CN116288502A - Preparation method of bismuth-doped hollow nanosphere electrode and formic acid production application thereof - Google Patents
Preparation method of bismuth-doped hollow nanosphere electrode and formic acid production application thereof Download PDFInfo
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000002077 nanosphere Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 76
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- 230000008569 process Effects 0.000 claims abstract description 11
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- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 47
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- 238000003756 stirring Methods 0.000 claims description 34
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
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- 239000004744 fabric Substances 0.000 claims description 11
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
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- 239000007788 liquid Substances 0.000 claims description 4
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- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
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- 238000005273 aeration Methods 0.000 claims description 3
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- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract 1
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
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- -1 bismuth oxide metal oxide Chemical class 0.000 description 1
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- 238000003763 carbonization Methods 0.000 description 1
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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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- 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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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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
- 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
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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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
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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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
Abstract
The invention belongs to the technical field of electrochemistry, and provides a preparation method of a bismuth-doped porous hollow nanosphere electrode and an electric reduction CO thereof 2 And (5) formic acid production application. The method is characterized in that the method can reduce carbon dioxide under mild conditions with high efficiencyFormic acid. The electrochemical reduction method is adopted, so that the method has the advantages of simple process flow, convenient operation, mild reaction conditions, high formic acid yield and stable effect. The adopted bismuth doped porous hollow nanosphere electrode has CO 2 Good reduction performance, high current efficiency of producing formic acid, high yield of formic acid, long service life, easy processing, low cost and the like.
Description
Technical Field
The present invention belongs to electrochemistryTechnical field, in particular to a preparation method of a bismuth-doped porous hollow nano carbon sphere electrode and electric reduction CO thereof 2 And (5) formic acid production application.
Background
The use of fossil fuels in large quantities not only results in CO in the atmosphere 2 The ever increasing emissions raise environmental concerns and the over-exploitation of fossil fuels also raises energy crisis. CO is processed by 2 Conversion to fuel or valuable carbonaceous feedstock is by CO 2 Not only reduces CO in the atmosphere 2 The content of the water-based energy source is used for relieving the greenhouse effect and providing a new thought for solving the problem of energy source regeneration. CO 2 Is a linear molecule, has zero dipole moment and standard heat of generation of-398.38 kJ mol -1 Is the final product of many chemical or biological combustion reactions, the molecules are in the lowest energy state, CO 2 The molecule is very stable and inert. Currently, CO 2 The conversion method comprises chemical conversion, catalytic hydrogenation, photocatalytic reduction, electrochemical reduction and the like. The electrochemical method has mild reaction conditions and can be usually carried out at normal temperature and normal pressure; can be powered by renewable energy sources (wind energy, solar energy, tidal energy, etc.); the equipment is simple; the selectivity and activity of the reduction product can be easily adjusted by controlling the reaction conditions, namely CO conversion 2 Is an effective way of valuable compounds. Electrocatalytic CO 2 The reduction to formic acid is realized through a two-electron transfer process, so that the problem of poor product selectivity caused in a multi-electron transfer process can be avoided. The Sn-loaded redox graphene electrode has higher electro-reduction methanogenic selectivity (ACS Catalysis, 2021, 11, 3310-3318.) but at present, the electro-catalytic reduction of CO is performed 2 CO is still present in the formic acid production 2 High activation energy barrier, CO 2 Poor reactivity and low formic acid production rate. For the existing electrocatalytic CO 2 The invention provides a preparation method of a bismuth-doped porous hollow nano carbon sphere electrode and an electric reduction CO, which are insufficient in technology 2 And (5) formic acid production application. The partial limiting function is formed by utilizing the hollow cavity of the carbon sphere, so that the CO on the surface of the active site of the metal bismuth is improved 2 Concentration, thereby reducing CO 2 An activation energy barrier for increasing CO 2 Reducing the formic acid production rate, reducing greatlyCO in the air 2 The concentration realizes the recycling of the water.
