CN114345411B - Composite material and preparation method and application thereof - Google Patents
Composite material and preparation method and application thereof Download PDFInfo
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- CN114345411B CN114345411B CN202210056581.5A CN202210056581A CN114345411B CN 114345411 B CN114345411 B CN 114345411B CN 202210056581 A CN202210056581 A CN 202210056581A CN 114345411 B CN114345411 B CN 114345411B
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 229910000510 noble metal Chemical class 0.000 claims abstract description 13
- 150000001879 copper Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000000725 suspension Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 150000002940 palladium Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- -1 palladium ions Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a composite material, a preparation method and application thereof, and belongs to the technical field of nano catalytic materials, wherein the preparation method comprises the following steps: uniformly dispersing graphene oxide in a water solvent, then adjusting the pH value of the graphene oxide to 8-8.5, adding dopamine hydrochloride, and stirring the mixture at normal temperature for reaction for 3-24 hours to obtain a first mixed solution; uniformly dispersing metal salt in the first mixed solution, adding a precipitator, uniformly mixing, adding a reducing agent, uniformly mixing, and reacting at 70-90 ℃ for 2-4 hours to obtain the composite material; the metal salts include copper salts and noble metal salts. The preparation method is simple, the composite material prepared by the method has low cost and high catalysis efficiency, the catalyst cost is effectively reduced, the catalysis performance of the material is ensured, and the method has very important significance in the aspect of practical application.
Description
Technical Field
The invention relates to the technical field of nano catalytic materials, in particular to a composite material and a preparation method and application thereof.
Background
The hydrogen energy is used as sustainable clean energy, has the characteristics of full combustion, high energy utilization rate, clean and pollution-free products and the like, and is an important energy source capable of replacing fuel. Therefore, the development of the hydrogen production performance of the hydrogen storage material is an important direction of current research.
Ammonia borane (NH) 3 BH 3 AB) has extremely high hydrogen storage content (19.6 wt percent), and good stability, and is one of the preferred materials of the hydrogen storage materials. However, in the prior art, in order to accelerate the reaction rate, the catalyst for accelerating the reaction rate in the hydrolysis hydrogen production reaction of ammonia borane is mainly a noble metal catalyst, such as a platinum metal (Pt) catalyst, a ruthenium metal (Ru) catalyst, a silver metal (Ag) catalyst, etc., which can effectively improve the hydrogen production rate and the reaction performance, but is expensive and cannot be widely used.
The doping of other metals and noble metals can effectively reduce the cost of the catalyst, and noble metal particles are more effectively dispersed, so that the catalytic hydrogen production performance of the catalyst is improved.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a composite material, a preparation method and application thereof, wherein through reasonable design, dopamine hydrochloride is utilized to reduce and polymerize graphene oxide, so that the surface of the graphene has more functional groups capable of complexing metal ions, palladium salt and copper salt are added, palladium ions and copper ions are complexed with the functional groups on the surface of the graphene, a precipitant is added to enable the copper ions to become copper hydroxide precipitate, and the composite catalytic material with excellent catalytic hydrogen production performance is obtained under the action of the reducing agent.
The invention relates to a composite material and a preparation method and application thereof, which are realized by the following technical scheme:
the first object of the present invention is to provide a method for preparing a composite material, comprising the steps of:
uniformly dispersing graphene oxide in a water solvent, then adjusting the pH value of the graphene oxide to 8-8.5, adding dopamine hydrochloride, and stirring the mixture at normal temperature for reaction for 3-24 hours to obtain a first mixed solution;
uniformly dispersing metal salt in the first mixed solution, adding a precipitator, uniformly mixing, adding a reducing agent, uniformly mixing, and reacting at 70-90 ℃ for 2-4 hours to obtain the composite material;
wherein the metal salt comprises copper salt and noble metal salt.
Further, the copper salt is any one of copper nitrate, copper sulfate and copper chloride.
Further, the noble metal salt is any one of potassium palladium chloride, ruthenium chloride, silver nitrate and rhodium chloride.
Further, the dosage ratio of the metal salt to the graphene oxide is 0.02-0.08 mmol/1mg.
Further, the mass ratio of the dopamine hydrochloride to the graphene oxide suspension is 0.5-1:1.
Further, the molar ratio of the palladium salt to the copper salt is 0.01-0.25:1.
Further, the concentration of the graphene oxide suspension is 1-3 mg/mL.
Further, the metal salt is a mixture of palladium salt and copper salt, and the molar ratio of the palladium salt to the copper salt is 0.01-0.25:1.
Further, the molar ratio of the precipitant to the copper salt is 2-3:1.
Further, the dosage ratio of the reducing agent to the graphene oxide is 0.1-0.3 mmol/1mg.
Further, the precipitant is sodium hydroxide or potassium hydroxide.
