CN117463363A - Preparation method of carbon cloth supported nickel-palladium nano catalyst and solid hydrogen storage application thereof - Google Patents

Preparation method of carbon cloth supported nickel-palladium nano catalyst and solid hydrogen storage application thereof Download PDF

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CN117463363A
CN117463363A CN202311502449.3A CN202311502449A CN117463363A CN 117463363 A CN117463363 A CN 117463363A CN 202311502449 A CN202311502449 A CN 202311502449A CN 117463363 A CN117463363 A CN 117463363A
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carbon cloth
nickel
palladium
hydrogen storage
nano catalyst
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李永涛
秦智康
李海文
斯庭智
柳东明
张庆安
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Anhui University of Technology AHUT
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Anhui University of Technology AHUT
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • Y02E60/32—Hydrogen storage

Abstract

The invention provides a preparation method of a carbon cloth supported nickel-palladium nano catalyst and a solid hydrogen storage application thereof, and relates to the technical field of new energy solid hydrogen storage. The preparation method of the carbon cloth supported nickel-palladium nano catalyst comprises the following steps: and (3) immersing the carbon cloth in a nickel-palladium bimetallic salt precursor solution, drying after the immersion is finished, carrying out electrifying treatment on the obtained carbon cloth in a protective atmosphere, and carrying out heat treatment and cooling in sequence while carrying out electrifying treatment to obtain the carbon cloth supported nickel-palladium nano catalyst. The preparation method disclosed by the invention has the advantages of simple process, environment-friendly raw materials and easiness in large-scale production, and the prepared carbon cloth supported palladium-nickel nano catalyst and magnesium hydride are mixed to form the composite hydrogen storage system, so that the hydrogen storage performance of the magnesium hydride can be effectively improved, and meanwhile, the preparation method has higher cycle stability and wide application prospect in the field of new energy solid hydrogen storage.

Description

Preparation method of carbon cloth supported nickel-palladium nano catalyst and solid hydrogen storage application thereof
Technical Field
The invention relates to the technical field of new energy solid-state hydrogen storage, in particular to a preparation method of a carbon cloth supported nickel-palladium nano catalyst and a solid-state hydrogen storage application thereof.
Background
Hydrogen has attracted considerable attention as a clean and versatile energy carrier as a potential solution to the global challenges presented by climate change and energy sustainability. The use of hydrogen in fuel cells, transportation and industrial processes is expected to radically change energy systems, reduce greenhouse gas emissions and rely on fossil fuels. However, efficient storage of hydrogen remains a key bottleneck for its widespread use.
Solid-state hydrogen storage, especially metal hydride hydrogen storage, has high volume and gravity hydrogen storage capacity, has potential of safe application, and provides a method with wide prospect. In various metal hydride systems, magnesium hydride (MgH 2 ) Has become an ideal candidate for hydrogen storage applications. MgH (MgH) 2 The theoretical hydrogen storage capacity of the catalyst is as high as 7.6wt%, the raw materials are rich, and the cost is relatively low. In addition, magnesium has the characteristics of no toxicity, nonflammability and low reactivity, so that magnesium is an attractive hydrogen storage material from the viewpoint of safety. However, mgH 2 The practical use of (a) faces challenges such as slow kinetics and the higher thermodynamics required for hydrogen absorption and desorption. The strong chemical bond between magnesium and hydrogen typically results in pure MgH 2 The decomposition temperature of (2) is higher than 350 ℃, and the slow diffusion rate of H atoms in the hydride can also lead to MgH 2 The decomposition temperature of (2) is higher than 350 ℃.
