CN111729685A - Electrocatalytic material and preparation method and application thereof - Google Patents
Electrocatalytic material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 47
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 20
- 239000005457 ice water Substances 0.000 claims abstract description 18
- 238000007789 sealing Methods 0.000 claims abstract description 18
- 238000007654 immersion Methods 0.000 claims abstract description 17
- 230000020477 pH reduction Effects 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims description 39
- 230000007935 neutral effect Effects 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000004108 freeze drying Methods 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 2
- 239000001230 potassium iodate Substances 0.000 claims description 2
- 229940093930 potassium iodate Drugs 0.000 claims description 2
- 235000006666 potassium iodate Nutrition 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 abstract description 24
- 239000002131 composite material Substances 0.000 abstract description 16
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical group [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 197
- 239000000843 powder Substances 0.000 description 44
- 238000003756 stirring Methods 0.000 description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- 238000006722 reduction reaction Methods 0.000 description 21
- 238000005303 weighing Methods 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 229920000557 Nafion® Polymers 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 239000000178 monomer Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 13
- 230000009467 reduction Effects 0.000 description 11
- 229910021607 Silver chloride Inorganic materials 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 229910021397 glassy carbon Inorganic materials 0.000 description 10
- YECIFGHRMFEPJK-UHFFFAOYSA-N lidocaine hydrochloride monohydrate Chemical compound O.[Cl-].CC[NH+](CC)CC(=O)NC1=C(C)C=CC=C1C YECIFGHRMFEPJK-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- -1 Cl)—Sulfate Chemical class 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 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 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention is suitable for the technical field of electrochemistry, and provides an electrocatalytic material, a preparation method and application thereof, wherein the electrocatalytic material comprises the following steps: adding an initiator into an acid solution, and uniformly mixing to obtain a solution A; adding aniline and carbon nano tubes into an acid solution, and uniformly mixing to obtain a solution B; dropwise adding the solution A into the solution B, uniformly mixing, sealing, and immersing in an ice water bath for reaction to obtain a mixed product; and placing the mixed product into a dilute nitric acid solution for immersion acidification treatment. According to the invention, aniline and carbon nano tubes are subjected to in-situ polymerization to prepare the polyaniline/carbon nano tube composite electro-catalytic material, so that the problems of stacking and agglomeration caused by self-polymerization of polyaniline are solved, and further, the composite material is subjected to dilute nitric acid immersion acidification treatment to obtain novel nitrogen-oxygen functional groups on the surface of the material, so that the catalytic performance of the material is improved.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to an electrocatalytic material as well as a preparation method and application thereof.
Background
Hydrogen peroxide (H)2O2) Is an important chemical raw material, is widely applied to various fields, such as industrial papermaking bleaching, industrial wastewater treatment and medical and health industries, and is used for worldwide and industrially producing H according to actual investigation every year2O2The total amount of (a) reaches 4 million tons. And now produce H2O2The main route of (a) is through the process of oxidation of anthraquinone, which is costly and tends to produce many environmentally polluting organic intermediates in the production process. In addition, some H is also present2O2And safety issues in storage and transportation. In recent years, H has been synthesized by electrochemical methods2O2The method is a more popular research direction, and has the advantage that some potential dangers can be well avoided, and more importantly, the method is an environment-friendly method.
Electrochemical synthesis of H is well known2O2Is a clean and high-efficiency method. However, a catalyst with high performance is required in the middle of the reaction process, so that the research and research of a catalyst with high current density, high selectivity and good stability is still important. Among a plurality of catalysts, noble metal materials such as Pt, Pd, Hg and Au are researched firstly, experiments prove that the noble metal materials have high 2e catalytic activity and are obtained by theoretical calculation comparison, and alloys such as Pd-Hg and Pd-Au have more excellent performance. However, the greatest drawback of such materials is their high cost and scarcity, which greatly limits their better development and application. Carbon materials, especially heteroatom-doped carbon-based materials, have become a focus of recent research in this fieldSuch as nitrogen-doped carbon materials, oxygen-doped carbon materials, metal oxide and porous carbon composites. Among them, carbon nanotubes have been widely studied in recent years as a common carbon material. The structure of the carbon nano tube is the same as the lamellar structure of graphite, so the carbon nano tube has good electrical property and is an ideal carbon material electrocatalyst, but the carbon nano tube as a two-electron oxygen reduction catalyst has the problems of low selectivity, poor stability and the like.
