CN114086202B - Non-noble metal catalyst for glycerol oxidation-assisted hydrogen production - Google Patents

Non-noble metal catalyst for glycerol oxidation-assisted hydrogen production Download PDF

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CN114086202B
CN114086202B CN202111409709.3A CN202111409709A CN114086202B CN 114086202 B CN114086202 B CN 114086202B CN 202111409709 A CN202111409709 A CN 202111409709A CN 114086202 B CN114086202 B CN 114086202B
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hydrogen production
noble metal
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glycerol
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CN114086202A (en
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温珍海
冯辛
刘博文
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Nanchang Hangkong University
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    • 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
    • C25B3/23—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention discloses a non-noble metal catalyst for hydrogen production assisted by glycerol oxidation, which is prepared by adopting a hydrothermal method and calcining the Co catalyst in a tubular furnace in the air atmosphere to obtain Co growing on foamed nickel 3 O 4 A material. Prepared Co 3 O 4 @ NF Material is put into a three-electrode system to test the hydrogen production by glycerin-assisted water decomposition and the glycerin oxidation performance, and the initial potential (10 mA/cm) is measured 2 ) The voltage is 1.22V, which is close to the theoretical potential of 1.23V of the traditional electrolyzed water, the energy consumption for producing hydrogen is reduced, and the product after the glycerol is oxidized is subjected to nuclear magnetic hydrogen spectrum test, the product is formic acid and the Faraday efficiency reaches 97.4 percent. If the catalyst material is applied to the initial potential (10 mA/cm) measured by an acid-base asymmetric electrolytic cell by utilizing electrochemical neutralization energy 2 ) The voltage is 0.55V, exceeds the voltage required in the traditional electrolytic cell, and greatly reduces the energy consumption of the electrocatalytic reaction.

Description

Non-noble metal catalyst for glycerol oxidation-assisted hydrogen production
Technical Field
The invention relates to the field of materials, in particular to the technical field of electrocatalysis, and specifically relates to a non-noble metal catalyst for hydrogen production assisted by glycerol oxidation.
Background
Fossil fuels are a limited resource, and power generation from fossil fuels has led to environmental problems such as pollution caused by carbon dioxide emissions and climate change. Thus, there is a need for clean and sustainable hydrogen production in future renewable energy infrastructures, for example by electrocatalytic hydrogen production, which is a very promising approach. The conventional water electrolysis technique uses a Hydrogen Evolution Reaction (HER) as a cathode reaction and an Oxygen Evolution Reaction (OER) as an anode reaction. However, in conventional aqueous electrolysis systems, the cathode HER rate is often limited by the rate of the anode OER reaction, since the kinetics of the latter are slow. The construction of a hybrid water electrolysis system by replacing OER with other thermodynamically more favorable anodic reactions, particularly those that can produce valuable products, is an innovative strategy to increase the overall energy conversion efficiency of the electrolytic water to hydrogen production. So far, whatThe most common catalysts reported in the literature for the electrocatalytic oxidation of HER and glycerol are noble metal or noble metal and non-noble metal composite catalysts, but their large-scale production is limited by high cost, scarcity, poor stability, etc. Foamed nickel based Co 3 O 4 The non-noble metal catalyst can catalyze glycerin to assist water decomposition to prepare hydrogen and catalyze glycerin oxidation, has good application prospect, and can couple Glycerin Oxidation Reaction (GOR) and HER to form a dual-function hybrid water electrolysis system, so that high-purity formic acid can be obtained, and the hydrogen can be generated by electrochemically assisting water decomposition. And nickel foam based Co 3 O 4 The non-noble metal catalyst can be applied to an acid-base asymmetric device by adopting an electrochemical method, the traditional acid-base neutralization heat energy is converted into electric energy, and the energy consumption required by the reaction can be greatly reduced by utilizing the electrochemical neutralization energy.
Disclosure of Invention
The invention aims to provide a non-noble metal catalyst for hydrogen production assisted by glycerol oxidation, which aims at preparing Co growing on foamed nickel 3 O 4 The non-noble metal catalyst is used for electrocatalytic oxidation of glycerol to obtain formic acid and assisting the cathodic hydrogen evolution reaction to generate hydrogen; the technical problem to be solved is to prepare Co which uniformly grows on the foamed nickel 3 O 4 The catalyst is a non-noble metal catalyst, and the nano-flake material formed by calcining in the air has the characteristics of large specific surface area, good conductivity and excellent catalytic activity.
