CN109201113B - Functionalized metal organic framework composite material and preparation method thereof - Google Patents
Functionalized metal organic framework composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000013183 functionalized metal-organic framework Substances 0.000 title abstract description 11
- 239000010931 gold Substances 0.000 claims abstract description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052737 gold Inorganic materials 0.000 claims abstract description 42
- 239000002105 nanoparticle Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 150000001844 chromium Chemical class 0.000 claims abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 162
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 57
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 45
- 239000011651 chromium Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 28
- 239000012265 solid product Substances 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical class [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 12
- ODHCTXKNWHHXJC-VKHMYHEASA-N 5-oxo-L-proline Chemical compound OC(=O)[C@@H]1CCC(=O)N1 ODHCTXKNWHHXJC-VKHMYHEASA-N 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- ODHCTXKNWHHXJC-UHFFFAOYSA-N acide pyroglutamique Natural products OC(=O)C1CCC(=O)N1 ODHCTXKNWHHXJC-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- -1 1-ethyl- (3-dimethylaminopropyl) carbonyl Chemical group 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims 1
- 229910000071 diazene Inorganic materials 0.000 claims 1
- 238000006011 modification reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 32
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 238000011068 loading method Methods 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 description 8
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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- 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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- 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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- 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
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Abstract
The invention provides a pyrrolidone functionalized metal organic framework/gold nanoparticle composite material and a preparation method thereof, belonging to the technical field of material chemistry and catalytic chemistry. The pyrrolidone functional metal organic framework material is prepared by coordinating dibenzoic acid and metal chromium salt in a six-coordination form, and then modifying an open metal center of the dibenzoic acid and metal chromium salt with a pyrrolidone functional site. The preparation method of the pyrrolidone functional metal organic framework/gold nanoparticle composite material comprises the step of taking the pyrrolidone functional metal organic framework material as a substrate and carrying out gold nanoparticle loading on the substrate. According to the composite material provided by the invention, due to the electron-donating effect of the pyrrolidone group modified on the metal organic framework material on the gold nanoparticles, the composite material can realize efficient alcohol oxidation reaction under the conditions that water is used as a solvent and molecular oxygen in air is used as an oxidant. The pyrrolidone functionalized metal organic framework/gold nanoparticle composite material has the advantages of good selectivity, simple separation, mild required reaction conditions, environmental protection and the like.
Description
Technical Field
The invention relates to the technical field of material chemistry and catalytic chemistry, in particular to a pyrrolidone functionalized metal organic framework/gold nanoparticle composite material and a preparation method thereof.
Background
Noble metal materials have been the focus of scientific research as a highly efficient catalyst. With the rise of nanotechnology, the synthesis and application of noble metal nanomaterials are widely studied. Among them, gold nanoparticles exhibit extremely excellent performance in the field of selective catalytic alcohol oxidation, and have an important propulsion effect on industrial fields such as fine chemicals and pharmaceutical production. However, gold nanoparticles as a homogeneous catalytic material need to be recycled through a complicated separation process, which not only complicates the production process but also increases the economic cost. Currently, gold nanoparticles are loaded on other materials to be an effective means for realizing the heterogenization (RSC advance.2016,6, 28688-.
Metal Organic Frameworks (MOFs) materials are porous crystalline materials constructed from inorganic Metal nodes and Organic ligands. As the MOFs material has the characteristics of large specific surface area, adjustable pore size structure, multiple functions and the like, the MOFs material has excellent application performance in the fields of gas adsorption/separation, energy storage, proton conduction, fluorescence detection, heterogeneous catalysis and the like. In addition, the MOFs material is a good carrier material as a porous material with stable structure and diversity. At present, research on the combination of MOFs materials and noble metal nanoparticle materials to obtain composite functional materials has been widely studied.
However, the loading of the gold nanoparticles by using the porosity of the MOFs material can not improve the performance of the gold nanoparticles, and how to design the functional MOFs material and enhance the catalytic performance of the gold nanoparticles through the synergistic effect has practical significance in realizing milder reaction conditions and environmental protection.