To overcome theseThe challenge is that many approaches have been taken to improve the performance of hydrogen storage magnesium hydrides. Catalytic doping has become a powerful and efficient strategy at present. Especially under the decoration of transition metals (such as Ni, ti and Co), the catalyst is doped to form intermediate phase during reaction to reduce MgH 2 Further promoting absorption and desorption of hydrogen. In fact, the catalytic effect of a single transition metal is limited, and doping a second transition metal element to form a bimetallic catalyst can make up for the deficiency, realize a synergistic effect and further improve the catalytic effect of the hydrogen storage system. In addition, the preparation of the catalyst affects the apparent morphology and structural characteristics of the catalyst itself, in which case the selection of an appropriate catalyst support, the reduction of the particle size of the catalyst to the nanometer level, and the like are also considered to be other effective methods. In order to diffuse and distribute the catalyst and avoid agglomeration, different carbon materials are generally selected as growth carriers of the metal nano-catalyst so as to promote preferential nucleation of the catalyst on the surface of a host. For example, patent CN115301240A discloses a carbon-coated CoNi bimetallic hydrogen storage catalyst, a preparation method and application thereof, wherein the carbon-coated CoNi catalyst is obtained by organic thermal decomposition and the rest MgH is obtained 2 Compounding to a great extent promote MgH 2 Hydrogen storage performance, but the catalyst preparation time is too long, the conditions are complicated, and the flow is complex.
Aiming at the problems, a simple and rapid method for synthesizing the nano catalyst with good dispersion and uniform components is developed, so that the process cost is reduced and MgH is improved 2 Hydrogen storage properties are necessary.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon cloth supported nickel-palladium nano catalyst and a solid hydrogen storage application thereof, so as to solve the problems in the prior art. Aiming at the defects that metal nano particles are easy to agglomerate, component segregation is easy to prepare and the preparation is complex in the catalyst preparation process, the invention provides a preparation method of a carbon cloth supported nickel-palladium nano catalyst, carbon cloth with good conductivity is used as a growth carrier, palladium-nickel bimetallic salt precursor is adopted for impregnation, and strong current is introduced, and rapid heating and cooling are carried out to obtain uniform negative carbon clothThe method of the invention can realize the controllable catalyst components of the supported nickel-palladium nano catalyst, thereby being used in MgH 2 The hydrogen storage reaction of the catalyst has good catalytic activity, and particularly the absorption and desorption kinetics and the circulation stability are obviously improved.
In order to achieve the above object, the present invention provides the following solutions:
one of the technical schemes of the invention is as follows: the preparation method of the carbon cloth supported nickel-palladium nano catalyst comprises the following steps:
and (3) immersing the carbon cloth in a nickel-palladium bimetallic salt precursor solution, drying after the immersion is finished, carrying out electrifying treatment on the obtained carbon cloth in a protective atmosphere, and carrying out heat treatment and cooling in sequence while carrying out electrifying treatment to obtain the carbon cloth supported nickel-palladium nano catalyst.
As a further preferred aspect of the present invention, the total concentration of nickel-palladium bimetal in the nickel-palladium bimetal salt precursor solution is 0.05mol/L, and the molar ratio of nickel to palladium is 0.9:0.1-0.25:0.75.
The nickel-palladium bimetallic salt precursor solution is prepared by dissolving palladium salt and nickel salt in a solvent; the palladium salt is any one of palladium chloride, palladium nitrate and palladium sulfate; the nickel salt is any one of nickel chloride, nickel nitrate and nickel sulfate;
the solvent is preferably an ethanol-based solvent; more preferably a solvent having a volume ratio of ethanol to water of 48:2.
As a further preferred aspect of the present invention, the heat treatment is performed by: maintaining at 1300-1500 deg.c for 30-120 s; the cooling mode is as follows: cooling from 1300-1500 ℃ to room temperature within 5 s. The room temperature according to the invention is 25 ℃.
As a further preferred aspect of the present invention, the energizing process is a direct current process, the current intensity is 375A, the pulse period is 100ms, and the duty ratio is 50%.
As a further preferred aspect of the present invention, the carbon cloth is pretreated; the step of preprocessing comprises the following steps: and (3) treating the carbon cloth for 0.5-1h at the temperature of 100-300 ℃ under the condition of hydrogen pressure. Preferably, the hydrogen pressure is 2-4MPa.
