CN114232012B - Ionic liquid modified nano carbon material catalyst and preparation method and application thereof - Google Patents
Ionic liquid modified nano carbon material catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 64
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 44
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005289 physical deposition Methods 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- 239000006230 acetylene black Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 2
- NUUDMTGMAZJCBY-UHFFFAOYSA-N 1-decyl-3-methyl-2h-imidazole Chemical compound CCCCCCCCCCN1CN(C)C=C1 NUUDMTGMAZJCBY-UHFFFAOYSA-N 0.000 claims description 2
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 claims description 2
- FIOYZGZRZWNKTB-UHFFFAOYSA-N 1-methyl-3-tetradecyl-2h-imidazole Chemical compound CCCCCCCCCCCCCCN1CN(C)C=C1 FIOYZGZRZWNKTB-UHFFFAOYSA-N 0.000 claims description 2
- 229940075397 calomel Drugs 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 101100112111 Caenorhabditis elegans cand-1 gene Proteins 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 17
- 238000000840 electrochemical analysis Methods 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 229910000474 mercury oxide Inorganic materials 0.000 description 5
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- -1 1-butyl-3-methylimidazole potassium Chemical compound 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical class C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 102000003814 Interleukin-10 Human genes 0.000 description 1
- 108090000174 Interleukin-10 Proteins 0.000 description 1
- FMMSEFNIWDFLKK-UHFFFAOYSA-N [O].OO Chemical compound [O].OO FMMSEFNIWDFLKK-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
Abstract
The invention discloses an ionic liquid modified nano carbon material catalyst and a preparation method and application thereof, and belongs to the technical field of electrochemical synthesis and catalysis. The ionic liquid is loaded on the nano carbon by using a physical deposition method, and the catalyst has the advantages of solving the problems of high price, low storage capacity and the like of the noble metal catalyst. The prepared ionic liquid modified nano carbon catalyst can efficiently realize high-selectivity preparation of hydrogen peroxide by electrochemical oxygen reduction, meanwhile, the catalyst keeps higher stability for a long time, and the catalyst is convenient to prepare and low in cost, and has wide development prospect in preparation of hydrogen peroxide by electrosynthesis oxygen reduction.
Description
Technical Field
The invention relates to the technical field of electrochemical synthesis and catalysis, in particular to an ionic liquid modified nano carbon material catalyst and a preparation method and application thereof.
Background
With the increasing consumption of non-renewable fossil resources, searching for cleaner energy substitutes meeting the requirements of green chemistry sustainable development to meet the ever-increasing energy demands is becoming a problem to be solved. Hydrogen peroxide is an environmentally friendly oxidizing agent and is widely used in the fields of chemical industry, sanitation and environmental remediation. At present, hydrogen peroxide is mainly produced by an anthraquinone oxidation process, but the method has the problems of high energy consumption, low yield, potential safety hazard, impurities in the prepared hydrogen peroxide and the like. In contrast, the preparation of hydrogen peroxide by a two-electron electrochemical oxygen reduction reaction in an aqueous solution using a simple electrochemical device is a green and convenient method, and is attracting attention. However, in the electrochemical synthesis hydrogen peroxide reaction system, the selectivity of hydrogen peroxide is reduced because many electrode materials tend to generate water through competitive four-electron oxygen reduction reaction, rather than converting the two-electron oxygen reduction reaction into hydrogen peroxide. Second, active sites on the catalyst are easily corroded and it is difficult to achieve sustainable electrocatalytic behavior, thus the dilemma of difficulty in improving stability while ensuring high selectivity of the catalyst still exists. It is therefore an aim to study the electrosynthesis of hydrogen peroxide by the two-electron oxygen reduction reaction, in order to meet the concept of sustainable development and to reduce the use of non-renewable energy sources with a broad development prospect, the core of this technology is the development of a new and efficient and stable electrocatalyst with low cost.