Disclosure of Invention
The invention aims to improve the catalytic performance of gold nanoparticles in a composite material, so that the conditions required in the catalytic alcohol oxidation reaction are milder and more environment-friendly, and the problem that an organic solvent and an inorganic salt oxidant are required in the existing catalytic reaction is solved.
The invention provides a pyrrolidone functionalized MOFs/gold nanoparticle composite material, which increases the catalytic performance of gold nanoparticles due to the electron donating effect of a pyrrolidone group modified on the MOFs material on the gold nanoparticles, and realizes the synergistic catalysis of the functionalized MOFs material and the gold nanoparticles.
The preparation method of the pyrrolidone functionalized MOFs/gold nanoparticle composite material provided by the invention comprises the following steps:
the method comprises the following steps: adding chromium metal salt, p-dibenzoic acid, 40% hydrofluoric acid aqueous solution and deionized water 1 into a hydrothermal reaction kettle, and reacting for 8-24 hours at 180-220 ℃; cooling to room temperature, filtering, and washing with deionized water and absolute ethyl alcohol for 3-5 times respectively; respectively using deionized water 2 and N, N-Dimethylformamide (DMF) as solvents, and heating and stirring at 50-80 ℃ for 10-24 hours; cooling to room temperature, centrifuging, and vacuum-drying at 100-150 ℃ for 12-15 hours under the condition that the vacuum degree is 133Pa to obtain a MOFs material (MIL-101-Cr) containing a chromium open metal center; the molar ratio of the chromium metal salt to the p-dibenzoic acid to the hydrofluoric acid to the deionized water 1 to the deionized water 2 to the DMF is 1: 1.5-3: 0.75-1.5: 200-300: 500-700.
Step two: dispersing the MIL-101-Cr obtained in the step one in an anhydrous benzene solvent; adding ethylenediamine under the conditions of nitrogen protection and stirring, and reacting for 8-24 hours at the temperature of 60-100 ℃; cooling to room temperature, filtering, washing with ethanol for 3-5 times, and vacuum drying at 80-150 deg.C under vacuum degree of 133Pa for 12-15 hr to obtain MOFs material (MIL-101-NH) with open metal center modified ethylenediamine2) (ii) a The mol ratio of MIL-101-Cr, ethylenediamine and anhydrous benzene is 1: 3-5: 50-70.
Step three: at room temperature, adding MIL-101-NH2Dispersing in a mixed solution of dichloromethane and DMF; adding L-pyroglutamic acid, 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (EDC.HCl), triethylamine and Dimethylaminopyridine (DMAP) under the conditions of nitrogen protection and stirring, and reacting for 8-24 hours at the temperature of 25-50 ℃; cooling to room temperature, filtering, washing with ethanol and deionized water for 3-5 times respectively, and vacuum-drying at 80-150 ℃ for 12-15 hours under the condition that the vacuum degree is 133Pa to obtain a pyrrolidone-modified MOFs material (MIL-101-Py); MIL-101-NH2The molar ratio of L-pyroglutamic acid, EDC.HCl, triethylamine, DMAP, dichloromethane and DMF is as follows: 1: 1.5-2.5: 2-3.75: 0.1-0.2: 10-20: 100-200.
Step four: dispersing the MIL-101-Py in anhydrous methanol 1 at room temperature; dropwise adding a chloroauric acid methanol solution with the concentration of 0.25mol/L under the conditions of nitrogen protection and stirring, and reacting for 8-12 hours at 25 ℃; centrifugally separating out a solid product, and washing for 3-5 times by using a methanol solution; the obtained solid was dispersed again in anhydrous methanol 2; dropwise adding 3.5mol/L sodium borohydride methanol solution under the conditions of nitrogen protection and stirring; reacting for 5-30 minutes at 25 ℃; and centrifugally separating a solid product, and washing the solid product for 3-5 times by using a methanol solution to obtain the gold nanoparticle-loaded functional MOFs composite material Au/MIL-101-Py. The mol ratio of MIL-101-Py, anhydrous methanol 1, chloroauric acid methanol solution, anhydrous methanol 2 and sodium borohydride methanol solution is as follows: 1: 20-50: 0.25-0.5: 20-50: 5-8.
The chromium metal salt is preferably chromium nitrate nonahydrate or chromium chloride.