Disclosure of Invention
The invention aims at the existing electrocatalytic CO 2 The deficiency of the reduction technology provides a method for reducing CO with high efficiency and high yield under mild conditions 2 Preparation method of novel electrocatalytic electrode for producing formic acid and electric reduction CO thereof 2 Is used for producing formic acid. In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
a preparation method of a bismuth doped porous hollow nano carbon sphere electrode is characterized by comprising the following steps:
step 1: preparing bismuth-containing precursor microspheres: adding a certain mass of propyl orthosilicate into a mixed solution of ethanol and water at normal temperature, adding ammonia water under stirring, stirring at room temperature, respectively adding 0.05-1.0 g of bismuth nitrate, resorcinol and formaldehyde into the mixed solution, continuously stirring, carrying out suction filtration separation, respectively washing with high-purity water and ethanol, and drying to obtain bismuth-containing precursor microspheres;
step 2: preparing the bismuth doped porous nano carbon spheres: placing different bismuth-containing precursor microsphere powders with certain mass into a quartz boat, placing into a tubular resistance furnace for calcination, and heating to 5-10 ℃ for min in order to keep uniform pore structure of the carbon material -1 Preserving heat at 800-1000 ℃ for 4 h to ensure complete carbonization of the material, calcining under argon atmosphere, and cooling to room temperature to obtain black powder bismuth doped porous carbon nanospheres;
step 3: preparing a bismuth doped porous hollow nano carbon sphere: adding a certain mass of black powder bismuth doped porous carbon nanospheres into a concentrated NaOH solution, continuously stirring, carrying out suction filtration, separation and water washing to be neutral, repeating the process for a plurality of times, and drying the obtained black powder catalyst in vacuum for later use;
step 4: preparing a bismuth doped porous hollow nano carbon sphere electrode: adding the bismuth doped porous hollow nano carbon sphere catalyst into a mixed solution of high-purity water and Nafion, ultrasonically mixing, then dripping the suspension liquid onto carbon cloth, and drying at normal temperature to obtain the working electrode.
Preferably, it is: the step 1 further comprises the following steps: adding ammonia water under the stirring condition, stirring at room temperature for 15 minutes, respectively adding 0.05-1.0 g of bismuth nitrate, resorcinol and formaldehyde into the mixed solution, continuously stirring for 24 hours, carrying out suction filtration and separation, respectively washing with high-purity water and ethanol for 3 times, and drying at 80 ℃ to obtain bismuth-containing precursor microspheres, wherein the ethanol is prepared by the following steps: high purity water: ammonia water: the volume ratio of (2) is 70:10:3, propyl orthosilicate: resorcinol: the molar ratio of formaldehyde is 25-30: 5-13: 40-50, wherein bismuth nitrate is used as a bismuth source of a synthetic catalyst, the doping amount of metal bismuth in the catalytic material is obtained by controlling the addition amount, propyl orthosilicate, resorcinol and formaldehyde are precursors of silicon and carbon, and carbon-coated silica nanospheres with different sizes and different thicknesses can be obtained by controlling the addition amount of the propyl orthosilicate, the resorcinol and the formaldehyde.
Preferably, it is: adding black powder of a certain quality into 10 mol L -1 And (3) continuously stirring 72 h in the NaOH concentrated solution, removing silicon dioxide generated in the reaction process by etching the obtained black powder material by using a strong alkali solution to obtain the hollow nano carbon sphere material, and carrying out suction filtration, separation and washing until the hollow nano carbon sphere material is neutral, wherein the process is repeated for 3 times. The obtained black powder catalyst is dried in vacuum at 120 ℃ for standby.
Preferably, it is: the step 4 further comprises the following steps: in order to obtain electrode materials with different catalytic layer thicknesses, 3-10 mg of bismuth doped porous hollow nano carbon sphere catalyst is added into a mixed solution of 2.85-mL high-purity water and 0.15 mL 5 wt% Nafion, so that the catalyst is ensured to be uniformly dispersed in the solution, the solution is ultrasonically mixed for 30 min, and then the suspension is dripped onto carbon cloth or carbon paper to be used as a working electrode after being dried at normal temperature.
