CN113249743B - Catalyst for electrocatalytic oxidation of glycerol and preparation method thereof - Google Patents

Catalyst for electrocatalytic oxidation of glycerol and preparation method thereof Download PDF

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CN113249743B
CN113249743B CN202110538887.XA CN202110538887A CN113249743B CN 113249743 B CN113249743 B CN 113249743B CN 202110538887 A CN202110538887 A CN 202110538887A CN 113249743 B CN113249743 B CN 113249743B
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catalyst
glycerol
nickel
roasting
nife
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CN113249743A (en
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吴钢锋
陈为
陈益钢
吴敏芳
李守杰
朱畅
陈奥辉
耿文浩
冯光辉
宋艳芳
董笑
李桂花
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University of Shanghai for Science and Technology
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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides

Abstract

The invention discloses a catalyst for electrocatalysis glycerin oxidation and a preparation method thereof, and the method comprises the following steps: (1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by adopting a solvothermal method or a hydrothermal method x A catalyst precursor; (2) Growing NiFe (OH) on the obtained product in the step (1) x And (3) roasting the nickel carrier of the catalyst precursor in a roasting atmosphere to obtain the electro-catalytic glycerol oxidation catalyst. The preparation method of the invention has simple steps and low cost; the obtained catalyst for electrocatalytic oxidation of glycerin has high electrocatalytic activity (when glycerin is oxidized into formic acid, the Faraday efficiency of the obtained formic acid can reach 95%, and the yield of the formic acid can reach 1169 mu mol cm ‑2 ·h ‑1 ) The stability is strong; and at 100mA cm ‑2 After the electrolysis is continued for 240 hours under the current density, the potential of the electrolytic cell is almost not attenuated, and the service life is long.

Description

Catalyst for electrocatalytic oxidation of glycerol and preparation method thereof
Technical Field
The invention belongs to the technical field of inorganic nano catalytic materials, and particularly relates to a catalyst for electrocatalytic oxidation of glycerol and a preparation method thereof.
Background
With the continuous consumption of fossil energy, the huge market demand for renewable biodiesel not only promotes the rapid development of the biodiesel industry, but also leads to the massive surplus of glycerin as a biodiesel production byproduct, so that how to comprehensively utilize the abundant glycerin, and avoid resource waste, thereby becoming one of the problems to be solved at present.
Glycerol can be used as a raw material to obtain high value-added chemicals through methods such as oxidation, hydrogenation, dehydration, etherification, esterification and oligomerization. The glycerol oxidation method comprises the following steps: biological fermentation, chemical oxidation, electrochemical oxidation, etc., and can obtain high value-added chemicals such as glyceric acid, dihydroxyacetone, glyceraldehyde, glycolic acid, formic acid, etc. after glycerol is oxidized.
The electrochemical oxidation method is simple and convenient to operate, consumes electric energy, has mild reaction conditions, does not pollute the environment, can well avoid a plurality of defects caused by a chemical oxidation method (oxidant pollutes the environment) and a fermentation method (low efficiency and difficult product separation), and is a sustainable development mode. In addition, the electrochemical oxidation method can also control the oxidation product of the glycerol by regulating and controlling the electrode potential, the electrolyte solution, the concentration of the glycerol and the structure and the composition of the catalyst, and higher product selectivity is an important advantage. However, the catalysts used in the electrocatalytic oxidation of glycerol at present are mainly noble metal catalysts, such as Au, pt, pd, etc., and these noble metals have limited reserves and high prices, and cannot be used commercially on a large scale.
In order to solve the problems, the Chinese patent application with the publication number of CN112481656A discloses a bifunctional catalyst with high selectivity for producing formic acid by electrocatalysis of glycerol oxidation conversion and high efficiency for producing hydrogen by electrolyzing water, and a preparation method of the bifunctional catalystThe method comprises the following steps: (1) Electrodeposition of Ni/Ni (OH) on conductive three-dimensional substrates 2 Nanosheet, resulting in a deposit Ni/Ni (OH) 2 A substrate behind the nanosheet; (2) Depositing Ni/Ni (OH) described in step (1) 2 And soaking the substrate after the nano-sheets in a cobalt acetate solution, heating to perform cation exchange treatment, and taking out to obtain the high-selectivity bifunctional catalyst for producing formic acid and efficiently electrolyzing water to produce hydrogen by the oxidation conversion of the glycerol under the electrocatalysis.