The mol ratio of the chromium metal salt to the p-dibenzoic acid to the hydrofluoric acid to the deionized water 1 is preferably 1: 1.5-2.5: 0.75-1.25: 250-300.
In the first step, the reaction temperature in the reaction kettle is preferably 200-220 ℃, and the reaction time is preferably 8-18 hours.
The mol ratio of the MIL-101-Cr, the ethylenediamine and the anhydrous benzene is preferably 1: 3-4: 55-65.
The MIL-101-NH2The molar ratio of L-pyroglutamic acid, EDC.HCl, triethylamine, DMAP, dichloromethane and DMF is preferably: 1: 2.0-2.5: 2.5-3.5: 0.1-0.2: 10-20: 150-200.
The mol ratio of the MIL-101-Py, the anhydrous methanol 1, the chloroauric acid methanol solution, the anhydrous methanol 2 and the sodium borohydride methanol solution is preferably 1: 30-50: 0.3-0.5: 20-40: 5-7.
The reaction general formula of the pyrrolidone functionalized MOFs/gold nanoparticle composite material Au/MIL-101-Py catalytic alcohol oxidation is as follows:
wherein R is H, OH, CH3Or OCH3。
The invention has the following advantages:
1. the pyrrolidone functionalized MOFs material as a substrate has very high specific surface area which can reach 1319m2The pore volume of the larger pore channel structure is 0.720cm3The gold nanoparticle/g has the original crystal structure and good chemical stability, and can realize the effective loading of the gold nanoparticles in the pore channels.
2. The loaded gold nanoparticles are uniform in size, about 2-5 nm, and are uniformly dispersed in the MOFs carrier material.
3. Due to the electron donating effect of the modified pyrrolidone functional site on the gold nanoparticles, the catalytic performance of the gold nanoparticles can be improved, so that the pyrrolidone functional MOFs/gold nanoparticles composite material can realize efficient alcohol oxidation reaction under the conditions that water is used as a solvent and molecular oxygen in air is used as an oxidant. In addition, the composite catalytic material has the advantages of good selectivity, simple separation and the like
Drawings
FIG. 1 MIL-101-Cr, MIL-101-NH prepared in example 12Comparing the infrared spectrum with that of the MIL-101-Py;
FIG. 2 MIL-101-Cr, MIL-101-NH prepared in example 12Nitrogen adsorption-desorption attached figures of MIL-101-Py and Au/MIL-101-Py under 77K and 0-1 atmospheric pressure are measured;
FIG. 3 MIL-101-Cr, MIL-101-NH prepared in example 12XRD spectrograms of the MIL-101-Py, the Au/MIL-101-Py and the Au/MIL-101-Py after being recycled for three times;
FIG. 4 Transmission Electron microscopy of Au/MIL-101-Py prepared in example 1;
FIG. 5 is a photoelectron spectrum of X-ray gold element in Au/MIL-101-Py prepared in example 1;
Detailed Description
The invention will be described in further detail with reference to the drawings and examples, which are provided for better understanding of the invention and are not intended to limit the scope of the invention.
Example 1
The method comprises the following steps: adding 0.001mol of chromium nitrate nonahydrate, 0.0015mol of p-dibenzoic acid, 0.00075mol of hydrofluoric acid and 0.2mol of deionized water 1 into a hydrothermal reaction kettle, and reacting for 9 hours at 220 ℃; cooling to room temperature, filtering, and washing with deionized water and anhydrous ethanol for 3 times; respectively using 0.5mol of deionized water 2 and DMF as solvents, heating and stirring for 24 hours at 50 ℃; cooling to room temperature, centrifuging, and vacuum drying at 150 deg.C under 133Pa to obtain MIL-101-Cr containing chromium open metal center.
