Composite material of metal nano particles and microporous coordination polymer and preparation method thereof

Abstract

The invention provides a composite material of metal nano particles and a microporous coordination polymer and a preparation method thereof. The metal nano particles of the composite material are palladium or platinum nano particles. The microporous coordination polymer is an iron-based microporous coordination polymer MIL-53(Fe) having a topological structure, the general formula may be written as Fe (OH).H2O, wherein L is an organic ligand, iron ions are connected by oxygen and carboxyl of the organic ligand to form zigzag chains, and these chains are connected by the organic ligand to form an ID open-framework structure. Stirring is performed at normal temperature and normal pressure to dissolve iron salts in an organic solvent to form a brown solution, the organic ligand is added until dissolving, the solution of the metal nano particles is added to prepare a mixed solution, and reaction is performed on the obtained mixed solution to obtain the target object. Based on the added iron salt, the yield is 35-87%, and the mass content of the metal nano particles is 0.01-20%. The composite material has high thermal stability and large specific area, can be used for deep desulfurization of the oil products, and has selective catalytic action on some special molecules.

Description

technical field

[0001] The patent of the invention relates to a composite material and a preparation method of metal nanoparticles and microporous coordination polymers. Background technique

[0002] So far, more than 10,000 kinds of coordination polymers have been synthesized, some of which have been widely accepted due to their very high thermal stability and chemical stability (organic solvents, water, acid or alkali, air, etc.). s concern. These coordination polymers include HKUST-1, MIL-53, MIL-100, MIL-101, ZIF-8 and UIO-66, etc. MIL-53 has attracted people's attention due to its large one-dimensional pore structure. The pore size changes with the adsorption or desorption of solvent molecules, which is called "breathing". The lower limit and upper limit of the channel size are respectively 0.8nm and 1.3nm, which are close to ZSM-5 and faujasite with a silica-based zeolite structure. One of the applications of porous materials is catalysis, especially shape-selectiv...

Examples

Embodiment 1

[0035] Example 1 A composite material of metal nanoparticles and microporous coordination polymers, characterized in that the metal nanoparticles are palladium or platinum nanoparticles, and the microporous coordination polymers are iron-based microporous coordination polymers MIL- 53(Fe), MIL-53(Fe) has a topological structure, and its general formula can be written as Fe(OH)L·H 2 O, where L is an organic ligand, iron ions are connected by oxygen and the carboxyl group of the organic ligand to form a "zigzag" chain, and then these chains are connected by an organic ligand to form a 1D pore structure.

[0036] A method for preparing a composite material of metal nanoparticles and microporous coordination polymers, the steps and conditions are as follows:

[0037] Step 1, under stirring at normal temperature and pressure, 270 mg of FeCl 3 . 6H 2 O (1.0mmol) dissolved in 10ml N , N’ - Dimethylformamide (130 mmol) forms a brown solution;

[0038] Step 2, add 249mg terepht...

Embodiment 2

[0040] Example 2 A method for preparing a composite material of metal nanoparticles and microporous coordination polymers, the steps and conditions are as follows:

[0041] Step 1, under stirring at normal temperature and pressure, 414 mg of Fe(NO 3 ) 3 . 9H 2 O (1.0mmol) dissolved in 15ml N , N’ - Dimethylformamide (130 mmol) forms a brown solution;

[0042] Step 2, the brown solution prepared in step 1 was added organic ligand 332mg terephthalic acid (2mmol) until dissolved;

[0043] Step 3, adding the brown solution prepared in step 2 to a concentration of 1 mg / 1 mL of 5.7 nm metal nanoparticles platinum methanol solution, Fe(NO 3 ) 3 . 9H 2 O : H 2 The molar ratio of BDC: DMF: Pt is 1: 2: 195: 0.005, and then the brown solution is stirred for half an hour, reacted at 130°C for 24 hours, the product is separated by centrifugation at 5000 rpm for 10 minutes, and washed three times with ethanol , and dried to obtain a composite material of platinum nanoparticl...

