CN117845254A - Chlorine doped indium oxide electrode and preparation method and application thereof - Google Patents
Chlorine doped indium oxide electrode and preparation method and application thereof Download PDFInfo
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- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 63
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 51
- 239000000460 chlorine Substances 0.000 title claims abstract description 44
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 131
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 235000019253 formic acid Nutrition 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000013216 MIL-68 Substances 0.000 claims abstract description 26
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000009467 reduction Effects 0.000 claims abstract description 25
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 23
- 239000002086 nanomaterial Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000001291 vacuum drying Methods 0.000 claims abstract description 13
- 229910021617 Indium monochloride Inorganic materials 0.000 claims abstract description 12
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229920000557 Nafion® Polymers 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
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- 239000000463 material Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 37
- 229910002091 carbon monoxide Inorganic materials 0.000 description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 25
- 238000006722 reduction reaction Methods 0.000 description 24
- 238000012360 testing method Methods 0.000 description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 description 16
- 239000001569 carbon dioxide Substances 0.000 description 16
- 125000001309 chloro group Chemical group Cl* 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 15
- 229920006395 saturated elastomer Polymers 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 7
- 102000020897 Formins Human genes 0.000 description 6
- 108091022623 Formins Proteins 0.000 description 6
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- 239000002184 metal Substances 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a chlorine doped indium oxide electrode, a preparation method and application thereof, wherein the method comprises the following steps: first, inCl 3 ·4H 2 O and trimesic acid are dissolved In dimethylformamide, and are subjected to centrifugation, washing and drying after hydrothermal reaction to obtain MIL-68 (In) nano material; vacuum drying MIL-68 (In) nanometer material, grinding, calcining under inert atmosphere, and carbonizing to obtain In 2 O 3 A catalyst; then In is added 2 O 3 Adding the catalyst into ethanol, adding Nafion solution, ultrasonically and then dripping the mixture on carbon paper to obtain load In 2 O 3 Carbon paper of the catalyst; finally adding cetyl trimethyl ammonium bromide into isopropanol to obtain a surface modifier which is dripped on the load In 2 O 3 And drying the front and back sides of the carbon paper of the catalyst to obtain the chlorine doped indium oxide electrode. The invention adjusts the InCl by a hydrothermal-calcining method 3 ·4H 2 The ratio of O and trimesic acid synthesizes three In with different morphologies 2 O 3 The nano material can be applied to electrocatalytic reduction of CO after being modified by CTAB 2 In the preparation of formic acid, the catalyst has higher electrocatalytic activity and formic acid selectivity.
Description
Technical Field
The invention relates to the technical field of metal catalysts, in particular to a chlorine doped indium oxide electrode, and a preparation method and application thereof.
Background
The conversion of carbon dioxide to fuels and chemicals helps to establish a carbon neutral cycle to mitigate rapid consumption of fossil resources and increasing carbon dioxide emissions. Due to research progress in renewable energy power generation such as solar energy and wind energy, electrocatalytic carbon dioxide reduction reaction (CO 2 RR) has become one of the most attractive ways of carbon dioxide conversion, which is electroreduction to value-added fuels and chemicals, powered by renewable electricity, providing tremendous prospects for the mitigation of current energy crisis and greenhouse gas emissions. Reduction of carbon dioxide to chemical raw materials and fuels by green electricity is not only an effective way to solve the increasingly serious environmental pollution and energy crisis, but also can produce value added chemicals and fuels such as carbon monoxide (CO), formic acid/formic acid (HCOO) - HCOOH), ethylene (C 2 H 4 ) And ethanol (C) 2 H 5 OH). According to the technical and economic analysis, the current C1 products (HCOO - HCOOH and CO) are commercially more profitable than the multi-carbon products. However, achieving high C1 activity and selectivity at low overpotential is still strongly dependent on Au and Ag-based noble metal catalysts.
Metal catalysts are commonly used for electrocatalytic CO due to their high activity and stability 2 RR. Along with CO 2 RR conversion to formate, hydrogen Evolution (HER) is a critical competing reaction. The metal has great influence on the aspect of electrocatalytic carbon dioxide reduction, and the local coordination environment around the active site of the metal is used for improving CO 2 The catalytic activity of RR plays an important role. In the carbon dioxide electroreduction reaction (CO 2 RR) formate-producing various latent catalysts, pBlock metals and their compounds, such as indium (In), tin (Sn) and bismuth (Bi), have proven to be good electrocatalysts for the conversion of carbon dioxide to formic acid, not only effectively inhibiting the HER reaction, but also having the advantages of good electrical conductivity, easy alloying, easy reaction with oxygen, etc., in CO 2 RR has been widely studied. Indium (In) is the most promising selective CO production as a formate catalyst, which is of increasing interest due to its low toxicity and environmental friendliness 2 One of the RR electrocatalysts. However, in-based electrocatalysts have disadvantages of low Faradic Efficiency (FE) at negative potential, poor durability, etc., thus severely hampering their practical application. Thus, research has found that efficient innovative In-based materials are useful for increasing CO 2 RR performance is of great importance.