The pretreatment of the carbon cloth can remove impurities and hydrophilic groups on the surface of the carbon cloth, and prevent the components and the performance of the catalyst from being influenced in subsequent reactions; the hydrogen atmosphere heat treatment can thoroughly remove the surface groups of the carbon cloth.
As a further preferred aspect of the present invention, the drying temperature is 80℃and the time is 4 to 6 hours.
The technical scheme of the invention can realize the rapid preparation of the nickel-palladium nano catalyst, and the more preferable technical scheme comprises the following steps:
step one, mixing and dissolving palladium salt and nickel salt in ethanol-based solution according to a molar ratio, wherein the concentration of the solution is 0.05mol/L, and then magnetically stirring (300-600 r/min) for 4-6h to obtain nickel-palladium bimetallic salt precursor solution;
step two, cleaning the carbon cloth with ethanol, standing and airing, and then carrying out high-temperature pretreatment for 0.5-1h at 100-300 ℃ under the condition of 2-4Mpa hydrogen pressure;
cutting the pretreated carbon cloth into small pieces with the size of 2cm multiplied by 5cm, immersing the small pieces in a nickel-palladium bimetallic salt precursor solution, and then carrying out vacuum drying treatment at 80 ℃ for 4-6 hours;
fixing the treated carbon cloth by using graphite sheets and connecting the carbon cloth with graphite electrodes at two ends;
and fifthly, switching on current (direct current, current intensity is 375A, pulse period is 100ms, duty ratio is 50%) under protective atmosphere, maintaining the temperature at 1300-1500 ℃ for 30-120 s, and then cooling the temperature from 1300-1500 ℃ to room temperature within 5 s.
The second technical scheme of the invention is as follows: the carbon cloth supported nickel-palladium nano catalyst prepared by the preparation method is provided.
The third technical scheme of the invention: the application of the carbon cloth supported nickel-palladium nano catalyst in catalyzing the hydrogen storage performance of magnesium hydride is provided.
The fourth technical scheme of the invention: a composite hydrogen storage system is provided, which comprises the carbon cloth supported nickel-palladium nano catalyst and magnesium hydride.
As a further preferred aspect of the present invention, the composite hydrogen storage system is prepared from the carbon cloth supported nickel palladium nano catalyst based magnesium hydride according to a mass ratio of 25:75, mixing and ball milling under a protective atmosphere.
More preferably, the ball-material ratio of the mixed ball mill is 40:1, the ball milling rotating speed is 400r/min, and the ball milling time is 10h.
The invention discloses the following technical effects:
the invention synthesizes the carbon cloth supported palladium-nickel nano catalyst with average size of 20-40 nm by adopting a carbon carrier thermal shock method and uniform dispersion. The catalyst preparation method disclosed by the invention is simple in process, environment-friendly in raw materials, easy for large-scale production, and high in popularization and application value in the aspect of catalyzing solid hydrogen storage of magnesium hydride.