After the electrocatalyst electrocatalysis is used for catalyzing the oxidation of the glycerol, the faradaic efficiency of the obtained formic acid reaches 97.25 percent, but the electrocatalyst is used at 100mA/cm 2 The time for which glycerol can be continuously electrolyzed at a current density is short (about 90 hours), and after 90 hours, the constant current chronopotentiometry potential gradually decays.
Disclosure of Invention
The invention aims to provide a catalyst for electrocatalytic oxidation of glycerol and a preparation method thereof, wherein the electrocatalytic oxidation catalyst for the glycerol has high electrocatalytic activity and can continuously electrolyze the glycerol for over 240 hours.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method of preparing a catalyst for electrocatalytic glycerol oxidation, comprising the steps of:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by adopting a solvothermal method or a hydrothermal method x A catalyst precursor;
(2) Growing NiFe (OH) on the obtained product in the step (1) x And (3) roasting the nickel carrier of the catalyst precursor in a roasting atmosphere to obtain the oxidation catalyst for electrocatalytic glycerol.
The invention directly grows NiFe (OH) on a nickel carrier by a hydrothermal method x Catalyst precursor, then grown with NiFe (OH) x Roasting the nickel carrier of the catalyst precursor to make NiFe (OH) x Catalyst precursor conversion to NiFe 2 O 4 The nano-sheet has simple and convenient steps and low cost; due to the NiFe with spinel structure 2 O 4 The nano-sheet has excellent oxidation and conductivity,the obtained catalyst for electrocatalytic oxidation of glycerin has high electrocatalytic activity (when glycerin is oxidized into formic acid, the Faraday efficiency of the obtained formic acid can reach 95 percent, and the yield of the formic acid can reach 1169 mu mol cm -2 ·h -1 ) The stability is strong; and at 100mA cm -2 After the electrolysis is continued for 240 hours under the current density, the potential of the electrolytic cell is almost not attenuated, and the service life is long.
Therefore, the invention also provides a catalyst for electrically catalyzing glycerol oxidation, which is prepared by adopting the preparation method. The nickel surface of the substrate of the catalyst vertically grows a plurality of ultra-thin NiFe which are mutually staggered 2 O 4 Nano-sheet, niFe 2 O 4 A plurality of nano porous structures are formed among the nano sheets, the specific surface area of the catalyst can be increased by the nano porous structures, more active sites are exposed, and the porous structures are beneficial to the electrolyte entering and fully contacting with the catalyst and more beneficial to the electrocatalytic oxidation of glycerol.
In electrocatalytic oxidation of glycerin using the catalyst, the reaction conditions are preferably set to: the concentration of glycerol in the electrolyte is 0.005-5mol/L, the pH of the electrolyte is 9-14, the reaction temperature is 10-60 ℃, and the applied potential is 0-2V.
More preferably, the reaction conditions are set as follows: the electrolyte is a mixed aqueous solution containing 0.1mol/L of glycerol and 1mol/L of sodium hydroxide, the reaction temperature is normal temperature, and the applied potential is 0.3-1.0V. The reaction condition is mild, and the method is green and environment-friendly.
In the preparation method of the electrocatalytic glycerol oxidation catalyst, in the step (1), the hydrothermal method refers to that the nickel carrier and the mixed solution are jointly transferred into a hydrothermal reaction kettle and subjected to hydrothermal reaction at 20-300 ℃ for 1-48h.
Preferably, the hydrothermal reaction is carried out at 60-150 ℃ for 5-30h.
In the preparation method of the catalyst for electrocatalytic oxidation of glycerol, in the step (1), the ferric salt is at least one of ferric nitrate, ferric chloride, ferrous chloride and ferric sulfate; preferably at least one of ferric nitrate, ferric chloride and ferric sulfate; this is because ferric ions are more likely to react with the nickel substrateTo obtain Ni 2+ 。
In the above method for preparing the catalyst for electrocatalytic oxidation of glycerin, in the step (1), the precipitant is at least one of urea and hexamethylenetetramine.
