CN114345411A - Composite material and preparation method and application thereof - Google Patents
Composite material and preparation method and application thereof Download PDFInfo
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- CN114345411A CN114345411A CN202210056581.5A CN202210056581A CN114345411A CN 114345411 A CN114345411 A CN 114345411A CN 202210056581 A CN202210056581 A CN 202210056581A CN 114345411 A CN114345411 A CN 114345411A
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- 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 14
- 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
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- 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 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 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
- 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
- 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
- 239000003125 aqueous solvent Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 description 11
- 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
- 239000013078 crystal Substances 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
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000012360 testing method Methods 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
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 4
- 150000002940 palladium Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000002604 ultrasonography 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
- 238000013461 design Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 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
- 239000002244 precipitate Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910000085 borane 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
- 238000007796 conventional method Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960003638 dopamine Drugs 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
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 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
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
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 and a preparation method and application thereof, belonging to the technical field of nano catalytic materials and comprising 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 and reacting for 3-24 hours at normal temperature 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 salt includes copper salt and noble metal salt. The preparation method is simple, the composite material prepared by the method is low in cost and high in catalysis efficiency, the catalyst cost is effectively reduced, the catalytic performance of the material is guaranteed, and the preparation 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 a sustainable clean energy, has the characteristics of sufficient combustion, high energy utilization rate, clean and pollution-free products and the like, and is an important energy capable of replacing fuels. Therefore, the development of hydrogen-generating performance of hydrogen storage materials becomes an important direction of current research.
Ammonia borane (NH)3BH3AB) has extremely high hydrogen storage content (19.6 wt%), has good stability, and is one of the preferred materials for hydrogen storage materials. However, in the prior art, in order to accelerate the reaction rate, the catalyst for accelerating the reaction rate in the ammonia borane hydrolysis hydrogen production reaction is mainly a noble metal catalyst, such as a platinum metal (Pt) catalyst, a ruthenium metal (Ru) catalyst, a silver metal (Ag) catalyst, and the like, and these noble metal catalysts can effectively improve the hydrogen production rate and enhance the reaction performance, but are expensive and cannot be widely used.
The catalyst cost can be effectively reduced by doping other metals and the noble metal, and the 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 and a preparation method and application thereof, through reasonable design, dopamine hydrochloride is utilized to reduce and polymerize graphene oxide, so that more functional groups capable of complexing metal ions are arranged on the surface of graphene, 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 precipitator is added to enable the copper ions to become copper hydroxide precipitates, and the composite catalytic material with excellent catalytic hydrogen production performance is obtained under the action of a reducing agent.
The composite material and the preparation method and the application thereof 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 and reacting for 3-24 hours at normal temperature 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 a copper salt and a 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 chloropalladate, 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:1 mg.
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 a palladium salt and a 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:1 mg.
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 adopting alkali, wherein the alkali is any one of ammonia water, sodium hydroxide and potassium hydroxide.
The second object of the present invention is to provide a composite material obtained according to the above-mentioned preparation method.
The third purpose of the invention is to provide the application of the composite material in catalytic hydrogen production, and the composite material is used as a catalyst.
Compared with the prior art, the invention has the following beneficial effects:
the invention reasonably designs a composite material of graphene, palladium and noble metal particles and the like to explore a catalytic material with excellent catalytic performance, reduces and polymerizes graphene oxide by dopamine hydrochloride to ensure that the surface of the graphene has more functional groups capable of complexing metal ions, adds noble metal salt and copper salt, complexes the noble metal ions and the copper ions with the functional groups on the surface of the graphene, adds a precipitator to ensure that the copper ions become copper hydroxide precipitate, and obtains the composite material with excellent catalytic hydrogen production performance under the action of the reducer.
The composite material provided by the invention has good catalytic performance in the hydrolysis hydrogen production reaction of ammonia borane. In the hydrolysis hydrogen production reaction of ammonia borane, the catalyst amount is 15mg, and when the initial amount of the ammonia borane is 45mg, 88.5mL of hydrogen can be produced after the reaction is carried out for 3.5 min; when the initial amount of ammonia borane is 30mg, 54mL of hydrogen can be produced after reaction for 3.5min, and the hydrogen production speed is 15.4 mL/min. The composite material has low content of noble metal, 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 the aspect of practical application.
Drawings
FIG. 1 is an SEM image of a composite material provided in example 2 of the present invention;
figure 2 is the XRD pattern of the composite material provided in example 2 of the present invention.