The carbon cloth supported palladium-nickel nano catalyst prepared by the method is mixed with magnesium hydride to form a composite hydrogen storage system, so that the hydrogen storage performance of the magnesium hydride can be effectively improved, and meanwhile, the carbon cloth supported palladium-nickel nano catalyst has higher cycle stability and has wide application prospect in the field of new energy solid hydrogen storage.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a carbon cloth supported nickel palladium nano-catalyst prepared by adopting carbon thermal shock;
FIG. 2 is an XRD spectrum of a carbon cloth supported palladium-nickel nanocatalyst prepared in examples 1-4 of the invention;
FIG. 3 is a thermogravimetric TG curve of the carbon cloth supported palladium-nickel nanocatalysts prepared in examples 1-4 of the invention;
FIG. 4 is an XRD finishing curve of the carbon cloth supported palladium-nickel nanocatalysts prepared in examples 1-4 of the invention; wherein (a) is Ni prepared in example 4 0.25 Pd 0.75 (c) prepared in example 2Ni 0.75 Pd 0.25 @ CC, (c) is Ni prepared in example 3 0.50 Pd 0.50 @ CC, (d) is Ni prepared in example 1 0.90 Pd 0.10 @CC；
FIG. 5 is an SEM image of a carbon cloth-supported palladium-nickel nanocatalyst prepared according to examples 1-4 of the invention; wherein, (a) is Ni prepared in example 4 0.25 Pd 0.75 @ CC, (b) is Ni prepared in example 3 0.50 Pd 0.50 (c) is Ni prepared in example 2 0.75 Pd 0.25 @ CC, (d) is Ni prepared in example 1 0.90 Pd 0.10 @CC；
FIG. 6 is a graph showing the temperature rise and hydrogen release of the composite hydrogen storage systems prepared in examples 1-4 and comparative examples 1-3 according to the present invention;
FIG. 7 is a constant temperature hydrogen release graph of the composite hydrogen storage systems prepared in examples 1-4 and comparative examples 1-3 of the present invention;
FIG. 8 is a graph showing the constant temperature hydrogen absorption of the composite hydrogen storage systems prepared in examples 1-4 and comparative examples 1-3 according to the present invention;
FIG. 9 is a JMAK curve and Arrhenius curve of the composite hydrogen storage system prepared in examples 1-4 of the present invention; wherein the figures (a) - (d) are MgH respectively 2 -Ni 0.90 Pd 0.10 @CC、MgH 2 -Ni 0.75 Pd 0.25 @CC、MgH 2 -Ni 0.50 Pd 0.50 @CC、MgH 2 -Ni 0.25 Pd 0.75 JMAK curve at CC; graphs (e) - (h) are MgH respectively 2 -Ni 0.90 Pd 0.10 @CC、MgH 2 -Ni 0.75 Pd 0.25 @CC、MgH 2 -Ni 0.50 Pd 0.50 @CC、MgH 2 -Ni 0.25 Pd 0.75 Arrhenius curve @ CC;
FIG. 10 shows MgH prepared in example 1 of the present invention 2 -Ni 0.90 Pd 0.10 A cyclic stability diagram of the @ CC composite hydrogen storage system;
FIG. 11 shows MgH prepared in comparative example 3 of the present invention 2 Cycling stability profile of the hydrogen storage system.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
FIG. 1 is a flow chart of the preparation of a carbon cloth supported nickel palladium catalyst by using carbon thermal shock.
Example 1
Preparation of carbon cloth supported nickel-palladium nano catalyst (molar ratio of nickel to palladium is 0.9:0.1) and composite hydrogen storage system:
preparing a carbon cloth supported nickel-palladium nano catalyst:
firstly, precisely weighing 0.2916g of nickel chloride and 0.0443g of palladium chloride, adding the nickel chloride and the palladium chloride into an alcohol-based solution consisting of 48ml of ethanol and 2ml of distilled water, controlling the total metal molar concentration in the solution to be 0.05mol/L, and stirring the solution for 6 hours at a rotating speed of 500r/min by using a magnetic stirrer to obtain a nickel-palladium bimetallic salt precursor solution;
step two, washing the carbon cloth with ethanol, standing, airing, then pressing with hydrogen at 4MPa, heating to 100 ℃, and continuously treating for 0.5h;
cutting the pretreated carbon cloth into small pieces with the size of 2cm multiplied by 5cm, immersing in 3ml of nickel-palladium bimetallic salt precursor solution, and controlling the immersion density to 300 mu L/cm 2 Then vacuum drying treatment is carried out for 6 hours at 80 ℃;
fixing the treated carbon cloth by using graphite sheets and connecting the carbon cloth with graphite electrodes at two ends;
step five, switching on 375A current under protective atmosphere, wherein the pulse period is 100ms, the duty ratio is 50%, the temperature is kept at 1300 ℃ for 30s, and then the Ni can be obtained by using 5s of time to rapidly cool to room temperature 0.90 Pd 0.10 Catalyst @ CC.