Disclosure of Invention
The invention aims to provide a chlorine doped indium oxide electrode which has high electrocatalytic activity and formic acid selectivity.
Another object of the present invention is to provide a method for preparing a chlorine-doped indium oxide electrode, in being synthesized by a hydrothermal-calcination method 2 O 3 Catalyst and modification of In by cetyltrimethylammonium bromide 2 O 3 The catalyst is used for obtaining the chlorine doped indium oxide electrode, and the method is simple and has controllable parameters, thereby being applicable to industrialized mass production.
A third object of the present invention is to provide the electrochemical reduction of CO by the chlorine-doped indium oxide electrode 2 Use in the preparation of formic acid.
The invention solves the technical problems by adopting the following technical scheme.
The invention provides a preparation method of a chlorine doped indium oxide electrode, which comprises the following steps:
s1, preparation of MIL-68 (In) nano material: inCl is added to 3 ·4H 2 O and trimesic acid are dissolved In Dimethylformamide (DMF), and are subjected to centrifugation, washing and drying after hydrothermal reaction to obtain the MIL-68 (In) nanomaterial;
S2、In 2 O 3 and (3) synthesizing a catalyst: will be spentVacuum drying and grinding the MIL-68 (In) nano material, calcining under inert atmosphere and carbonizing to obtain the In 2 O 3 A catalyst;
s3, the In is 2 O 3 Adding the catalyst into ethanol, adding Nafion solution, performing ultrasonic treatment for 25-35 min, and then dripping the solution on carbon paper to obtain the load In 2 O 3 Carbon paper of the catalyst;
s4, adding Cetyl Trimethyl Ammonium Bromide (CTAB) into isopropanol, performing ultrasonic treatment for 25-30 min to obtain a surface modifier, and then dripping the surface modifier on the load In 2 O 3 And drying the front and back sides of the carbon paper of the catalyst to obtain the chlorine doped indium oxide electrode.
The invention provides a chlorine doped indium oxide electrode, which is prepared according to the preparation method.
The invention provides the method for electrocatalytic reduction of CO by the chlorine doped indium oxide electrode 2 Use in the preparation of formic acid.
The chlorine doped indium oxide electrode and the preparation method and application thereof have the beneficial effects that:
the invention adjusts the InCl by a hydrothermal-calcining method 3 ·4H 2 The ratio of O and trimesic acid synthesizes three In with different morphologies 2 O 3 The nano material can be used as a high-performance catalyst for stable and efficient carbon dioxide electroreduction after being modified by CTAB. In is embedded In the chlorine doped indium oxide electrode 2 O 3 The carbon atoms In the crystal lattice can regulate the electronic structure of In and increase In 2 O 3 Localization of negative surface charges to enhance CO simultaneously 2 Activity and selectivity of formic acid in RR. Chlorine atoms are uniformly distributed on the surface of the catalyst, so that electrons can be promoted to transfer to a reactant to improve the selectivity of formic acid. In addition, CTAB modified In 2 O 3 The catalyst can inhibit HER in the electrocatalytic process, so that the selectivity of HCOOH products is improved, and a proper amount of CTAB inhibits electrons from accumulating on the surface of the catalyst, so that the corrosion of the catalyst is prevented. In addition, in 2 O 3 Synergistic action between CTAB and chlorine atom in the catalyst causes CO 2 Can better suckAttached to the catalyst surface and selectively converted to HCOOH.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows In of examples 1 to 3 of the present invention 2 O 3 SEM image of the catalyst;
FIG. 2 shows In of examples 1 to 3 of the present invention 2 O 3 XRD pattern of the catalyst;
FIG. 3 shows In example 1 of the present invention 2 O 3 XPS spectrum of the catalyst;
FIG. 4 is a LSV graph of chlorine doped indium oxide electrodes of examples 1-3 of the present invention;
FIG. 5 is a graph of Faraday efficiency of chlorine doped indium oxide electrodes of examples 1-3 of the present invention;
FIG. 6 is a graph of i-t curves for chlorine doped indium oxide electrodes of examples 1-3 of the present invention at different reduction potentials;
FIG. 7 is a CV cycle graph of chlorine doped indium oxide electrodes of examples 1 to 3 of the present invention;
FIG. 8 is a graph of current density versus time for a chlorine-doped indium oxide electrode of example 1 of the present invention;
fig. 9 is a graph showing the impedance of chlorine-doped indium oxide electrodes according to examples 1 to 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The chlorine doped indium oxide electrode, the preparation method and the application thereof are specifically described below.
The embodiment of the invention provides a preparation method of a chlorine doped indium oxide electrode, which comprises the following steps:
s1, preparation of MIL-68 (In) nano material: inCl is added to 3 ·4H 2 O and trimesic acid are dissolved In dimethylformamide for 25-35 min In an ultrasonic way, and the MIL-68 (In) nanomaterial is obtained after centrifugal, washing and drying after hydrothermal reaction.
