CN113603697B - Preparation method and application of water-soluble porphyrin-stabilized metal nanoparticle catalyst - Google Patents
Preparation method and application of water-soluble porphyrin-stabilized metal nanoparticle catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 48
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 230000007062 hydrolysis Effects 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 14
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 51
- 239000010948 rhodium Substances 0.000 claims description 27
- 229910052703 rhodium Inorganic materials 0.000 claims description 25
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- -1 aldehyde compound Chemical class 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- NDQXKKFRNOPRDW-UHFFFAOYSA-N 1,1,1-triethoxyethane Chemical compound CCOC(C)(OCC)OCC NDQXKKFRNOPRDW-UHFFFAOYSA-N 0.000 claims description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 125000004429 atom Chemical group 0.000 abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000003381 stabilizer Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910000085 borane Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002678 macrocyclic compounds Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QBQQANPKYCNDDH-UHFFFAOYSA-N OC=1C2=C(C3=C(C(=C(N3O)C=C3C=CC(C=C4C=CC(=CC(C1)=N2)N4)=N3)C3=CC=CC=C3)O)O Chemical class OC=1C2=C(C3=C(C(=C(N3O)C=C3C=CC(C=C4C=CC(=CC(C1)=N2)N4)=N3)C3=CC=CC=C3)O)O QBQQANPKYCNDDH-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- OWCDMRFUFMERMZ-UHFFFAOYSA-N benzenesulfonamide;hydrochloride Chemical compound Cl.NS(=O)(=O)C1=CC=CC=C1 OWCDMRFUFMERMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0254—Nitrogen containing compounds on mineral substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/16—Reducing
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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Abstract
The invention provides a preparation method of a novel water-soluble porphyrin-stabilized metal nanoparticle catalyst and application of the novel water-soluble porphyrin-stabilized metal nanoparticle catalyst in catalyzing ammonia borane hydrolysis to produce hydrogen, wherein metal salt is used as a raw material, and water-soluble porphyrin (TPP-PEG) 350 ) As a stabilizer, the two are mixed in deionized water with sufficient stirring, and then metal ions are reduced to atoms under the action of a reducing agent, sodium borohydride. Metal atom and water-soluble porphyrin (TPP-PEG) 350 ) The oxygen on the PEG chain is combined with the nitrogen atom on the large ring, so that the metal nano-particles are stabilized on porphyrin molecules to catalyze the hydrolysis of ammonia borane to produce hydrogen. By comparing the hydrogen production efficiency of ammonia borane under the conditions of different metal catalysts, different amount of catalysts, different stabilizer contents, different ammonia borane concentrations and the like, the catalyst is found to have good hydrogen production performance for catalyzing ammonia borane, and a circulation experiment is carried out to show that the catalyst has good stability and circulation performance.
Description
Technical Field
The invention belongs to the field of functional materials, and relates to a preparation method and application of a novel water-soluble porphyrin-stabilized nanoparticle catalyst.
Background
Hydrogen is considered to be an environmentally friendly fuel due to its harmless by-product and regenerability, and is expected to be a clean energy source to solve the shortage of fossil materials, and ammonia borane and formic acid have been widely used for research. Ammonia borane is considered one of the most promising chemical hydride candidates due to its very high capacity and excellent stability under ambient conditions.
To date, there have been many reports on the preparation and optimization of metal nanoparticle catalysts. It has been found that the catalytic activity of metal nanoparticle catalysts depends to a large extent on the metal nanoparticles and the support and the interaction between them. The high surface energy of the ultra-small nanoparticles may agglomerate due to thermodynamic instability, thereby degrading their catalytic performance. Therefore, it is very important to use an appropriate support to stabilize the metal nanoparticle catalyst. Such as activated carbon, graphene, MOF and MOF derived nanomaterials. Water has been actively studied as an environmental condition for homogeneous catalysis because it provides a green catalytic condition. For example, water-soluble polymers have been synthesized as stabilizers to anchor metal nanoparticles for applications in the field of catalysis. Tetrahydroxyphenyl porphyrins (THPP) have been used to anchor metal nanoparticles, suggesting that O and N atoms can bind to metal nanoparticles. The PEG-350 modified porphyrin has good water solubility, and due to the existence of O atoms and macrocycles in the porphyrin, the porphyrin has good stabilizing effect on metal nanoparticles, so that the catalytic performance is improved.