Detailed Description
The technical solution 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 otherwise defined, all terms of art 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 limit the scope of the present invention. Unless otherwise specifically stated, the various starting materials, reagents, instruments and equipment used in the following examples of the present invention are either commercially available or prepared by conventional 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, carrying out ultrasonic treatment on the graphene oxide suspension in an ultrasonic cleaner for 1h, and then transferring the graphene oxide suspension into a three-neck flask to obtain a graphene oxide suspension with the concentration of 2.0 mg/mL;
taking 20mL of the obtained graphene oxide suspension, adjusting the pH value of the graphene oxide suspension to 8 by using ammonia water, and then adding 35mg of dopamine hydrochloride to polymerize on the surface of the graphene oxide, wherein the polymerization reaction time is 20 h; after completion of the polymerization, 1mmol of Cu (NO) was added3)2·3H2O, 0.25mmol of K2Pd2Cl4Adding 2mmol of NaOH, dissolving NaOH, adding 6mmol of ascorbic acid as a reducing agent, and heatingReducing for 3h at the temperature of 80 ℃, and obtaining the product after the reaction is finished and through 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, carrying out ultrasonic treatment on the graphene oxide suspension in an ultrasonic cleaner for 1h, and then transferring the graphene oxide suspension into a three-neck flask to obtain a graphene oxide suspension with the concentration of 2.0 mg/mL;
taking 20mL of the obtained graphene oxide suspension, adjusting the pH value of the graphene oxide suspension to 8 by using ammonia water, and then adding 35mg of dopamine hydrochloride to polymerize on the surface of the graphene oxide, wherein the polymerization reaction time is 20 h; after completion of the polymerization, 1.1mmol of Cu (NO) was added3)2·3H2O, 0.15mmol of K2Pd2Cl4Adding 2mmol of NaOH, dissolving the NaOH, adding 6mmol of reducing agent ascorbic acid, heating to 80 ℃, reducing for 3h, and after the reaction is finished, carrying out suction filtration, washing and drying to obtain the product.
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, carrying out ultrasonic treatment on the graphene oxide suspension in an ultrasonic cleaner for 1h, and then transferring the graphene oxide suspension into a three-neck flask to obtain a graphene oxide suspension with the concentration of 2.0 mg/mL;
taking 20mL of the obtained graphene oxide suspension, adjusting the pH value of the graphene oxide suspension to 8 by using ammonia water, and then adding 35mg of dopamine hydrochloride to polymerize on the surface of the graphene oxide, wherein the polymerization reaction time is 20 h; after completion of the polymerization, 1.2mmol of Cu (NO) was added3)2·3H2O, 0.05mmol of K2Pd2Cl4Adding 2mmol of NaOH, dissolving the NaOH, adding 6mmol of reducing agent ascorbic acid, heating to 70 ℃, reducing for 4 hours, and after the reaction is finished, carrying out suction filtration, washing and drying to obtain the product.
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 ultrasound to obtain a graphene oxide suspension with the concentration of 1.0mg/mL, adjusting the pH value of the graphene oxide suspension to 8.5 by using ammonia water, adding dopamine hydrochloride with corresponding mass according to the mass ratio of 0.6:1 of dopamine hydrochloride to graphene oxide to polymerize the dopamine hydrochloride on the surface of the graphene oxide for 3 hours, sequentially adding copper sulfate and ruthenium chloride to react, then adding NaOH to precipitate redundant copper ions, then adding sodium borohydride to mix uniformly, heating to 90 ℃, reducing for 2 hours, and performing 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/1 mg.
In this embodiment, the dosage ratio of sodium borohydride to graphene oxide is 0.1mmol/1 mg.
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 ultrasound to obtain a graphene oxide suspension with the concentration of 3.0mg/mL, adjusting the pH value of the graphene oxide suspension to 8.3 by using ammonia water, adding dopamine hydrochloride with corresponding mass according to the mass ratio of the dopamine hydrochloride to the graphene oxide of 1:1 to polymerize the dopamine hydrochloride on the surface of the graphene oxide for 24 hours, sequentially adding copper chloride and silver nitrate to react, then adding NaOH to precipitate redundant copper ions, then adding glucose to mix uniformly, heating to 90 ℃, reducing for 1 hour, and performing 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 embodiment, the ratio of the total amount of silver nitrate and copper chloride to the amount of graphene oxide is 0.08mmol/1 mg.
In this example, the dosage ratio of glucose to graphene oxide was 0.3mmol/1 mg.
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 ultrasound to obtain a graphene oxide suspension with the concentration of 2.0mg/mL, adjusting the pH value of the graphene oxide suspension to 8.2 by using ammonia water, adding dopamine hydrochloride with corresponding mass according to the mass ratio of 1:1 of dopamine hydrochloride to graphene oxide to polymerize the dopamine hydrochloride on the surface of the graphene oxide for 24 hours, sequentially adding copper nitrate and rhodium chloride to react, then adding potassium hydroxide to precipitate redundant copper ions, then adding potassium borohydride to mix uniformly, heating to 90 ℃, reducing for 1 hour, and after the reaction is finished, carrying out suction filtration, washing and drying 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/1 mg.