Further, in a preferred embodiment of the present invention, the InCl 3 ·4H 2 The mass ratio of O to the trimesic acid is 0.79-3.15: 1, the InCl 3 ·4H 2 The mass volume ratio of O to the dimethylformamide is 0.07-0.2: 1.
further, in the preferred embodiment of the present invention, the temperature of the hydrothermal reaction is 90-110 ℃, the hydrothermal reaction time is 22-26 hours, the drying temperature is 75-85 ℃, and the drying time is 10-14 hours. The hydrothermal reaction of the invention is carried out In a stainless steel autoclave with a 50mL Teflon lining, the reaction is carried out to obtain a product through centrifugation, and the product is washed three times with ethanol and water respectively and then dried to obtain the MIL-68 (In) nanomaterial. Preferably, the hydrothermal reaction temperature is 100 ℃, the hydrothermal reaction time is 24 hours, the drying temperature is 80 ℃, and the drying time is 12 hours.
S2、In 2 O 3 And (3) synthesizing a catalyst: vacuum drying the MIL-68 (In) nano material, grinding, calcining under inert atmosphere, and carbonizing to obtain the In 2 O 3 A catalyst. The invention synthesizes the chlorine doped indium oxide nano material by adopting a simple hydrothermal-calcining method to be used for preparing formic acid by electrocatalytic carbon dioxide reduction. Wherein, the formic acid can be formic acid monomer, formic acid ion and/or formate. By adjusting InCl 3 ·4H 2 In obtained by ratio of O and trimesic acid 2 O 3 The catalyst has both nanometer spherical particles and octahedron nanometer morphology, and chlorine atoms are uniformly doped on the surface of indium oxide.
Further, in the preferred embodiment of the present invention, the temperature of the vacuum drying is 140 to 160 ℃, and the vacuum drying time is 1.5 to 2.5 hours. Preferably, the vacuum drying temperature is 150 ℃ and the vacuum drying time is 2 hours.
Further, in a preferred embodiment of the present invention, the step of carbonizing after calcining under an inert atmosphere is as follows: the MIL-68 (In) nano material is placed into a magnetic boat after vacuum drying and grinding, then the magnetic boat is placed into a tube furnace and calcined In Ar atmosphere, and finally the magnetic boat is placed into a muffle furnace for carbonization, wherein the calcination temperature is 450-550 ℃, the calcination time is 1.5-2.5 h, the heating rate of the tube furnace is 5 ℃/min, the carbonization temperature is 450-550 ℃, the carbonization time is 1.5-2.5 h, and the heating rate of the muffle furnace is 5 ℃/min. Preferably, the calcination temperature is 500 ℃, the calcination time is 2 hours, the carbonization temperature is 500 ℃, and the carbonization time is 2 hours.
S3, the In is 2 O 3 Adding the catalyst into ethanol, adding Nafion solution, performing ultrasonic treatment for 25-35 min, and then dripping the solution on carbon paper to obtain the load In 2 O 3 And (3) carbon paper of the catalyst. Preferably, the carbon paper is hydrophobic carbon paper.
Further, in a preferred embodiment of the present invention, the In 2 O 3 The mass volume ratio of the catalyst to the ethanol to the Nafion solution is 1:1.5 to 2.5:1.5 to 2.5 (g/. Mu.L).
Further, in a preferred embodiment of the present invention, the load In 2 O 3 In the carbon paper of the catalyst, the In 2 O 3 The loading of the catalyst is 2.2-2.8 mg cm -2 . Preferably, in 2 O 3 The loading of the catalyst was 2.5mg cm -2 。
S4, adding cetyl trimethyl ammonium bromide into isopropanol, performing ultrasonic treatment for 25-30 min to obtain a surface modification, and then dripping the surface modification on the load In 2 O 3 And drying the front and back sides of the carbon paper of the catalyst in a vacuum oven at 60 ℃ to obtain the chlorine doped indium oxide electrode.
Further, in the preferred embodiment of the present invention, the mass-to-volume ratio of the cetyltrimethylammonium bromide to the isopropyl alcohol is 35 to 45:1 (mg/mL).
In is embedded In the chlorine doped indium oxide electrode 2 O 3 The carbon atoms In the crystal lattice can regulate the electronic structure of In and increase In 2 O 3 Localization of the negative surface charge thereby simultaneously enhancing the activity and selectivity of CRR formic acid. Chlorine atoms are uniformly distributed on the surface of the catalyst, so that electrons can be promoted to transfer to a reactant, and the selectivity of formic acid is improved. In addition, CTAB modified In 2 O 3 The catalyst can inhibit HER in the electrocatalytic process, so that the selectivity of HCOOH products is improved, and a proper amount of CTAB inhibits electrons from accumulating on the surface of the catalyst, so that the corrosion of the catalyst is prevented. In addition, in 2 O 3 Synergistic action between CTAB and chlorine atom in the catalyst causes CO 2 Can be better adsorbed on the surface of the catalyst and selectively converted into HCOOH.