Therefore, the existing electrocatalyst has the problems of high cost, scarcity, low selectivity and poor stability.
Disclosure of Invention
The embodiment of the invention aims to provide an electrocatalysis material, and aims to solve the problems of high cost, scarcity, low selectivity and poor stability of the existing electrocatalysis.
The embodiment of the invention is realized by a preparation method of an electrocatalytic material, which comprises the following steps:
adding an initiator into an acid solution, and uniformly mixing to obtain a solution A;
adding aniline and carbon nano tubes into an acid solution, and uniformly mixing to obtain a solution B;
dropwise adding the solution A into the solution B, uniformly mixing, sealing, immersing in an ice water bath for reaction, washing to be neutral, and drying to obtain a mixed product;
and (3) placing the mixed product into a dilute nitric acid solution for immersion acidification treatment, washing to be neutral, and drying to obtain the catalyst.
Another object of an embodiment of the present invention is to provide an electrocatalytic material prepared according to the preparation method of the electrocatalytic material.
Another object of the embodiments of the present invention is to provide an application of the electrocatalytic material prepared by the preparation method of the electrocatalytic material in preparing hydrogen peroxide through electrocatalysis.
According to the embodiment of the invention, aniline and carbon nano tubes are subjected to in-situ polymerization to prepare the polyaniline/carbon nano tube composite electro-catalytic material; the polyaniline is uniformly coated on the surface of the carbon nano tube through anchor points provided by functional groups on the surface of the carbon nano tube, so that the problems of stacking and agglomeration caused by self polymerization of the polyaniline are solved, and the adopted in-situ polymerization method has mild reaction conditions, simple operation and short process flow, and is beneficial to popularization of large-scale preparation and production of the composite electro-catalytic material; in addition, the invention further carries out dilute nitric acid immersion acidification treatment on the composite electrocatalytic material, so that a novel nitrogen-oxygen functional group is obtained on the surface of the material, the catalytic performance of the composite electrocatalytic material is improved, and meanwhile, the content of polyaniline on the surface of the carbon nano tube is adjustable, the immersion acidification time is controllable, and the electrochemical performance of the composite electrocatalytic material is favorably improved.
Drawings
FIG. 1 is a TEM image of an electrocatalytic material as provided in example 2 of the present invention;
FIG. 2 is an XPS peak profile of an electrocatalytic material provided in example 4 of the present invention;
FIG. 3 is a RRDE graph of an electrocatalytic material provided in example 5 of the present invention;
FIG. 4 is a graph showing the nitrogen content of the electrocatalytic materials provided in examples 1, 3 and 5 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Polyaniline is a high molecular compound, has special electrical and optical properties, and can have conductivity and electrochemical properties after being doped. Polyaniline has been widely studied and applied due to its simple synthesis process, good chemical and environmental stability, and the like. Different from the doping mechanism of other conducting polymers which generate cation vacancy under the action of an oxidant, the electron number is not changed in the doping process of polyaniline, but H is generated by the decomposition of doped protonic acid+And for anions (e.g. Cl)—Sulfate, phosphate, etc.) into the main chain, with the N-atom in the amine and imine groupsThe proton combination forms a polaron and a dipole delocalized into P bonds of the whole molecular chain, so that the polyaniline has higher conductivity. The unique doping mechanism makes the doping and de-doping of polyaniline completely reversible, the doping degree is influenced by factors such as pH value and potential, and the like, and shows corresponding change of appearance color, and the polyaniline also has electrochemical activity and electrochromic property. However, in practical applications, there are some problems, such as the tendency to stack and agglomerate when used as a catalyst, which affects the electrochemical performance. Meanwhile, polyaniline has different microscopic morphologies such as fibrous shape, spherical shape, flower shape and the like, and has important influence on electrochemical performance.