Preparation of a composite hydrogen storage system:
ni in example 1 0.90 Pd 0.10 Catalyst @ CC and MgH 2 According to the mass ratio of 25:75 ball milling is carried out under a protective atmosphere, the ball-milling ball-material ratio is 40:1, the ball milling rotating speed is 400r/min, the ball milling time is 10h, and MgH is obtained 2 -Ni 0.90 Pd 0.10 A @ CC composite hydrogen storage system.
Example 2
Preparation of carbon cloth supported nickel-palladium nano catalyst (molar ratio of nickel to palladium is 0.75:0.25) and composite hydrogen storage system:
preparing a carbon cloth supported nickel-palladium nano catalyst:
firstly, precisely weighing 0.2430g of nickel chloride and 0.1108g of palladium chloride, adding the nickel chloride and the 0.1108g of palladium chloride into an alcohol-based solution consisting of 48ml of ethanol and 2ml of distilled water, controlling the total metal molar concentration in the solution to be 0.05mol/L, and stirring the solution for 6 hours at a rotating speed of 500r/min by using a magnetic stirrer to obtain a nickel-palladium bimetallic salt precursor solution;
step two, washing the carbon cloth with ethanol, standing, airing, then pressing with hydrogen at 4MPa, heating to 100 ℃, and continuously treating for 0.5h;
cutting the pretreated carbon cloth into small pieces with the size of 2cm multiplied by 5cm, immersing in 3ml of nickel-palladium bimetallic salt precursor solution, and controlling the immersion density to 300 mu L/cm 2 Then vacuum drying treatment is carried out for 6 hours at 80 ℃;
fixing the treated carbon cloth by using graphite sheets and connecting the carbon cloth with graphite electrodes at two ends;
step five, switching on 375A current under protective atmosphere, wherein the pulse period is 100ms, the duty ratio is 50%, the temperature is kept at 1300 ℃ for 30s, and then the Ni can be obtained by using 5s of time to rapidly cool to room temperature 0.75 Pd 0.25 Catalyst @ CC.
Preparation of a composite hydrogen storage system:
ni in example 2 0.75 Pd 0.25 Catalyst @ CC and MgH 2 According to the mass ratio of 25:75 ball milling is carried out under a protective atmosphere, the ball-milling ball-material ratio is 40:1, the ball milling rotating speed is 400r/min, the ball milling time is 10h, and MgH is obtained 2 -Ni 0.75 Pd 0.25 A @ CC composite hydrogen storage system.
Example 3
Preparation of carbon cloth supported nickel-palladium nano catalyst (molar ratio of nickel to palladium is 0.50:0.50) and composite hydrogen storage system:
preparing a carbon cloth supported nickel-palladium nano catalyst:
firstly, precisely weighing 0.1620g of nickel chloride and 0.2217g of palladium chloride, adding the nickel chloride and the 0.2217g of palladium chloride into an alcohol-based solution consisting of 48ml of ethanol and 2ml of distilled water, controlling the total metal molar concentration in the solution to be 0.05mol/L, and stirring the solution for 6 hours at a rotating speed of 500r/min by using a magnetic stirrer to obtain a nickel-palladium bimetallic salt precursor solution;
step two, washing the carbon cloth with ethanol, standing, airing, then pressing with hydrogen at 4MPa, heating to 100 ℃, and continuously treating for 0.5h;
cutting the pretreated carbon cloth into small pieces with the size of 2cm multiplied by 5cm, and soaking in 3mlControlling the impregnation density to 300 mu L/cm in the nickel-palladium bimetallic salt precursor solution 2 Then vacuum drying treatment is carried out for 6 hours at 80 ℃;
fixing the treated carbon cloth by using graphite sheets and connecting the carbon cloth with graphite electrodes at two ends;
step five, switching on 375A current under protective atmosphere, wherein the pulse period is 100ms, the duty ratio is 50%, the temperature is kept at 1300 ℃ for 30s, and then the Ni can be obtained by using 5s of time to rapidly cool to room temperature 0.50 Pd 0.50 Catalyst @ CC.