The invention also provides a chlorine doped indium oxide electrode which is prepared according to the preparation method.
The invention also provides the method for electrocatalytic reduction of CO by the chlorine-doped indium oxide electrode 2 Use in the preparation of formic acid. Electrocatalytic reduction of CO 2 The battery used for preparing formic acid comprises an anode chamber, a cathode chamber and an electrolyte. Wherein the electrolyte is KHCO containing proton donor 3 Is a solution of (a) and (b). The battery uses the chlorine doped indium oxide electrode as a working electrode. When in use, the working electrode is placed in the cathode chamber, and saturated CO is introduced into the electrolyte of the cathode chamber 2 CO is generated by applying electric potential 2 Reducing to formic acid.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The present example provides a chlorine doped indium oxide electrode made according to the following method:
(1) Preparation of MIL-68 (In): 0.7917g of InCl is first added 3 ·4H 2 O and 0.252g of trimesic acid were dissolved in 5mL of DMF for 30min under ultrasound. The solution was then placed in 50mL Teflon linerIn a stainless steel autoclave, heating was carried out at 100℃for 24 hours. The product MIL-68 (In) is obtained by centrifugation, then washed three times with ethanol and water, and dried for 12 hours at 80 ℃ to obtain MIL-68 (In) nanomaterial.
(2) Synthesis of In 2 O 3 Catalyst: vacuum drying MIL-68 (In) nanomaterial at 150deg.C for 2 hr, grinding, placing into a magnetic boat, and heating at 500deg.C (rising rate of 5deg.C for min) under Ar atmosphere -1 ) Calcining in a tube furnace for 2h, and finally placing the material in 500 ℃ (heating rate 5 ℃ for min) -1 ) Carbonizing In a muffle furnace for 2h to obtain In 2 O 3 Catalyst (i.e. 2:1-In) 2 O 3 A catalyst).
(3)Cl-In 2 O 3 Preparation of an electrode: 5mg of In 2 O 3 Adding catalyst into 10 μl ethanol, adding 10 μl Nafion solution, and sonicating for 30min, and pipetting the solution with a pipetting gun to drop-coat on total area of 1cm 2 On carbon paper (model 060) to obtain a load In 2 O 3 And (3) carbon paper of the catalyst. Wherein In on carbon paper 2 O 3 The loading of the catalyst was 2.5mg cm -2 . Finally, 200mg of CTAB is added into 5mL of isopropanol and ultrasonic treatment is carried out for 30min, thus obtaining a surface modifier, and then In is loaded 2 O 3 Catalyst carbon paper (1X 1 cm) 2 ) The front and back sides of (C) were coated with 25. Mu.L of the surface modifier, followed by drying In a vacuum oven at 60℃to obtain chlorine-doped indium oxide electrodes (Cl-In) 2 O 3 An electrode).
Example 2
In this example, a chlorine doped indium oxide electrode is provided, which is prepared according to the following steps:
(1) Preparation of MIL-68 (In): 0.3988g of InCl is first added 3 ·4H 2 O and 0.252g of trimesic acid were dissolved in 5mL of DMF for 30min under ultrasound. The solution was then placed in a 50mL teflon lined stainless steel autoclave and heated at 100 ℃ for 24 hours. The product MIL-68 (In) is obtained by centrifugation, then washed three times with ethanol and water, and dried for 12 hours at 80 ℃ to obtain MIL-68 (In) nanomaterial.
(2) Synthesis of In 2 O 3 Catalyst: vacuum drying MIL-68 (In) nanomaterial at 150deg.C for 2 hr, grinding, placing into a magnetic boat, and heating at 500deg.C (rising rate of 5deg.C for min) under Ar atmosphere -1 ) Calcining in a tube furnace for 2h, and finally placing the material in 500 ℃ (heating rate 5 ℃ for min) -1 ) Carbonizing In a muffle furnace for 2h to obtain In 2 O 3 Catalyst (i.e. 1:1-In) 2 O 3 A catalyst).
(3)Cl-In 2 O 3 Preparation of an electrode: 5mg of In 2 O 3 Adding catalyst into 10 μl ethanol, adding 10 μl Nafion solution, and sonicating for 30min, and pipetting the solution with a pipetting gun to drop-coat on total area of 1cm 2 On carbon paper (model 060) to obtain a load In 2 O 3 And (3) carbon paper of the catalyst. Wherein In on carbon paper 2 O 3 The loading of the catalyst was 2.5mg cm -2 . Finally, 200mg of CTAB is added into 5mL of isopropanol and ultrasonic treatment is carried out for 30min, thus obtaining a surface modifier, and then In is loaded 2 O 3 Catalyst carbon paper (1X 1 cm) 2 ) The front and back sides of (C) were coated with 25. Mu.L of the surface modifier, followed by drying In a vacuum oven at 60℃to obtain chlorine-doped indium oxide electrodes (Cl-In) 2 O 3 An electrode).