To date, many materials have been identified as viable catalysts for the electrocatalytic oxygen reduction synthesis of hydrogen peroxide, such as noble metal based alloys and transition metal based composites, are advanced catalysts for the electrosynthesis of hydrogen peroxide, but their practical use has been limited due to the scarcity of noble metal resources and the heavy metal pollution of the environment by transition metals. In contrast, the nano carbon material with the advantages of rich storage, low price, high specific surface area, high conductivity and the like is considered to be one of the most potential alternative metal-based catalysts, and has wide application prospect in electrochemistry. However, the application of nanocarbon materials in electrochemical catalytic synthesis of hydrogen peroxide is still in the early stage of concept verification, and the yield of hydrogen peroxide in this process is generally low, mainly because of low selectivity and poor stability of the di-electron oxygen reduction. To solve this problem, the development of a strong catalyst with high activity, high selectivity and long-term stability is critical to achieving efficient electroreduction of oxygen to hydrogen peroxide.
Disclosure of Invention
The invention aims to provide an ionic liquid modified nano carbon material catalyst, a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the ionic liquid modified nano carbon material catalyst is formed by modifying ionic liquid on a nano carbon material carrier, wherein the particle size of the carrier is 5-30 nm.
The nano carbon material carrier is one or more of acetylene black, carbon black, graphene and carbon nano tubes.
The ionic liquid is one or more of 1-butyl-3-methylimidazole bis (trifluoro potassium sulfonyl imide) salt (IL 4), 1-hexyl-3-methylimidazole bis (trifluoro potassium sulfonyl imide) salt (IL 6), 1-decyl-3-methylimidazole bis (trifluoro potassium sulfonyl imide) salt (IL 10) and 1-tetradecyl-3-methylimidazole bis (trifluoro potassium sulfonyl imide) salt (IL 14).
In the ionic liquid, the macroscopic color of the cationic alkyl chain length lower than C10 is transparent viscous liquid, and the macroscopic color of the cationic alkyl chain length exceeding C10 is white powdery crystal; the density of the ionic liquid is 1.2-1.5 g/cm 3 (25℃、1atm)。
The ionic liquid modified nano carbon material catalyst is prepared by a physical deposition method, and the preparation method specifically comprises the following steps:
(1) Preparing ionic liquid, a nano carbon material carrier and an isopropanol solvent, and preparing a mixed material;
(2) And (3) loading the ionic liquid on the nano carbon material substrate by using a physical deposition method to obtain the ionic liquid modified nano carbon material catalyst.
In the step (1), the preparation process of the mixed material is as follows: adding the ionic liquid and the nano carbon material into an isopropanol solvent, dispersing, and controlling the dosage of the ionic liquid and the nano carbon material to make the loaded ionic liquid be 10-40% of the weight of the nano carbon material; the ratio of the nano carbon material to the isopropanol solvent is (3-10) mg (1-3) mL.
In the step (2), the physical deposition method refers to sequentially carrying out ultrasonic treatment, rotary evaporation and vacuum drying treatment on the mixed material to obtain the catalyst; wherein: the ultrasonic treatment time is 60-120min, the rotary steaming temperature is 40-60 ℃, and the vacuum drying treatment temperature is 60-100 ℃.
The ionic liquid modified nano carbon material catalyst is applied to the reaction of preparing hydrogen peroxide by electrochemical catalytic oxygen reduction. The catalyst is applied in the process: the catalytic reaction is carried out in a single electrolytic cell of a three-electrode system, the working electrode is a ring plate electrode, the reference electrode is a calomel electrode, the counter electrode is a platinum wire electrode, the electrolyte is 0.05 mol/l-0.2 mol/l potassium hydroxide solution, and the reaction voltage is 0-2V RHE The reaction time is 0.5-2 h.
The ionic liquid modified nano carbon material catalyst is applied to the reaction of preparing hydrogen peroxide by electrochemical catalytic oxygen reduction, and the selectivity of the hydrogen peroxide is 70-95%.
