CN114525519A - Preparation method and application of non-noble metal alkaline electrolyzed water catalyst - Google Patents

Preparation method and application of non-noble metal alkaline electrolyzed water catalyst Download PDF

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CN114525519A
CN114525519A CN202210146717.1A CN202210146717A CN114525519A CN 114525519 A CN114525519 A CN 114525519A CN 202210146717 A CN202210146717 A CN 202210146717A CN 114525519 A CN114525519 A CN 114525519A
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preparation
autoclave
nife
carbon paper
noble metal
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刘进轩
王慧
方敏
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Nanjing Junbo Technology Co ltd
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Nanjing Junbo Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—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
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
    • 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

A preparation method and application of a non-noble metal alkaline electrolyzed water catalyst belong to the technical field of electrochemical energy storage materials. The preparation method comprises the following steps: respectively dissolving and dispersing gallic acid monohydrate, nickel chloride hexahydrate and ferrous chloride tetrahydrate in a KOH aqueous solution; transferring the mixed solution into a reaction kettle, vertically putting the carbon paper into the reaction kettle, sealing, heating, reacting, and naturally cooling; taking out the carbon paper, washing with deionized water and ethanol, and finally vacuum drying. In a standard three-electrode system, the prepared electrocatalyst is directly used as a working electrode and placed in 1M KOH electrolyte for electrocatalytic oxygen evolution reaction. The prepared electrocatalyst has excellent OER activity and good cycling stability under high current density.