Example 3
In this example, a chlorine doped indium oxide electrode is provided, which is prepared according to the following steps:
(1) Preparation of MIL-68 (In): 0.3988g of InCl is first added 3 ·4H 2 O and 0.504g of trimesic acid were sonicated for 30min and dissolved in 5mL of DMF. The solution was then placed in a 50mL teflon lined stainless steel autoclave and heated at 100 ℃ for 24 hours. The product MIL-68 (In) is obtained by centrifugation, then washed three times with ethanol and water, and dried for 12 hours at 80 ℃ to obtain MIL-68 (In) nanomaterial.
(2) Synthesis of In 2 O 3 Catalyst: vacuum drying MIL-68 (In) nanomaterial at 150deg.C for 2 hr, grinding, placing into a magnetic boat, and heating at 500deg.C (rising rate of 5deg.C for min) under Ar atmosphere -1 ) Calcining in a tube furnace for 2h, and finally placing the material in 500 ℃ (heating rate 5 ℃ for min) -1 ) Carbonizing In a muffle furnace for 2h to obtain In 2 O 3 Catalyst (i.e. 1:2-In) 2 O 3 A catalyst).
(3)Cl-In 2 O 3 Preparation of an electrode: 5mg of In 2 O 3 Adding catalyst into 10 μl ethanol, adding 10 μl Nafion solution, and sonicating for 30min, and pipetting the solution with a pipetting gun to drop-coat on total area of 1cm 2 On carbon paper (model 060) to obtain a load In 2 O 3 And (3) carbon paper of the catalyst. Wherein In on carbon paper 2 O 3 The loading of the catalyst was 2.5mg cm -2 . Finally, 200mg of CTAB is added into 5mL of isopropanol and ultrasonic treatment is carried out for 30min, thus obtaining a surface modifier, and then In is loaded 2 O 3 Catalyst carbon paper (1X 1 cm) 2 ) The front and back sides of (C) were coated with 25. Mu.L of the surface modifier, followed by drying In a vacuum oven at 60℃to obtain chlorine-doped indium oxide electrodes (Cl-In) 2 O 3 An electrode).
Test example 1
In this test example, in examples 1 to 3 were each examined by a scanning electron microscope 2 O 3 The structure of the catalyst was analyzed.
As shown In FIG. 1, in examples 1 to 3 2 O 3 SEM image of the catalyst. In fig. 1, fig. 1 (a) and 1 (b) are 1 of example 2:1-In 2 O 3 SEM images of the catalyst, fig. 1 (c) and 1 (d) are 1 of example 3: 2-In 2 O 3 SEM images of the catalyst, fig. 1 (e) and 1 (f) are 2 of example 1:1-In 2 O 3 SEM image of the catalyst. The typical morphology of the three samples can be seen from fig. 1. 1:1-In 2 O 3 The indium oxide formed by calcining the catalyst in air presents a large number of directly exposed oxide nanospheres. 1:2-In 2 O 3 The catalyst has an octahedral structure, and the structure is relatively complete, 2:1-In 2 O 3 The catalyst is of an octahedral structure, but the surface of the catalyst is provided with partial bulges and defects, which shows that more chlorine doping plays an important role in carbon dioxide reduction. Stability test in connection with example 8 can be found 2:1-In 2 O 3 Can be under the reduction potentialThe oxidation state of indium can be effectively maintained, so that higher catalytic activity and stability are maintained.
Test example 2
In each of examples 1 to 3 was subjected to X-ray diffractometry In this test example 2 O 3 The catalyst was analyzed.
As shown In FIG. 2, in examples 1 to 3 2 O 3 XRD pattern of the catalyst. As can be seen from fig. 2, in 2 O 3 In, the characteristic peak at 30.61℃is In 2 O 3 (222) Crystal face, at 1:2-In 2 O 3 Shifted to 30.73 °, at 2:1-In 2 O 3 Intermediate shift to 30.807 deg., in after chlorine atom doping 2 O 3 Is significantly expanded. 1:2-In 2 O 3 Ratio 1:1-In 2 O 3 Forward movement, it is shown that at the same time more carbon atoms are doped, which also causes expansion of the lattice spacing.
Test example 3
In this test example, XPS was used for the In of example 1 2 O 3 The surface chemistry of the catalyst was characterized.
In of example 1 as shown In FIG. 3 2 O 3 XPS spectrum of the catalyst. As can be seen from fig. 3, 2:1-In 2 O 3 The XPS spectrum of the catalyst corresponds to different peaks at 441.19eV, 448.7eV, 530eV, 199eV and 284.8eV respectively, wherein the highest energy peaks 441.19eV and 448.7eV are respectively attributed to In 3d 3/2 And In 3d 5/2 The XPS spectra show three different peaks at 530eV, 199eV and 284.8eV, attributable to O atoms and doped C and small amounts of Cl atoms, and fig. 3 (b), 3 (C) and 3 (d) show peaks of In 3d, O1 s, cl 2p, respectively. The doping of Cl In is further illustrated by FIG. 3 (d) 2 O 3 In the catalyst.