Further, the reducing agent is any one of ascorbic acid, glucose, sodium borohydride and potassium borohydride.
Further, the pH is adjusted by using alkali, wherein the alkali is any one of ammonia water, sodium hydroxide and potassium hydroxide.
A second object of the present invention is to provide a composite material produced according to the above-mentioned production method.
A third object of the present invention is to provide a use of the above composite material in catalytic hydrogen production, using the composite material as a catalyst.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a catalytic material with excellent catalytic performance is reasonably designed and explored for composite materials such as graphene, palladium and noble metal particles, and the graphene oxide is reduced and polymerized by using dopamine hydrochloride, so that the graphene surface has more functional groups capable of complexing metal ions, noble metal salt and copper salt are added, noble metal ions and copper ions are complexed with the functional groups on the graphene surface, a precipitant is added to enable the copper ions to become copper hydroxide precipitate, and the composite material with excellent catalytic hydrogen production performance is obtained under the action of a reducing agent.
The composite material provided by the invention has good catalytic performance in the ammonia borane hydrolysis hydrogen production reaction. In the ammonia borane hydrolysis hydrogen production reaction, the catalyst amount is 15mg, and when the initial ammonia borane amount is 45mg, 88.5mL of hydrogen can be produced in 3.5 min; when the initial amount of ammonia borane is 30mg, 54mL of hydrogen can be produced after 3.5min of reaction, and the hydrogen production speed is 15.4mL/min. The composite material has low noble metal content, can effectively reduce the cost of the catalyst, is a catalytic material with low cost, simple production method and high catalytic efficiency, and has very important significance in practical application.
Drawings
FIG. 1 is an SEM image of a composite material according to example 2 of the present invention;
fig. 2 is an XRD pattern of the composite material provided in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention. Unless otherwise specifically indicated, the various materials, reagents, instruments and equipment used in the following examples of the invention are commercially available or may be prepared by existing methods.
Example 1
The embodiment provides a composite material, and the preparation method of the composite material of the embodiment comprises the following steps:
uniformly dispersing 100mg of graphene oxide in 50mL of deionized water, ultrasonically treating the graphene oxide suspension in an ultrasonic cleaner for 1h, and transferring the graphene oxide suspension into a three-neck flask to obtain graphene oxide suspension with the concentration of 2.0 mg/mL;
taking 20mL of the graphene oxide suspension obtained, regulating the pH value of the graphene oxide suspension to 8 by ammonia water, and then adding 35mg of dopamine hydrochloride to polymerize the graphene oxide suspension on the surface of the graphene oxide, wherein the polymerization reaction time is 20h; after polymerization was completed, 1mmol of Cu (NO) 3 ) 2 ·3H 2 O,0.25mmol K 2 Pd 2 Cl 4 Adding 2mmol of NaOH, adding 6mmol of reducing agent ascorbic acid after the NaOH is dissolved, heating to 80 ℃ for reduction for 3 hours, and obtaining the product after the reaction is finished by suction filtration, washing and drying.
Example 2
The embodiment provides a composite material, and the preparation method of the composite material of the embodiment comprises the following steps:
uniformly dispersing 100mg of graphene oxide in 50mL of deionized water, ultrasonically treating the graphene oxide suspension in an ultrasonic cleaner for 1h, and transferring the graphene oxide suspension into a three-neck flask to obtain graphene oxide suspension with the concentration of 2.0 mg/mL;
taking 20mL of the graphene oxide suspension, regulating the pH value of the graphene oxide suspension to 8 by ammonia water, and then adding 35mg of dopamine hydrochloride to polymerize the graphene oxide suspension on the surface of the graphene oxide, wherein the polymerization reaction time is 20h; after polymerization was completed, 1.1mmol of Cu (NO) 3 ) 2 ·3H 2 O,0.15mmol of K 2 Pd 2 Cl 4 Adding 2mmol of NaOH, adding 6mmol of reducing agent ascorbic acid after the NaOH is dissolved, heating to 80 ℃ for reduction for 3 hours, and obtaining the product after the reaction is finished by suction filtration, washing and drying.
Example 3
The embodiment provides a composite material, and the preparation method of the composite material of the embodiment comprises the following steps:
uniformly dispersing 100mg of graphene oxide in 50mL of deionized water, ultrasonically treating the graphene oxide suspension in an ultrasonic cleaner for 1h, and transferring the graphene oxide suspension into a three-neck flask to obtain graphene oxide suspension with the concentration of 2.0 mg/mL;
taking 20mL of the graphene oxide suspension, regulating the pH value of the graphene oxide suspension to 8 by ammonia water, and then adding 35mg of dopamine hydrochloride to polymerize the graphene oxide suspension on the surface of the graphene oxide, wherein the polymerization reaction time is 20h; after polymerization was completed, 1.2mmol of Cu (NO) 3 ) 2 ·3H 2 O,0.05mmol of K 2 Pd 2 Cl 4 Adding 2mmol of NaOH, adding 6mmol of reducing agent ascorbic acid after the NaOH is dissolved, heating to 70 ℃ for reduction for 4 hours, and obtaining the product after the reaction is finished by suction filtration, washing and drying.