The invention also discloses a bismuth-doped porous hollow nano carbon sphere electrode, which is obtained by adopting the preparation method of the bismuth-doped porous hollow nano carbon sphere electrode; the method is characterized in that: the electrode surface carbon sphere is prepared by a normal temperature solvent stirring method, the size of the electrode surface carbon sphere is in the range of 100 nm-200 nm diameter, and the surface pore size of the electrode is in the range of 2-5 nm.
The invention also discloses an electric reduction CO 2 The application method of formic acid production comprises the steps of taking the bismuth doped porous hollow nano carbon sphere electrode as a working electrode, taking a platinum sheet as an anode and silver/chlorineThe silver electrode is used as a reference electrode for electrochemical reduction of CO 2 Applying voltage or 10-50 mA cm at-0.8 to-1.4V -2 Applying current for 1-3L h -1 Under the condition of carbon dioxide flow, carrying out electrochemical reduction carbon dioxide reaction to realize; the electrochemical reduction of CO 2 The reaction is carried out in a closed double-pool reactor, the two pools are separated by Nafion 117 proton exchange membrane, potassium bicarbonate, potassium hydroxide and sodium sulfate are used as supporting electrolyte, a bismuth doped porous hollow nano carbon sphere electrode is used as a cathode, a platinum sheet electrode is used as an anode, and CO is introduced into the solution before the reaction starts 2 And continuously aeration is carried out during the reaction.
Advantageous effects
The bismuth doped porous hollow nano carbon sphere has the advantages of porous carbon walls and a hollow nano cavity structure, and the hollow carbon sphere structure has a higher electrochemical active area and can provide more reactive sites; the porous carbon wall with controllable pore diameter is CO 2 Mass transfer provides an effective path, and the hollow nanospheres can be used for enriching CO in a limited space 2 Increase local CO 2 Concentration of intensified CO 2 Activated to produce formic acid, the formic acid production rate can reach 613 mol L -1 h -1 g -1 。
The preparation process of the bismuth doped porous hollow nano carbon sphere has the advantages of simple flow, convenient operation, mild reaction conditions, stable material structure, long service life and CO 2 The effect of reducing and producing formic acid is stable and reliable, and the industrial application is easy to realize.
Drawings
FIG. 1 is a view of a bismuth-doped porous hollow nanocarbon sphere scanning electron microscope.
Fig. 2 is a transmission electron microscope image of the bismuth-doped porous hollow nanocarbon sphere.
Fig. 3 is a crystal structure diagram of the bismuth-doped porous hollow nanocarbon ball prepared in example 1. FIG. 4 shows that the bismuth-doped porous hollow nanocarbon ball prepared in example 1 is 0.1 mol L -1 Electrical reduction of CO in potassium bicarbonate electrolyte 2 The formic acid production rate is plotted against the applied voltage.
Fig. 5 is a crystal structure diagram of the bismuth-doped porous hollow nanocarbon ball prepared in example 2.
Fig. 6 is a spherical aberration electron microscope image of the bismuth-doped porous hollow nano carbon sphere prepared in example 2.
FIG. 7 shows that the bismuth-doped porous hollow nanocarbon ball prepared in example 2 is in an amount of 1 mol L -1 Continuous 4 h electrical reduction of CO in potassium hydroxide electrolyte 2 Producing formic acid.
Description of the embodiments
Embodiments of the present invention will be described below with reference to the accompanying drawings, but the present invention is not limited to the following embodiments.