The technical scheme adopted by the invention is as follows: a non-noble metal catalyst for preparing hydrogen by oxidizing glycerin is prepared from Co 3 O 4 The catalyst is grown on a foamed nickel substrate, and the preparation method comprises the following steps:
step one, pretreating a foamed nickel substrate;
respectively carrying out ultrasonic treatment on the cut foamed nickel in hydrochloric acid, absolute ethyl alcohol and deionized water for 10 minutes to carry out pretreatment on the foamed nickel;
step two, co 3 O 4 Preparation of @ NF;
respectively dissolving cobalt nitrate hexahydrate and 2-methylimidazole in methanol to obtain a solution A and a solution B, uniformly stirring, and mixing and stirring the solution A and the solution B to obtain a solution C;
then the solution C and clean foam nickel react for 12 hours at 140 ℃ in a reaction kettle, and Co growing on the foam nickel is obtained by washing, vacuum drying and calcining in the air atmosphere 3 O 4 A catalyst.
Further, the size of the foamed nickel in the first step is preferably 2cm × 3cm.
Further, the concentration of the hydrochloric acid solution in the first step is 3M.
Further, the mass concentration of the cobalt nitrate hexahydrate in the solution A in the second step is 210-220g/L.
Further, the mass concentration of the 2-methylimidazole in the solution B in the second step is 8.1-8.3g/L.
Further, the volume ratio of the solution A to the solution B in the second step is 1.
Further, in the second step, the solution A and the solution B need to be stirred for 15-20min.
Further, the solution C in the second step needs to be stirred for 3-5min.
Further, in the second step, washing is carried out in an ultrasonic machine for 20s by using methanol and absolute ethyl alcohol in the washing process three times.
Further, the temperature of the calcining process in the second-step middle-tube type furnace is increased to 350 ℃ at the speed of 2 ℃ per minute, and the temperature is kept for 2 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of the catalyst is to adopt a hydrothermal method and then calcine the Co grown on the foam Nickel (NF) in a tubular furnace in the air atmosphere 3 O 4 A material. Mixing Co 3 O 4 @ NF was put into a three-electrode system to test its glycerol-assisted water decomposition hydrogen production and glycerol oxidation performance, and the initial potential (10 mA/cm) was measured 2 ) 1.22V, which is close to the theoretical potential of 1.23V of the traditional electrolyzed water, reduces the energy consumption of hydrogen production, and carries out nucleation on the product after the glycerol is oxidizedThe product is formic acid and the Faraday efficiency reaches 97.4 percent by magnetic hydrogen spectrum test. If electrochemical neutralization is used, the initial potential (10 mA/cm) measured using an acid-base asymmetric electrolytic cell can be used 2 ) Is 0.55V, exceeds the voltage required in the traditional electrolytic cell, and greatly reduces the energy consumption of the electrocatalytic reaction.
(2) By Co 3 O 4 The nano flaky material grows on the foamed nickel, is simple and easy to control, and has wide application prospect in the field of electrocatalysis glycerol oxidation. The product has extremely high selectivity, stable chemical property, simple preparation and simple operation, and can effectively improve the selectivity and catalytic activity of the catalyst at low potential. Is a high-efficiency catalyst for electrocatalysis glycerin oxidation. But also is a catalyst which has no pollution to the environment and has huge potential.
The method has the advantages of low preparation cost, simple and convenient operation and high hydrogen production performance by glycerol oxidation and auxiliary water decomposition. The catalyst grows on the foam nickel substrate in a nanosheet form and has good charge conduction capability. The foamed nickel is used as a substrate, has good catalytic activity and conductivity, and has good industrial application prospects.
Drawings
FIG. 1 shows Co obtained in example 1 of the present invention 3 O 4 The Scanning Electron Microscope (SEM) spectrum of @ NF.
FIG. 2 shows Co obtained in example 1 of the present invention 3 O 4 The Scanning Electron Microscope (SEM) spectrum of @ NF.
FIG. 3 shows Co obtained in example 1 of the present invention 3 O 4 Scanning Electron Microscope (SEM) spectra for @ NF.
FIG. 4 shows Co obtained in example 1 of the present invention 3 O 4 X-ray diffraction (XRD) pattern of @ NF.
FIG. 5 shows Co obtained in example 1 of the present invention 3 O 4 GOR and OER (LSV) comparison plots of @ NF.
FIG. 6 shows Co obtained in example 1 of the present invention 3 O 4 The @ NF material is used for electrocatalytic glycerol oxidation product nuclear magnetic hydrogen spectrum (1H NMR) test chart.