Test examples 4 to 9 electrocatalytic performance tests were performed on chlorine doped indium oxide electrodes of examples 1 to 3, respectively. All electrochemical performances were carried out on a CHI 760D electrochemical workstation (Shanghai Chenhua) at ambient pressure and room temperature, studied in a gas-tight H-type electrochemical cell. The cells are separated by a Nafion 117 proton exchange membrane to prevent CO at the anode 2 Reoxidation of the reduced product. All electrochemical measurements were performed on an electrochemical workstation of a three-electrode configuration unit to prepare electrodes as working electrodes, platinum sheets (1 cm 2 ) Is a counter electrode. At 0.1M KHCO 3 An Ag/AgCl electrode (saturated KCl) is used as a reference electrode in the electrolyte. The area of the working electrode is 1X 1cm 2 The anode and cathode compartments contained 32.5mL of electrolyte. 32.5mL of 0.1M KHCO before measurement 3 High purity CO for solution 2 Or N 2 The continuous foaming is saturated for at least 30 minutes. Under certain magnetic stirring, CO 2 Continuous entry into the cathode chamber at a rate of 20SCCM to improve CO 2 And mass transport of the product at the surface of the working electrode. All potential values were measured for Ag/AgCl and then converted to RHE (reversible hydrogen electrode). The potential reference formula is:
E(V vs.RHE)＝E(V vs.Ag/AgCl)+0.197V+0.0591pH
all electrode potentials are converted to electrode potentials relative to the Reversible Hydrogen Electrode (RHE), and the potential values referred to in the test examples are compared to the reversible hydrogen electrode potential unless specifically stated. At 5mVs before electrochemical testing -1 Is subjected to CV cycles to activate the catalyst.
Test example 4
The test examples are respectively carried out on CO 2 Saturated 0.1M KHCO 3 In electrolyte and in N 2 Saturated 0.1M KHCO 3 LSV tests were performed on the chlorine doped indium oxide electrodes of examples 1 to 3 in the electrolyte.
The LSV graphs of the chlorine doped indium oxide electrodes of examples 1 to 3 are shown in fig. 4. Wherein FIG. 4 (a) is CO 2 Saturated 0.1M KHCO 3 LSV plot in electrolyte; FIG. 4 (b) is N 2 Saturated 0.1M KHCO 3 LSV plot in electrolyte. As can be seen from FIG. 4, the LSV curve shows the presence of CO 2 Current density ratio in saturated electrolyte at N 2 The current density recorded In the saturated electrolyte is high, so the In synthesized 2 O 3 The catalyst has carbon dioxide reduction performance. The initial potential was correspondingly shifted forward, indicating that the chlorine content had a considerable effect on the cathode reactivity, while the surface was activeThe introduction of sex agent also causes CO 2 The performance of RR is improved.
The invention further adopts potentiostatic method to explore products, which are used for calculating corresponding FE, and on-line Gas Chromatography (GC) and ion chromatography (AS-DV) are used for detecting gas/liquid products. The experiment detects H 2 And formate products, and all samples formate showed a Faraday efficiency exhibiting a volcanic trend in the range of-0.80 to-1.60V. 2:1-In 2 O 3 The catalyst has higher current density and low overpotential, and is used for preparing 0.1MKHCO 3 23mA cm was reached in the H-type cell in the electrolyte -2 And 1:1-In 2 O 3 And 1:2-In 2 O 3 The highest current density of the catalyst reaches 18mAcm respectively -2 And 16mAcm -2 ，2：1-In 2 O 3 The catalyst starts electrocatalytic carbon dioxide reduction at a potential of-0.5 v vs. rhe, while the reduction potentials of carbon dioxide of the other two catalysts are not much different, both being-0.6 v vs. rhe. Thus, more chlorine atom doping is performed to improve In 2 O 3 The formic acid production has positive effects. By CO in 2 And N 2 Saturated 0.1MKHCO 3 Comparison of LSV in electrolyte can be found in CO 2 The saturation condition has higher current density.
Test example 5
In this test example, the liquid phase products were collected in a constant potential range of-0.8 to-1.6 v vs. rhe, respectively, to investigate the faraday efficiencies of the chlorine-doped indium oxide electrodes of examples 1 to 3. Wherein at least CO is introduced at each potential 2 The electrolyte was saturated for half an hour.