Step two: dispersing 0.001mol of the MIL-101-Cr in 0.05mol of anhydrous benzene at room temperature; adding 0.003mol of ethylenediamine under the conditions of nitrogen protection and stirring, and reacting for 24 hours at 60 ℃; cooling to room temperature, filtering, washing with benzene for 3 times, vacuum drying at 150 deg.C under vacuum degree of 133Pa for 12 hr to obtain open metal center modified ethylenediamine MIL-101-NH2。
Step three: at room temperature, 0.001mol of MIL-101-NH is added2Dispersing in a mixed solution of 0.01mol of dichloromethane and 0.1mol of DMF; adding 0.0015mol of L-pyroglutamic acid, 0.002mol of EDC.HCl, 0.002mol of triethylamine and 0.0001mol of DMAP under the conditions of nitrogen protection and stirring, and reacting for 24 hours at 25 ℃; cooling to room temperature, filtering, washing with ethanol and deionized water for 3 times respectively, and vacuum drying at 150 deg.C under vacuum degree of 133Pa for 12 hr to obtain pyrrolidone-modified MIL-101-Py.
Step four: dispersing 0.001mol of the MIL-101-Py in 0.02mol of anhydrous methanol 1 at room temperature; dropwise adding 1mL of chloroauric acid methanol solution with the concentration of 0.25mol/L under the conditions of nitrogen protection and stirring, and reacting for 8 hours at 25 ℃; centrifugally separating out a solid product, and washing 3 times by using a methanol solution; the obtained solid was dispersed again in 0.02mol of anhydrous methanol 2; dropwise adding 0.15mL of 3.5mol/L sodium borohydride methanol solution under the conditions of nitrogen protection and stirring; reacting at 25 ℃ for 30 minutes; and centrifugally separating a solid product, and washing the solid product for 3 times by using a methanol solution to obtain the gold nanoparticle-loaded functional MOFs composite material Au/MIL-101-Py.
For MIL-101-Cr and MIL-101-NH synthesized in example 12The structures of MIL-101-Py and Au/MIL-101-Py were characterized.
In the pyrrolidone functionalized MOFs/gold nanoparticle composite material prepared by the method, the mass fraction of gold loaded in the chromium metal organic framework material is 0.56%.
FIG. 1 shows MIL-101-Cr and MIL-101-NH prepared in example 12Comparison of the MIL-101-Py infrared spectrogram; as can be seen from FIG. 1, MIL-101-NH is compared to MIL-101-Cr2And MIL-101-Py at 1056cm-1The characteristic peak of the C-N bond appears, which proves that the ethylenediamine is successfully modified in the MIL-101-Cr; the MIL-101-Py infrared spectrum is 1689cm-1The C ═ O bond characteristic peak appears, which proves that the pyrrolidone functional site is successfully grafted on the MIL-101-NH2In (1).
FIG. 2 shows MIL-101-Cr and MIL-101-NH prepared in example 12MIL-101-Py and Au/MIL-101-Py-A nitrogen adsorption-desorption figure under 77K and 0-1 atmospheric pressure, and typical I-type adsorption isotherms illustrate MIL-101-Cr and MIL-101-NH2MIL-101-Py and Au/MIL-101-Py have a microporous structure.
FIG. 3 shows MIL-101-Cr and MIL-101-NH prepared in example 12XRD spectrograms of the MIL-101-Py, the Au/MIL-101-Py and the Au/MIL-101-Py after being recycled prove that the MOFs material after post-modification and gold nanoparticle loading still keeps a long-range ordered crystal structure, and the structure of the Au/MIL-101-Py is still kept unchanged after being recycled.
FIG. 4 is a transmission electron micrograph of Au/MIL-101-Py prepared in example 1, wherein the gold nanoparticles are uniformly dispersed in the MIL-101-Py and have a particle size of about 2 to 5 nm.
FIG. 5 is the X-ray photoelectron spectrum of gold element in Au/MIL-101-Py prepared in example 1, wherein the electron binding energy of Au 4f is 83.4eV, which is lower than that of ordinary zero-valent Au 4f, and the electron donating effect of pyrrolidone on gold nanoparticles is proved.
The catalytic performance of Au/MIL-101-Py provided in example 1 on alcohol oxidation was investigated; the reaction conditions were as follows: Au/MIL-101-Py 300 mg; 250mg of potassium carbonate; 0.001mol of alcohol compound; 10mL of water; reaction temperature: 35 ℃; the reaction time was 10 hours. The general reaction formula for catalytic alcohol oxidation is:
the reaction yield was 99.5% when R ═ H;
the reaction yield was 98.8% when R ═ OH;
in which R is CH3The reaction yield was 95.6%;
when R is OCH3The reaction yield was 88.7%; the results show that Au/MIL-101-Py provided by the example 1 can efficiently catalyze various alcohols to oxidize to produce corresponding ketone compounds under mild and environment-friendly conditions without organic solvents and by taking molecular oxygen in air as an oxidant.