Description

Preparation method and application of non-noble metal alkaline electrolyzed water catalyst
Technical Field
The invention belongs to the technical field of electrochemical energy storage materials, and relates to a preparation method and a post-treatment method of Metal Organic Frameworks (MOFs), wherein an electrocatalyst with high activity and high conductivity is obtained based on loading of nickel-iron-based MOF on Carbon Paper (CP).
Background
Human survival and development are closely related to the continuous supply of energy. The increasing consumption of fossil fuels severely pollutes the environment, prompting significant research interest in seeking clean, renewable and sustainable alternatives. Hydrogen energy is considered one of the most potential energy carriers for fossil energy. Electrochemical water splitting is a promising strategy for producing new clean hydrogen fuels. Noble metals such as Ru and Ir based catalysts have been identified as highly efficient electrocatalysts, but their scarcity, high cost and low stability severely limit their applications. Therefore, the development of the electrocatalyst without noble metal materials is of great significance for realizing large-scale commercialization of the water electrolysis technology.
Among the numerous transition metal-based alternatives, the metal-organic framework (MOF) has attracted considerable interest in recent years as a family of porous crystalline materials formed by metal ion (or cluster) centers and organic linkers. MOFs have the characteristics of homogeneous and heterogeneous catalysts due to the unique structure, the high surface area of the MOFs is favorable for exposing more active sites, and the porous structure can realize rapid mass transfer. In addition, the MOFs material can be conveniently recycled after reaction in physical and chemical states due to high crystallinity. However, most of the bulk MOFs still have the problems of slow mass permeability, poor conductivity, and limited metal active sites in the electrocatalytic reaction, which greatly limits their performance as electrocatalysts. Therefore, in order to improve the electrocatalytic properties of MOFs, materials are converted into various metal compounds or porous carbon nanocomposites through pyrolysis/chemical reactions. The disadvantage is that the above method may agglomerate the metal ions into nanoparticles or destroy the pore structure of the MOFs, thereby severely losing the metal active sites of the electrocatalyst. In such a context, from the viewpoint of the structural tunability of MOFs, it can be directly used as a water decomposition electrocatalyst without additional treatment. However, as a highly efficient water-splitting catalyst, how to reduce the overpotential of the reaction remains a great challenge to researchers.
Disclosure of Invention
In light of the technical problems, the invention aims to provide a preparation method of a NiFe-MOF electrocatalyst, which has simple pretreatment, cheap and easily-obtained raw materials and mild conditions.
An MOFs electrode, NiFe-GA is uniformly grown on a Carbon Paper (CP) substrate through one-step hydrothermal reaction; GA is gallic acid) and is directly used for an electrocatalytic reaction electrode.
The technical means adopted by the invention are as follows:
a preparation method of a non-noble metal alkaline electrolyzed water catalyst comprises the following steps:
(1) cleaning the conductive substrate carbon paper, and drying;
(2) gallic acid monohydrate (GA, 2-4 mmol), nickel chloride hexahydrate (NiCl)2·6H2O, 0-2 mmol) and ferrous chloride tetrahydrate (FeCl)2·4H2O, 0-2 mmol) are respectively dissolved in KOH aqueous solution and treated by ultrasonic;
(3) transferring the mixture into a Teflon-lined 15mL stainless steel autoclave, vertically placing CP into the autoclave, then sealing the autoclave and maintaining at 100-130 ℃ for 12-24 hours;
(4) after the autoclave is naturally cooled, taking the CP out of the autoclave and washing the CP with deionized water and ethanol to remove weakly adsorbed catalyst and impurities;
(5) the obtained sample was dried in a vacuum oven at 60 ℃.
Further, the carbon paper is cut into areas: 2 x 2cm2(ii) a Thickness: 0.28mm, and sequentially carrying out ultrasonic treatment in the prepared 1M HCl, acetone, deionized water and absolute ethyl alcohol for 20-30 minutes.
Furthermore, gallic acid monohydrate is dissolved in a prepared KOH aqueous solution (5mL, 0.06-0.16M), nickel chloride hexahydrate and ferrous chloride tetrahydrate are respectively dissolved in a prepared KOH aqueous solution (2.5mL, 0.06-0.16M), and ultrasonic treatment is carried out for 20-30 minutes.
Further, slowly raising the temperature under the hydrothermal condition, and keeping the temperature for 12-24 hours at 120 ℃.
Further, the high-pressure autoclave is naturally cooled to 30-40 ℃ in an oven, and the front and back surfaces of the CP are respectively washed three times by deionized water and ethanol after being clamped out by a pair of tweezers, so that impurities and the catalyst with weak adhesive force are removed.
And further, drying the washed CP in a vacuum drying oven for 6-12 hours.
Furthermore, the ultrasonic frequency of the used ultrasonic equipment is 50-53 KHz.
The invention also provides application of the catalyst prepared by the preparation method of the MOFs directly as an electrocatalyst, wherein in a standard three-electrode system (Hg/HgO is used as a reference electrode, a platinum wire is used as a counter electrode and a working electrode), the MOFs electrocatalyst is directly used for placing the working electrode in electrolyte to carry out electrocatalytic water decomposition Oxygen Evolution Reaction (OER).
Further, the electrolyte adopts a prepared 1M KOH solution.
The invention adopts a one-pot hydrothermal method, fully mixes the pretreated CP, gallic acid suspension and metal salt suspension, and then puts them into a Teflon stainless steel high-pressure kettle for heating reaction, so as to synthesize the transition metal-based MOFs material, without high-temperature calcination post-treatment, without destroying the special structure of the MOFs material, and directly used for water decomposition reaction.
Compared with the prior art, the invention has the following advantages:
1. the transition metal-based MOFs electrocatalyst prepared by the invention can uniformly grow in situ on carbon paper, does not need to drip a binder required by an electrode, and can be directly used as an electrode material without high-temperature post-treatment.
2. The one-pot hydrothermal method is a method for preparing a material by dissolving or dispersing and recrystallizing powder in an aqueous solution as a solvent in a sealed container which is self-generating in pressure. Compared with a vacuum coating and ball milling method which requires a complex operation synthesis process and an expensive chemical vapor deposition method supported by equipment, the one-pot hydrothermal method has the advantages of low cost, simplicity and convenience in operation, controllable preparation process and the like, and has great advantages in the aspect of material preparation.
3. The electrochemical performance is an important index for evaluating the quality of the electrocatalyst. In a 1M KOH system, NiFe-GA-CP is at 10mA cm-2And 100 mA-cm-2Has a smaller over-potential at the current density of (a),the NiFe-GA-CP has a large active surface area and small impedance, accelerates a charge transfer process, and shows excellent OER activity. NiFe-GA-CP at 10mA cm-2And 100mA · cm-2The stability is more than 60 hours under the high current density, and before and after the stability test, the electrochemical performance is not obviously reduced, which shows that the electrochemical stability is good.