Embodiment 3

[0044] Example 3 A method for preparing a composite material of metal nanoparticles and microporous coordination polymers, the steps and conditions are as follows:

[0045] Step 1, under stirring at normal temperature and pressure, 414 mg of Fe(NO 3 ) 3 . 9H 2 O (1.0mmol) dissolved in 15ml N , N’ - Dimethylformamide (130 mmol) forms a brown solution;

[0046] Step 2, add 166 mg of terephthalic acid (1 mmol) as an organic ligand to the brown solution prepared in step 1 until dissolved;

[0047] Step 3, adding the brown solution prepared in step 2 to a concentration of 1 mg / 1 mL of 8.2 nm metal nanoparticles platinum methanol solution, Fe(NO 3 ) 3 . 9H 2 O: H 2 The molar ratio of BDC:DMF is 1:2:195:0.005, and then the brown solution is stirred for half an hour, and the product is separated by centrifugation at 5000 rpm for 10 minutes, washed with ethanol three times, and dried to obtain platinum nanoparticles and iron-based Composite materials of microporous coor...

technical field

[0001] The patent of the invention relates to a composite material and a preparation method of metal nanoparticles and microporous coordination polymers. Background technique

[0002] So far, more than 10,000 kinds of coordination polymers have been synthesized, some of which have been widely accepted due to their very high thermal stability and chemical stability (organic solvents, water, acid or alkali, air, etc.). s concern. These coordination polymers include HKUST-1, MIL-53, MIL-100, MIL-101, ZIF-8 and UIO-66, etc. MIL-53 has attracted people's attention due to its large one-dimensional pore structure. The pore size changes with the adsorption or desorption of solvent molecules, which is called "breathing". The lower limit and upper limit of the channel size are respectively 0.8nm and 1.3nm, which are close to ZSM-5 and faujasite with a silica-based zeolite structure. One of the applications of porous materials is catalysis, especially shape-selectiv...

Examples

Embodiment 1

[0035] Example 1 A composite material of metal nanoparticles and microporous coordination polymers, characterized in that the metal nanoparticles are palladium or platinum nanoparticles, and the microporous coordination polymers are iron-based microporous coordination polymers MIL- 53(Fe), MIL-53(Fe) has a topological structure, and its general formula can be written as Fe(OH)L·H 2 O, where L is an organic ligand, iron ions are connected by oxygen and the carboxyl group of the organic ligand to form a "zigzag" chain, and then these chains are connected by an organic ligand to form a 1D pore structure.

[0036] A method for preparing a composite material of metal nanoparticles and microporous coordination polymers, the steps and conditions are as follows:

[0037] Step 1, under stirring at normal temperature and pressure, 270 mg of FeCl 3 . 6H 2 O (1.0mmol) dissolved in 10ml N , N’ - Dimethylformamide (130 mmol) forms a brown solution;

[0038] Step 2, add 249mg terepht...

Embodiment 2

[0040] Example 2 A method for preparing a composite material of metal nanoparticles and microporous coordination polymers, the steps and conditions are as follows:

[0041] Step 1, under stirring at normal temperature and pressure, 414 mg of Fe(NO 3 ) 3 . 9H 2 O (1.0mmol) dissolved in 15ml N , N’ - Dimethylformamide (130 mmol) forms a brown solution;

[0042] Step 2, the brown solution prepared in step 1 was added organic ligand 332mg terephthalic acid (2mmol) until dissolved;

[0043] Step 3, adding the brown solution prepared in step 2 to a concentration of 1 mg / 1 mL of 5.7 nm metal nanoparticles platinum methanol solution, Fe(NO 3 ) 3 . 9H 2 O : H 2 The molar ratio of BDC: DMF: Pt is 1: 2: 195: 0.005, and then the brown solution is stirred for half an hour, reacted at 130°C for 24 hours, the product is separated by centrifugation at 5000 rpm for 10 minutes, and washed three times with ethanol , and dried to obtain a composite material of platinum nanoparticl...

Embodiment 3

[0044] Example 3 A method for preparing a composite material of metal nanoparticles and microporous coordination polymers, the steps and conditions are as follows:

[0045] Step 1, under stirring at normal temperature and pressure, 414 mg of Fe(NO 3 ) 3 . 9H 2 O (1.0mmol) dissolved in 15ml N , N’ - Dimethylformamide (130 mmol) forms a brown solution;

[0046] Step 2, add 166 mg of terephthalic acid (1 mmol) as an organic ligand to the brown solution prepared in step 1 until dissolved;

[0047] Step 3, adding the brown solution prepared in step 2 to a concentration of 1 mg / 1 mL of 8.2 nm metal nanoparticles platinum methanol solution, Fe(NO 3 ) 3 . 9H 2 O: H 2 The molar ratio of BDC:DMF is 1:2:195:0.005, and then the brown solution is stirred for half an hour, and the product is separated by centrifugation at 5000 rpm for 10 minutes, washed with ethanol three times, and dried to obtain platinum nanoparticles and iron-based Composite materials of microporous coor...

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