The principle of the invention is as follows:
the nano carbon material carrier used in the invention is provided with a plurality of tiny micropores, and when the ionic liquid is deposited on the surface of the carbon nano material carrier, a part of ionic liquid enters the nano micropores at the same time, and finally the appearance is presented as a nano sheet structure (if a tubular carbon nano tube is used as a carrier, the final catalyst is in a tubular structure). When hydrogen peroxide is prepared by electrocatalytic oxygen reduction reaction, the ionic liquid can improve the solubility of oxygen, so that the oxygen concentration on the surface and in the holes of the catalyst is improved, and the ionic liquid loaded on the surface of the nano carbon material can also protect the active site of the reaction. Therefore, the addition of the ionic liquid enables the electrocatalytic oxygen reduction reaction to have higher hydrogen peroxide selectivity.
The invention has the following advantages:
1. the ionic liquid modified carbon nanomaterial is used as a catalyst for preparing hydrogen peroxide by electrocatalytic oxygen reduction reaction, has excellent activity and high selectivity, improves the yield of products, and has the selectivity of up to 95 percent for hydrogen peroxide.
2. The reaction of electrocatalytic synthesis of hydrogen peroxide oxygen by adopting the ionic liquid modified nano carbon catalyst is carried out at room temperature, and a potassium hydroxide aqueous solution is used as electrolyte, so that no organic solvent is required to be added, and the catalyst is nontoxic and pollution-free and accords with the green chemical standard.
3. The ionic liquid modified nano carbon catalyst is synthesized by adopting a physical deposition method, the chemical property of the catalyst can be regulated and controlled by changing the concentration of the ionic liquid, and the preparation method is simple, convenient and easy to operate, short in required time, low in cost and good in catalytic performance.
Drawings
FIG. 1 is a transmission electron microscope image and an element distribution diagram of an ionic liquid modified acetylene black catalyst prepared by the invention; wherein: (a) is a transmission electron microscopy of the catalyst; (b) is the elemental profile of the catalyst.
Fig. 2 is a graph of linear sweep voltammetry measured for an acetylene black, ionic liquid modified acetylene black catalyst.
FIG. 3 shows the selectivity of electrocatalytic oxygen reduction to hydrogen peroxide measured with acetylene black, ionic liquid modified acetylene black catalysts.
Detailed Description
For a further understanding of the present invention, the present invention is described below with reference to the examples, which are only illustrative of the features and advantages of the present invention and are not intended to limit the scope of the claims of the present invention.
In the examples below, the mixture was prepared with a ratio of carrier to isopropanol solvent of 5mg to 1mL.
When the mixed material is subjected to physical deposition, the ultrasonic time is 150min, the rotary evaporation temperature is 50 ℃, and the vacuum drying treatment temperature is 80 ℃.
Example 1
Mixing and stirring ionic liquid 1-butyl-3-methylimidazole potassium bistrifluorosulfonimide salt (IL 4), acetylene Black (AB) and isopropanol to prepare a mixed material, and carrying out ultrasonic treatment, rotary evaporation and vacuum drying to obtain the catalyst IL4@AB of the ionic liquid (IL 4) loaded on the acetylene black, wherein the loading amount of the ionic liquid is 20wt%. The ratio of catalyst to 0.3wt.% Nafion solution was 3mg:1ml of the resulting mixture was prepared into an electrode ink.
The IL4@AB catalyst is applied to the reaction of synthesizing hydrogen peroxide by electrocatalytic oxygen reduction, a three-electrode system is adopted, electrode ink of an ionic liquid-supported acetylene black catalyst is used as a working electrode (the electrode ink is 10 mu l), a platinum wire is used as a counter electrode, and a mercury/mercury oxide electrode is used as a reference electrode; at the position ofIn the single electrolytic cell, a potassium hydroxide solution having a concentration of 0.1mol/l was used as the electrolyte. Through electrochemical test (FIG. 2), the initial overpotential was 0.71V RHE The selectivity to hydrogen peroxide after the reaction was 70% (fig. 3).