In order to solve the problems of high cost, scarcity, low selectivity and poor stability of the existing electrocatalyst, the embodiment of the invention provides a polyaniline/carbon nanotube composite electrocatalyst material, which is prepared by in-situ polymerization of aniline and carbon nanotubes, wherein aniline uniformly coats the surface of the carbon nanotubes through anchor points provided by functional groups on the surface of the carbon nanotubes, so that the problems of stacking and agglomeration of polyaniline caused by self-polymerization are avoided; in addition, the invention further carries out dilute nitric acid immersion acidification treatment on the composite electrocatalytic material, so that a novel nitrogen-oxygen functional group is obtained on the surface of the material, the catalytic performance of the composite electrocatalytic material is improved, and meanwhile, the content of polyaniline on the surface of the carbon nano tube is adjustable, the immersion acidification time is controllable, and the electrochemical performance of the composite electrocatalytic material is favorably improved.
The embodiment of the invention provides a preparation method of an electrocatalytic material, which comprises the following steps:
adding an initiator into an acid solution, and uniformly mixing to obtain a solution A;
adding aniline and carbon nano tubes into an acid solution, and uniformly mixing to obtain a solution B;
dropwise adding the solution A into the solution B, uniformly mixing, sealing, immersing in an ice water bath for reaction, washing to be neutral, and drying to obtain a mixed product;
and (3) placing the mixed product into a dilute nitric acid solution for immersion acidification treatment, washing to be neutral, and drying to obtain the catalyst.
In a preferred embodiment of the present invention, the step of adding the initiator into the acid solution and mixing uniformly to obtain the solution a specifically includes:
adding 0.1-0.5 millimole of initiator into 50-200 ml of 0.5-2 mol/L acid solution, and uniformly mixing to obtain solution A.
In the embodiment of the invention, the initiator is one or more of ammonium persulfate, potassium persulfate, sodium persulfate, potassium dichromate, potassium iodate, ferric chloride, hydrogen peroxide, manganese dioxide, benzoyl peroxide and cerium sulfate in any proportion.
More preferably, the initiator is preferably ammonium persulfate, preferably in an amount of 0.1 millimole.
In the embodiment of the invention, the acid solution is one or more of hydrochloric acid, sulfuric acid and perchloric acid in any proportion.
In a preferred embodiment of the present invention, the step of adding aniline and carbon nanotubes into an acid solution and mixing them uniformly to obtain a solution B specifically includes:
adding 0.1-0.5 millimole of aniline and 50-200 mg of carbon nano tubes into 50-200 ml of hydrochloric acid solution with the concentration of 0.5-2 mol/L, and uniformly mixing to obtain solution B.
In the embodiment of the invention, the aniline and the carbon nano tube are added into the acid solution and uniformly mixed to obtain the acid solution in the step B, and the initiator is added into the acid solution and uniformly mixed to obtain the acid solution in the step A.
In the embodiment of the invention, the carbon nanotube is one of an aminated carbon nanotube, a carboxylated carbon nanotube and a hydroxylated carbon nanotube or a plurality of the aminated carbon nanotubes in any proportion. The carbon nanotubes can be purchased from China age.
In the embodiment of the invention, the amount of the carbon nanotubes is preferably 100-150 mg.
In a preferred embodiment of the present invention, the step of adding the solution a dropwise into the solution B, mixing uniformly, sealing, immersing in an ice-water bath for reaction, washing to neutrality, and drying to obtain a mixed product specifically includes:
and dropwise adding the solution A into the solution B, uniformly mixing, sealing, immersing in an ice water bath, reacting for 6-36 hours, washing to be neutral, and freeze-drying for 12-24 hours to obtain a mixed product.
In a preferred embodiment of the present invention, the step of placing the mixed product in a dilute nitric acid solution for immersion acidification treatment, washing to neutrality, and drying to obtain the product specifically comprises:
and (3) placing 50-500 mg of the mixed product into 50-500 ml of dilute nitric acid solution with the concentration of 1-5 mol/L for immersion acidification treatment for 4-12 h, washing to be neutral, and freeze-drying to obtain the catalyst.
The invention also provides an electrocatalytic material prepared by the preparation method of the electrocatalytic material.
The invention also provides application of the electrocatalytic material prepared by the preparation method of the electrocatalytic material in preparing hydrogen peroxide through electrocatalysis.