In the above method for preparing the catalyst for electrocatalytic oxidation of glycerol, in the step (1), the solvent of the mixed solution is at least one of methanol, ethanol and water;
in the mixed solution, the molar concentration of iron ions is 0.01-0.1mol/L, and the molar concentration of a precipitator is 0.01-0.1mol/L.
Preferably, in the step (1), the solvent of the mixed solution is formed by mixing water and alcohol (methanol and/or ethanol), and the mixing ratio is 2:8-8:2. The composition of the reaction solvent has an influence on the morphology of the catalyst, and when the mixed solvent is adopted, the obtained catalyst has better morphology.
In the preparation method of the electro-catalytic glycerol oxidation catalyst, in the step (1), the nickel carrier is firstly ultrasonically cleaned by sequentially adopting the organic solvent and the acidic solvent, and then hydrothermal reaction is carried out;
the organic solvent is at least one of acetone, ethanol and ethyl acetate, preferably at least one of acetone and ethanol;
the acidic solvent is at least one of hydrochloric acid, sulfuric acid and nitric acid, preferably at least one of hydrochloric acid and nitric acid.
In the above method for preparing the catalyst for electrocatalytic oxidation of glycerin, in the step (2), the calcination atmosphere is at least one of an air atmosphere, a chlorine atmosphere and an oxygen atmosphere.
In the above method for preparing the catalyst for electrocatalytic oxidation of glycerol, the oxygen atmosphere contains an inert diluent gas, and the inert diluent gas is at least one of nitrogen, argon, helium, krypton, neon and xenon. The inert gas is added for diluting the oxygen concentration, so that the influence of excessive oxidation on the conductivity of the catalyst due to long-time reaction at high temperature is avoided; meanwhile, the reaction is better and safer to carry out in the low-concentration oxygen atmosphere.
In the preparation method of the electro-catalysis glycerol oxidation catalyst, the roasting is carried out for 1-50h at 100-500 ℃ and 0-3 MPa; namely, the roasting temperature is increased to 100-500 ℃ from room temperature at the heating rate of 1-20 ℃/min, and then the roasting and heat preservation are carried out for 1-50h under the pressure of 0-3 MPa.
Preferably, the roasting temperature is increased to 250-350 ℃ from 20-30 ℃ at the heating rate of 1-10 ℃/min, and then the roasting and heat preservation are carried out for 1-20h under the pressure of 0-1 MPa.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention directly grows NiFe (OH) on a nickel carrier by a hydrothermal method x Catalyst precursor, then grown with NiFe (OH) x Roasting the nickel carrier of the catalyst precursor to make NiFe (OH) x Catalyst precursor conversion to NiFeO 4 The nano-sheet has simple and convenient steps and low cost; niFeO due to having spinel structure 4 The nanosheet has excellent oxidizability and conductivity, so that the obtained catalyst for electrocatalytic oxidation of glycerol has high electrocatalytic activity (when glycerol is oxidized into formic acid, the Faraday efficiency of the obtained formic acid can reach 95%, and the yield of the formic acid can reach 1169 mu mol cm) -2 ·h -1 ) The stability is strong; and at 100mA cm -2 After the electrolysis is continued for 240 hours under the current density, the potential of the electrolytic cell is almost not attenuated, and the service life is long.
(2) In the invention, a plurality of interlaced ultrathin NiFe vertically grow on the surface of the substrate nickel of the catalyst 2 O 4 Nano-sheet, niFe 2 O 4 A plurality of nano porous structures are formed among the nano sheets, the specific surface area of the catalyst can be increased by the nano porous structures, more active sites are exposed, and the porous structures are beneficial to the electrolyte entering and fully contacting with the catalyst and more beneficial to the electrocatalytic oxidation of glycerol.