Fig. 5 shows faraday efficiencies of the chlorine-doped indium oxide electrodes of examples 1 to 3. Wherein, fig. 5 (a) is a faraday efficiency diagram of the reduction product of the chlorine-doped indium oxide electrode of example 2; FIG. 5 (b) is a graph of Faraday efficiency of the reduction product of the chlorine-doped indium oxide electrode of example 3; fig. 5 (c) is a faraday efficiency plot of the reduction product of the chlorine doped indium oxide electrode of example 1. As can be seen from FIG. 5, the main reduction products of the three catalysts are hydrogen and formic acid over a wide potential range of-0.8 to-1.6V vs. RHE. At a potential of-1.2V vs. RHE, 2：1-In 2 O 3 The Faraday efficiency of the catalyst can reach 98 percent, 1:1-In 2 O 3 The catalyst formic acid had a faraday efficiency of 81%; at-1.4 Vvs. RHE, 1:2-In 2 O 3 The highest faradaic efficiency of the catalyst for formic acid production was 59%. For hydrogen evolution reactions, and 2:1-In 2 O 3 Has good hydrogen evolution inhibiting capability, H 2 Up to 25%, and 1:1-In 2 O 3 The Faraday efficiency of the catalyst is higher than that of the other two catalysts, and the Faraday efficiency of the hydrogen can be up to 60%, so that the doping of chlorine atoms has an effect on electrocatalytic carbon dioxide reduction.
Test example 6
The test example is described in CO 2 Saturated 0.1M KHCO 3 In the solution, electrolysis was performed for half an hour at each potential and 1mL of the cathode chamber solution was collected, and the solution was diluted ten times for measurement of formic acid.
FIG. 6 shows i-t graphs of the chlorine-doped indium oxide electrodes of examples 1 to 3 at different reduction potentials. Wherein, FIG. 6 (a) is an i-t graph of the reduction product of the chlorine-doped indium oxide electrode of example 1; FIG. 6 (b) is an i-t plot of the reduction product of the chlorine-doped indium oxide electrode of example 3; FIG. 6 (c) is an i-t plot of the reduction product of the chlorine doped indium oxide electrode of example 2. It can be seen from the i-t curve of FIG. 6 that at-1.6V vs. RHE, the current densities of the three catalysts are highest, where 2:1-In 2 O 3 The current density of the catalyst reaches 17.5mA cm -2 ；1：1-In 2 O 3 The current density of the catalyst reaches 15mA cm -2 ；1：2-In 2 O 3 The current density of the catalyst is at most 13mA cm -2 . Higher chlorine atom doping to In 2 O 3 The catalyst has high electrocatalytic activity. Since 1:2-In 2 O 3 Catalyst and 1:1-In 2 O 3 The first potential of the catalyst was-0.8 v vs. rhe, which corresponds to the catalyst having been activated, and thus the current density tended to stabilize. And 2:1-In 2 O 3 The first potential of the catalyst is-1 v vs. rhe, thus 2:1-In 2 O 3 The catalyst has a current density rise at the front 300s under the potential of-1V vs. RHE, so that the catalyst has the activation function and then tends to be stable.
Test example 7
The test example researches different InCl 3 In content of 2 O 3 The intrinsic activity of the catalyst is calculated by deriving a double-layer capacitance (Cdl) by adopting a cyclic voltammogram, calculating to obtain the electrochemical active surface area (ECSA), and performing CV circulation on the catalyst by changing the scanning rate, and scanning for 20 circles to obtain CV circulation curves of three chlorine doped indium oxide electrodes, so that the active surface area of the catalyst is analyzed.
Fig. 7 shows CV cycle diagrams of chlorine-doped indium oxide electrodes of examples 1 to 3. Wherein, fig. 7 (a) is a CV cycle graph of the chlorine doped indium oxide electrode of example 2; FIG. 7 (b) is a CV cycle graph of the chlorine doped indium oxide electrode of example 3; FIG. 7 (c) is a CV cycle graph of the chlorine doped indium oxide electrode of example 1; fig. 7 (d) is a graph of the charge-current density difference versus the scan rate for the chlorine-doped indium oxide electrodes of examples 1 to 3. As can be seen from fig. 7, 2:1-In 2 O 3 Cdl of the catalyst was 1.46mF cm -2 ；1：2-In 2 O 3 Cdl of the catalyst was 1.24mF cm -2 ；1：1-In 2 O 3 Cdl of the catalyst was 3.16mF cm -2 . It is explained that the proper number of chlorine atoms has a great effect on increasing the active surface area, and that more chlorine atom doping has a promoting effect on increasing the active site. Thus, the chlorine atom doping has a great deal of relation to the selectivity of the formic acid product.
Test example 8
The test example is described in CO 2 Saturated 0.1M KHCO 3 In the electrolyte, electrolysis of the control potential was performed at-1.2 v vs. rhe to investigate the stability of the chlorine doped indium oxide electrode of example 1.
Fig. 8 is a graph showing the relationship between the current density and time of the chlorine-doped indium oxide electrode of example 1. As can be seen from fig. 8, the current density remained good in the H-type cell, indicating that the stability of the catalyst was good.
Test example 9
Test example impedance of chlorine doped indium oxide electrodes of examples 1 to 3 was measured at open circuit potential and frequency was in the range of 1MHz to 10 -1 Hz。
Fig. 9 shows impedance diagrams of chlorine-doped indium oxide electrodes according to examples 1 to 3. As can be seen from fig. 9, 2:1-In 2 O 3 The catalyst has a smaller resistance, indicating that the mass transfer resistance is low.