Preparation of a composite hydrogen storage system:
ni in example 3 0.50 Pd 0.50 Catalyst @ CC and MgH 2 According to the mass ratio of 25:75 ball milling is carried out under a protective atmosphere, the ball-milling ball-material ratio is 40:1, the ball milling rotating speed is 400r/min, the ball milling time is 10h, and MgH is obtained 2 -Ni 0.50 Pd 0.50 A @ CC composite hydrogen storage system.
Example 4
Preparation of carbon cloth supported nickel-palladium nano catalyst (molar ratio of nickel to palladium is 0.25:0.75) and composite hydrogen storage system:
preparing a carbon cloth supported nickel-palladium nano catalyst:
firstly, precisely weighing 0.0810g of nickel chloride and 0.3325g of palladium chloride, adding the nickel chloride and the 0.3325g of palladium chloride into an alcohol-based solution consisting of 48ml of ethanol and 2ml of distilled water, controlling the total metal molar concentration in the solution to be 0.05mol/L, and stirring the solution for 6 hours at a rotating speed of 500r/min by using a magnetic stirrer to obtain a nickel-palladium bimetallic salt precursor solution;
step two, washing the carbon cloth with ethanol, standing, airing, then pressing with hydrogen at 4MPa, heating to 100 ℃, and continuously treating for 0.5h;
cutting the pretreated carbon cloth into small pieces with the size of 2cm multiplied by 5cm, immersing in 3ml of nickel-palladium bimetallic salt precursor solution, and controlling the immersion density to 300 mu L/cm 2 Then vacuum drying treatment is carried out for 6 hours at 80 ℃;
fixing the treated carbon cloth by using graphite sheets and connecting the carbon cloth with graphite electrodes at two ends;
step five, switching on under protective atmosphere375A current, pulse period of 100ms, duty cycle of 50%, holding at 1300deg.C for 30s, and rapidly cooling to room temperature for 5s to obtain Ni 0.25 Pd 0.75 Catalyst @ CC.
Preparation of a composite hydrogen storage system:
ni in example 4 0.25 Pd 0.75 Catalyst @ CC and MgH 2 According to the mass ratio of 25:75 ball milling is carried out under a protective atmosphere, the ball-milling ball-material ratio is 40:1, the ball milling rotating speed is 400r/min, the ball milling time is 10h, and MgH is obtained 2 -Ni 0.25 Pd 0.75 A @ CC composite hydrogen storage system.
The carbon cloth supported nickel palladium nanocatalysts prepared in examples 1-4 were structurally characterized:
FIG. 2 shows Ni rapidly prepared by thermal shock with carbon in examples 1 to 4 x Pd 1-x The X-ray diffraction pattern (XRD) of the catalyst @ CC (x=0.25, 0.5, 0.75, 0.90) shows that the invention successfully synthesizes the nickel-palladium nano catalyst supported by carbon cloth, meanwhile, the intensity of the main diffraction peak is regularly shifted to the left side with the increase of the Pd content, and meanwhile, no phase separation phenomenon is found, which indicates that Pd is successfully doped into the Ni matrix, resulting in lattice expansion, and that the nickel-palladium catalyst exists in the form of solid solution alloy.
FIG. 3 shows Ni rapidly prepared by thermal shock with carbon in examples 1 to 4 x Pd 1-x The thermal weight curve (TG) of the catalyst at the temperature of @ CC (x=0.25, 0.5, 0.75 and 0.90) shows that when the temperature reaches more than 450 ℃, the thermal decomposition of the carbon cloth causes rapid weight loss of the catalyst, and the final residual weight percentage is stabilized in the range of 17.1-23.8 wt%, namely Ni x Pd 1-x (x=0.25, 0.5, 0.75, 0.90) the loading of the catalyst on the carbon cloth.
FIG. 4 shows Ni rapidly prepared by thermal shock with carbon in examples 1 to 4 x Pd 1-x XRD refinement results of @ CC (x=0.25, 0.5, 0.75, 0.90) catalysts, the refinement results indicate Ni x Pd 1-x The phase content of (x=0.25, 0.5, 0.75, 0.90) was about 20wt%, which was consistent with TG results.
