CN112359373B - Amorphous composite material, preparation method and application thereof - Google Patents
Amorphous composite material, preparation method and application thereof Download PDFInfo
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- CN112359373B CN112359373B CN201910671788.1A CN201910671788A CN112359373B CN 112359373 B CN112359373 B CN 112359373B CN 201910671788 A CN201910671788 A CN 201910671788A CN 112359373 B CN112359373 B CN 112359373B
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- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 18
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 13
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 13
- 239000005300 metallic glass Substances 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 9
- 239000005750 Copper hydroxide Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000012716 precipitator Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- 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 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 238000000840 electrochemical analysis Methods 0.000 abstract description 3
- 239000002135 nanosheet Substances 0.000 abstract description 3
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 17
- 239000010949 copper Substances 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- 230000004075 alteration Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The application discloses a composite amorphous material, which comprises graphene oxide and amorphous metal hydroxide; the amorphous metal hydroxide is supported on the graphene oxide; the graphene oxide is a nanosheet with the thickness of 0.5-2 nm; the amorphous metal hydroxide is a nanocluster. The material is used as high selectivity 2e‑An oxygen reduction electrocatalyst, said material exhibiting a hydrogen peroxide selectivity of 95% in an oxygen reduction electrochemical test.
Description
Technical Field
The present application relates to a high selectivity 2e-An oxygen reduction electrocatalyst material and a preparation method thereof belong to the field of chemical materials.
Background
Hydrogen peroxide is an important industrial fuel and is widely used in the fields of synthesis of chemical products, textile and pulp bleaching. At present, hydrogen peroxide is mainly produced by an anthraquinone method, and the process relates to a series of hydrogenation and oxidation processes of anthraquinone molecules, so that the method is not suitable for large-scale equipment and causes great waste. In addition, the synthesis of hydrogen peroxide directly from hydrogen and oxygen has become an alternative process, but there is a potential risk of explosion of the mixture of hydrogen and oxygen. Another desirable method is to produce hydrogen peroxide by electrolytic reduction of oxygen in an electrolytic cell using water as the proton source and without the hazards of mixed gas explosion and harmful gas emissions. In a small factory, the electrochemical device can operate at room temperature and pressure. Therefore, in order to improve the production efficiency of hydrogen peroxide, it is necessary to design 2e having high selectivity and high activity-The oxygen reduces the electrocatalyst.
By consulting the literature, copper-based materials are reported to be applied to OER and 4e due to low cost, abundant resources and high catalytic activity-And (4) carrying out oxygen reduction reaction. In addition, the amorphous material has a large number of lattice defects and active sites, so that the amorphous material is widely applied to the field of electrocatalysis. At present, the synthesis method of electrochemical deposition and photochemical deposition of metallorganics is only used for preparing amorphous thin film catalyst materials, and the method is not suitable for large-scale production, so that the design and development of an electrocatalytic material suitable for large-scale production are very important.
Disclosure of Invention
According to one aspect of the present application, an amorphous composite material is provided that can achieve a 95% hydrogen peroxide selectivity with an electron transfer number n of 2.1.
The amorphous composite material is characterized by comprising graphene oxide and amorphous metal hydroxide;
the amorphous metal hydroxide is supported on the graphene oxide;
the graphene oxide is a nanosheet with the thickness of 0.5-2 nm;
the amorphous metal hydroxide is nano-cluster amorphous copper hydroxide.
Optionally, the amorphous metal hydroxide is selected from at least one of amorphous copper hydroxide and amorphous cobalt hydroxide.
Optionally, the loading amount of the amorphous metal hydroxide on the graphene oxide is 10 wt% to 25 wt%.
The graphene oxide is a nanosheet with a thickness of 1.3 nm.
According to another aspect of the present application, a method for preparing the amorphous composite material is provided. The method is simple and suitable for large-scale industrial production. The material is graphene oxide supported amorphous copper hydroxide (A-Cu (OH)2/GO). In the oxygen reduction reaction, the amorphous material has higher hydrogen peroxide selectivity than the crystalline material, and shows good cycle stability.
The preparation method of the amorphous composite material is characterized by comprising the following steps:
and adding a precipitator into the solution containing the metal salt and the graphene oxide, adjusting the pH value to 8.5-9.5, and stirring at room temperature to obtain the composite amorphous material.
Optionally, the precipitating agent is an alkali solution;
the mass concentration of the alkali solution is 25-28%;
the mass ratio of the metal salt to the graphene oxide is (0.6-3.0): (0.8 to 1.1).
Optionally, the alkali solution is selected from at least one of ammonia, sodium hydroxide, potassium hydroxide.
Optionally, the alkali solution is ammonia.