Example 2
The method comprises the following steps: adding 0.001mol of chromium nitrate nonahydrate, 0.002mol of p-dibenzoic acid, 0.0001mol of hydrofluoric acid and 0.2mol of deionized water 1 into a hydrothermal reaction kettle, and reacting at 200 ℃ for 12 hours; cooling to room temperature, filtering, and washing with deionized water and anhydrous ethanol for 3 times; respectively using 0.5mol of deionized water 2 and DMF as solvents, heating and stirring for 24 hours at 50 ℃; cooling to room temperature, centrifuging, and vacuum drying at 150 deg.C under 133Pa to obtain MIL-101-Cr containing chromium open metal center.
Step two: dispersing 0.001mol of the MIL-101-Cr in 0.05mol of anhydrous benzene at room temperature; adding 0.004mol of ethylenediamine under the conditions of nitrogen protection and stirring, and reacting for 20 hours at 80 ℃; cooling to room temperature, filtering, washing with benzene for 3 times, vacuum drying at 150 deg.C under vacuum degree of 133Pa for 12 hr to obtain open metal center modified ethylenediamine MIL-101-NH2。
Step three: at room temperature, 0.001mol of MIL-101-NH is added2Dispersing in a mixed solution of 0.015mol of dichloromethane and 0.15mol of DMF; adding 0.002mol of L-pyroglutamic acid, 0.0025mol of EDC.HCl, 0.0025mol of triethylamine and 0.00015mol of DMAP under the conditions of nitrogen protection and stirring, and reacting for 24 hours at 25 ℃; cooling to room temperature, filtering, washing with ethanol and deionized water for 3 times respectively, and vacuum drying at 150 deg.C under vacuum degree of 133Pa for 12 hr to obtain pyrrolidone-modified MIL-101-Py.
Step four: dispersing 0.001mol of the MIL-101-Py in 0.02mol of anhydrous methanol 1 at room temperature; dropwise adding 1.2mL of chloroauric acid methanol solution with the concentration of 0.25mol/L under the conditions of nitrogen protection and stirring, and reacting for 8 hours at 25 ℃; centrifugally separating out a solid product, and washing 3 times by using a methanol solution; the obtained solid was dispersed again in 0.02mol of anhydrous methanol 2; dropwise adding 0.175mL of 3.5mol/L sodium borohydride methanol solution under the conditions of nitrogen protection and stirring; reacting at 25 ℃ for 30 minutes; and centrifugally separating a solid product, and washing the solid product for 3 times by using a methanol solution to obtain the gold nanoparticle-loaded functional MOFs composite material Au/MIL-101-Py.
The catalytic performance of Au/MIL-101-Py provided in example 2 on alcohol oxidation was investigated; the reaction conditions were the same as in example 1.
The reaction yield was 99.1% when R ═ H;
the reaction yield was 98.2% when R ═ OH;
in which R is CH3The reaction yield was 94.0%;
when R is OCH3The reaction yield was 89.1%.
Example 3
The method comprises the following steps: adding 0.001mol of chromium nitrate nonahydrate, 0.002mol of p-dibenzoic acid, 0.0001mol of hydrofluoric acid and 0.2mol of deionized water 1 into a hydrothermal reaction kettle, and reacting at 200 ℃ for 12 hours; cooling to room temperature, filtering, and washing with deionized water and anhydrous ethanol for 4 times; respectively using 0.6mol of deionized water 2 and DMF as solvents, heating and stirring for 24 hours at 60 ℃; cooling to room temperature, centrifuging, and vacuum drying at 120 deg.C under vacuum degree of 133Pa for 12 hr to obtain MIL-101-Cr containing chromium open metal center.