In summary, the present invention provides for the modification of InCl by hydrothermal-calcination 3 ·4H 2 The ratio of O and trimesic acid synthesizes three In with different morphologies 2 O 3 Nanomaterial, which can be used as a high performance catalyst for the efficient electroreduction of carbon dioxide. Modification of In by CTAB 2 O 3 Catalyst pair electrochemical CO 2 The selectivity of the reduction product is affected. CTAB modified In 2 O 3 The catalyst can inhibit HER in the electrocatalytic process, thereby improving the selectivity of HCOOH products. And a proper amount of CTAB inhibits electrons from accumulating on the surface of the catalyst, thereby preventing the corrosion of the catalyst. In an H-cell, 2:1-In 2 O 3 Has FE of more than 90 percent for formate and 23mA cm at the same time -2 The highest value of FE reaches 98% especially at-1.2 Vvs RHE, which is superior to In of other two ratios 2 O 3 A catalyst.
In addition, the invention also respectively researches the chlorine doped In with different contents 2 O 3 Catalyst pair CO 2 Effect of RR performance. 2:1-In 2 O 3 The catalyst has more chlorine atoms uniformly distributed on the surface of the catalyst, and can promote electron transfer to reactants. By comparison, found that 1:2-In 2 O 3 The catalyst has more carbon atom doping, but has lower current density and CO 2 The overpotential of RR is high, while 2:1-In 2 O 3 The catalyst has a small amount of carbon atoms doped, and chlorine atoms are distributed on the surface of the catalyst, so that the selectivity of formic acid is improved. Synergistic interaction between CTAB and chlorine atom allows CO 2 Can be better adsorbed on the surface of the catalyst and selectively converted into HCOOH.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (10)
1. The preparation method of the chlorine doped indium oxide electrode is characterized by comprising the following steps of:
s1, preparation of MIL-68 (In) nano material: inCl is added to 3 ·4H 2 O and trimesic acid are dissolved In dimethylformamide, and the MIL-68 (In) nano material is obtained after centrifugation, washing and drying after hydrothermal reaction;
S2、In 2 O 3 and (3) synthesizing a catalyst: vacuum drying the MIL-68 (In) nano material, grinding, calcining under inert atmosphere, and carbonizing to obtain the In 2 O 3 A catalyst;
s3, the In is 2 O 3 Adding the catalyst into ethanol, adding Nafion solution, performing ultrasonic treatment for 25-35 min, and then dripping the solution on carbon paper to obtain the load In 2 O 3 Carbon paper of the catalyst;
s4, adding cetyl trimethyl ammonium bromide into isopropanol, performing ultrasonic treatment for 25-30 min to obtain a surface modification, and then dripping the surface modification on the load In 2 O 3 And drying the front and back sides of the carbon paper of the catalyst to obtain the chlorine doped indium oxide electrode.
2. The method according to claim 1, wherein in step S1, the InCl 3 ·4H 2 The mass ratio of O to the trimesic acid is 0.79-3.15: 1, the InCl 3 ·4H 2 The mass volume ratio of O to the dimethylformamide is 0.07-0.2: 1.
3. the method according to claim 1, wherein in step S1, the hydrothermal reaction is performed at a temperature of 90 to 110 ℃ for 22 to 26 hours, the drying is performed at a temperature of 75 to 85 ℃ for 10 to 14 hours.
4. The method according to claim 1, wherein in step S2, the vacuum drying is performed at 140 to 160 ℃ for 1.5 to 2.5 hours.
5. The method according to claim 1, wherein in step S2, the step of carbonizing after calcining under an inert atmosphere is: the MIL-68 (In) nano material is placed into a magnetic boat after vacuum drying and grinding, then the magnetic boat is placed into a tube furnace and calcined In Ar atmosphere, and finally the magnetic boat is placed into a muffle furnace for carbonization, wherein the calcination temperature is 450-550 ℃, the calcination time is 1.5-2.5 h, the heating rate of the tube furnace is 5 ℃/min, the carbonization temperature is 450-550 ℃, the carbonization time is 1.5-2.5 h, and the heating rate of the muffle furnace is 5 ℃/min.
6. The method according to claim 1, wherein In step S3, the In 2 O 3 The mass volume ratio of the catalyst to the ethanol to the Nafion solution is 1:1.5 to 2.5:1.5 to 2.5 (g/. Mu.L).
7. The method according to claim 1, wherein In step S3, the load In is 2 O 3 In the carbon paper of the catalyst, the In 2 O 3 The loading of the catalyst is 2.2-2.8 mg cm -2 。
8. The preparation method according to claim 1, wherein in step S4, the mass-to-volume ratio of the cetyltrimethylammonium bromide to the isopropyl alcohol is 35-45: 1 (mg/mL).
9. A chlorine-doped indium oxide electrode produced according to the production method of any one of claims 1 to 8.
10. The electrocatalytic reduction of CO with a chlorine-doped indium oxide electrode of claim 9 2 Use in the preparation of formic acid.
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