In conclusion, the method for preparing the three-dimensional self-supporting material by the one-pot hydrothermal method is simple and easy to operate, does not need subsequent high-temperature treatment, and is easy for large-scale production; the prepared material has obvious advantages in the aspects of catalytic oxygen evolution reaction and energy conversion, and the prepared composite material has very small overpotential and excellent electrochemical stability under high current density in the OER process.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments will be briefly described below.
FIG. 1 shows the X-ray diffraction pattern of a metal organic framework compound NiFe-GA-CP prepared by a hydrothermal method.
FIG. 2 shows a Fourier transform infrared spectrum of a metal organic framework compound NiFe-GA prepared by a hydrothermal method.
FIG. 3 is a scanning electron microscope image of a metal organic framework compound NiFe-GA-CP prepared by a hydrothermal method.
FIG. 4 is a transmission electron microscope image of a metal organic framework compound NiFe-GA-CP prepared by a hydrothermal method.
FIG. 5 shows the EDS spectrum of a metallo-organic framework NiFe-GA-CP prepared by a hydrothermal method.
FIG. 6 (a) is the LSV curve of the metal organic framework compound NiFe-GA-CP prepared by hydrothermal method and its comparative sample; (b) the metal organic frame compound NiFe-GA-CP prepared by a hydrothermal method and the Tafel slope of a comparison sample thereof; (c) an impedance diagram of a metal organic framework compound NiFe-GA-CP prepared by a hydrothermal method and a comparison sample thereof; (d) is the active surface area of a metal organic framework compound NiFe-GA-CP prepared by a hydrothermal method and a comparison sample thereof.
FIG. 7 shows the i-t test for a metallo-organic framework compound NiFe-GA-CP prepared by a hydrothermal method.
FIG. 8 is an LSV curve before and after i-t testing of NiFe-GA-CP
FIG. 9 shows the X-ray diffraction pattern of NiFe-GA-CP after OER reaction.
FIG. 10 is a scanning electron micrograph of NiFe-GA-CP after OER reaction.
FIG. 11 is a transmission electron micrograph of NiFe-GA-CP after i-t testing.
Detailed Description
In order that the invention may be more readily understood, the following examples are preferred and the accompanying drawings are included for the purpose of illustrating the invention. The starting materials are available from open commercial sources unless otherwise specified.
EXAMPLE 1 preparation of non-noble Metal alkaline electrolyzed Water catalyst
Mixing Carbon Paper (CP) (area: 2 × 2 cm)2(ii) a Thickness: 0.28mm) are sequentially soaked in 1M HCl, acetone, deionized water and absolute ethyl alcohol for 30 minutes by ultrasonic treatment to remove impurities attached to the surface;
keeping the CP in a vacuum drying oven at 60 ℃ for 6 hours to enable the carbon paper to be in a dry state;
gallic acid monohydrate (GA,4mmol) was dispersed and dissolved in KOH aqueous solution (5mL, 0.16M), nickel chloride hexahydrate (NiCl)2·6H2O,1.75mmol) and iron (II) chloride tetrahydrate (FeCl)2·4H2O,0.25mmol) was dissolved in KOH aqueous solution (2.5mL, 0.16M), respectively, and sonicated for 30 minutes until completely dispersed in KOH solution;
the mixture was quickly transferred to a teflon lined 15mL stainless steel autoclave and CP was placed vertically in the autoclave;
sealing the high-pressure kettle, slowly heating to 120 ℃ at the heating rate of 2 ℃/min, keeping the temperature at 120 ℃ for 24 hours, and naturally cooling to room temperature;
taking out the CP from the autoclave and washing the CP with deionized water and ethanol for three times respectively to remove weakly adsorbed catalyst and impurities;
the obtained sample was kept at 60 ℃ under vacuum for 12 hours.
Comparative example GA-Ni
Using the method of example 1, the mixture was simply replaced as follows: gallic acid monohydrate (GA,4mmol) was dispersed and dissolved in KOH aqueous solution (5mL, 0.16M), nickel chloride hexahydrate (NiCl)2·6H2O,2mmol) was dissolved in aqueous KOH (5mL, 0.16M) and sonicated for 30 minutes until completely dispersed in KOH solution.
Comparative example GA-Fe
Using the method of example 1, the mixture was simply replaced as follows: gallic acid monohydrate (GA,4mmol) was dispersed and dissolved in KOH aqueous solution (5mL, 0.16M), iron (II) chloride tetrahydrate (FeCl)2·4H2O,2mmol) were dissolved in aqueous KOH solution (5mL, 0.16M), and sonicated for 30 minutes until completely dispersed in KOH solution.
EXAMPLE 2 use of the Water Electrolysis catalyst
The application of the non-noble metal basic electrolyzed water catalyst in the example 1 in the electrocatalytic water decomposition OER comprises the following steps:
(1) preparation of working electrode
Shearing the prepared dried NiFe-GA-CP into 1 × 2cm2Directly to the working electrode;
(2) electrocatalytic oxygen evolution reaction
All electrochemical tests were performed at room temperature in a conventional three-electrode system using Pt wire as the counter electrode, the prepared catalyst and comparative sample as the working electrode, and Hg/HgO electrode as the reference electrode. 1M KOH was used as the electrolyte for all electrochemical tests. Before the electrochemical OER test, the electrodes were activated by CV for 10 cycles at a sweep rate of 50 mV. multidot.s-1。
Example 3
(1) Characterization before NiFe-GA-CP catalytic reaction
As can be seen from the XRD pattern of fig. 1, NiFe-GA-CP showed the same XRD pattern as NiFe-GA powder and simulated NiFe-GA except that the peak at 2 θ ═ 26.5 ° was from carbon paper. In FIG. 2, a Fourier transform infrared (FT-IR) spectrum was used to characterize NiFe-GA. Upsilon of GAOHAnd upsilonC＝OAt 3480, 3350, 3270cm-1And 1695cm-1The peak at (A) completely disappeared in NiFe-GA, indicating that carboxyl and hydroxyl groups are coordinated with Ni and Fe. The above results, combined, strongly demonstrate the successful production of NiFe-GA on carbon paper. In FIG. 3, a Scanning Electron Microscope (SEM) in which the carbon paper was covered with honeycomb hexagonal prism-shaped NiFe-GA, and a Transmission Electron Microscope (TEM) in FIG. 4 also confirmed the unique prism structure of NiFe-GA. The elemental analysis of FIG. 5 reveals that C, O, Fe and Ni elements are uniformly distributed in the NiFe-GA electrocatalyst.
(2) NiFe-GA-CP electrochemical test
The electrochemical performance is an important index for evaluating the quality of the electrocatalyst, and the LSV shown in (a) of FIG. 6 shows that the NiFe-GA-CP is 10mA cm-2And 100mA · cm-2The overpotentials of (1) were 185 and 236mV, respectively, which are significantly better than the reference terms (Ni-GA-CP, Fe-GA-CP, and CP). (b) The medium NiFe-GA-CP has the minimum Tafel slope of 28.74mV dec-1Indicating faster OER kinetics. (c) In (d), NiFe-GA-CP has a small impedance and a large active surface area, which accelerates the electron transfer process, exhibiting excellent OER activity. In fig. 7, the excellent high-current stability of the catalyst is shown, and after stability test, the electrochemical performance is not obviously reduced, which shows that the catalyst has potential application value as an industrial hydrogen production electrocatalyst.
(3) Characterization after electrochemical testing of NiFe-GA-CP
As can be seen from the X-ray diffraction spectra and the scanning electron microscope of FIGS. 9 and 10, the structure and the morphology of NiFe-GA-CP are not significantly changed after the electrochemical OER test, which indicates the good structural stability of the NiFe-GA-CP as an electrocatalyst.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (2)