Step two: dispersing 0.001mol of the MIL-101-Cr in 0.05mol of anhydrous benzene at room temperature; adding 0.004mol of ethylenediamine under the conditions of nitrogen protection and stirring, and reacting for 20 hours at 80 ℃; cooling to room temperature, filtering, washing with benzene for 4 times, vacuum drying at 120 deg.C under vacuum degree of 133Pa for 12 hr to obtain open metal center modified ethylenediamine MIL-101-NH2。
Step three: at room temperature, 0.001mol of MIL-101-NH is added2Dispersing in a mixed solution of 0.015mol of dichloromethane and 0.15mol of DMF; adding 0.002mol of L-pyroglutamic acid,0.0025mol of EDC.HCl, 0.0025mol of triethylamine and 0.00015mol of DMAP, reacting for 20 hours at 35 ℃; cooling to room temperature, filtering, washing with ethanol and deionized water for 3 times respectively, and vacuum drying at 120 deg.C under vacuum degree of 133Pa for 12 hr to obtain pyrrolidone-modified MIL-101-Py.
Step four: dispersing 0.001mol of the MIL-101-Py in 0.02mol of anhydrous methanol 1 at room temperature; dropwise adding 1.2mL of chloroauric acid methanol solution with the concentration of 0.25mol/L under the conditions of nitrogen protection and stirring, and reacting for 8 hours at 25 ℃; centrifugally separating out a solid product, and washing 3 times by using a methanol solution; the obtained solid was dispersed again in 0.02mol of anhydrous methanol 2; dropwise adding 0.175mL of 3.5mol/L sodium borohydride methanol solution under the conditions of nitrogen protection and stirring; reacting at 25 ℃ for 30 minutes; and centrifugally separating a solid product, and washing the solid product for 4 times by using a methanol solution to obtain the gold nanoparticle-loaded functional MOFs composite material Au/MIL-101-Py.
The catalytic performance of Au/MIL-101-Py provided in example 3 on alcohol oxidation was investigated; the reaction conditions were the same as in example 1.
The reaction yield was 98.1% when R ═ H;
the reaction yield was 98.5% when R ═ OH;
in which R is CH3The reaction yield was 94.5%;
when R is OCH3The reaction yield was 88.4%.
Example 4
The method comprises the following steps: adding 0.001mol of chromium nitrate nonahydrate, 0.0025mol of p-dibenzoic acid, 0.0001mol of hydrofluoric acid and 0.25mol of deionized water 1 into a hydrothermal reaction kettle, and reacting at 200 ℃ for 12 hours; cooling to room temperature, filtering, and washing with deionized water and anhydrous ethanol for 4 times; respectively using 0.6mol of deionized water 2 and DMF as solvents, heating and stirring for 20 hours at 60 ℃; cooling to room temperature, centrifuging, and vacuum drying at 120 deg.C under vacuum degree of 133Pa for 12 hr to obtain MIL-101-Cr containing chromium open metal center.
Step two: dispersing 0.001mol of the MIL-101-Cr in 0.06mol of anhydrous benzene at room temperature; adding 0.004mol of ethylenediamine into the mixture under the protection of nitrogen and stirring conditions to obtain a mixture of 1Reacting for 12 hours at 00 ℃; cooling to room temperature, filtering, washing with benzene for 4 times, vacuum drying at 120 deg.C under vacuum degree of 133Pa for 12 hr to obtain open metal center modified ethylenediamine MIL-101-NH2。
Step three: at room temperature, 0.001mol of MIL-101-NH is added2Dispersing in a mixed solution of 0.0175mol of dichloromethane and 0.175mol of DMF; adding 0.002mol of L-pyroglutamic acid, 0.0025mol of EDC.HCl, 0.0025mol of triethylamine and 0.00015mol of DMAP under the conditions of nitrogen protection and stirring, and reacting for 20 hours at 35 ℃; cooling to room temperature, filtering, washing with ethanol and deionized water for 3 times respectively, and vacuum drying at 120 deg.C under vacuum degree of 133Pa for 12 hr to obtain pyrrolidone-modified MIL-101-Py.