Drawings
FIG. 1 is a scanning electron micrograph of an electrocatalytic glycerol oxidation catalyst prepared according to the present invention;
FIG. 2 is a graph showing the test of the catalytic efficiency of the electrocatalytic oxidation of glycerol catalysts prepared according to the present invention at different voltages;
in the figure, peak V (vs. Ag/AgCl) represents voltage (volt, ag/AgCl electrode), faraday efficiency (%) represents Faraday efficiency (percentage), and Current density (mA/cm) -2 ) Represents the current density (milliampere/square centimeter), as follows;
FIG. 3 is a graph of the results of a stability test of a catalyst prepared according to the present invention for electrocatalytic oxidation of glycerol;
in the figure, time (h) represents electrolysis Time (hours), and Glycerol concentration (mM) represents formic acid concentration (millimoles per liter);
FIG. 4 is a scanning electron microscope image of the electrocatalytic oxidation catalyst of glycerol prepared by the present invention after 240 hours of use.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the accompanying drawings and the detailed description.
Example 1
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing the nickel sheet in acetone and 2M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel plate treated as above was placed in a bath containing 0.01M Fe (NO) 3 ) 3 Mixing with 0.02M urea (solvent is prepared by mixing 6ml methanol and 24ml water), performing ultrasonic treatment at 20 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 80 deg.C oven for 12h, cooling to room temperature after reaction, taking out, and treating the product with ethanol and deionized water to obtain the product with NiFe (OH) x Cleaning a nickel sheet of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the nickel sheet with the catalyst precursor in air atmosphere at a gas flow rate of150ml/min, the roasting temperature is increased to 250 ℃ from room temperature at the heating rate of 10 ℃/min, then the roasting heat preservation is carried out for 3h, and the reaction pressure is kept at 0.1MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.4V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 79%, and the yield is 80 mu mol cm -2 ·h -1 。
Example 2
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing the nickel foil in acetone and 2M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foil treated as described above was placed in a container containing 0.01M Fe (NO) 3 ) 3 Mixing with 0.02M urea (solvent is prepared by mixing 6ml methanol and 24ml water), performing ultrasonic treatment at 20 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 80 deg.C oven for 16h, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning a nickel foil of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the nickel foil with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 250 ℃ from room temperature at the heating rate of 10 ℃/min, then roasting and preserving heat for 3h, and the reaction pressure is kept at 0.2MPa; after the reaction was completed, the catalyst for electrocatalytic oxidation of glycerin (NiFe) of the present example was obtainedO 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.4V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 82 percent, and the yield is 100 mu mol cm -2 ·h -1 。
Example 3
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing the nickel screen in acetone and 2M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel mesh treated as above was placed in a bath containing 0.01M Fe (NO) 3 ) 3 Mixing with 0.02M urea (solvent is prepared by mixing 6ml methanol and 24ml water), performing ultrasonic treatment at 30 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 12 hr, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning a nickel net of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the nickel net with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 10 ℃/min, then roasting and preserving heat for 3h, and the reaction pressure is kept at 0.1MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is 0.1mol/L of glycerol and 1mol/L of hydrogen and oxygenThe mixed aqueous solution of sodium chloride was applied with a constant potential of 0.4V at room temperature, and glycerin was oxidized to formic acid, which had a Faraday efficiency of 85% and a yield of 120. Mu. Mol/cm -2 ·h -1 。
Example 4
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing foamed nickel in acetone and 2M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.01M Fe (NO) 3 ) 3 Mixing with 0.04M urea (solvent is prepared by mixing 6ml methanol and 24ml water), performing ultrasonic treatment at 30 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 20 hr, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning foam nickel of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere for roasting to obtain the electro-catalysis glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the foamed nickel with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 10 ℃/min, then roasting and preserving heat for 3h, and the reaction pressure is kept at 0.2MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.5V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 88 percent, and the yield is 325 mu mol cm -2 ·h -1 。
Example 5