Optionally, the metal salt in the solution containing the metal salt and the graphene oxide is selected from at least one of metal chloride and metal nitrate compound;
the solution containing the metal salt and the graphene oxide comprises a solvent;
the solvent is at least one of glycol, water and ethanol;
the concentration of the metal salt in the solution containing the metal salt and the graphene oxide is 0.001-0.007M;
the concentration of the graphene oxide in the solution containing the metal salt and the graphene oxide is 1.5-2.5 mg/ml.
Preferably, the metal salt is selected from at least one of copper chloride, copper nitrate and copper sulfate;
preferably, the solvent is a mixed solvent of ethylene glycol and water; wherein the volume ratio of the ethylene glycol to the water is (3-5) to (1-2).
Optionally, the stirring time at room temperature is not less than 10 minutes.
Optionally, the method for preparing the amorphous composite material further comprises:
adding a precipitator into a solution containing metal salt and graphene oxide, adjusting the pH value to 8.5-9.5, and stirring at room temperature to obtain a precipitate;
and drying the precipitate to obtain the composite amorphous material.
Optionally, the drying is freeze drying.
Optionally, the stirring time at room temperature is 10-30 minutes.
Specifically, A-Cu (OH)2The preparation method of the/GO oxygen reduction catalytic material mainly comprises the following process steps:
(1) uniformly dispersing copper ions and graphene oxide in a mixed solution of ethylene glycol and water;
(2) precipitating the copper ions by means of aqueous ammonia to obtain A-Cu (OH)2/GO；
(3) Washing with deionized water for three times, and freeze drying.
According to another aspect of the present application, there is provided a catalyst comprising at least one of the amorphous composite material and the amorphous composite material prepared by the method for preparing the amorphous composite material.
According to another aspect of the present application, there is provided a high selectivity 2e-The oxygen reduction electrocatalyst is characterized in that the catalyst contains at least one of the amorphous composite material and the amorphous composite material prepared by the preparation method of the amorphous composite material.
Alternatively, the high selectivity 2e-The oxygen reduction electrocatalyst shows hydrogen peroxide selectivity of over 90% in oxygen reduction electrochemistry.
Alternatively, the high selectivity 2e-The oxygen reduction electrocatalyst shows a stability of 20 hours or more in oxygen reduction electrochemistry.
In particular, the high selectivity 2e-An oxygen reduction electrocatalyst, characterized in that the material is an amorphous composite material having a large number of lattice defects and active sites and is capable of exhibiting a hydrogen peroxide selectivity of 95% in an oxygen reduction electrochemical test.
According to another aspect of the present application, there is provided a method for preparing hydrogen peroxide by oxygen electrolytic reduction, characterized in that hydrogen peroxide is prepared by performing oxygen electrolytic reduction using a cathode catalyst in an aqueous solution electrolytic cell;
the cathode catalyst contains at least one of the amorphous composite material and the amorphous composite material prepared by the preparation method of the amorphous composite material.
The beneficial effects that this application can produce include:
1) the amorphous composite material provided by the application is amorphous copper hydroxide (A-Cu (OH) loaded by graphene oxide2/GO). In the oxygen reduction reaction, the amorphous material has higher hydrogen peroxide selectivity than the crystalline material, and shows good cycle stability.
2) The preparation method of the amorphous composite material is different from the conventional method for preparing the amorphous oxide at high temperature and high pressure by using a solvent method, a simple large-scale method is developed at room temperature, the needed amorphous copper hydroxide only needs to be added into a mixed solution of ethylene glycol and water to serve as a precipitator, and the method is simple and is suitable for large-scale industrial production.
3) High selectivity 2e provided by the present application-Oxygen reduction electrocatalyst, A-Cu (OH)2the/GO can realize the selectivity of 95% hydrogen peroxide, and the electron transfer number is n which is 2.1.
4) The method for preparing hydrogen peroxide by electrolytic reduction of oxygen is simple, environment-friendly and easy to realize commercial production.
Drawings
FIG. 1 shows A-Cu (OH) in example 1 of the present invention2X-ray diffraction pattern of/GO.
Fig. 2 is an atomic mechanical microscope image (AFM) of graphene in example 1 of the present invention, wherein (a) is an AFM photograph; (b) is a graph of the height distribution of the AFM image.
FIG. 3 shows A-Cu (OH) in example 1 of the present invention2High resolution XPS results for Cu2p for/GO.
FIG. 4 shows A-Cu (OH) in example 1 of the present invention2Transmission electron microscopy of/GO.
FIG. 5 shows A-Cu (OH) in example 1 of the present invention2Spherical aberration electron microscope image of/GO.
FIG. 6 shows A-Cu (OH) in example 1 of the present invention2The selectivity and electron transfer number of the obtained hydrogen peroxide product were calculated by a rotating ring disk electrode set in 0.1M KOH electrolyte.