1. A preparation method of a non-noble metal alkaline electrolyzed water catalyst is characterized in that NiFe-MOF is uniformly grown on a conductive substrate through solvothermal reaction, and is directly used as an electrocatalytic material after being cleaned by ethanol and deionized water and dried;
the method specifically comprises the following steps:
(1) cleaning the conductive substrate carbon paper, and drying;
(2) respectively dissolving gallic acid monohydrate, nickel chloride hexahydrate and ferrous chloride tetrahydrate in KOH aqueous solution, and performing ultrasonic treatment to obtain a mixed solution;
the concentration of gallic acid monohydrate in the mixed solution is 0.06-0.16M, the concentration of nickel chloride hexahydrate is 0.06-0.16M, and the concentration of ferrous chloride tetrahydrate is 0.06-0.16M;
(3) transferring the mixed solution into a Teflon-lined stainless steel autoclave, vertically putting a conductive substrate into the autoclave, sealing the autoclave and keeping the autoclave at 100-130 ℃ for 12-24 hours;
(4) and naturally cooling the autoclave, taking out, cleaning and drying to obtain the electro-catalytic material.
2. The electrocatalytic material prepared by the preparation method according to claim 1 is applied to electrocatalytic water decomposition oxygen analysis reaction.
CN202210146717.1A 2022-02-17 2022-02-17 Preparation method and application of non-noble metal alkaline electrolyzed water catalyst Pending CN114525519A (en)

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Application publication date: 20220524