A preparation method of a bismuth doped porous hollow nano carbon sphere electrode is characterized by comprising the following steps:
step 1: preparing bismuth-containing precursor microspheres: adding a certain mass of propyl orthosilicate into a mixed solution of ethanol and water at normal temperature, adding ammonia water under stirring, stirring at room temperature, respectively adding 0.05-1.0 g of bismuth nitrate, resorcinol and formaldehyde into the mixed solution, continuously stirring, carrying out suction filtration separation, respectively washing with high-purity water and ethanol, and drying to obtain bismuth-containing precursor microspheres; the step 1 further comprises the following steps: adding ammonia water under the stirring condition, stirring at room temperature for 15 minutes, respectively adding 0.05-1.0 g of bismuth nitrate, resorcinol and formaldehyde into the mixed solution, continuously stirring for 24 hours, carrying out suction filtration and separation, respectively washing with high-purity water and ethanol for 3 times, and drying at 80 ℃ to obtain bismuth-containing precursor microspheres, wherein the ethanol is prepared by the following steps: high purity water: ammonia water: the volume ratio of (2) is 70:10:3, propyl orthosilicate: resorcinol: the molar ratio of formaldehyde is 25-30: 5-13: 40-50 parts;
step 2: preparing the bismuth doped porous nano carbon spheres: placing different bismuth-containing precursor microsphere powders with certain mass into a quartz boat, placing into a tubular resistance furnace for calcination, and cooling at 5-10 ℃ for min -1 Calcining at 800-1000 ℃ in argon atmosphere, and cooling to room temperature to obtain black powder bismuth doped porous carbon nanospheres;
step 3: preparing a bismuth doped porous hollow nano carbon sphere: adding a certain mass of black powder bismuth doped porous carbon nanospheres into a concentrated NaOH solution, continuously stirring, filtering, separating, washing with water to neutrality, repeating the process for multiple times, and vacuum drying the obtained black powder catalyst for later use to obtain the catalyst morphologyAs shown in fig. 1, the catalyst is spherical, and as shown in fig. 2, the prepared catalyst is of a hollow nanosphere structure; preferably, it is: adding black powder of a certain quality into 10 mol L -1 Stirring is continuously carried out on the concentrated NaOH solution for 72 and h, water is separated by suction filtration and washed to be neutral, and the process is repeated for 3 times. The obtained black powder catalyst is dried in vacuum at 120 ℃ for standby;
step 4: preparing a bismuth doped porous hollow nano carbon sphere electrode: adding a bismuth doped porous hollow nano carbon sphere catalyst into a mixed solution of high-purity water and Nafion, ultrasonically mixing, then dripping suspension liquid onto carbon cloth, and drying at normal temperature to serve as a working electrode; the step 4 further comprises the following steps: 3-10 mg of bismuth doped porous hollow nano carbon sphere catalyst is added into a mixed solution of 2.85-mL high-purity water and 0.15 mL 5 wt% Nafion, after ultrasonic mixing for 30 min, the suspension is dripped onto carbon cloth, and the carbon cloth is dried at normal temperature to be used as a working electrode.
The invention discloses a bismuth-doped porous hollow nano carbon sphere electrode, which is obtained by adopting the preparation method of the bismuth-doped porous hollow nano carbon sphere electrode; the electrode surface carbon sphere is prepared by a normal temperature solvent stirring method, the size of the electrode surface carbon sphere is in the range of 100 nm-200 nm diameter, and the surface pore size of the electrode is in the range of 2-5 nm.
Examples
The invention provides a preparation method of a bismuth-doped hollow nano carbon sphere, which is implemented according to the following steps:
(1) adding propyl orthosilicate into a mixed solution of ethanol and water, adding ammonia water under stirring, stirring at room temperature for 15 minutes, respectively adding 0.5 g bismuth nitrate, resorcinol and formaldehyde into the mixed solution, continuously stirring for 24 hours, performing suction filtration and separation, respectively cleaning with high-purity water and ethanol for 3 times, and drying at 80 ℃ to obtain bismuth-containing precursor microspheres, wherein the ethanol: high purity water: ammonia water: the volume ratio of (2) is 70:10:3, propyl orthosilicate: resorcinol: the molar ratio of formaldehyde is 29:11:45;
(2) placing different bismuth-containing precursor microsphere powders with certain mass into a quartz boat, calcining in a tubular resistance furnace, and standing at 10deg.C for min -1 Is heated up at a rate of (a) to (b),calcining for 4 hours at 900 ℃ in an argon atmosphere, and cooling to room temperature to obtain black powder bismuth doped porous carbon nanospheres;
(3) adding a certain mass of bismuth doped porous carbon nanospheres into 10 mol L -1 Stirring is continuously carried out on the concentrated NaOH solution for 72 and h, water is separated by suction filtration and washed to be neutral, and the process is repeated for 3 times. The obtained black powder bismuth doped porous hollow nano carbon sphere catalyst is dried in vacuum at 120 ℃;
(4) adding 10 mg bismuth doped porous hollow nano carbon sphere catalyst into a mixed solution of 2.85 mL high-purity water and 0.15 mL 5 wt% Nafion, ultrasonically mixing for 30 min, dripping the suspension liquid onto carbon cloth, and drying at normal temperature to obtain the working electrode.