The technical effects of the preparation method of the electrocatalytic material of the present invention are further described below with reference to specific examples, but the specific implementation methods mentioned in these examples are only illustrative and explanatory of the technical solution of the present invention, and do not limit the implementation scope of the present invention.
Example 1
Accurately weighing 0.1 millimole of ammonium persulfate, dissolving in 100 ml of 1mol/L HCl solution, and continuously stirring for 30min on a magnetic stirrer to be marked as solution A; accurately measuring 0.1 millimole aniline monomer, dissolving the aniline monomer in 100 ml HCl solution with the concentration of 1mol/L, simultaneously weighing 100mg carboxylated carbon nanotube powder, dispersing the powder in the solution, and stirring the solution for 30min, and marking the solution as solution B; dropwise adding the solution A into the solution B, keeping stirring continuously, and sealing the mixed solution after about 1 h; and immersing the sealed reaction solution in an ice-water bath for reaction for 24 hours. Will reactAnd (3) centrifugally washing the finished solution (which is dark green) by using a centrifugal machine, washing the solution to be neutral by using ethanol and deionized water in sequence, and freeze-drying the solution for 12 hours to obtain solid powder (the electro-catalytic material). Dissolving the prepared catalyst in Nafion solution and coating the Nafion solution on the surface of a glassy carbon ring disk electrode, respectively taking AgCl and Pt as a reference electrode and a counter electrode, and introducing oxygen into 0.1M KOH solution for electrochemical reduction to prepare H2O2Testing of the electrocatalytic Material by two-Electron oxygen reduction reaction preparation H Using a rotating disk electrode device2O2The selectivity of (3) was 55%.
Example 2
Accurately weighing 0.1 millimole of ammonium persulfate, dissolving in 100 ml of 1mol/L HCl solution, and continuously stirring for 30min on a magnetic stirrer to be marked as solution A; accurately measuring 0.1 millimole aniline monomer, dissolving the aniline monomer in 100 ml HCl solution with the concentration of 1mol/L, simultaneously weighing 100mg carboxylated carbon nanotube powder, dispersing the powder in the solution, and stirring the solution for 30min, and marking the solution as solution B; dropwise adding the solution A into the solution B, keeping stirring continuously, and sealing the mixed solution after about 1 h; and immersing the sealed reaction solution in an ice-water bath for reaction for 24 hours. And (3) centrifugally washing the solution (which is dark green) after the reaction by using a centrifugal machine, washing the solution to be neutral by using ethanol and deionized water sequentially, and freeze-drying the solution for 12 hours to obtain solid powder. Weighing 50 mg of solid powder product, adding the solid powder product into 50 ml of dilute nitric acid solution with the concentration of 3mol/L, uniformly mixing, immersing and acidifying for 4 hours, carrying out suction filtration on the treated sample, washing to be neutral, and freeze-drying for 12 hours to finally obtain black powder (electro-catalytic material). Dissolving the prepared catalyst in Nafion solution and coating the Nafion solution on the surface of a glassy carbon ring disk electrode, respectively taking AgCl and Pt as a reference electrode and a counter electrode, and introducing oxygen into 0.1M KOH solution for electrochemical reduction to prepare H2O2Testing of the electrocatalytic Material by two-Electron oxygen reduction reaction preparation H Using a rotating disk electrode device2O2The selectivity of (3) was 75%.
Example 3
Ammonium persulphate was weighed accurately at 0.1 millimole, dissolved in 100 ml of 1mol/L HCl solution and stirred on a magnetic stirrerContinuously stirring for 30min, and marking as a solution A; accurately measuring 0.1 millimole aniline monomer, dissolving the aniline monomer in 100 ml HCl solution with the concentration of 1mol/L, simultaneously weighing 100mg carboxylated carbon nanotube powder, dispersing the powder in the solution, and stirring the solution for 30min, and marking the solution as solution B; dropwise adding the solution A into the solution B, keeping stirring continuously, and sealing the mixed solution after about 1 h; and immersing the sealed reaction solution in an ice-water bath for reaction for 24 hours. And (3) centrifugally washing the solution (which is dark green) after the reaction by using a centrifugal machine, washing the solution to be neutral by using ethanol and deionized water sequentially, and freeze-drying the solution for 12 hours to obtain solid powder. Weighing 50 mg of solid powder product, adding the solid powder product into 50 ml of 3mol/L dilute nitric acid solution, uniformly mixing, immersing and acidifying for 6 hours, carrying out suction filtration on the treated sample, washing to be neutral, and freeze-drying for 12 hours to finally obtain black powder (an electro-catalytic material). Dissolving the prepared catalyst in Nafion solution and coating the Nafion solution on the surface of a glassy carbon ring disk electrode, respectively taking AgCl and Pt as a reference electrode and a counter electrode, and introducing oxygen into 0.1M KOH solution for electrochemical reduction to prepare H2O2Testing of the electrocatalytic Material by two-Electron oxygen reduction reaction preparation H Using a rotating disk electrode device2O2The selectivity of (A) was 78%.
