Ternary nanometer catalyst used for hydrolyzing ammonia borane to release hydrogen and preparation method of ternary nanometer catalyst

A nano-catalyst, ammonia borane technology, applied in the field of hydrogen storage materials, can solve the problems of large active component particles, easy sintering and aggregation, easy aggregation, etc.

Inactive Publication Date: 2017-01-25
HUBEI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

For non-supported catalysts, it is easy to make the active component particles larger, prone to sintering and aggregation, and the mechanical strength is low. However, MOFs are used as the carrier to support metals. It is uniformly embedded inside and outside, and evenly dispersed. Therefore, it is of great significance to develop a low-cost and high-activity supported catalyst for catalyzing ammonia borane water to explain hydrogen.
[0003] Chinese patent "A Preparation Method of Binary Transition Metal Catalyst Catalyzing Hydrolysis of Ammoniaborane Patent No. 201110339872, Application Date 2011.11.1" uses in-situ synthesis method to synthesize binary transition metal FeCo alloy as catalyst for hydrogen production from ammonia borane The catalyst has high catalytic activity and low reaction activation energy. However, due to the magnetic properties of the metal nanoparticles FeCo in this invention, they are easy to aggregate with each other, resulting in easy reduction in catalytic performance and poor recycling performance.
[0004] Chi

Method used

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  • Ternary nanometer catalyst used for hydrolyzing ammonia borane to release hydrogen and preparation method of ternary nanometer catalyst
  • Ternary nanometer catalyst used for hydrolyzing ammonia borane to release hydrogen and preparation method of ternary nanometer catalyst
  • Ternary nanometer catalyst used for hydrolyzing ammonia borane to release hydrogen and preparation method of ternary nanometer catalyst

Examples

Experimental program
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Effect test

Embodiment 1

[0023] Example 1: Preparation of ternary RuCuCo@MIL-101 nanocatalyst

[0024] Weigh terephthalic acid (823.0 mg, 5.0 mmol), Cr(NO 3 ) 3 9H 2 O (2007.0 mg, 5.0 mmol), HF (0.12 mL, 40 wt%) and deionized water (24 mL) were stirred and added to a 50 mL stainless steel reactor with a polytetrafluoroethylene liner, sealed, and kept at a constant temperature of 200 °C Under reaction 8 h. After cooling to room temperature, a green suspension was obtained, which was filtered through a filter cloth with a pore size of 100 um. Then the filtrate containing MIL-101 particles was suction filtered, washed with deionized water, dried, stirred in ethanol solution at 70ºC for 6h and NH 4 F (30 mM) solution was stirred at 60ºC for 6h, filtered and dried to obtain MIL-101.

[0025] Weigh 200.0 mg of the above MIL-101, 29.0 mgCu(NO 3 ) 2 •3H 2 O, 35.0 mg of Co(NO 3 ) 2 •6H 2 O and 6 mL 0.01 M RuCl 3 Add it into 30 mL deionized water, sonicate for 10 min to obtain a uniformly dispersed ...

Embodiment 2

[0027]Example 2: Preparation of one-component Ru@MIL-101 catalyst

[0028] Weigh 200.0 mg of MIL-101 from Example 1 above and 6 mL of 0.01 M RuCl 3 Add it into 30 mL deionized water, sonicate for 10 min to obtain a uniformly dispersed suspension and continue stirring for 24 h. Then, weigh 50.0 mg of NaBH 4 The solid was dissolved in 10 mL of deionized water, and the solution was added dropwise to the above suspension to reduce the metal ions in the solution, and stirring was continued for 6 h after the dropwise addition was completed. The Ru@MIL-101 catalyst was obtained after the product was filtered, washed, and vacuum-dried overnight. The average particle size of the supported metal Ru was measured by TEM to be 1.9nm.

Embodiment 3

[0029] Example 3: Preparation of binary CuCo@MIL-101 catalyst

[0030] Weigh 200.0 mg of the MIL-101 of the above-mentioned Example 1, 29.0 mg of Cu(NO 3 ) 2 •3H 2 O and 35.0 mg of Co(NO 3 ) 2 •6H 2 O was added to 30 mL of deionized water, sonicated for 10 min to obtain a uniformly dispersed suspension, and then continued to stir for 24 h. Then, weigh 50.0 mg of NaBH 4 The solid was dissolved in 10 mL of deionized water, and the solution was added dropwise to the above suspension to reduce the metal ions in the solution, and stirring was continued for 6 h after the dropwise addition was completed. The CuCo@MIL-101 catalyst was obtained after the product was filtered, washed and vacuum dried overnight. The average particle diameter of supported CuCo metal is 7.8nm as measured by TEM.

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Abstract

The invention provides a ternary nanometer catalyst used for hydrolyzing ammonia borane to release hydrogen and a preparation method of the ternary nanometer catalyst. The catalyst takes a metal-organic framework material of MIL-101 as a carrier and sodium borohydride as a reducing agent, and the multiple catalyst of RuCuCo@MIL-101 is obtained by reducing precursors of ruthenium salts, copper salts and cobalt salts. The specific surface area of the multiple catalyst synthesized with the preparation method reaches up to 2868m<2>/g, the grain size is around 6.9nm, good catalytic activity is exerted by catalyzing the ammonia borane to be hydrolyzed to release the hydrogen under the room temperature, transformation frequency (TOF) is 241.2mol H2 min<1> (mol Ru)<1>, and activation energy (Ea) is 48 kJ mol<1>. The catalyst is still good in stability after circulation tests are performed for 5 times; the ternary nanometer catalyst doped with non-noble metal has the advantages of even distribution of the metal particles, large specific surface area, more in catalytic active sites and the like, and compared with a conventional noble-metal catalyst, the ternary nanometer catalyst is low in cost, simple in preparation, easy to obtain raw materials, suitable for industrial production and good in application prospect.

Description

technical field [0001] The invention belongs to the field of hydrogen storage materials, and relates to a trimetal-loaded catalyst for efficiently catalyzing ammonia borane water to decompose hydrogen and a preparation method thereof. Background technique [0002] With the global environmental deterioration and energy crisis, there is an urgent need for a clean, efficient and renewable energy to replace fossil energy. Among many new energy sources, hydrogen energy is an ideal energy source. Among the many hydrogen storage materials that have come out, ammonia borane (NH 3 BH 3 , AB) is a hydrogen storage material with great application potential. The hydrogen content of ammonia borane is as high as 19.6 wt.%. It is non-toxic, stable at room temperature, and environmentally friendly. In the absence of a catalyst, it does not hydrolyze and release hydrogen at room temperature. Therefore, the preparation of catalysts with excellent performance is the core technology for wh...

Claims

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Application Information

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IPC IPC(8): B01J31/22B01J31/28C01B3/06
CPCY02E60/36B01J31/28B01J31/1691B01J35/006B01J35/1028C01B3/068C01B2203/1052C01B2203/1064C01B2203/1082
Inventor 周立群杨坤洲熊星
Owner HUBEI UNIV
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