The diameter of the bismuth doped hollow nano carbon sphere obtained by controlling the addition amount of the metal bismuth, the propyl orthosilicate, the resorcinol and the formaldehyde is about 120 nm, the thickness of the carbon layer is about 20 nm, and the content of the metal bismuth is 1.06 wt%. Hollow cavity of carbon nanosphere can be used as nano reactor to improve CO 2 Reaction rate; the moderate thickness of the carbon layer not only ensures the structural integrity of the hollow carbon sphere, but also can effectively shorten the reactant CO 2 And the thickness of the mass transfer layer of the formic acid product, the mass transfer resistance is reduced, and the CO is increased 2 And mass transfer efficiency of formic acid; the doping amount of the bismuth metal is 1.06 wt%, bismuth oxide metal oxide can be formed, as shown in figure 3, and the proper doping amount of the bismuth ensures that bismuth oxide particles are uniformly distributed on the surface of the carbon sphere to provide more CO 2 Reactive sites.
The bismuth doped hollow nano carbon sphere electrode obtained by the method is applied to the electric reduction of CO 2 The application method for producing the formic acid is specifically implemented according to the following steps:
electrocatalytic reduction of CO 2 The reaction was carried out in a closed double-cell reactor, the two cells being separated by a Nafion 117 proton exchange membrane, at 0.1 mol L -1 Potassium bicarbonate is used as supporting electrolyte, a bismuth doped porous hollow nano carbon sphere electrode is used as a cathode, a platinum sheet electrode is used as an anode, and CO is introduced into the solution before the reaction starts 2 Continuously aerating the solution during the reaction to make the reaction solution in CO 2 Saturated state. At 1.5L h -1 Under the condition of carbon dioxide flow, electricity is regulated and controlledPressing at-0.8 to-1.4V, performing electrochemical reduction reaction on carbon dioxide, and collecting the generated gas product by using a gas collecting device. FIG. 4 is a graph showing the change of formic acid production with applied voltage, the concentration of formic acid production increases and decreases with the negative bias of applied voltage, and the concentration of formic acid production reaches 568 mmol L at-1.1. 1.1V -1 h -1 g -1 。
Examples
The invention provides a preparation method of a bismuth-doped hollow nano carbon sphere, which is implemented according to the following steps:
(1) adding propyl orthosilicate into a mixed solution of ethanol and water, adding ammonia water under stirring, stirring at room temperature for 15 minutes, respectively adding 0.15 g bismuth nitrate, resorcinol and formaldehyde into the mixed solution, continuously stirring for 24 hours, performing suction filtration and separation, respectively cleaning with high-purity water and ethanol for 3 times, and drying at 80 ℃ to obtain bismuth-containing precursor microspheres, wherein the ethanol: high purity water: ammonia water: the volume ratio of (2) is 70:10:3, propyl orthosilicate: resorcinol: the molar ratio of formaldehyde is 29:11:45.
(2) placing different bismuth-containing precursor microsphere powders with certain mass into a quartz boat, calcining in a tubular resistance furnace, and standing at 10deg.C for min -1 Calcining for 4 hours at 900 ℃ in argon atmosphere, and cooling to room temperature to obtain the black powder bismuth doped porous carbon nanospheres.