Example 2
Mixing and stirring ionic liquid 1-hexyl-3-methylimidazole potassium bistrifluoro sulfonimide salt (IL 6), acetylene Black (AB) and isopropanol to prepare a mixed material, and carrying out ultrasonic treatment, rotary steaming and vacuum drying to obtain the catalyst IL6@AB of the ionic liquid (IL 6) loaded on the acetylene black, wherein the loading amount of the ionic liquid is.20wt%. The ratio of catalyst to 0.3wt% Nafion solution was 3mg:1ml of the resulting mixture was prepared into an electrode ink.
The IL6@AB catalyst is applied to the reaction of synthesizing hydrogen peroxide by electro-oxygen reduction, a three-electrode system is adopted, electrode ink of an ionic liquid-supported acetylene black catalyst is used as a working electrode (the electrode ink is 10 mu l), a platinum wire is used as a counter electrode, and a mercury/mercury oxide electrode is used as a reference electrode; in a single electrolytic cell, a potassium hydroxide solution having a concentration of 0.1mol/l was used as the electrolyte. Through electrochemical test (FIG. 2), the initial overpotential was 0.69V RHE The selectivity to hydrogen peroxide after the reaction was 74% (fig. 3).
Example 3
Mixing and stirring ionic liquid 1-decyl-3-methylimidazole potassium bistrifluoro sulfonimide salt (IL 10), acetylene Black (AB) and isopropanol to prepare a mixed material, and carrying out ultrasonic treatment, rotary evaporation and vacuum drying to obtain the catalyst IL14@AB of the ionic liquid (IL 10) loaded on the acetylene black, wherein the loading amount of the ionic liquid is 20wt%. The ratio of catalyst to 0.3wt% Nafion solution was 3mg:1ml of the resulting mixture was prepared into an electrode ink.
The IL10@AB catalyst is applied to the reaction of synthesizing hydrogen peroxide by electro-oxygen reduction, a three-electrode system is adopted, electrode ink of an ionic liquid-supported acetylene black catalyst is used as a working electrode (the electrode ink is 10 mu l), a platinum wire is used as a counter electrode, and a mercury/mercury oxide electrode is used as a reference electrode; in a single electrolytic cell, a potassium hydroxide solution having a concentration of 0.1mol/l was used as the electrolyte. Through electrochemical test (FIG. 2), the initial overpotential was 0.63V RHE The selectivity to hydrogen peroxide after the reaction was 83% (fig. 3).
Example 4
The ionic liquid 1-tetradecyl-3-methylimidazole potassium bistrifluoro sulfonimide salt (IL 14), acetylene Black (AB) and isopropanol are mixed and stirred to prepare a mixed material, and the mixed material is subjected to ultrasonic treatment, rotary evaporation and vacuum drying to obtain the catalyst IL14@AB of the ionic liquid (IL 14) loaded on the acetylene black, wherein the loading amount of the ionic liquid is 20wt% (shown in figure 1). The ratio of catalyst to 0.3wt% Nafion solution was 3mg:1ml of the resulting mixture was prepared into an electrode ink.
The IL14@AB catalyst is applied to the reaction of synthesizing hydrogen peroxide by electro-oxygen reduction, a three-electrode system is adopted, electrode ink of an ionic liquid-supported acetylene black catalyst is used as a working electrode (the electrode ink is 10 mu l), a platinum wire is used as a counter electrode, and a mercury/mercury oxide electrode is used as a reference electrode; in a single electrolytic cell, a potassium hydroxide solution having a concentration of 0.1mol/l was used as the electrolyte. Through electrochemical test (FIG. 2), the initial overpotential was 0.55V RHE The selectivity of hydrogen peroxide after the reaction was 90% (fig. 3).