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing foamed nickel in acetone and 2M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above is placed in a container containing 0.01M Fe (NO) 3 ) 3 Mixing with 0.04M urea (solvent is prepared by mixing 6ml methanol and 24ml water), performing ultrasonic treatment at 30 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 16h, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning foam nickel of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the foamed nickel with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 320 ℃ from room temperature at the heating rate of 10 ℃/min, then roasting and preserving heat for 2h, and the reaction pressure is kept at 0.1MPa; after the reaction was completed, the catalyst for electrocatalytic oxidation of glycerin (NiFe) of the present example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.5V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 88 percent, and the yield is 340 mu mol cm -2 ·h -1 。
Example 6
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing foamed nickel in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.03M Fe (NO) 3 ) 3 Mixing with 0.08M urea (solvent is prepared by mixing 15ml methanol and 15ml water), performing ultrasonic treatment at 30 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 20 hr, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning foam nickel of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the foamed nickel with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and preserving heat for 3h, and the reaction pressure is kept at 0.1MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.5V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 90 percent, and the yield is 350 mu mol cm -2 ·h -1 。
Example 7
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
concrete bagComprises the following steps: sequentially placing foamed nickel in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.03M Fe (NO) 3 ) 3 Mixing with 0.06M urea (solvent is prepared by mixing 15ml methanol and 15ml water), performing ultrasonic treatment at 20 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 16h, cooling to room temperature after reaction, taking out, and treating with ethanol and deionized water to obtain NiFe (OH) x Cleaning foam nickel of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the foamed nickel with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 10 ℃/min, then roasting and preserving heat for 2h, and the reaction pressure is kept at 0.4MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.5V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 91.6 percent, and the yield is 360 mu mol cm -2 ·h -1 。
Example 8
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing foamed nickel in ethanol and 3M hydrochloric acid, and ultrasonically cleaning for 15min; then, the nickel foam treated as above is placed in a container containing 0.03M Fe (NO) 3 ) 3 Mixed solution of 0.08M ureaThe solution (solvent is formed by mixing 15ml methanol and 15ml water) is firstly treated by ultrasonic treatment for 30min at the temperature of 30 ℃, then transferred to a hydrothermal reaction kettle, subjected to hydrothermal reaction for 20h in a drying oven at the temperature of 100 ℃, cooled to room temperature after the reaction is finished, taken out, and treated by ethanol and deionized water to obtain NiFe (OH) x Cleaning foam nickel of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the foamed nickel with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and preserving heat for 3h, and the reaction pressure is kept at 0.1MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 ) The scanning electron micrograph of the catalyst is shown in FIG. 1.
As can be seen from FIG. 1, in the catalyst prepared by the invention, a plurality of ultra-thin NiFeO layers which are mutually staggered are vertically grown on the surface of the substrate nickel 4 Nanosheets, niFeO 4 A plurality of nano porous structures are formed among the nano sheets, the specific surface area of the catalyst can be increased by the nano porous structures, more active sites are exposed, and the porous structures are beneficial to the electrolyte entering and fully contacting with the catalyst and more beneficial to the electrocatalytic oxidation of glycerol.
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, different voltages are applied at normal temperature, the catalytic efficiency of the catalyst for oxidizing glycerol into formic acid under different voltages is tested, and the test result is shown in figure 2.
As can be seen from FIG. 2, the Faraday efficiency of formic acid was the highest, reaching 95% when a constant potential of 0.6V was applied, with a yield of 750. Mu. Mol. Cm -2 ·h -1 。
Further, taking the catalyst prepared in this example as an example, the stability of the catalyst of the present invention is tested by the following method: putting the catalyst in an electrolyte (a mixed aqueous solution containing 0.1mol/L of glycerol and 1mol/L of sodium hydroxide), and applying a constant voltage of 0.6V for electrolysis; the electrolyte is changed every 12 hours and is continuously electrolyzed for 240 hours, and the test result is shown in figure 3; the morphology of the catalyst was observed again after the test was completed and the observation results are shown in fig. 4.
As can be seen from FIG. 3, the current density at 100mA cm -2 After the electrolysis is continued for 240 hours under the current density, the potential of the electrolytic cell is almost not attenuated, and the service life is long. Moreover, as can be seen from FIG. 4, after 240 hours of stability test reaction, the morphology of the catalyst has almost no change, and NiFe 2 O 4 The nanosheet structure remained intact.