Example 4
Accurately weighing 0.1 millimole of ammonium persulfate, dissolving in 100 ml of 1mol/L HCl solution, and continuously stirring for 30min on a magnetic stirrer to be marked as solution A; accurately measuring 0.1 millimole aniline monomer, dissolving the aniline monomer in 100 ml HCl solution with the concentration of 1mol/L, simultaneously weighing 100mg carboxylated carbon nanotube powder, dispersing the powder in the solution, and stirring the solution for 30min, and marking the solution as solution B; dropwise adding the solution A into the solution B, keeping stirring continuously, and sealing the mixed solution after about 1 h; and immersing the sealed reaction solution in an ice-water bath for reaction for 24 hours. And (3) centrifugally washing the solution (which is dark green) after the reaction by using a centrifugal machine, washing the solution to be neutral by using ethanol and deionized water sequentially, and freeze-drying the solution for 12 hours to obtain solid powder. Weighing 50 mg of solid powder product, adding the solid powder product into 50 ml of 3mol/L dilute nitric acid solution, uniformly mixing, immersing and acidifying for 10 hours, carrying out suction filtration on a treated sample, washing to be neutral, freeze-drying for 12 hours, and finallyA black powder (electrocatalytic material) was obtained. Dissolving the prepared catalyst in Nafion solution and coating the Nafion solution on the surface of a glassy carbon ring disk electrode, respectively taking AgCl and Pt as a reference electrode and a counter electrode, and introducing oxygen into 0.1M KOH solution for electrochemical reduction to prepare H2O2Testing of the electrocatalytic Material by two-Electron oxygen reduction reaction preparation H Using a rotating disk electrode device2O2The selectivity of (A) was 83%.
Example 5
Accurately weighing 0.1 millimole of ammonium persulfate, dissolving in 100 ml of 1mol/L HCl solution, and continuously stirring for 30min on a magnetic stirrer to be marked as solution A; accurately measuring 0.1 millimole aniline monomer, dissolving the aniline monomer in 100 ml HCl solution with the concentration of 1mol/L, simultaneously weighing 100mg carboxylated carbon nanotube powder, dispersing the powder in the solution, and stirring the solution for 30min, and marking the solution as solution B; dropwise adding the solution A into the solution B, keeping stirring continuously, and sealing the mixed solution after about 1 h; and immersing the sealed reaction solution in an ice-water bath for reaction for 24 hours. And (3) centrifugally washing the solution (which is dark green) after the reaction by using a centrifugal machine, washing the solution to be neutral by using ethanol and deionized water sequentially, and freeze-drying the solution for 12 hours to obtain solid powder. Weighing 50 mg of solid powder product, adding the solid powder product into 50 ml of 3mol/L dilute nitric acid solution, uniformly mixing, immersing and acidifying for 12h, carrying out suction filtration on the treated sample, washing to be neutral, and freeze-drying for 12h to finally obtain black powder (an electro-catalytic material). Dissolving the prepared catalyst in Nafion solution and coating the Nafion solution on the surface of a glassy carbon ring disk electrode, respectively taking AgCl and Pt as a reference electrode and a counter electrode, and introducing oxygen into 0.1M KOH solution for electrochemical reduction to prepare H2O2Testing of the electrocatalytic Material by two-Electron oxygen reduction reaction preparation H Using a rotating disk electrode device2O2The selectivity of (a) was 90%.