FIG. 7 shows Co obtained in example 1 of the present invention 3 O 4 The comparison graph of GOR performance of the @ NF material in an acid-base asymmetric electrolytic cell and a symmetric alkali-base symmetric electrolytic cell.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Preparation of Co in the invention 3 O 4 @NF；
Step one, pretreating foamed nickel; cutting the foamed nickel into the size of 2cm multiplied by 3cm, and respectively carrying out ultrasonic treatment on the cut foamed nickel in hydrochloric acid with the concentration of 3M, absolute ethyl alcohol and deionized water for 10min;
step two, solution A: 4.365g of cobalt nitrate hexahydrate is dispersed in 20ml of methanol and is put under a magnetic stirrer to be stirred uniformly; and B, liquid B: 0.164g of 2-methylimidazole is taken and dispersed in 20ml of methanol, and the mixture is put under a magnetic stirrer to be stirred uniformly;
and step three, putting the solution A under a magnetic stirrer, pouring the solution B into the solution A, and stirring for 3-5min until the solution B is uniform to obtain a solution C.
And step four, putting the solution C and the processed foamed nickel into a reaction kettle, carrying out hydrothermal reaction for 12 hours at 140 ℃, then washing with methanol and absolute ethyl alcohol for three times for 20s each time, and then carrying out vacuum drying in a vacuum drying box at 60 ℃ for 12 hours to obtain the precursor.
And step five, placing the dried precursor in a porcelain boat, then placing the porcelain boat in a high-temperature tube furnace, raising the temperature to 350 ℃ at the rate of 2 ℃ per minute, and preserving the temperature for 2 hours.
The invention provides a non-noble metal catalyst for hydrogen production assisted by glycerol oxidation, which is prepared by a hydrothermal method and calcining in a tube furnace in the air atmosphere to obtain Co growing on Nickel Foam (NF) 3 O 4 A material. Prepared Co 3 O 4 @ NF Material is put into a three-electrode system to test the hydrogen production by glycerin-assisted water decomposition and the glycerin oxidation performance, and the initial potential (10 mA/cm) is measured 2 ) Is 1.22V, is close to the theoretical potential of 1.23V of the traditional electrolyzed water, reduces the energy consumption of hydrogen production,and the product after the glycerol is oxidized is subjected to nuclear magnetic hydrogen spectrum test, the product is formic acid and the Faraday efficiency reaches 97.4%. If the catalyst material is applied to the initial potential (10 mA/cm) measured by an acid-base asymmetric electrolytic cell by utilizing electrochemical neutralization energy 2 ) The voltage is 0.55V, exceeds the voltage required in the traditional electrolytic cell, and greatly reduces the energy consumption of the electrocatalytic reaction. The nano-film grows on the foam nickel substrate in a nano-film form, has good charge transmission capability, exposes more active sites, and grows Co by taking the foam nickel as the substrate 3 O 4 The catalyst material has higher current density and catalytic activity for glycerol oxidation, and has good industrial application prospect.
The cobalt nitrate hexahydrate and the 2-methylimidazole used in the invention are compared with those prepared by the conventional method for preparing Co 3 O 4 Growing on a foamed nickel substrate with different drugs, and growing on a foamed nickel substrate, which is the innovation point of the invention, is firstly compared with the Co prepared by the prior art 3 O 4 Catalyst Co of the invention 3 O 4 The nano-sheet array grows on the foam nickel substrate, and the uniform nano-sheet array grows on the foam nickel substrate, so that the nano-sheet array has a higher specific surface area, exposes more active sites and has higher catalytic performance. Co based on foamed nickel 3 O 4 Compared with the common non-noble metal catalyst, the non-noble metal catalyst has higher current density, higher catalytic reaction rate, greatly reduced energy consumption required by the reaction, higher catalytic activity for catalyzing glycerol and better reduction of the required potential for electrocatalysis of glycerol oxidation.
Unless otherwise specified, the raw materials used in the examples of the present invention were purchased commercially and used without further treatment except for nickel foam and carbon rod; the test conditions of the instrument all adopt the parameters recommended by the manufacturer.
A non-noble metal catalyst for hydrogen production assisted by glycerol oxidation comprises the following steps:
example 1
1. Pretreatment of nickel foam
Cutting the foamed nickel into the size of 2cm multiplied by 3cm, and then putting the cut foamed nickel into hydrochloric acid with the concentration of 3M, absolute ethyl alcohol and deionized water for ultrasonic treatment for 10min respectively;
2. preparation of Co 3 O 4 @NF
Respectively dissolving 4.365g of cobalt nitrate hexahydrate and 0.164g of 2-methylimidazole in 20ml of methanol to obtain a solution A and a solution B, uniformly stirring, placing the solution A under a magnetic stirrer, pouring the solution B into the solution A, and stirring for 3-5min until the solution C is uniformly obtained. And putting the solution C and the processed foam nickel into a reaction kettle, carrying out hydrothermal reaction for 12h at 140 ℃, then washing with methanol and absolute ethyl alcohol for three times, and carrying out vacuum drying for 12h at 70 ℃ to obtain the precursor. Finally, the dried precursor is placed in a porcelain boat, then is placed in a high-temperature tube furnace, the temperature is raised to 350 ℃ at the rate of 2 ℃ per minute, and the temperature is kept for 2h to obtain the Co growing on the nickel foam as shown in figure 1, figure 2, figure 3 and figure 4 3 O 4 A nanosheet catalyst.