Comparative example 1
The experiment of the reaction of synthesizing hydrogen peroxide by electro-oxygen reduction is carried out in a single-chamber electrolytic cell by adopting a three-electrode system, wherein acetylene black is used as a working electrode, a platinum wire is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, the used acetylene black electrode ink is 10 mu l, a potassium hydroxide solution with the concentration of 0.1mol/l is used as an electrolyte, and the initial overpotential is 0.65V through electrochemical test (figure 2) RHE The selectivity to hydrogen peroxide after the reaction was 48% (fig. 3).
Claims (7)
1. The application of the ionic liquid modified nano carbon material catalyst is characterized in that: the ionic liquid modified nano carbon material catalyst is applied to the reaction of preparing hydrogen peroxide by electrochemical catalytic oxygen reduction; the catalyst is formed by modifying ionic liquid on a nano carbon material carrier, wherein the particle size of the carrier is 5-30 nm; the nano carbon material carrier is one or more of acetylene black, carbon black, graphene and carbon nanotubes; the ionic liquid is one or more of 1-butyl-3-methylimidazole bis (trifluoro) potassium sulfonyl imide salt, 1-hexyl-3-methylimidazole bis (trifluoro) potassium sulfonyl imide salt, 1-decyl-3-methylimidazole bis (trifluoro) potassium sulfonyl imide salt and 1-tetradecyl-3-methylimidazole bis (trifluoro) potassium sulfonyl imide salt.
2. The use of the ionic liquid modified nanocarbon material catalyst according to claim 1, wherein: in the ionic liquid, the macroscopic color of the cationic alkyl chain length lower than C10 is transparent viscous liquid, and the macroscopic color of the cationic alkyl chain length exceeding C10 is white powdery crystal; the density of the ionic liquid is 1.2-1.5 g/cm 3 The density was 25℃and 1 atm.
3. The use of the ionic liquid modified nanocarbon material catalyst according to claim 1, wherein: the catalyst is prepared by a physical deposition method and specifically comprises the following steps:
(1) Preparing ionic liquid, a nano carbon material carrier and an isopropanol solvent, and preparing a mixed material;
(2) And (3) loading the ionic liquid on the nano carbon material substrate by using a physical deposition method to obtain the ionic liquid modified nano carbon material catalyst.
4. The use of the ionic liquid modified nanocarbon material catalyst according to claim 3, wherein: in the step (1), the preparation process of the mixed material is as follows: adding the ionic liquid and the nano carbon material into an isopropanol solvent, dispersing, and controlling the dosage of the ionic liquid and the nano carbon material to make the loaded ionic liquid be 10-40% of the weight of the nano carbon material; the ratio of the nano carbon material to the isopropanol solvent is (3-10) mg (1-3) mL.
5. The use of the ionic liquid modified nanocarbon material catalyst according to claim 3, wherein: in the step (2), the physical deposition method refers to sequentially carrying out ultrasonic treatment, rotary evaporation and vacuum drying treatment on the mixed material to obtain the catalyst; wherein: the ultrasonic treatment time is 60-120min, the rotary steaming temperature is 40-60 ℃, and the vacuum drying treatment temperature is 60-100 ℃.
6. The use of the ionic liquid modified nanocarbon material catalyst according to claim 1, wherein: the catalyst is applied in the process: the catalytic reaction is carried out in a single electrolytic cell of a three-electrode system, the working electrode is a ring plate electrode, the reference electrode is a calomel electrode, the counter electrode is a platinum wire electrode, the electrolyte is 0.05 mol/l-0.2 mol/l potassium hydroxide solution, and the reaction voltage is 0-2V RHE The reaction time is 0.5-2 h.
7. The use of the ionic liquid modified nanocarbon material catalyst according to claim 1, wherein: the ionic liquid modified nano carbon material catalyst is applied to the reaction of preparing hydrogen peroxide by electrochemical catalytic oxygen reduction, and the selectivity of the hydrogen peroxide is 70-95%.
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