Disclosure of Invention
Based on the background, the invention aims to provide a preparation method and application of novel water-soluble porphyrin-stabilized metal nanoparticles.
The water-soluble porphyrin (hereinafter referred to as TPP-PEG) of the invention 350 ) Stabilized metal nanoparticle catalyst based on water-soluble porphyrin (TPP-PEG) 350 ) Uniformly mixing porphyrin aqueous solution dissolved in deionized water and metal salt solution dissolved in deionized water as raw materials, dropwise adding sodium borohydride solution into the mixed solution, reducing metal particles in the mixed solution into atoms by utilizing the reducibility of sodium borohydride, and mixing the metal atoms and water-soluble porphyrin (TPP-PEG) 350 ) The oxygen on the PEG chain and the nitrogen atom on the macrocycle combine to stabilize the metal nanoparticle on the porphyrin molecule. Due to water-soluble porphyrin (TPP-PEG) 350 ) Is uniformly dispersed in the solution, thereby obtaining uniformly dispersed metal nanoparticles. Tests show that the metal nanoparticle catalyst has good performance of catalyzing ammonia borane hydrolysis to produce hydrogen.
The water-soluble porphyrin PEG-350 modified porphyrin has the following structural formula:
wherein n represents the number in the unit and has a value of 7-9.
The preparation method of the water-soluble porphyrin comprises the following steps:
(1) dissolving polyethylene glycol monomethyl ether 350 and p-toluenesulfonyl chloride in dichloromethane, adding triethylamine, and reacting overnight to obtain a PEG compound;
(2) dissolving the compound in the step (1) and p-hydroxybenzaldehyde in acetonitrile, and adding potassium carbonate to react for 2h to obtain a PEG modified aldehyde compound;
(3) dissolving the PEG modified aldehyde compound obtained in the step (2) and pyrrole in redistilled dichloromethane, adding boron trifluoride diethyl ether, triethyl orthoacetate and tetrachlorobenzoquinone to react for 20-25h in a dark place under the atmosphere of nitrogen, and then carrying out spin drying separation on the mixed solution to obtain the water-soluble porphyrin TPP-PTG 350 The reaction formula is as follows:
In the step (1), the molar ratio of the polyethylene glycol monomethyl ether 350 to the p-toluenesulfonyl chloride is 1: 1.
The molar ratio of the PEG compound to the p-hydroxybenzaldehyde in the step (2) is 1.1: 1.
In the step (3), the molar ratio of the PEG-modified aldehyde compound to the pyrrole solvent to the boron trifluoride diethyl ether to the triethyl orthoacetate to the tetrachlorobenzoquinone is 10:10:1:1: 7.5.
The preparation method of the novel water-soluble porphyrin-stabilized metal nanoparticle catalyst comprises the following preparation steps:
(1) mixing water soluble porphyrin (TPP-PEG) 350 ) Dissolving in deionized water, stirring under ice bath condition to uniformity, slowly adding metal solution into the porphyrin aqueous solution, and stirring under ice bath condition to uniformity;
(2) slowly adding a sodium borohydride solution into the mixed solution obtained in the step (1), and reacting for 2 hours under the ice bath conditionThen, after the reaction is finished, water-soluble porphyrin (TPP-PEG) can be obtained 350 ) A stable metal nanoparticle solution.
The mass ratio of the water-soluble porphyrin, the metal solution and the sodium borohydride is 1:1-4: 10-40.
Further preferred is a ratio of the amounts of the water-soluble porphyrin, the metal solution and the sodium borohydride in the range of 1:1: 10.
The metal salt solution comprises halide salt solution or nitrate salt solution of rhodium, ruthenium or palladium.
The metal salt solution comprises one of rhodium nitrate, ruthenium trichloride or potassium tetrachloropalladate aqueous solution.