Example 4
The embodiment provides a composite material, and the preparation method of the composite material of the embodiment comprises the following steps:
uniformly dispersing graphene oxide in deionized water under ultrasonic treatment to obtain graphene oxide suspension with the concentration of 1.0mg/mL, regulating the pH value of the graphene oxide suspension to 8.5 by ammonia water, adding dopamine hydrochloride with the corresponding mass to the mass ratio of 0.6:1 of the graphene oxide, polymerizing the dopamine hydrochloride on the surface of the graphene oxide for 3 hours, sequentially adding copper sulfate and ruthenium chloride for reaction, adding NaOH to precipitate redundant copper ions, adding sodium borohydride for uniform mixing, heating to 90 ℃ for reduction for 2 hours, and carrying out suction filtration, washing and drying after the reaction is finished to obtain the product.
In this example, the molar ratio of ruthenium chloride to copper sulfate was 0.042:1.
In this example, the ratio of the total amount of ruthenium chloride and copper sulfate to the amount of graphene oxide was 0.02mmol/1mg.
In this example, the ratio of sodium borohydride to graphene oxide was 0.1mmol/1mg.
In this example, the molar ratio of NaOH to copper sulfate was 2.5:1.
Example 5
The embodiment provides a composite material, and the preparation method of the composite material of the embodiment comprises the following steps:
uniformly dispersing graphene oxide in deionized water under ultrasonic treatment to obtain graphene oxide suspension with the concentration of 3.0mg/mL, regulating the pH value of the graphene oxide suspension to 8.3 by ammonia water, adding dopamine hydrochloride with the corresponding mass to the mass ratio of 1:1 to polymerize the graphene oxide on the surface of the graphene oxide for 24 hours, sequentially adding copper chloride and silver nitrate to react, adding NaOH to precipitate redundant copper ions, adding glucose to uniformly mix, heating to 90 ℃ to reduce for 1 hour, and carrying out suction filtration, washing and drying after the reaction is finished to obtain the product.
In this example, the molar ratio of silver nitrate to copper chloride was 0.01:1.
In this example, the ratio of the total amount of silver nitrate and copper chloride to the amount of graphene oxide was 0.08mmol/1mg.
In this example, the dosage ratio of glucose to graphene oxide was 0.3mmol/1mg.
In this example, the molar ratio of NaOH to copper chloride was 3:1.
Example 6
The embodiment provides a composite material, and the preparation method of the composite material of the embodiment comprises the following steps:
the embodiment provides a composite material, and the preparation method of the composite material of the embodiment comprises the following steps:
uniformly dispersing graphene oxide in deionized water under ultrasonic treatment to obtain graphene oxide suspension with the concentration of 2.0mg/mL, regulating the pH value of the graphene oxide suspension to 8.2 by ammonia water, adding dopamine hydrochloride with the corresponding mass to the mass ratio of 1:1 of the graphene oxide, polymerizing the dopamine hydrochloride on the surface of the graphene oxide for 24 hours, sequentially adding copper nitrate and rhodium chloride for reaction, adding potassium hydroxide for precipitating redundant copper ions, adding potassium borohydride for uniformly mixing, heating to 90 ℃ for reduction for 1 hour, and carrying out suction filtration, washing and drying after the reaction is finished to obtain the product.
In this example, the molar ratio of rhodium chloride to copper nitrate was 0.01:1.
In this example, the ratio of the total amount of rhodium chloride and copper nitrate to the amount of graphene oxide was 0.08mmol/1mg.
In this example, the dosage ratio of potassium borohydride to graphene oxide was 0.3mmol/1mg.
In this example, the molar ratio of potassium hydroxide to copper nitrate was 3:1.
Comparative example 1
The specific preparation method of this comparative example was the same as in example 2, except that dopamine hydrochloride was not added to the graphene oxide suspension.
Comparative example 2
The specific preparation method of the comparative example is the same as that of example 2, except that graphene oxide and dopamine hydrochloride are not added, and 1.1mmol of Cu (NO 3 ) 2 ·3H 2 O,0.15mmol of K 2 Pd 2 Cl 4 To 20mL of water was added, followed by 2mmol of NaOH and 6mmol of ascorbic acid.
Comparative example 3
The specific preparation method of this comparative example is the same as in example 2, except that K is not added 2 Pd 2 Cl 4 Only 1mmol of Cu (NO) 3 ) 2 ·3H 2 O, 2mmol of NaOH and 6mmol of ascorbic acid are added.