(3) Adding a certain mass of bismuth doped porous carbon nanospheres into 10 mol L -1 Stirring is continuously carried out on the concentrated NaOH solution for 72 and h, water is separated by suction filtration and washed to be neutral, and the process is repeated for 3 times. The obtained black powder bismuth doped porous hollow nano carbon sphere catalyst is dried in vacuum at 120 ℃.
(4) 10 mg bismuth doped porous hollow nano carbon sphere catalyst is added into 2.85 mL high-purity water and 0.15 mL 5 wt% Nafion, after ultrasonic mixing for 30 min, the suspension is dripped onto carbon cloth, and the carbon cloth is dried at normal temperature to be used as a working electrode.
The diameter of the bismuth doped hollow nano carbon sphere obtained by controlling the addition amount of the metal bismuth, the propyl orthosilicate, the resorcinol and the formaldehyde is about 120 nm, the thickness of the carbon layer is about 20 nm, and the content of the metal bismuth is 0.25 wt percent. Hollow cavity of carbon nanosphere can be used as nano reactor to improve CO 2 Reaction rate; the moderate thickness of the carbon layer not only ensures the structural integrity of the hollow carbon sphere, but also can effectively shorten the reactant CO 2 And the thickness of the mass transfer layer of the formic acid product, the mass transfer resistance is reduced, and the CO is increased 2 And mass transfer efficiency of formic acid; when the bismuth nitrate addition amount is 0.15 and g, the metal bismuth doping amount of the obtained catalytic material is 0.25 and wt%, the crystal structure diagram shown in fig. 5 has no peak of metal bismuth and bismuth oxide, and the metal bismuth is found to be distributed in the form of single atoms in the hollow carbon sphere from the spherical aberration electron microscope result in fig. 6; the monoatomic bismuth can not only prevent metal bismuth from aggregating to form metal particles, but also has high dispersibility, and meanwhile, the monoatomic bismuth has high atomic utilization rate and unsaturated coordination structure and can be CO 2 The reaction provides more active sites.
The invention also provides application of the bismuth-doped hollow nano carbon sphere in electric reduction of CO 2 The application method for producing the formic acid is specifically implemented according to the following steps:
electrocatalytic reduction of CO 2 The reaction was carried out in a closed double-cell reactor, the two cells being separated by a Nafion 117 proton exchange membrane at 1 mol L -1 Potassium hydroxide is used as supporting electrolyte, a bismuth doped porous hollow nano carbon sphere electrode is used as a cathode, a platinum sheet electrode is used as an anode, and CO is introduced into the solution before the reaction starts 2 The reaction solution is put into CO 2 Saturated state. CO after the reaction is started 2 The aeration pipeline is connected with the cathode polar plate for 2.0L h -1 Under the condition of carbon dioxide flow, regulating and controlling applied current to be 20 mA cm -2 Electrochemical reduction of CO 2 And (3) reacting. The electrolyte remained in a flowing state during the reaction, and the flow rate was 3 mL min -1 . As can be seen from FIG. 7, CO is electroreduced at 4 h in succession 2 In the process, the yield of formic acid can reach 613 mol L -1 h -1 g -1 The Faraday efficiency of formic acid production reaches 100%.
