J].European Journal of Inorganic Chemistry,2015,2014(26):4268-4272]Hu Z et al used 2-sodium sulfonate-1, 4-terephthalic acid (BDC-SO)3Na) as organic ligand to synthesize the product containing-SO3H, MOF material (NUS-6). The method firstly BDC-SO3Na (1.3g, 4.8mmol) and ZrCl4(1.2g, 5.2mmol) was dissolved in 50mL of a mixed solvent of water and acetic acid (volume ratio 30/20), followed by reaction at 80 ℃ for 24 hours, and the product was washed with water 3 times, then soaked with anhydrous methanol at room temperature for 3 days, and the methanol was refreshed daily. Finally, vacuum drying at 150 ℃ for 24h to obtain NUS-6. Due to-SO3The presence of Na groups results in ligands which are more sterically hindered and more difficult to coordinate with Metal ions, resulting in incomplete reactions and very low yields [ Hu Z, Peng Y, Gao Y, et al direct Synthesis of High Porous Metal-Organic Frameworks and Strong branched acid: The destructive Role of Hafnium in efficiency and Selective reaction [ J Z].Chemistry of Materials,2016:2659-2667]。
In general, there are few reports on the preparation method of the sulfonic acid group-containing UiO-66, and the reported method has disadvantages of long reaction time, many synthesis steps, low synthesis efficiency, and the like.
Disclosure of Invention
For UiO-66-SO3H production method, the present inventors have conducted on UiO-66-SO3The preparation method of H is intensively researched, and the discovery that the zirconium MOF catalyst UiO-66-SO can be rapidly prepared by taking metal zirconium salt, 2-sulfonic acid group monosodium terephthalate and terephthalic acid as raw materials and performing ultrasonic-assisted dissolution3H。
The invention adopts the following technical scheme:
zirconium MOF catalyst UiO-66-SO3The preparation method of H comprises the following steps:
(1) zirconium salt, 2-sulfonic acid group monosodium terephthalate (H)2BDC-SO3Na) and terephthalic acid (H)2BDC) is added withDissolving in a reaction bottle of a polycarboxylic acid solution for 3-10 min by ultrasonic wave assistance, and reacting at 40-60 ℃ for 10-24 h.
(2) After the reaction is finished, cooling the materials to room temperature, carrying out centrifugal separation, washing the obtained white powder with a solvent for 3-6 times, and then carrying out vacuum drying at 10-20 kPa and 200-300 ℃ to constant weight to obtain UiO-66-SO3And H, powder.
The zirconium salt is Zr (NO)3)4·5H2O、ZrCl4And ZrOCl2·8H2O；
The zirconium salt and H2BDC-SO3Na and H2The molar ratio of BDC is 1.00: 0.10 to 0.50: 0.50 to 1.00, preferably 1: 0.20-0.35: 0.70 to 0.90;
the molar ratio of the zirconium salt to the monocarboxylic acid is 1.0: 5.0-30.0, preferably 1.0: 7.0 to 20.0;
the monocarboxylic acid solution consists of monocarboxylic acid and corresponding solvent in the volume ratio of VSolvent(s):VMonocarboxylic acids20: 1, wherein the monocarboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, benzoic acid and trifluoroacetic acid, and the corresponding solvents are deionized water, methanol, DMF, N-Diethylformamide (DEF) and 1-methyl-2-pyrrolidone (NMP);
the washing solvent is deionized water, methanol, ethanol, DMF, DEF, NMP, acetone and trichloromethane; the mass ratio of the zirconium salt to the washing solvent is 1.0: 3.0-5.0.
Compared with the prior art, the preparation method has the advantages that: simple synthesis steps, high reaction speed, high yield, larger particle size of particles, complete crystal form and good thermal stability.
Drawings
FIG. 1 shows UiO-66-SO3X-ray diffraction pattern of H powder.
FIG. 2 shows UiO-66-SO3H, scanning electron micrograph.
FIG. 3 shows UiO-66-SO3And H, thermogravimetric analysis result.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
All percentages used in the present invention are mass percentages unless otherwise indicated.
The various chemical starting materials and solvents used in the examples were analytical reagents.
UiO-66-SO3The crystal structure of H was characterized using a Rigaku Smart Lab III X-ray diffractometer (Japan science Co.). The specific parameters of the instrument are as follows: a Cu-Kalpha target (K: 0.150406nm,40kV and 30mA), a graphite monochromator, a scanning speed of 10 degrees/min and a 2 theta angle range of 5 degrees to 80 degrees.
UiO-66-SO3The crystal morphology of H was observed by Hitachi S-4800 scanning electron microscope (Japan Electron Co., Ltd.).
Thermogravimetric analysis (TGA) A thermal analyzer model Netzsch STA 449F5 (Steed, Germany) was used. The analysis conditions were as follows: air atmosphere, air flow rate of 50mL/min, temperature range of 25-800 deg.C, and heating rate of 10 deg.C/min.
Example 1
Zirconium MOF catalyst UiO-66-SO3The preparation method of H comprises the following steps:
(1) 1.17g (5mmol) of ZrCl40.27g (1mmol) of monosodium 2-sulfoterephthalate (H)2BDC-SO3Na) and 0.66g (4mmol) of terephthalic acid (H)2BDC) was added to a reaction flask containing 5mL (86.8mmol) of acetic acid and 100mL of DMF, followed by ultrasonic-assisted dissolution for 5min, and reaction was carried out at 50 ℃ for 20 h.