Example 9
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing foamed nickel in ethanol and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.04M Fe (NO) 3 ) 3 Mixing with 0.08M urea (solvent is prepared by mixing 15ml methanol and 15ml water), performing ultrasonic treatment at 30 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 20 hr, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning foam nickel of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the foamed nickel with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and preserving heat for 2h, and the reaction pressure is kept at 0.1MPa; reaction ofAfter completion of the reaction, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.6V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 92 percent, and the yield is 675 mu mol cm -2 ·h -1 。
Example 10
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing the nickel foil in acetone and 1M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.04M Fe (NO) 3 ) 3 Mixing with 0.08M urea (solvent is prepared by mixing 15ml methanol and 15ml water), performing ultrasonic treatment at 40 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 18h, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning a nickel foil of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere for roasting to obtain the electro-catalysis glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the nickel foil with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and insulating for 2h, and the reaction pressure is kept at 0.2MPa; after the reaction was completed, the catalyst for electrocatalytic oxidation of glycerin (NiFe) of the present example was obtained 2 O 4 )。
The catalyst obtained in this example was used for electrocatalytic oxidation of glycerolProducing formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.6V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 86 percent, and the yield is 625 mu mol cm -2 ·h -1 。
Example 11
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing foamed nickel in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.03M Fe (NO) 3 ) 3 Mixing with 0.08M urea (solvent is prepared by mixing 15ml methanol and 15ml water), performing ultrasonic treatment at 30 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 20 hr, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning foam nickel of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the foamed nickel with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and preserving heat for 3h, and the reaction pressure is kept at 0.1MPa; after the reaction was completed, the catalyst for electrocatalytic oxidation of glycerin (NiFe) of the present example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.7V is applied at normal temperature, the glycerol is oxidized into formic acid, and the formic acid is faradaicThe first efficiency was 87%, and the yield was 980. Mu. Mol. Cm -2 ·h -1 。
Example 12
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing the nickel foil in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above is placed in a container containing 0.03M Fe (NO) 3 ) 3 Mixing with 0.08M urea (solvent is prepared by mixing 15ml methanol and 15ml water), performing ultrasonic treatment at 30 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 20 hr, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning a nickel foil of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the nickel foil with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and insulating for 3h, and the reaction pressure is kept at 0.1MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.6V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 89%, and the yield is 655 mu mol cm -2 ·h -1 。
Example 13
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing foamed nickel in ethanol and 3M hydrochloric acid, and ultrasonically cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.03M Fe (NO) 3 ) 3 Mixing with 0.08M urea (solvent is prepared by mixing 15ml methanol and 15ml water), performing ultrasonic treatment at 30 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 10 hr, cooling to room temperature after reaction, taking out, and treating with ethanol and deionized water to obtain NiFe (OH) x Cleaning foam nickel of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the foamed nickel with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 150ml/min, the roasting temperature is increased to 250 ℃ from room temperature at the heating rate of 10 ℃/min, then roasting and preserving heat for 2h, and the reaction pressure is kept at 0.2MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.6V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 84%, and the yield is 615 mu mol cm -2 ·h -1 。
Example 14
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (O) on the nickel carrier by a hydrothermal methodH) x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing the nickel foil in ethanol and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.02M Fe (NO) 3 ) 3 Mixing with 0.06M urea (solvent is prepared by mixing 24ml methanol and 6ml water), performing ultrasonic treatment at 30 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 18h, cooling to room temperature after reaction, taking out, and treating with ethanol and deionized water to obtain NiFe (OH) x Cleaning a nickel foil of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere for roasting to obtain the electro-catalysis glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the nickel foil with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and insulating for 3h, and the reaction pressure is kept at 0.1MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the embodiment is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.6V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 82 percent, and the yield is 595 mu mol cm -2 ·h -1 。
Example 15