Example 6
0.1 millimole of cerium sulfate was accurately weighed and dissolved in 100 ml of 1mol/L H2SO4Stirring in the solution for 30min on a magnetic stirrer, and marking as solution A; accurately measuring 0.1 millimole aniline monomer dissolved in 100 ml H with the concentration of 1mol/L2SO4In the solution, 100mg of carboxylated carbon nanotube powder is weighed and dispersed in the solution at the same time, and stirred for 30min, and the solution is marked as solution B; dropwise adding the solution A into the solution B, keeping stirring continuously, and sealing the mixed solution after about 1 h; and immersing the sealed reaction solution in an ice-water bath for reaction for 24 hours. And (3) centrifugally washing the solution after the reaction by using a centrifugal machine, washing the solution to be neutral by using ethanol and deionized water sequentially, and freeze-drying the solution for 12 hours to obtain solid powder. Dissolving the prepared catalyst in Nafion solution and coating the Nafion solution on the surface of a glassy carbon ring disk electrode, respectively taking AgCl and Pt as a reference electrode and a counter electrode, and introducing oxygen into 0.1MKOH solution for electrochemical reduction to prepare H2O2Testing of the electrocatalytic Material by two-Electron oxygen reduction reaction preparation H Using a rotating disk electrode device2O2The selectivity of (A) was 50%.
Example 7
Accurately weighing 0.2 millimole of potassium persulfate, dissolving in 100 ml of HCl solution with the concentration of 2mol/L, and continuously stirring on a magnetic stirrer for 30min, and marking as solution A; accurately measuring 0.1 millimole aniline monomer, dissolving the aniline monomer in 100 ml HCl solution with the concentration of 2mol/L, simultaneously weighing 150 mg hydroxylated carbon nanotube powder, dispersing the powder in the solution, and stirring for 30min, and marking as solution B; dropwise adding the solution A into the solution B, keeping stirring continuously, and sealing the mixed solution after about 1 h; and immersing the sealed reaction solution in an ice-water bath for reaction for 24 hours. And (3) centrifugally washing the solution after the reaction by using a centrifugal machine, washing the solution to be neutral by using ethanol and deionized water sequentially, and freeze-drying the solution for 12 hours to obtain solid powder. Dissolving the prepared catalyst in Nafion solution and coating the Nafion solution on the surface of a glassy carbon ring disk electrode, respectively taking AgCl and Pt as a reference electrode and a counter electrode, and introducing oxygen into 0.1MKOH solution for electrochemical reduction to prepare H2O2Testing of the electrocatalytic Material by two-Electron oxygen reduction reaction preparation H Using a rotating disk electrode device2O2The selectivity of (a) was 58%.
Example 8
0.2 millimole of sodium persulfate was accurately weighed, dissolved in 50 ml of 2mol/L HCl solution and filteredContinuously stirring for 30min on a magnetic stirrer, and marking as a solution A; accurately measuring 0.2 millimole aniline monomer, dissolving the aniline monomer in 50 ml HCl solution with the concentration of 2mol/L, simultaneously weighing 50 mg carboxylated carbon nanotube powder, dispersing the powder in the solution, and stirring the solution for 30min, and marking the solution as solution B; dropwise adding the solution A into the solution B, keeping stirring continuously, and sealing the mixed solution after about 0.5 h; and immersing the sealed reaction solution in an ice-water bath for reaction for 24 hours. And (3) centrifugally washing the solution after the reaction by using a centrifugal machine, washing the solution to be neutral by using ethanol and deionized water sequentially, and freeze-drying the solution for 10 hours to obtain solid powder. Dissolving the prepared catalyst in Nafion solution and coating the Nafion solution on the surface of a glassy carbon ring disk electrode, respectively taking AgCl and Pt as a reference electrode and a counter electrode, and introducing oxygen into 0.1MKOH solution for electrochemical reduction to prepare H2O2Testing of the electrocatalytic Material by two-Electron oxygen reduction reaction preparation H Using a rotating disk electrode device2O2The selectivity of (b) was 45%.