The preparation process flow of the bismuth-doped porous hollow nano carbon sphere is simple, the hollow carbon sphere structure has higher electrochemical active area, and more reactive sites can be provided; the porous carbon wall with controllable pore diameter is CO 2 Mass transfer provides an effective path, hollowNanospheres can be used for enriching CO in limited space 2 Increase local CO 2 Concentration of intensified CO 2 Activating to produce formic acid. The doping amount of the metal bismuth and the doping form of the bismuth can be regulated and controlled by controlling the adding amount of the bismuth nitrate, and the formic acid production rate can reach 613 mol L under the optimized condition -1 h -1 g -1 。
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A preparation method of a bismuth doped porous hollow nano carbon sphere electrode is characterized by comprising the following steps:
step 1: preparing bismuth-containing precursor microspheres: adding certain mass of propyl orthosilicate into a mixed solution of ethanol and water at normal temperature, adding ammonia water under stirring, respectively adding bismuth nitrate, resorcinol and formaldehyde into the mixed solution after stirring at room temperature, continuously stirring, carrying out suction filtration and separation, respectively washing with high-purity water and ethanol, and drying to obtain bismuth-containing precursor microspheres;
step 2: preparing the bismuth doped porous nano carbon spheres: placing different bismuth-containing precursor microsphere powders with certain mass into a quartz boat, placing into a tubular resistance furnace for calcination, and cooling at 5-10 ℃ for min -1 Calcining for 4-6 hours at 800-1000 ℃ in an argon atmosphere, and cooling to room temperature to obtain black powder bismuth doped porous carbon nanospheres;
step 3: preparing a bismuth doped porous hollow nano carbon sphere: adding a certain mass of black powder bismuth doped porous carbon nanospheres into a concentrated NaOH solution, continuously stirring, carrying out suction filtration, separation and water washing to be neutral, repeating the process for a plurality of times, and drying the obtained black powder catalyst in vacuum for later use;
step 4: preparing a bismuth doped porous hollow nano carbon sphere electrode: adding the bismuth doped porous hollow nano carbon sphere catalyst into a mixed solution of high-purity water and Nafion, ultrasonically mixing, then dripping the suspension liquid onto carbon cloth, and drying at normal temperature to obtain the working electrode.
2. The method for preparing the bismuth-doped porous hollow nano carbon sphere electrode according to claim 1, wherein the method comprises the following steps: the step 1 further comprises the following steps: adding ammonia water under the stirring condition, stirring at room temperature for 15 minutes, respectively adding 0.05-1.0 g of bismuth nitrate, resorcinol and formaldehyde into the mixed solution, continuously stirring for 24 hours, carrying out suction filtration and separation, respectively washing with high-purity water and ethanol for 3 times, and drying at 80 ℃ to obtain bismuth-containing precursor microspheres, wherein the ethanol is prepared by the following steps: high purity water: ammonia water: the volume ratio of (2) is 70:10:3, propyl orthosilicate: resorcinol: the molar ratio of formaldehyde is 25-30: 5-13: 40-50.
3. The method for preparing the bismuth-doped porous hollow nano carbon sphere electrode according to claim 1, wherein the method comprises the following steps: the step 4 further comprises the following steps: 3-10 mg of bismuth doped porous hollow nano carbon sphere catalyst is added into a mixed solution of 2.85-mL high-purity water and 0.15 mL 5 wt% Nafion, after ultrasonic mixing for 30 min, the suspension is dripped onto carbon cloth, and the carbon cloth is dried at normal temperature to be used as a working electrode.
4. A bismuth-doped porous hollow nanocarbon sphere electrode obtained by the preparation method of the bismuth-doped porous hollow nanocarbon sphere electrode according to claim 1; the method is characterized in that: the electrode surface carbon sphere is prepared by a normal temperature solvent stirring method, the size of the electrode surface carbon sphere is in the range of 100 nm-200 nm diameter, and the surface pore size of the electrode is in the range of 2-5 nm.
5. Electroreduction of CO 2 The application method for producing formic acid is characterized by comprising the following steps: the method takes the bismuth doped porous hollow nano carbon sphere electrode as the working electrode, the platinum sheet as the anode and the silver/silver chloride electricityExtreme reference electrode for electrochemical reduction of CO 2 Applying voltage or 10-50 mA cm at-0.8 to-1.4V -2 Applying current for 1-3L h -1 Under the condition of carbon dioxide flow, carrying out electrochemical reduction carbon dioxide reaction to realize; the electrochemical reduction of CO 2 The reaction is carried out in a closed double-pool reactor, the two pools are separated by Nafion 117 proton exchange membrane, potassium bicarbonate, potassium hydroxide and sodium sulfate are used as supporting electrolyte, a bismuth doped porous hollow nano carbon sphere electrode is used as a cathode, a platinum sheet electrode is used as an anode, and CO is introduced into the solution before the reaction starts 2 And continuously aeration is carried out during the reaction.
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