Step four: dispersing 0.001mol of the MIL-101-Py in 0.02mol of anhydrous methanol 1 at room temperature; dropwise adding 1.2mL of chloroauric acid methanol solution with the concentration of 0.25mol/L under the conditions of nitrogen protection and stirring, and reacting for 8 hours at 25 ℃; centrifugally separating out a solid product, and washing 3 times by using a methanol solution; the obtained solid was dispersed again in 0.02mol of anhydrous methanol 2; dropwise adding 0.175mL of 3.5mol/L sodium borohydride methanol solution under the conditions of nitrogen protection and stirring; reacting at 25 ℃ for 30 minutes; and centrifugally separating a solid product, and washing the solid product for 4 times by using a methanol solution to obtain the gold nanoparticle-loaded functional MOFs composite material Au/MIL-101-Py.
The catalytic performance of Au/MIL-101-Py provided in example 4 on alcohol oxidation was investigated; the reaction conditions were the same as in example 1.
When R ═ H, the reaction yield was 97.1%;
when R ═ OH, the reaction yield was 97.5%;
in which R is CH3The reaction yield was 94.0%;
when R is OCH3The reaction yield was 86.9%.
Example 5
The method comprises the following steps: adding 0.001mol of chromium chloride, 0.003mol of p-dibenzoic acid, 0.00015mol of hydrofluoric acid and 0.3mol of deionized water 1 into a hydrothermal reaction kettle, and reacting for 24 hours at 180 ℃; cooling to room temperature, filtering, and washing with deionized water and anhydrous ethanol for 5 times; respectively using 0.7mol of deionized water 2 and DMF as solvents, heating and stirring for 20 hours at 60 ℃; cooling to room temperature, centrifuging, and vacuum drying at 120 deg.C under vacuum degree of 133Pa for 12 hr to obtain MIL-101-Cr containing chromium open metal center.
Step two: dispersing 0.001mol of the MIL-101-Cr in 0.06mol of anhydrous benzene at room temperature; adding 0.005mol of ethylenediamine under the conditions of nitrogen protection and stirring, and reacting for 8 hours at 100 ℃; cooling to room temperature, filtering, washing with benzene for 5 times, vacuum drying at 120 deg.C under vacuum degree of 133Pa for 12 hr to obtain open metal center modified ethylenediamine MIL-101-NH2。
Step three: at room temperature, 0.001mol of MIL-101-NH is added2Dispersing in a mixed solution of 0.02mol of dichloromethane and 0.2mol of DMF; adding 0.002mol of L-pyroglutamic acid, 0.003mol of EDC.HCl, 0.003mol of triethylamine and 0.0002mol of DMAP under the conditions of nitrogen protection and stirring, and reacting for 8 hours at 50 ℃; cooling to room temperature, filtering, washing with ethanol and deionized water for 5 times respectively, and vacuum drying at 120 deg.C under vacuum degree of 133Pa for 12 hr to obtain pyrrolidone-modified MIL-101-Py.
Step four: dispersing 0.001mol of the MIL-101-Py in 0.05mol of anhydrous methanol 1 at room temperature; dropwise adding 1.5mL of chloroauric acid methanol solution with the concentration of 0.25mol/L under the conditions of nitrogen protection and stirring, and reacting for 8 hours at 25 ℃; centrifugally separating out a solid product, and washing the solid product for 5 times by using a methanol solution; the obtained solid was dispersed again in 0.03mol of anhydrous methanol 2; dropwise adding 0.175mL of 3.5mol/L sodium borohydride methanol solution under the conditions of nitrogen protection and stirring; reacting at 25 ℃ for 30 minutes; and centrifugally separating a solid product, and washing the solid product for 5 times by using a methanol solution to obtain the gold nanoparticle-loaded functional MOFs composite material Au/MIL-101-Py.
The catalytic performance of Au/MIL-101-Py provided in example 5 on alcohol oxidation was investigated; the reaction conditions were the same as in example 1.
When R ═ H, the reaction yield was 97.7%;
the reaction yield was 96.1% when R ═ OH;
in which R is CH3The reaction yield was 94.3%;
when R is OCH3The reaction yield was 86.4%.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. It should be understood by those skilled in the art that various changes and substitutions may be made in accordance with the technical solution and the inventive concept of the present invention, and the same properties or uses should be considered as the protection scope of the present invention.