Test section
(one) Crystal phase Structure
The present invention tested the crystalline phase structure of the samples of examples 1-3 and comparative examples 1-3, examples 1, 2 and 3 having similar crystalline phase structures. Comparative example 1 and example 2 have similar crystalline phase structure, and comparative example 2 has RGO-free crystalline phase containing Pd, cu and Cu 2 O-crystal phase, showing that when Pd ion and Cu ion exist in the sample at the same time, the reducing agent has two kinds of Cu and Cu on the reduction product of Cu ion 2 O. Comparative example 1 shows that GO can be reduced to RGO by a reducing agent. Comparative example 3 sample had no Pd crystal phase present, only RGO and Cu crystal phases,
(II) catalytic Properties
The composite materials prepared in examples 1-3 and comparative examples 1-3 are used as catalysts for producing hydrogen by ammonia borane hydrolysis, and the catalytic performance of the composite materials is tested through the hydrogen production rate and volume.
The specific test conditions are as follows: catalyst 15mg was accurately weighed and placed in a three-necked flask, 10mL of water was added, 45mg of ammonia borane was accurately weighed and placed in the three-necked flask, and the reaction was started rapidly. The water bath temperature is 25 ℃, H is generated 2 Collected by drainage, H collected was recorded every 30s 2 Volume, to no more gas is generated. Specific test results of the cobaltosic oxide-polydopamine-graphene composite materials of examples 1 to 4 as working electrodes are shown in the following table 1:
table 1 results of the catalytic performance test of the composite materials provided in examples 1-4 and comparative examples 1-2
| Example | Hydrogen production (mL) | Average hydrogen productionRate (mL/min) |
| Example 1 | 69.8 | 5.8 |
| Example 2 | 88.5 | 25.3 |
| Example 3 | 70 | 5.8 |
| Comparative example 1 | 75 | 2.7 |
| Comparative example 2 | 66.5 | 2.4 |
| Comparative example 3 | 60.5 | 1.06 |
As can be seen from Table 1, the composites prepared in examples 1 to 3 all have excellent catalytic performance in the hydrolysis of ammonia borane to hydrogen. The proper proportion can improve the catalytic hydrogen production performance of the catalyst during palladium-copper compounding, and the GO substrate polymerized by the PDA can further improve the catalytic hydrogen production performance of the catalyst. And it can be seen that the composite material prepared in example 2 of the present invention has the best catalytic performance.
(III) SEM test
Taking the composite material prepared in example 2 as an example, SEM (scanning electron microscope) detection is carried out on the morphology of the composite material, and the result is shown in figure 1, and it can be seen that Cu particles with a cubic structure and Pd particles with smaller sizes are uniformly distributed on a graphene layer (shown as a layered substance in the figure) of which the surfaces are polymerized with polydopamine, the particle sizes are consistent, the size of the cubic copper nanoparticles is about 50nm, and the palladium particles are smaller.
(IV) XRD test
Taking the composite material prepared in the embodiment 2 as an example, XRD test shows that palladium ions are completely reduced into metal palladium particles after being reduced by a reducing agent, and copper ion reduction products are partially reduced into Cu besides copper particles 2 O, GO is also reduced to RGO.
It should be apparent that the embodiments described above are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (7)
1. A method of preparing a composite material, comprising the steps of:
uniformly dispersing graphene oxide in a water solvent, then adjusting the pH value of the graphene oxide to 8-8.5, adding dopamine hydrochloride, and stirring at normal temperature for reaction for 3-24 hours to obtain a first mixed solution;
uniformly dispersing metal salt in the first mixed solution, adding a precipitator, uniformly mixing, adding a reducing agent, uniformly mixing, and reacting at 70-90 ℃ for 2-4 hours to obtain the composite material;
wherein the metal salts include copper salts and noble metal salts;
the copper salt is any one of copper nitrate, copper sulfate and copper chloride;
the noble metal salt is any one of potassium palladium chloride, ruthenium chloride, silver nitrate and rhodium chloride;
the molar ratio of the noble metal salt to the copper salt is 0.01-0.25:1.
2. The preparation method of claim 1, wherein the dosage ratio of the metal salt to the graphene oxide is 0.02-0.08 mmol/1mg.
3. The preparation method of claim 1, wherein the mass ratio of the dopamine hydrochloride to the graphene oxide is 0.5-1:1.
4. The preparation method of claim 1, wherein graphene oxide is uniformly dispersed in an aqueous solvent to prepare a graphene oxide suspension with a concentration of 1-3 mg/mL.
5. The method of claim 1, wherein the precipitant is sodium hydroxide or potassium hydroxide;
the reducing agent is any one of ascorbic acid, glucose, sodium borohydride and potassium borohydride.
6. A composite material produced according to the production method of any one of claims 1 to 5.
7. Use of the composite material according to claim 6 for catalyzing the hydrolysis of ammonia borane to produce hydrogen.
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