And after the dripping of the metal solution is finished, stirring for 10-30min, and then dripping a sodium borohydride solution, wherein the dripping speed of the sodium borohydride solution is 2-10 min/mL.
The water-soluble porphyrin (TPP-PEG) 350 ) The application of the stable metal nanoparticle catalyst in catalyzing ammonia borane hydrolysis to produce hydrogen.
The water-soluble porphyrin synthesized by the invention is PEG-350 modified novel porphyrin, the PEG-350 modified novel porphyrin not only has good water solubility, but also has good stability to NPs due to the existence of O atoms and macrocycles in the porphyrin, thereby improving the hydrogen production efficiency of ammonia borane catalysis.
Drawings
FIG. 1 is TPP-PEG synthesized in example 1 350 Hydrogen spectrum of (2).
FIG. 2 is TPP-PEG synthesized in example 1 350 Mass spectrum of (2).
Fig. 3 is a transmission electron micrograph of the rhodium nanoparticle catalyst prepared in example 2.
Fig. 4 is a statistical plot of the particle size distribution of the rhodium nanoparticle catalyst prepared in example 2.
Fig. 5 is an X-ray photon energy spectrum of the rhodium nanoparticle catalyst prepared in example 2.
FIG. 6 is a graph of the reaction time of different metal nanoparticle catalysts prepared in example 2 to catalyze the hydrolysis of ammonia borane to produce hydrogen versus the volume of hydrogen produced.
FIG. 7 is a graph of the hydrogen production efficiency of rhodium nanoparticle catalysts catalyzed ammonia borane hydrolysis prepared in example 4 at different porphyrin/rhodium molar ratios.
Fig. 8 is a graph of ammonia borane hydrolysis hydrogen production efficiency at different amounts of species for the rhodium nanoparticle catalyst prepared in example 2.
Fig. 9 is a graph of ammonia borane hydrolysis hydrogen production efficiency at different ammonia borane concentrations for rhodium nanoparticle catalysts prepared in example 2.
Detailed Description
The reagents and purchase sites used in the present invention are as follows:
example 1
First, methoxypolyethylene glycol 350(17.5g, 50mmol, n in methoxypolyethylene glycol represents the number of units, and has a value of 8 to 9) and p-benzenesulfonamide chloride (10g, 50mmol) were dissolved in 150mL of dichloromethane, and 10mL of triethylamine was added to react overnight to give compound 1, and then the above compound 1(16.7g, 33mmol) and p-hydroxybenzaldehyde (3.66g, 30mmol) were reacted for two hours to give compound 2. Finally, compound 2(2.976g, 6mmol) and pyrrole (414uL, 6mmol) were dissolved in 600mL of dichloromethane and stirred for 15min, to which boron trifluoride diethyl ether (75 uL, 0.6mmol), triethyl orthoacetate (1.09mL, 0.6mmol), tetrachlorobenzoquinone (1.11g, 4.5mmol) were added and reacted under nitrogen atmosphere protected from light for 20 h. The product is subjected to rotary evaporation, separation and purification to obtain the final product TPP-PEG 350 The specific structural formula is as follows:
FIGS. 1 and 2 are TPP-PEG synthesized by the present invention 350 The obtained TPP-PEG can be determined from the hydrogen spectrum and the mass spectrum of the TPP-PEG 350 The structure of the product is consistent with that of the target product.
Example 2
The preparation scheme adopted by the invention comprises the following steps
The method comprises the following steps: will be 5X 10 -3 mmolTPP-PEG 350 Prepared in example 1 was dissolved in deionized water (8mL) and placed in a round bottom flask and stirred.
Step two: will be 5X 10 -3 And (3) dissolving the mmol rhodium nitrate solution in deionized water (1mL), dropwise adding the solution into the aqueous solution obtained in the step one, and stirring the solution in an ice bath environment until the solution is uniform.
Step three: will be 5X 10 -2 And (3) mmol sodium borohydride is dissolved in 1mL deionized water, and the solution is dripped into the ice bath mixed solution obtained in the second step at the dripping speed of 3min/mL, and the reaction is carried out for 2 hours. Obtaining the rhodium nanoparticle (RhNP/TPP-PEG) with stable water-soluble porphyrin 350 ) A catalyst.
