Method for improving catalytic selectivity of metal nanoparticle/porous coordination polymer composite catalyst and application thereof

A technology of metal nanoparticles and composite catalysts, applied in the direction of organic compound/hydride/coordination complex catalysts, carbon compound catalysts, physical/chemical process catalysts, etc., can solve the problem of reducing catalytic selectivity and difficult metal nanoparticles Problems such as the interior of the porous coordination polymer and the limitation of the preparation scale can achieve the effects of improving catalytic selectivity, improving chemical reaction site selectivity, and improving molecular size selectivity

Inactive Publication Date: 2017-11-14
NANJING UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, this method has its own inevitable shortcomings, that is, it is difficult to completely confine all the metal nanoparticles inside the porous coordination polymer, and the metal nanoparticles supported on the surface of the porous coordination polymer play a role in the selective catalytic reaction to

Method used

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  • Method for improving catalytic selectivity of metal nanoparticle/porous coordination polymer composite catalyst and application thereof
  • Method for improving catalytic selectivity of metal nanoparticle/porous coordination polymer composite catalyst and application thereof
  • Method for improving catalytic selectivity of metal nanoparticle/porous coordination polymer composite catalyst and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0032] Embodiment 1: the preparation of the ZIF-8 nanoparticle that size is 100~200nm

[0033]Reported methods were followed with modifications during preparation. Add zinc nitrate hexahydrate (2.08 g, 7 mmol) and 100 mL 99% methanol into a 250 mL screw-top glass bottle, and stir vigorously to completely dissolve the zinc nitrate. 100 mL of a methanol solution containing 2-methylimidazole (2.01 g, 24.5 mmol) was quickly added under vigorous stirring. The mixed solution was vigorously stirred at room temperature of 25-30° C. for 20 h. The fully reacted reaction mixture was evenly transferred to eight 50mL centrifuge tubes, centrifuged at 7000rpm for 5min, the supernatant was removed, and the white ZIF-8 solid was collected. The solids in each centrifuge tube were then washed 4 times with 25 mL of methanol. The resulting white solid was collected and dried in a vacuum desiccator at 25-30° C. for 12 h at room temperature. The obtained product was characterized by powder X-ray...

Embodiment 2

[0034] Embodiment 2: the preparation of Pt / ZIF-8 composite catalyst

[0035] Example 1 The Pt / ZIF-8 composite was prepared by the traditional impregnation method, washed with 30 mL of methanol for 5 times, and then dried in a vacuum desiccator at room temperature of 25-30°C for 12 hours. The resulting product has characterized its material structure and morphology by powder X-ray diffraction (PXRD) and transmission electron microscopy (TEM), and the content of Pt in the sample obtained by inductively coupled plasma (ICP) has been determined to be 1.88wt% (mass score ratio).

Embodiment 3

[0036] Embodiment 3: the application of Pt / ZIF-8 composite catalyst in the catalytic hydrogenation reaction of olefin

[0037] The Pt / ZIF-8 composite catalyst prepared in Example 2 was pre-vacuum-dried at 120° C. for 12 hours to be activated. Add the activated Pt / ZIF-8 composite catalyst (20 mg) and a magnetic stirring bar into a 5 mL glass bottle, and seal the glass bottle with a silica gel stopper. Use a vacuum pump to pump out the gas in the bottle, then inject pure hydrogen, and repeat this operation 5 times. Use a syringe to inject 2 mL of ethyl acetate solution containing or not containing poisoning agent (i.e. passivating agent), and the poisoning agent and its dosage are shown in Table 1: quinoline (100 μL), cyclohexanethiol (0.1 μL) , Trityl mercaptan (1 mg). The mixture was ultrasonically dispersed in a water bath at 30 °C for 10 min, and then stirred at room temperature at 25 °C for 1 h. Inject 1 mL of ethyl acetate solution containing n-hexene (62.5 μL) or cis-c...

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Abstract

The invention relates to a method for improving catalytic selectivity of a metal nanoparticle/porous coordination polymer composite catalyst and application thereof. A passivator with the size larger than the hole diameter of porous coordination polymer is utilized to passivate metal nanoparticles compounded on the outer surface of the porous coordination polymer to reduce or inhibit catalytic activity thereof; meanwhile, catalytic activity of the metal nanoparticles in hole channels of the porous coordination polymer is kept; thus, the catalytic selectivity of the metal nanoparticle/porous coordination polymer composite catalyst is improved. A poisoningpassivating effect of the passivator to a metal catalyst is utilized, and a trace of reagents of quinoline, mercaptan and the like are introduced into a catalytic reaction system to passivate a part of metal nanoparticles being unfavorable for selective catalyst in the composite catalyst. When the method is applied to catalytic hydrogenation reaction of olefin, molecular dimension selectivity or chemical reaction locus selectivity can be effectively improved. The method is simple, easy and practicable and provides a novel design idea for further improving the catalytic selectivity of the composite catalyst.

Description

technical field [0001] The invention relates to the technical field of selective catalysts, in particular to a method for improving the catalytic selectivity of a metal nanoparticle / porous coordination polymer composite catalyst and its application. Background technique [0002] In the field of modern chemical catalysis, people's requirements for catalysts are not only satisfied with their high-efficiency catalytic activity, but good catalytic selectivity has become a more critical factor, which stems from the chemical industry's demand for higher atom economy. In recent years, through precise control of the preparation process, scientists have developed a variety of noble metal nanocatalysts with different shapes and sizes such as Au, Ag, Pt, Pd, etc., using the shape, size and exposed active crystal faces of noble metal nanoparticles to adjust their catalytic selectivity. However, the preparation of noble metal nanoparticles with unique selectivity requires delicate proce...

Claims

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Application Information

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IPC IPC(8): B01J33/00B01J31/22C07C5/03C07C9/15C07C5/05C07C11/107
CPCB01J33/00B01J31/1691B01J31/1815B01J2231/645B01J2531/824C07C5/03C07C5/05C07C2531/22C07C9/15C07C11/107
Inventor 霍峰蔚黄维翁洁娜张伟娜
Owner NANJING UNIV OF TECH
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