(2) After the reaction is finished, the material is cooled to room temperature, and after centrifugal separation, the obtained white powder is washed for 4 times by 1.5mL of multiplied by 4 methanol and then is dried in vacuum at the temperature of 250 ℃ under the condition of 10-20 kPa to constant weight to obtain 1.22g of UiO-66-SO3H powder, mass yield (quality of the product obtained with zirconium salt, H2BDC-SO3Na and H2The sum of BDC) was 58.1% by mass.
The structure of the product obtained in the embodiment is characterized by X-ray diffraction, a scanning electron microscope and thermogravimetric analysis. FIG. 1 is an X-ray diffraction diagram of the product obtained in example 1 of the present invention; FIG. 2 is a scanning electron micrograph of a product obtained in example 1 of the present invention; FIG. 3 is a thermogravimetric analysis curve of the product obtained in example 1 of the present invention.
In FIG. 1, the peaks at 2 θ of 7.5 °, 8.5 °, 17.1 °, 25.8 ° and 30.7 ° correspond to the (111), (200), (222), (442) and (711) crystal planes of the UiO-66 crystal, respectively, which indicates that the prepared material has the characteristic peaks of the UiO-66 crystal and the crystal form is relatively complete.
FIG. 2 shows that synthesized UiO-66-SO3The particle size of the H powder is about 600nm, which is far larger than 280nm of UiO-66, the particle shape is like an octahedron, the surface is smooth, and the distribution is uniform.
The results in FIG. 3 show that synthetic UiO-66-SO3The temperature of 5 percent of weight loss of H is more than 300 ℃, the temperature during rapid decomposition is more than 500 ℃, namely the synthesized UiO-66-SO3H has good thermal stability.
Example 2
Zirconium MOF catalyst UiO-66-SO3The preparation method of H comprises the following steps:
(1) 3.46g (8mmol) of Zr (NO)3)4·5H2O，0.67g(2.5mmol)H2BDC-SO3Na and 1.16g (7mmol) H2BDC was added to a reaction flask containing 3mL (79.5mmol) of formic acid and 100mL of ethanol, followed by ultrasonic-assisted dissolution for 5min and reaction at 50 ℃ for 20 h.
(2) After the reaction is finished, cooling the materials to room temperature, performing centrifugal separation to obtain white powder, washing the white powder with 1.5mL of multiplied by 4 methanol for 4 times, and performing vacuum drying under the conditions of 10-20 kPa and 250 ℃ to obtain 2.04g of UiO-66-SO3Powder H, mass yield 37.8%.
The product of this example was tested in the manner characterized in example 1, and the results were substantially the same as example 1.
Example 3
Zirconium MOF catalyst UiO-66-SO3The preparation method of H comprises the following steps:
(1) 3.22g (10mmol) of ZrOCl were added2·8H2O，0.81g(3mmol)H2BDC-SO3Na and 1.16g (7mmol) H2BDC was added to a reaction flask containing 3mL (79.5mmol) of formic acid and 100mL of ethanol, followed by ultrasonic-assisted dissolution for 5min and reaction at 50 ℃ for 20 h.
(2) After the reaction is finished, cooling the materials to room temperature, performing centrifugal separation to obtain white powder, washing the white powder with 1.5mL of multiplied by 4 methanol for 4 times, and performing vacuum drying under the conditions of 10-20 kPa and 250 ℃ to constant weight to obtain 2.12g of UiO-66-SO3H powder, mass yield 40.8%.
The product of this example was tested in the manner characterized in example 1, and the results were substantially the same as example 1.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. Zirconium MOF catalyst UiO-66-SO3The preparation method of H is characterized by comprising the following preparation steps: adding zirconium salt, 2-sulfonic acid group monosodium terephthalate and terephthalic acid into a monocarboxylic acid solution, dissolving for 3-10 min by ultrasonic wave assistance, and reacting for 10-24 h at 40-60 ℃; after the reaction is finished, cooling the materials to room temperature, carrying out centrifugal separation, washing the obtained white powder with a solvent for 3-6 times, and then carrying out vacuum drying at 10-20 kPa and 200-300 ℃ to constant weight to obtain UiO-66-SO3And H, powder.
2. The zirconium MOF catalyst UiO-66-SO of claim 13The preparation method of H is characterized in that the zirconium salt is Zr (NO)3)4·5H2O、ZrCl4And ZrOCl2·8H2O, the zirconium salt, 2-sulfoterephthalic acid monosodium salt and terephthalic acid bisThe molar ratio of formic acid is 1.00: 0.10 to 0.50: 0.50 to 1.00.
3. The zirconium MOF catalyst UiO-66-SO of claim 13The preparation method of H is characterized in that the monocarboxylic acid solution consists of monocarboxylic acid and corresponding solvent, and the volume ratio of the monocarboxylic acid solution to the corresponding solvent is VSolvent(s):VMonocarboxylic acids20: 1, wherein the monocarboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, benzoic acid and trifluoroacetic acid, the corresponding solvents are deionized water, methanol, N-dimethylformamide, N-diethylformamide and 1-methyl-2-pyrrolidone, and the molar ratio of the zirconium salt to the monocarboxylic acids is 1.0: 5.0 to 30.0.
4. The zirconium MOF catalyst UiO-66-SO of claim 13The preparation method of the H is characterized in that the washing solvent is deionized water, methanol, ethanol, N-dimethylformamide, N-diethylformamide, 1-methyl-2-pyrrolidone, acetone and trichloromethane, and the mass ratio of the zirconium salt to the washing solvent is 1.0: 3.0-5.0.
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