The obtained Co 3 O 4 The @ NF nanosheet material is used as a working electrode, hg/HgO is used as a reference electrode, a carbon rod is used as a counter electrode, and the three electrode bodies are tested in a mixed solution of 1M KOH +0.5M glycerol to test the glycerol-assisted water decomposition hydrogen production and glycerol oxidation performances, wherein the initial potential (10 mA/cm) is measured as shown in the figure 2 ) It was 1.22V as shown in FIG. 5. The theoretical potential of the traditional electrolytic water is close to 1.23V, the energy consumption required by electrochemical hydrogen production is reduced, and the faradaic efficiency of electrocatalytic oxidation of glycerol into formic acid through nuclear magnetic hydrogen spectrum test reaches 97.4 percent as shown in figure 6. Prepared Co 3 O 4 The @ NF nanosheet material can be subjected to electrochemical neutralization by using an acid-base asymmetric electrolytic cell to obtain Co 3 O 4 The @ NF nanosheet material is used as a working electrode, the purchased commercial platinum carbon is used as a counter electrode, the middle part of the working electrode is separated by a bipolar membrane, the anolyte is a mixed solution of 1M KOH +0.5M glycerol, and the catholyte is 0.5M H 2 SO 4 Initial potential (10 mA/cm) measured in a two-electrode system 2 ) 0.55V as shown in figure 7, surpasses the voltage required in the traditional electrolytic cell, and greatly reduces the energy consumption of the electrocatalytic reaction.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

1. A non-noble metal catalyst for hydrogen production assisted by glycerol oxidation is characterized in that: mixing Co 3 O 4 The catalyst grows on the foamed nickel substrate, the preparation method includes the following steps:
step one, pretreating a foamed nickel substrate;
respectively carrying out ultrasonic treatment on the cut foam nickel in hydrochloric acid, absolute ethyl alcohol and deionized water for 10 minutes to carry out pretreatment on the foam nickel;
step two, co 3 O 4 Preparation of @ NF;
respectively dissolving cobalt nitrate hexahydrate and 2-methylimidazole in methanol to obtain a solution A and a solution B, uniformly stirring, and mixing and stirring the solution A and the solution B to obtain a solution C;
then the solution C and clean foam nickel react for 12 hours at 140 ℃ in a reaction kettle, and Co growing on the foam nickel is obtained by washing, vacuum drying and calcining in the air atmosphere 3 O 4 A catalyst;
in the second step, the mass concentration of the cobalt nitrate hexahydrate solution in the solution A is 210-220 g/L;
in the second step, the mass concentration of the 2-methylimidazole in the solution B is 8.1-8.3 g/L;
and the volume ratio of the solution A to the solution B in the second step is 1.
2. The non-noble metal catalyst for hydrogen production assisted by glycerol oxidation as set forth in claim 1, wherein: the preferred size of the nickel foam in step one is 2cm x 3cm.
3. The non-noble metal catalyst for hydrogen production assisted by glycerol oxidation as claimed in claim 1, wherein: the concentration of the hydrochloric acid solution in the first step is 3M.
4. The non-noble metal catalyst for hydrogen production assisted by glycerol oxidation as claimed in claim 1, wherein: in the second step, the solution A and the solution B need to be stirred for 15-20min.
5. The non-noble metal catalyst for hydrogen production assisted by glycerol oxidation as claimed in claim 1, wherein: and in the second step, the solution C needs to be stirred for 3-5min.
6. The non-noble metal catalyst for hydrogen production assisted by glycerol oxidation as set forth in claim 1, wherein: and in the second step, methanol and absolute ethyl alcohol are used for washing in the ultrasonic machine for 20s three times respectively in the washing process.
7. The non-noble metal catalyst for hydrogen production assisted by glycerol oxidation as claimed in claim 1, wherein: and in the second step, the temperature is raised to 350 ℃ at the rate of 2 ℃ per minute in the calcining process in the middle tube type furnace, and the temperature is kept for 2 hours.
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