FIG. 7 shows A-Cu (OH) in example 1 of the present invention2Per GO in H-cell with 1M KOH electrolyte, the material was loaded on carbon paper for 20 hours stability test.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
in the examples, X-ray diffraction analysis (XRD) of the samples was characterized using Miniflex 600.
In the examples, atomic mechanical microscopy (AFM) of the samples was characterized using Digital Instruments, Version 6.12.
In the examples, the X-ray photoelectron spectroscopy (XPS) of the samples was characterized by ESCALB 250Xi XPS (spectrometer with Al K.alpha.source).
In the examples, transmission electron microscopy of the samples was characterized using a high resolution transmission electron microscope (Tecnai F20).
In the examples, the electrochemical performance was tested using an electrochemical workstation model CHI760E from Chensinensis corporation.
In the examples, the spherical aberration electron microscope of the sample was tested by Titan cube Themis G2300.
In the examples, graphene oxide was obtained from shanxi institute of coal chemistry, academy of sciences of china.
Example 1 sample 1 preparation
A-Cu(OH)2GO preparation:
1) copper ion dissolution;
adding CuCl2·2H2O and 16mg of graphene oxide were dissolved in 40ml of a mixed solution of water and ethylene glycol (the volume ratio of ethylene glycol to water was 4: 1), and the solution was stirred to form 0.006M CuCl2And (3) uniformly mixing the solution.
2) Solvent controlled precipitation process;
and slowly dropwise adding 120ul of 28 mass percent ammonia water into the uniform mixed solution, adjusting the pH to 9, stirring for 10 minutes, centrifugally washing for three times by deionized water, and freeze-drying to obtain a solid powder sample, wherein the solid powder sample is recorded as a sample 1.
Example 2 samples 2-4 preparation
The procedure is as in example 1, except that 0.001M Cu (NO) is used3)2Homogeneous mixed solution, preparationThe sample of (2) is designated sample 2.
The procedure is as in example 1, except that 0.001M CuCl is used2The solution was uniformly mixed and the prepared sample was designated as sample 3.
The procedure is as in example 1, except that 0.007M CuCl is used2The solution was uniformly mixed and the prepared sample was designated as sample 4.
Example 3 structural characterization
XRD tests are carried out on the samples 1-4, and a typical XRD spectrum is shown in figure 1 and corresponds to the sample 1 in the example 1. Fig. 1 shows that the prepared sample has only one distinct graphene oxide (002) plane and no other distinct diffraction peaks, indicating that the prepared sample is in an amorphous phase. The XRD spectra of samples 2-4 are similar to those of FIG. 1, and differ only in the intensity of diffraction peaks.
AFM and corresponding height distribution tests were performed on samples 1 to 4, where a typical AFM is shown in fig. 2(a), and a typical height distribution graph is shown in fig. 2(b), corresponding to sample 1 in example 1. Fig. 2(a) and 2(b) show that the thickness of graphene oxide is about 1.3 nm. AFM and height profiles for samples 2-4 were similar to those of FIGS. 2(a) and 2 (b).
The XPS tests were performed on samples 1 to 4, and a typical XPS spectrum is shown in fig. 3, corresponding to sample 1 in example 1. FIG. 3 shows that in the Cu2p spectrogram, the main peak energy band position of Cu2p 3/2 is 934.4eV, which indicates that amorphous copper hydroxide is loaded on graphene instead of CuO, and Cu2The XPS plots for samples 2-4 are similar to FIG. 3.
TEM tests were performed on samples 1-4, and a typical TEM image is shown in FIG. 4, corresponding to sample 1 from example 1. FIG. 4 shows TEM images of samples 2-4 without significant agglomeration of particles on the graphene sheet similar to FIG. 4.
The samples 1 to 4 were subjected to a spherical aberration electron microscope test, and a typical spherical aberration electron microscope image is shown in fig. 6, which corresponds to the sample 1 in example 1. Fig. 5 shows that the spherical aberration electron microscope proves that the amorphous copper hydroxide is in a nanocluster form. The spherical aberration electron micrographs of samples 2-4 are similar to those of FIG. 5.
Example 4 Performance testing
An electrochemical performance test process;
the obtained solid powder was prepared in 2mg ml-1The solution of (1). The method comprises the following specific steps: 4mg of the solid powder of sample 1 was dissolved in 2ml of a mixed solution of ethanol and deionized water (the volume ratio of ethanol to deionized water was 1: 1), and subjected to ultrasonic treatment for one hour to form a uniform solution. The loading amount was 0.07mg cm-2The catalyst (a) was dropped onto a rotating disk electrode and a series of ORR performance tests were performed. The test conditions were: the electrochemical test adopts a three-electrode system, a saturated calomel electrode as a reference electrode, a carbon rod as a counter electrode, a Rotating Ring Disk Electrode (RRDE) as a working electrode, the ring voltage is set to be 1.2V vs. RHE, the rotating speed is 1600rpm, the electrolyte is 0.1M KOH, and the sweeping speed is 5mV s-1。
A typical test can be seen in FIG. 6, A-Cu (OH)2Selectivity to 95% hydrogen peroxide can be achieved with an electron transfer number n of 2.1. In addition, as can be seen from FIG. 7, A-Cu (OH)2the/GO shows excellent 20 hour stability. The method is simple, environment-friendly and easy to realize commercial production.