Respectively replacing rhodium nitrate solution with ruthenium trichloride and potassium tetrachloropalladate, and repeating the above operations to obtain water-soluble porphyrin-stabilized platinum nanoparticles (RuNP/TPP-PEG) 350 ) And palladium nanoparticles (PdNP/TPP-PEG) 350 ) A catalyst.
Example 3
Rhodium metal nanoparticles (RhNP/TPP-PEG) prepared according to example 2 350 ) Catalyst in catalyzing ammonia (NH) 3 BH 3 ) The method comprises the following specific steps of hydrolyzing borane to produce hydrogen:
NH 3 BH 3 +4H 2 O→NH 4 B(OH) 4 +3H 2 (g)
the method comprises the following steps: dissolving a proper amount of ammonia borane in deionized water to prepare 0.5mmol/L solution;
step two: will be 4X 10 -3 mmol RhNP/TPP-PEG 350 Dissolving in deionized water (4mL), then placing the solution in a reactor, sealing the reactor, and stirring;
step three: taking 1mL of ammonia borane solution in the step one by using an injector, quickly injecting the ammonia borane solution into the reactor in the step two, and starting timing;
step four: the volume of hydrogen at the corresponding time was recorded.
The RhNP/TPP-PEG in the second step is reacted 350 Respectively changed into RuNP/TPP-PEG 350 And PdNP/TPP-PEG 350 And obtaining a relational graph of the reaction time of the ruthenium nanoparticle catalyst and the palladium nanoparticle catalyst for catalyzing ammonia borane hydrolysis hydrogen production and the volume of the generated hydrogen.
FIG. 3 is a projection electron microscope image of the novel catalyst prepared by the invention, and it can be seen from FIG. 1 that rhodium nanoparticles are uniformly dispersed and have a particle size much smaller than 50nm, which indicates that the prepared nanoparticles have a smaller particle size.
FIG. 4 is a statistical graph of the particle size distribution of the novel catalyst prepared by the present invention, and it can be seen from FIG. 2 that the rhodium nanoparticles have a particle size distribution mainly between 5 and 7nm and an average particle size of 6.27 nm.
FIG. 5 is the X-ray photon energy spectrum of the novel catalyst prepared by the present invention, and from FIG. 5, the water-soluble porphyrin-stabilized rhodium nanoparticles (RhNP/TPP-PEG) can be seen 350 ) Chemical state of surface Rh, characteristic peaks at 306.69eV and 311.52eV correspond to zero-valent rhodium atoms, indicating RhNP/TPP-PEG 350 Rh of (a) is efficiently reduced.
FIG. 6 is a graph of the reaction time of different metal nanoparticle catalysts prepared by the method for catalyzing ammonia borane to hydrolyze and produce hydrogen and the volume of generated hydrogen. Wherein complete hydrolysis of a 0.5mmol/L ammonia borane solution may yield 1.5mmol of H 2 As can be seen from the figure, RhNP/TPP-PEG 350 And RuNP/TPP-PEG 350 The catalytic reaction can be finished within 5min, and the PdNP/TPP-PEG 350 Does not end within 30min, wherein RhNP/TPP-PEG 350 The hydrogen production effect is best.
Example 4
The preparation scheme adopted by the invention comprises the following steps
The method comprises the following steps: will be 5X 10 -2 mmolTPP-PEG 350 Dissolved in deionized water (8mL) and placed in a round bottom flask to stir.
Step two: will be 5X 10 -3 And (3) dissolving the mmol rhodium nitrate solution in deionized water (1mL), dropwise adding the solution into the aqueous solution obtained in the step one, and stirring the solution in an ice bath environment until the solution is uniform.
Step three: will be 5X 10 -2 mmol sodium borohydride is dissolved in 1mL deionized water, and the solution is dripped into the ice bath obtained in the second step at the dripping speed of 3min/mLReacting in the mixed solution for 2 hours to obtain the rhodium nanoparticle (RhNP/TPP-PEG) with stable water-soluble porphyrin 350 ) A catalyst.