Example 9
Accurately weighing 0.1 millimole of manganese dioxide, dissolving in 50 ml of 1mol/L HCl solution, and continuously stirring for 30min on a magnetic stirrer to obtain a solution A; accurately measuring 0.1 millimole of aniline monomer, dissolving the aniline monomer in 50 ml of HCl solution with the concentration of 1mol/L, simultaneously weighing 100mg of carboxylated carbon nanotube powder, dispersing the powder in the solution, and stirring the solution for 30min, and marking the solution as solution B; dropwise adding the solution A into the solution B, keeping stirring continuously, and sealing the mixed solution after about 0.5 h; the sealed reaction solution was immersed in an ice-water bath and reacted for 18 hours. And (3) centrifugally washing the solution after the reaction by using a centrifugal machine, washing the solution to be neutral by using ethanol and deionized water sequentially, and freeze-drying the solution for 10 hours to obtain solid powder. Dissolving the prepared catalyst in Nafion solution and coating the Nafion solution on the surface of a glassy carbon ring disk electrode, respectively taking AgCl and Pt as a reference electrode and a counter electrode, and introducing oxygen into 0.1M KOH solution for electrochemical reduction to prepare H2O2Testing of the electrocatalytic Material by two-Electron oxygen reduction reaction preparation H Using a rotating disk electrode device2O2The selectivity of (3) was 40%.
Example 10
Accurately weighing 0.1 millimole of ammonium persulfate, dissolving in 50 ml of 1mol/L HCl solution, and continuously stirring for 30min on a magnetic stirrer to be marked as solution A; accurately measuring 0.1 millimole of aniline monomer, dissolving the aniline monomer in 50 ml of HCl solution with the concentration of 1mol/L, simultaneously weighing 100mg of carboxylated carbon nanotube powder, dispersing the powder in the solution, and stirring the solution for 30min, and marking the solution as solution B; dropwise adding the solution A into the solution B, keeping stirring continuously, and sealing the mixed solution after about 0.5 h; and immersing the sealed reaction solution in an ice-water bath for reaction for 24 hours. And (3) centrifugally washing the solution (which is dark green) after the reaction by using a centrifugal machine, washing the solution to be neutral by using ethanol and deionized water sequentially, and freeze-drying the solution for 10 hours to obtain solid powder. Weighing 100mg of solid powder product, adding the solid powder product into 100 ml of dilute nitric acid solution of 4 mol/L, uniformly mixing, immersing and acidifying for 5 h, carrying out suction filtration on the treated sample, washing to be neutral, and freeze-drying for 10 h to finally obtain black powder (an electro-catalytic material). Dissolving the prepared catalyst in Nafion solution and coating the Nafion solution on the surface of a glassy carbon ring disk electrode, respectively taking AgCl and Pt as a reference electrode and a counter electrode, and introducing oxygen into 0.1M KOH solution for electrochemical reduction to prepare H2O2Testing of the electrocatalytic Material by two-Electron oxygen reduction reaction preparation H Using a rotating disk electrode device2O2The selectivity of (3) was 72%.
Further, the invention observes the internal structure of the material under a Transmission Electron Microscope (TEM) for the electrocatalytic material prepared in example 2, as shown in fig. 1, the magnification is 10 ten thousand times, and as is apparent from fig. 1, aniline uniformly coats the surface of the carbon nanotube through anchor points provided by functional groups on the surface of the carbon nanotube, thereby avoiding the problems of stacking and agglomeration caused by self-polymerization of polyaniline.
Further, the invention performs X-ray photoelectron spectroscopy (XPS) on the electrocatalytic material prepared in example 4 to test nitrogen element, as shown in FIG. 2, and it can be seen from FIG. 2 that the electrocatalytic material has a novel nitrogen-oxygen functional group.
Further, the present invention performed a rotating ring disk electrode test on the electrocatalytic material prepared in example 5, as shown in fig. 3, it can be seen from fig. 3 that the disk current of the electrocatalytic material reaches 0.6 mA, and the loop current reaches 0.15 mA.
Further, the nitrogen content of the electrocatalytic materials prepared in examples 1, 3 and 5 was tested, and the test results are shown in fig. 4, wherein PANI @ CNT was not treated by dilute nitric acid immersion acidification (example 1), PANI @ CNT-6h was treated by dilute nitric acid immersion acidification 6h (example 3), and PANI @ CNT-12h was treated by dilute nitric acid immersion acidification 12h (example 5).