In this embodiment, the dosage ratio of potassium borohydride to graphene oxide is 0.3mmol/1 mg.
In this example, the molar ratio of potassium hydroxide to copper nitrate was 3: 1.
Comparative example 1
This comparative example was prepared in the same manner as example 2, except that dopamine hydrochloride was not added to the graphene oxide suspension.
Comparative example 2
This comparative example was prepared in the same manner as example 2 except thatThe only difference is that 1.1mmol of Cu (NO) is added in the preparation process without adding graphene oxide and dopamine hydrochloride3)2·3H2O, 0.15mmol of K2Pd2Cl420mL of water was added, followed by 2mmol of NaOH and 6mmol of ascorbic acid.
Comparative example 3
This comparative example was prepared in the same manner as example 2 except that K was not added2Pd2Cl4Adding only 1mmol of Cu (NO)3)2·3H2O, 2mmol of NaOH and 6mmol of ascorbic acid are added.
Test section
(I) crystal phase structure
The present inventors tested the crystal phase structures of the samples of examples 1-3 and comparative examples 1-3, and examples 1, 2 and 3 had similar crystal phase structures. Comparative example 1 and example 2 have similar crystal phase structures, and comparative example 2 has no RGO crystal phase and contains Pd, Cu and Cu2O crystal phase, which shows that when Pd ions and Cu ions exist in the sample at the same time, the reducing agent has two types of Cu and Cu as the reduction products of Cu ions2And O. Comparative example 1 shows that GO can be reduced to RGO by a reducing agent. Comparative example 3 the 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 hydrogen production by ammonia borane hydrolysis, and the catalytic performance of the composite materials is tested according to the rate and volume of hydrogen production.
The specific test conditions were: accurately weighing 15mg of catalyst, placing the catalyst into a three-neck flask, adding 10mL of water, accurately weighing 45mg of ammonia borane, placing the ammonia borane into the three-neck flask, and quickly starting reaction. Water bath temperature 25 ℃ produced H2Collecting by draining, and recording the collected H every 30s2Volume, until no more gas is produced. Specific test results of the tricobalt tetroxide-polydopamine-graphene composite material of examples 1 to 4 as a working electrode are shown in table 1 below:
table 1 results of catalytic performance testing of the composites provided in examples 1-4 and comparative examples 1-2
| Examples of the invention | Hydrogen yield (mL) | Average hydrogen production rate (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 composite materials prepared in examples 1 to 3 all have excellent catalytic performance in the ammonia borane hydrolysis hydrogen production reaction. The hydrogen production performance of the catalyst can be improved by the proper proportion during palladium-copper compounding, and the hydrogen production performance of the catalyst can be further improved by the GO substrate and the GO substrate with PDA polymerization. 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, the morphology of the composite material is detected by SEM, and the result is shown in fig. 1, which shows that, on the graphene layer (shown as a layer in the figure) with poly-dopamine polymerized on the surface, Cu particles having a cubic structure and Pd particles having a smaller size are uniformly distributed, the particle sizes are consistent, the size of the cubic copper nanoparticles is about 50nm, and the palladium particles are smaller.
(IV) XRD test
In the present invention, the composite material prepared in example 2 is taken as an example, and XRD test is performed on the composite material, and it can be seen that palladium ions are completely reduced into metal palladium particles after reduction by the reducing agent, and copper ion reduction products are partially reduced into Cu in addition to copper particles2O, GO is also reduced to RGO.
It is to be understood that the above-described embodiments are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a composite material is characterized by comprising 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 and reacting for 3-24 hours at normal temperature 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 a copper salt and a noble metal salt.
2. The method according to claim 1, wherein the copper salt is any one of copper nitrate, copper sulfate and copper chloride.
3. The production method according to claim 1, wherein the noble metal salt is any one of potassium chloropalladate, ruthenium chloride, silver nitrate, and rhodium chloride.
4. The preparation method according to claim 1, wherein the amount ratio of the metal salt to the graphene oxide is 0.02-0.08 mmol:1 mg.
5. The preparation method according to claim 1, wherein the mass ratio of the dopamine hydrochloride to the graphene oxide is 0.5-1: 1.
6. The method according to claim 1, wherein the molar ratio of the noble metal salt to the copper salt is 0.01 to 0.25: 1.
7. The preparation method according to claim 1, wherein the graphene oxide is uniformly dispersed in the aqueous solvent to prepare a graphene oxide suspension with a concentration of 1-3 mg/mL.
8. The method according to 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.
9. A composite material produced by the production method according to any one of claims 1 to 8.
10. Use of a composite material according to claim 9 in the catalytic production of hydrogen.
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