Wherein TPP-PEG in the step one 350 The molar amounts of (A) and (B) are respectively changed to 1X 10 -2 mmol、2.5×10 -3 mmol、1.25×10 -3 mmol, repeating the above operations to obtain rhodium nanoparticle catalysts with porphyrin/rhodium ion molar ratios of 2:1, 1:2 and 1:4, labeled as RhNPs-1, RhNPs-2, RhNPs-3 and RhNPs-4.
Example 5
Rhodium nanoparticles (RhNP/TPP-PEG) prepared according to example 4 350 ) Catalyst in catalyzing ammonia (NH) 3 BH 3 ) The method comprises the following specific steps of hydrolyzing borane to produce hydrogen:
NH 3 BH 3 +4H 2 O→NH 4 B(OH) 4 +3H 2 (g)
the method comprises the following steps: dissolving a proper amount of ammonia borane in deionized water to prepare 0.5mmol/L solution;
step two: 2 x 10 to -3 mmol RhNP/TPP-PEG 350 Dissolving in deionized water (4mL), then placing the solution in a reactor, sealing the reactor, and stirring;
step three: taking 1mL of ammonia borane solution in the step one by using an injector, quickly injecting the ammonia borane solution into the reactor in the step two, and starting timing;
step four: the volume of hydrogen at the corresponding time was recorded.
FIG. 7 is a graph of the hydrogen production efficiency of rhodium nanoparticle catalysts prepared by the invention with different porphyrin/rhodium molar ratios in catalyzing ammonia borane hydrolysis, and it can be seen from the graph that the nano catalyst with the porphyrin/rhodium ion molar ratio of 1:1 shows the best hydrogen production performance.
Example 6
Different Metal nanoparticles (RhNP/TPP-PEG) prepared according to example 2 350 ) Catalyst in catalyzing ammonia (NH) 3 BH 3 ) The method comprises the following specific steps of hydrolyzing borane to produce hydrogen:
NH 3 BH 3 +4H 2 O→NH 4 B(OH) 4 +3H 2 (g)
the method comprises the following steps: dissolving a proper amount of ammonia borane in deionized water to prepare 0.5mmol/L solution;
step two: will be 4X 10 -3 mmol RhNP/TPP-PEG 350 Dissolving in deionized water (4mL), then placing the solution in a reactor, sealing the reactor, and stirring;
step three: taking 1mL of ammonia borane solution in the step one by using an injector, quickly injecting the ammonia borane solution into the reactor in the step two, and starting timing;
step four: the volume of hydrogen at the corresponding time was recorded.
Wherein, the RhNP/TPP-PEG in the second step 350 The amounts of substances are respectively changed to 1X 10 -3 mmol、2×10 - 3 mmol、3×10 -3 mmol, the ammonia borane hydrolysis hydrogen production effect of the rhodium nanoparticle catalyst under different substance amounts can be obtained
Fig. 8 is a graph of ammonia borane hydrolysis hydrogen production efficiency at different amounts of species for the rhodium nanoparticle catalyst prepared in example 2. From the figure, it can be seen that 4 × 10 -3 mmol RhNP/TPP-PEG 350 The hydrogen production efficiency is best.
Example 7
Different Metal nanoparticles (RhNP/TPP-PEG) prepared according to example 2 350 ) Catalyst in catalyzing ammonia (NH) 3 BH 3 ) The method comprises the following specific steps of hydrolyzing borane to produce hydrogen:
NH 3 BH 3 +4H 2 O→NH 4 B(OH) 4 +3H 2 (g)
the method comprises the following steps: dissolving a proper amount of ammonia borane in deionized water to prepare 0.5mmol/L solution;
step two: will be 4X 10 -3 mmol RhNP/TPP-PEG 350 Dissolving in deionized water (4mL), then placing the solution in a reactor, sealing the reactor, and stirring;
step three: taking 1mL of ammonia borane solution in the step one by using an injector, quickly injecting the ammonia borane solution into the reactor in the step two, and starting timing;
step four: the volume of hydrogen at the corresponding time was recorded.