Claims (1)
1. A preparation method of a pyrrolidone functional metal organic framework/gold nanoparticle composite material is characterized in that the functional metal organic framework material is an MIL-101-Cr substrate material formed by coordinating dibenzoic acid and metal chromium salt in a six-coordination form, and open metal centers of the functional metal organic framework material are modified with a pyrrolidone functional site through two-step post-modification reaction, so that the pyrrolidone functional metal organic framework material is obtained, wherein the pyrrolidone functional site has an electron donating effect on gold nanoparticles, and the catalytic performance of the gold nanoparticles can be improved, and the preparation method comprises the following steps:
the method comprises the following steps: adding chromium metal salt, p-dibenzoic acid, 40% hydrofluoric acid aqueous solution and deionized water 1 into a hydrothermal reaction kettle, and reacting for 8-24 hours at 180-220 ℃; cooling to room temperature, filtering, and washing with deionized water and absolute ethyl alcohol for 3-5 times respectively; with deionized water 2 andN,N-Dimethylformamide (DMF) as a solvent, heating and stirring at 50-80 ℃ for 10-24 hours; cooling to room temperature, centrifuging, and vacuum-drying at 100-150 ℃ for 12-15 hours under the condition that the vacuum degree is 133Pa to obtain an MOFs material MIL-101-Cr containing a chromium open metal center, which is formed by p-dibenzoic acid and metal chromium salt in a hexacoordinate form; the molar ratio of the chromium metal salt to the p-dibenzoic acid to the hydrofluoric acid to the deionized water 1 to the deionized water 2 to the DMF is 1: 1.5-3: 0.75-1.5: 200-300: 500-700;
step two: dispersing the MIL-101-Cr obtained in the step one in an anhydrous benzene solvent; adding ethylenediamine under the protection of nitrogen and stirring at 60 deg.CReacting for 8-24 hours at 100 ℃; cooling to room temperature, filtering, washing with ethanol for 3-5 times, and vacuum drying at 80-150 ℃ for 12-15 hours under the condition that the vacuum degree is 133Pa to obtain the MOFs material MIL-101-NH of open metal center modified ethylenediamine2(ii) a The mol ratio of MIL-101-Cr, ethylenediamine and anhydrous benzene is 1: 3-5: 50-70;
step three: at room temperature, adding MIL-101-NH2Dispersing in a mixed solution of dichloromethane and DMF; adding L-pyroglutamic acid, 1-ethyl- (3-dimethylaminopropyl) carbonyl diimine hydrochloride (EDC) under the protection of nitrogen and stirring.HCl), triethylamine and Dimethylaminopyridine (DMAP) are reacted for 8 to 24 hours at a temperature of between 25 and 50 ℃; cooling to room temperature, filtering, washing with ethanol and deionized water for 3-5 times respectively, and vacuum-drying at 80-150 ℃ for 12-15 hours under the condition that the vacuum degree is 133Pa to obtain the pyrrolidone-modified MOFs material MIL-101-Py; MIL-101-NH2L-pyroglutamic acid, EDC.The molar ratio of HCl, triethylamine, DMAP, dichloromethane and DMF is as follows: 1: 1.5-2.5: 2-3.75: 0.1-0.2: 10-20: 100-200;
step four: dispersing the MIL-101-Py in anhydrous methanol 1 at room temperature; dropwise adding a chloroauric acid methanol solution with the concentration of 0.25mol/L under the conditions of nitrogen protection and stirring, and reacting for 8-12 hours at 25 ℃; centrifugally separating out a solid product, and washing for 3-5 times by using a methanol solution; the obtained solid was dispersed again in anhydrous methanol 2; dropwise adding 3.5mol/L sodium borohydride methanol solution under the conditions of nitrogen protection and stirring; reacting for 5-30 minutes at 25 ℃; centrifugally separating out a solid product, and washing the solid product for 3-5 times by using a methanol solution to obtain a gold nanoparticle-loaded functional MOFs composite material Au/MIL-101-Py; the mol ratio of MIL-101-Py, anhydrous methanol 1, chloroauric acid methanol solution, anhydrous methanol 2 and sodium borohydride methanol solution is as follows: 1: 20-50: 0.25-0.5: 20-50: 5-8.
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