Other samples all showed similar hydrogen peroxide selectivity and stability.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. High-selectivity 2e-Oxygen reduction electrocatalyst, characterised in that said high selectivity 2e-The oxygen reduction electrocatalyst contains a composite amorphous material comprising graphene oxide and an amorphous metal hydroxide;
the amorphous metal hydroxide is supported on the graphene oxide;
the graphene oxide is a sheet material with the thickness of 0.5-2 nm;
the amorphous metal hydroxide is a nanocluster;
the amorphous metal hydroxide is amorphous copper hydroxide.
2. High selectivity 2e according to claim 1-The oxygen reduction electrocatalyst is characterized in that the supporting amount of the amorphous metal hydroxide on the graphene oxide is 10-25 wt%.
3. High selectivity 2e as claimed in any one of claims 1 to 2-The preparation method of the composite amorphous material is characterized by comprising the following steps:
and adding a precipitator into the solution containing the metal salt and the graphene oxide, adjusting the pH value to 8.5-9.5, and stirring at room temperature to obtain the composite amorphous material.
4. High selectivity 2e according to claim 3-The oxygen reduction electrocatalyst is characterized in that the precipitator is an alkali solution;
the mass concentration of the alkali solution is 25-28%;
the mass ratio of the metal salt to the graphene oxide is (0.6-3.0): (0.8-1.1).
5. High selectivity 2e according to claim 4-The oxygen reduction electrocatalyst is characterized in that the alkali solution is ammonia water.
6. High selectivity 2e according to claim 3-An oxygen reduction electrocatalyst, wherein the metal salt in the solution containing the metal salt and the graphene oxide is selected from at least one of metal chlorides and metal sulfate compounds;
the solution containing the metal salt and the graphene oxide comprises a solvent;
the solvent is at least one of glycol, water and ethanol;
the concentration of the metal salt in the solution containing the metal salt and the graphene oxide is 0.001-0.007M;
the concentration of the graphene oxide in the solution containing the metal salt and the graphene oxide is 1.5-2.5 mg/ml.
7. High selectivity 2e according to claim 3-The oxygen reduction electrocatalyst is characterized in that the metal salt is selected from at least one of copper chloride, copper nitrate and copper sulfate.
8. High selectivity 2e according to claim 6-The oxygen reduction electrocatalyst is characterized in that the solvent is a mixed solvent of ethylene glycol and water; wherein the volume ratio of the ethylene glycol to the water is (3-5) to (1-2).
9. High selectivity 2e according to claim 3-The oxygen reduction electrocatalyst is characterized in that the stirring time at room temperature is not less than 10 minutes.
10. A method for preparing hydrogen peroxide by oxygen electrolytic reduction is characterized in that in an aqueous solution electrolytic cell, a cathode catalyst is adopted to carry out oxygen electrolytic reduction to prepare hydrogen peroxide;
the cathode catalyst contains the high selectivity 2e of any one of claims 1 to 9-The oxygen reduces the electrocatalyst.
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| CN107359054A (en) * | 2016-05-09 | 2017-11-17 | 国家纳米科学中心 | Composite electrode material, preparation method and application thereof |
| CN108588742A (en) * | 2018-05-21 | 2018-09-28 | 吕逍 | A method of preparing electrolysis water base metal bifunctional catalyst |
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| CN110075847A (en) * | 2019-03-15 | 2019-08-02 | 浙江师范大学 | A kind of graphene ribbon/cobalt hydroxide composite nano materials and preparation method thereof |
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| CN104801307A (en) * | 2015-04-17 | 2015-07-29 | 中国科学院上海高等研究院 | Transition metal hydroxide-graphene oxide composite material as well as preparation and application thereof |
| CN107359054A (en) * | 2016-05-09 | 2017-11-17 | 国家纳米科学中心 | Composite electrode material, preparation method and application thereof |
| CN108588742A (en) * | 2018-05-21 | 2018-09-28 | 吕逍 | A method of preparing electrolysis water base metal bifunctional catalyst |
| CN110075847A (en) * | 2019-03-15 | 2019-08-02 | 浙江师范大学 | A kind of graphene ribbon/cobalt hydroxide composite nano materials and preparation method thereof |
| CN110038577A (en) * | 2019-05-20 | 2019-07-23 | 南昌航空大学 | Synthetic method of the one step growth in situ in the class alpha-phase nickel hydroxide nanometer sheet of carbon cloth substrate |
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