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing foamed nickel in acetone and 1M hydrochloric acid for ultrasonic cleaning for 15min; then, the foam nickel treated by the above treatment is placed inContaining 0.06M Fe (NO) 3 ) 3 Mixing with 0.06M urea (solvent is prepared by mixing 15ml methanol and 15ml water), performing ultrasonic treatment at 40 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 24 hr, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning foam nickel of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the foamed nickel with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and preserving heat for 3h, and the reaction pressure is kept at 0.1MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.7V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 85 percent, and the yield is 940 mu mol cm -2 ·h -1 。
Example 16
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing foamed nickel in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.02M Fe (NO) 3 ) 3 Mixing with 0.08M urea (solvent prepared by mixing 15ml methanol and 15ml water), ultrasonic treating at 40 deg.C for 30min, transferring to hydrothermal reaction kettle, and treating at 100 deg.CCarrying out hydrothermal reaction in an oven at the temperature of 18h, cooling to room temperature after the reaction is finished, taking out, and growing NiFe (OH) by using ethanol and deionized water x Cleaning foam nickel of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the foamed nickel with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 250 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and preserving heat for 3h, and the reaction pressure is kept at 0.2MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.7V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 82 percent, and the yield is 865 mu mol cm -2 ·h -1 。
Example 17
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing the nickel foil in ethanol and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.03M Fe (NO) 3 ) 3 Mixing with 0.08M urea (solvent is prepared by mixing 15ml methanol and 15ml water), performing ultrasonic treatment at 20 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 20 hr, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning a nickel foil of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the nickel foil with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 150ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and preserving heat for 3h, and the reaction pressure is kept at 0.1MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.7V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 85 percent, and the yield is 900 mu mol cm -2 ·h -1 。
Example 18
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing the nickel foil in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above is placed in a container containing 0.03M Fe (NO) 3 ) 3 Mixing with 0.06M urea (solvent is prepared by mixing 15ml methanol and 15ml water), performing ultrasonic treatment at 20 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 24 hr, cooling to room temperature after reaction, taking out, and treating with ethanol and deionized water to obtain NiFe (OH) x Cleaning a nickel foil of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere for roasting to obtain the electro-catalytic glycerin oxidation catalystAn agent;
the method specifically comprises the following steps: roasting the nickel foil with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 150ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and preserving heat for 3h, and the reaction pressure is kept at 0.1MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.6V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 86 percent, and the yield is 920 mu mol cm -2 ·h -1 。
Example 19
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing the nickel foil in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.08M Fe (NO) 3 ) 3 Mixing with 0.08M urea (solvent is prepared by mixing 6ml methanol and 24ml water), performing ultrasonic treatment at 20 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 10 hr, cooling to room temperature after reaction, taking out, and treating with ethanol and deionized water to obtain NiFe (OH) x Cleaning a nickel foil of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere for roasting to obtain the electro-catalysis glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the nickel foil with the catalyst precursor in air atmosphere, wherein the gas flow rate of the air atmosphere is 150ml/min, and the roasting temperature is 5 ℃/min from room temperatureThe temperature rise rate is increased to 280 ℃, then the roasting and heat preservation are carried out for 3 hours, and the reaction pressure is kept at 0.2MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.6V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 89%, and the yield is 665 mu mol cm -2 ·h -1 。
Example 20
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing the nickel foil in ethanol and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.03M Fe (NO) 3 ) 3 Mixing with 0.06M urea (solvent is prepared by mixing 15ml methanol and 15ml water), performing ultrasonic treatment at 20 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 20 hr, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning a nickel foil of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the nickel foil with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 150ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and preserving heat for 3h, and the reaction pressure is kept at 0.1MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.8V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 80 percent, and the yield is 1169 mu mol cm -2 ·h -1 。
Example 21
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing the nickel foil in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.03M Fe (NO) 3 ) 3 Mixing with 0.04M urea (solvent is prepared by mixing 15ml methanol and 15ml water), performing ultrasonic treatment at 30 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 18h, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning a nickel foil of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the nickel foil with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 150ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 10 ℃/min, then roasting and insulating for 3h, and the reaction pressure is kept at 0.2MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the embodiment is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is mixed water solution of 0.1mol/L glycerin and 1mol/L sodium hydroxideThe solution was applied with a constant potential of 0.8V at room temperature, and glycerin was oxidized to formic acid, which had a Faraday efficiency of 78% and a yield of 1103. Mu. Mol/cm -2 ·h -1 。