Wherein, the concentration of ammonia borane solution in the step one is respectively changed into 0.25mmol/L, 0.75mmol/L and 1mmol/L, and the operations are repeated to obtain the prepared rhodium nanoparticles (RhNP/TPP-PEG) 350 ) The catalyst has the effect of producing hydrogen by hydrolyzing ammonia borane under different ammonia borane concentrations.
Fig. 9 is a graph of ammonia borane hydrolysis hydrogen production efficiency at different ammonia borane concentrations for rhodium nanoparticle catalysts prepared in example 2. It can be seen from the graph that the rate of hydrogen generation increases with increasing ammonia borane concentration.
Claims (10)
1. The water-soluble porphyrin is characterized in that the water-soluble porphyrin is PEG-350 modified porphyrin, and the structural formula is as follows:
wherein n represents the number in the unit and has a value of 7-9.
2. The method of preparing a water-soluble porphyrin according to claim 1, characterized in that it comprises the following steps:
(1) dissolving polyethylene glycol monomethyl ether 350 and p-toluenesulfonyl chloride in dichloromethane, adding triethylamine, and reacting overnight to obtain a PEG compound;
(2) dissolving the compound in the step (1) and p-hydroxybenzaldehyde in acetonitrile, and adding potassium carbonate to react for 2h to obtain a PEG modified aldehyde compound;
(3) dissolving the PEG modified aldehyde compound obtained in the step (2) and pyrrole in redistilled dichloromethane, adding boron trifluoride diethyl ether, triethyl orthoacetate and tetrachlorobenzoquinone to react for 20-25h in a dark place under the atmosphere of nitrogen, and then carrying out spin drying separation on the mixed solution to obtain the water-soluble porphyrin TPP-PTG 350 The reaction formula is as follows:
3. The method for preparing water-soluble porphyrin according to claim 2, wherein the molar ratio of polyethylene glycol monomethyl ether 350 to p-toluenesulfonyl chloride in step (1) is 1: 1.
4. The method for preparing water-soluble porphyrin according to claim 2, wherein the molar ratio of the PEG compound to the p-hydroxybenzaldehyde in the step (2) is 1.1: 1.
5. The method for preparing a water-soluble porphyrin according to claim 2, wherein the molar ratio of the PEG-modified aldehyde compound, the pyrrole, the boron trifluoride diethyl ether, the triethyl orthoacetate and the tetrachlorobenzoquinone in step (3) is 10:10:1:1: 7.5.
6. The application of the water-soluble porphyrin prepared by the method of claim 1 in preparing a metal nanoparticle catalyst with stable water-soluble porphyrin is characterized in that the preparation method comprises the following steps:
(1) dissolving water-soluble porphyrin in deionized water, stirring the solution under an ice bath condition until the solution is uniform, adding a metal solution into the aqueous solution of the porphyrin, and stirring the solution and the aqueous solution of the porphyrin under the ice bath condition until the solution and the porphyrin are uniformly mixed;
(2) and (2) slowly adding the sodium borohydride solution into the mixed solution obtained in the step (1), reacting under an ice bath condition, and obtaining the metal nanoparticle solution with stable water-soluble porphyrin after the reaction is finished.
7. Use according to claim 6, characterized in that the ratio of the quantities of the substances water-soluble porphyrin, metal solution and sodium borohydride is between 1 and 2: 1-4: 10-40.
8. The use according to claim 6, wherein the metal solution comprises a halide salt solution of rhodium, ruthenium or palladium, or a nitrate salt solution.
9. The use of claim 6, wherein after the dropwise addition of the metal solution, stirring is carried out for 10-30min, and then the sodium borohydride solution is added dropwise, wherein the dropwise addition speed of the sodium borohydride solution is 2-10 min/mL.
10. The application of the water-soluble porphyrin-stabilized metal nanoparticle catalyst prepared according to any one of claims 6-9 in catalyzing ammonia borane hydrolysis to produce hydrogen.
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