In summary, in the embodiment of the present invention, aniline and carbon nanotubes are polymerized in situ to obtain a polyaniline/carbon nanotube composite electrocatalytic material; the polyaniline is uniformly coated on the surface of the carbon nano tube through anchor points provided by functional groups on the surface of the carbon nano tube, so that the problems of stacking and agglomeration caused by self polymerization of the polyaniline are solved, and the adopted in-situ polymerization method has mild reaction conditions, simple operation and short process flow, and is beneficial to popularization of large-scale preparation and production of the composite electro-catalytic material; in addition, the invention further carries out dilute nitric acid immersion acidification treatment on the composite electrocatalytic material, so that a novel nitrogen-oxygen functional group is obtained on the surface of the material, the catalytic performance of the composite electrocatalytic material is improved, and meanwhile, the content of polyaniline on the surface of the carbon nano tube is adjustable, the immersion acidification time is controllable, and the electrochemical performance of the composite electrocatalytic material is favorably improved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method of preparing an electrocatalytic material, said method comprising:
adding an initiator into an acid solution, and uniformly mixing to obtain a solution A;
adding aniline and carbon nano tubes into an acid solution, and uniformly mixing to obtain a solution B;
dropwise adding the solution A into the solution B, uniformly mixing, sealing, immersing in an ice water bath for reaction, washing to be neutral, and drying to obtain a mixed product;
and (3) placing the mixed product into a dilute nitric acid solution for immersion acidification treatment, washing to be neutral, and drying to obtain the catalyst.
2. The method for preparing the electrocatalytic material as set forth in claim 1, wherein the carbon nanotubes are one or more of aminated carbon nanotubes, carboxylated carbon nanotubes and hydroxylated carbon nanotubes in any ratio.
3. The method for preparing an electrocatalytic material as set forth in claim 1, wherein said initiator is one or more selected from the group consisting of ammonium persulfate, potassium persulfate, sodium persulfate, potassium dichromate, potassium iodate, ferric chloride, hydrogen peroxide, manganese dioxide, benzoyl peroxide, and cerium sulfate.
4. The method for preparing an electrocatalytic material as set forth in claim 1, wherein the acid solution is one or more of hydrochloric acid, sulfuric acid, perchloric acid.
5. The preparation method of the electrocatalytic material as set forth in claim 1, wherein the step of adding the initiator into the acid solution and mixing uniformly to obtain the solution a specifically comprises:
adding 0.1-0.5 millimole of initiator into 50-200 ml of 0.5-2 mol/L acid solution, and uniformly mixing to obtain solution A.
6. The method for preparing the electrocatalytic material as set forth in claim 1, wherein the step of adding aniline and carbon nanotubes into an acid solution and mixing them uniformly to obtain a solution B comprises:
adding 0.1-0.5 millimole of aniline and 50-200 mg of carbon nano tubes into 50-200 ml of acid solution with the concentration of 0.5-2 mol/L, and uniformly mixing to obtain solution B.
7. The preparation method of the electrocatalytic material as set forth in claim 1, wherein the step of adding the solution a dropwise into the solution B, mixing uniformly, sealing, immersing in an ice-water bath for reaction, washing to neutrality, and drying to obtain a mixed product specifically comprises:
and dropwise adding the solution A into the solution B, uniformly mixing, sealing, immersing in an ice water bath, reacting for 6-36 hours, washing to be neutral, and freeze-drying for 12-24 hours to obtain a mixed product.
8. The method for preparing the electrocatalytic material as set forth in claim 1, wherein the step of immersing and acidifying the mixed product in a dilute nitric acid solution, washing to neutrality and drying comprises:
and (3) placing 50-500 mg of the mixed product into 50-500 ml of dilute nitric acid solution with the concentration of 1-5 mol/L for immersion acidification treatment for 4-12 h, washing to be neutral, and freeze-drying to obtain the catalyst.
9. An electrocatalytic material prepared by the method of any one of claims 1 to 8.
10. Use of an electrocatalytic material prepared by the preparation method of the electrocatalytic material as claimed in any one of claims 1 to 8 in the electrocatalytic preparation of hydrogen peroxide.
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