Example 22
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing the nickel foil in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.06M Fe (NO) 3 ) 3 Mixing with 0.04M urea (solvent is prepared by mixing 15ml methanol and 15ml water), performing ultrasonic treatment at 30 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 18h, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning a nickel foil of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere to be roasted to obtain the electro-catalytic glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the nickel foil with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 300 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and preserving heat for 3h, and the reaction pressure is kept at 0.3MPa; after the reaction was completed, the electrocatalytic glycerol oxidation catalyst (NiFe) of this example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.8V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 76%, and the yield is 1002 mu mol cm -2 ·h -1 。
Example 23
The embodiment of the invention relates to a preparation method of a catalyst for electrocatalytic oxidation of glycerol, which comprises the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by a hydrothermal method x A catalyst precursor;
the method specifically comprises the following steps: sequentially placing the nickel foil in ethanol and 3M hydrochloric acid for ultrasonic cleaning for 15min; then, the nickel foam treated as above was placed in a bath containing 0.03M Fe (NO) 3 ) 3 Mixing with 0.04M urea (solvent is prepared by mixing 6ml methanol and 24ml water), performing ultrasonic treatment at 30 deg.C for 30min, transferring to hydrothermal reaction kettle, performing hydrothermal reaction in 100 deg.C oven for 24 hr, cooling to room temperature after reaction, taking out, and adding ethanol and deionized water to obtain NiFe (OH) x Cleaning a nickel foil of a catalyst precursor, and drying for later use;
(2) Growing NiFe (OH) on the obtained product in the step (1) x The nickel carrier of the catalyst precursor is placed in a roasting atmosphere for roasting to obtain the electro-catalysis glycerol oxidation catalyst;
the method specifically comprises the following steps: roasting the nickel foil with the catalyst precursor in an air atmosphere, wherein the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is increased to 320 ℃ from room temperature at the heating rate of 5 ℃/min, then roasting and preserving heat for 3h, and the reaction pressure is kept at 0.2MPa; after the reaction was completed, the catalyst for electrocatalytic oxidation of glycerin (NiFe) of the present example was obtained 2 O 4 )。
The catalyst obtained in the example is used for electrocatalytic oxidation of glycerol to produce formic acid, and the conditions of the electrocatalytic oxidation reaction are as follows: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerol and 1mol/L sodium hydroxide, a constant potential of 0.6V is applied at normal temperature, the glycerol is oxidized into formic acid, the Faraday efficiency of the formic acid is 92.5 percent, and the yield is 685 mu mol cm -2 ·h -1 。

Claims (6)

1. A preparation method of a catalyst for electrocatalytic oxidation of glycerol is characterized by comprising the following steps:
(1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing a NiFe (OH) x catalyst precursor on the nickel carrier by adopting a hydrothermal method;
the solvent of the mixed solution is formed by mixing water and alcohol, and the mixing proportion is 2:8-8:2;
in the mixed solution, the molar concentration of iron ions is 0.01-0.1mol/L, and the molar concentration of a precipitator is 0.01-0.1mol/L;
the hydrothermal method is characterized in that the nickel carrier and the mixed solution are jointly transferred into a reaction kettle and subjected to hydrothermal reaction for 5-30h at the temperature of 60-150 ℃;
(2) Putting the nickel carrier which is obtained in the step (1) and is grown with the precursor of the NiFe (OH) x catalyst into a roasting atmosphere for roasting to obtain the electro-catalytic glycerol oxidation catalyst;
the roasting is carried out for 1-20h at 250-350 ℃ and 0.1-1 MPa.
2. The method for preparing a catalyst for the electrocatalytic oxidation of glycerol according to claim 1, wherein in the step (1), the iron salt is at least one of ferric nitrate, ferric chloride, ferrous chloride and ferric sulfate; the precipitant is at least one of urea and hexamethylenetetramine.
3. The method for preparing a catalyst for electrocatalytic oxidation of glycerol according to any one of claims 1-2, wherein in the step (1), the nickel carrier is firstly ultrasonically cleaned by sequentially adopting the organic solvent and the acidic solvent, and then is subjected to hydrothermal reaction;
the organic solvent is at least one of acetone, ethanol and ethyl acetate;
the acidic solvent is at least one of hydrochloric acid, sulfuric acid and nitric acid.
4. The method for preparing a catalyst for electrocatalytic oxidation of glycerin according to any one of claims 1 to 2, wherein in the step (2), the calcination atmosphere is at least one of an air atmosphere, a chlorine atmosphere and an oxygen atmosphere.
5. The method of claim 4, wherein the oxygen atmosphere contains an inert diluent gas, and the inert diluent gas is at least one of nitrogen, argon, helium, krypton, neon, and xenon.
6. Use of a catalyst for electrocatalytic oxidation of glycerol, wherein said catalyst is prepared by the method of any one of claims 1 to 5 for preparing a catalyst for electrocatalytic oxidation of glycerol.
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