• 专利标题:   Preparing dual-supported nickel-palladium nano-catalyst useful for catalytic hydrolysis of formic acid aqueous solution to produce hydrogen, comprises e.g. adding zinc nitrate hexahydrate into methanol, dissolving palladium (II) chloride and sodium chloride in water, and stirring and washing.
  • 专利号:   CN113426469-A, CN113426469-B
  • 发明人:   LIANG J, SHANG H, LIU Y, BAI Y, LI S
  • 专利权人:   UNIV HEBEI TECHNOLOGY
  • 国际专利分类:   C01B003/22, B01J035/02, B01J027/24
  • 专利详细信息:   CN113426469-A 24 Sep 2021 B01J-027/24 202192 Chinese
  • 申请详细信息:   CN113426469-A CN10717212 28 Jun 2021
  • 优先权号:   CN10717212

▎ 摘  要

NOVELTY - Preparing dual-supported nickel-palladium nano-catalyst comprises (1) adding zinc nitrate hexahydrate, cobalt nitrate hexahydrate and 2-methylimidazole into methanol and mixing, and obtaining bimetallic organic framework (bZIF) after grinding, (2) calcining bZIF in argon atmosphere, and cooling and grinding to obtain nitrogen doped porous carbon (bNC) (3) adding graphene oxide (GO) aqueous solution and bNC to ultrapure water, (4) adding 3-aminopropyltriethoxysilane (APTS) to bNCG aqueous solution, and continuously stirring to obtain black flocculent mixed liquid, (5) dissolving palladium (II) chloride and sodium chloride in ultrapure water, (6) adding prepared sodium tetrachloropalladate aqueous solution and nickel (II) chloride aqueous solution to mixed solution, (7) adding sodium borohydride as reducing agent to mixed solution, and magnetically stirring and reducing, and (8) centrifuging after mixture has no bubbles, and washing with water. USE - The nano-catalyst is useful for catalytic hydrolysis of formic acid aqueous solution to produce hydrogen (claimed). ADVANTAGE - The method: combines the advantages of both metal-organic frameworks (MOFs)-derived porous carbon and graphene; has simpler structure and composition of the catalyst; and is safer and more efficient than the use of pungent chemical substances or the technology of high-temperature calcination modification. DETAILED DESCRIPTION - Preparing dual-supported nickel-palladium nano-catalyst comprises (1) adding zinc nitrate hexahydrate, cobalt nitrate hexahydrate and 2-methylimidazole into methanol and mixing, drying at temperature of 50-70degrees Celsius, obtaining the bimetallic organic framework (bZIF) after grinding, where the molar ratio of zinc nitrate hexahydrate and cobalt nitrate hexahydrate to 2-methylimidazole is 1:1-5, and adding 0.6-5.4 mmol zinc nitrate hexahydrate to every 80 ml methanol, where the molar ratio is zinc and cobalt is 1:9-9:1, (2) calcining bZIF obtained in the previous step at 800-1000degrees Celsius for 2-5 hours in argon atmosphere, and cooling and grinding to obtain nitrogen doped porous carbon (bNC) (3) adding the graphene oxide (GO) aqueous solution and bNC to the ultrapure water, mixing and stirring, ultrasonically processing for 15-30 minutes to obtain uniformly dispersed bNCG aqueous solution, and adding 5-40 mg bNC and 5-40 mg GO to every 10 ml ultrapure water, (4) adding 3-aminopropyltriethoxysilane (APTS) to the bNCG aqueous solution described in the step (3), continuously stirring to obtain black flocculent mixed liquid, and adding 0.2-0.8 ml 3-aminopropyltriethoxysilane to every 10 ml ultrapure water in the step (3), (5) dissolving palladium (II) chloride and sodium chloride in a molar ratio of 1:2 in ultrapure water and stirring for 3-4 hours to obtain brown sodium tetrachloropalladate aqueous solution with solution concentration of 0.01-0.1 M, (6) adding the prepared sodium tetrachloropalladate aqueous solution and nickel (II) chloride aqueous solution to the mixed solution of the step (4), continuously stirring for 10-20 minutes, where the molar ratio of nickel (II) chloride and sodium tetrachloropalladate can be 1:9-9:1, and adding 0.01-0.08 mmol of palladium for every 5-40 mg of bNC, (7) adding sodium borohydride as reducing agent to the mixed solution obtained in the step (6), and magnetically stirring and reducing at room temperature for 20-40 minutes, where the molar ratio of nickel (II) chloride and sodium tetrachloropalladate to sodium borohydride is 1:5-26, and (8) centrifuging at 8500-10000 revolutions per minute for 6-10 minutes at low temperature after the mixture obtained in the step (7) has no bubbles, and washing with water to obtain nickel-palladium/ammonia-bNCG catalyst. An INDEPENDENT CLAIM is also included for use method of the dual-supported nickel-palladium nano-catalyst, comprising dispersing the obtained catalyst in water, dropping in the formic acid aqueous solution, hydrolyzing to produce hydrogen at reaction temperature of 25-60degrees Celsius, adding 0.01-0.08 mmol of catalyst to every 10 ml of water, where the concentration of the formic acid aqueous solution is 0.2-5 M, the molar ratio of catalyst to formic acid is 0.01-0.5:2, and the molar amount of the catalyst is based on the total molar amount of metal nickel and palladium.