FIG. 5 is an implementationNi rapidly prepared by thermal shock with carbon in examples 1 to 4 x Pd 1-x Scanning electron microscope images (SEM) of catalysts @ CC (x=0.25, 0.5, 0.75, 0.90), which indicated Ni obtained by thermal shock with carbon x Pd 1-x (x=0.25, 0.5, 0.75, 0.90) catalyst uniformly grows and disperses well on carbon cloth, no agglomeration phenomenon occurs, and Ni 0.9 Pd 0.1 The growth effect of @ CC is preferably an average size of 28.6nm.
Comparative example 1 preparation of Single Nickel catalyst and composite Hydrogen storage System
Preparation of a single nickel catalyst:
firstly, precisely weighing 0.3240g of nickel chloride, adding the nickel chloride into an alcohol-based solution consisting of 48ml of ethanol and 2ml of distilled water, controlling the total metal molar concentration in the solution to be 0.05mol/L, and stirring the solution for 6 hours at a rotating speed of 500r/min by using a magnetic stirrer to obtain a precursor metal salt solution;
step two, washing the carbon cloth with ethanol, standing, airing, then pressing with hydrogen at 4MPa, heating to 100 ℃, and continuously treating for 0.5h;
cutting the pretreated carbon cloth into small pieces with the size of 2cm multiplied by 5cm, immersing the small pieces in 3ml of precursor solution, and controlling the immersion density to 300 mu L/cm 2 Then vacuum drying treatment is carried out at 80 ℃ for 6 hours;
fixing the treated carbon cloth by using graphite sheets and connecting the carbon cloth with graphite electrodes at two ends;
and fifthly, switching on 375A current under protective atmosphere, wherein the pulse period is 100ms, the duty ratio is 50%, the temperature is kept at 1300 ℃ for 30s, and then the temperature is quickly cooled to room temperature by using 5s, so that the Ni@CC catalyst can be obtained.
Preparation of a composite hydrogen storage system:
the Ni@CC catalyst of comparative example 1 and MgH 2 According to the mass ratio of 25:75 ball milling is carried out under a protective atmosphere, the ball-milling ball-material ratio is 40:1, the ball milling rotating speed is 400r/min, the ball milling time is 10h, and MgH is obtained 2 -Ni@CC composite hydrogen storage system.
Comparative example 2 preparation of carbon cloth doped MgH 2 Composite hydrogen storage system
Carbon clothAnd MgH 2 According to the mass ratio of 25:75 ball milling is carried out under a protective atmosphere, the ball-milling ball-material ratio is 40:1, the ball milling rotating speed is 400r/min, the ball milling time is 10h, and MgH is obtained 2 -a CC composite hydrogen storage system.
Comparative example 3 preparation of MgH 2 Hydrogen storage system
MgH is processed 2 Ball milling is carried out under the protective atmosphere, the ball-milling ball-material ratio is 40:1, the ball milling rotating speed is 400r/min, and the ball milling time is 10h, thus obtaining As-milled MgH 2 。
FIG. 6 shows MgH rapidly prepared by thermal shock with carbon in examples 1 to 4 2 -Ni x Pd 1-x Temperature rise hydrogen release curves of the composite hydrogen storage systems of @ CC (x=0.25, 0.5, 0.75, 0.90) and comparative examples 1 to 3, and the results show that MgH doped with nickel palladium catalyst 2 The composite hydrogen storage system exhibits a lower initial hydrogen desorption temperature, wherein MgH 2 -Ni 0.9 Pd 0.1 The effect of the @ CC composite material is optimal, the initial hydrogen release temperature is 486K and is far lower than MgH 2 577K of (a).
FIG. 7 shows MgH rapidly prepared by thermal shock with carbon in examples 1 to 4 2 -Ni x Pd 1-x Constant temperature hydrogen release curves of the composite hydrogen storage systems of @ CC (x=0.25, 0.5, 0.75, 0.90) and comparative examples 1 to 3, the results show that MgH doped with nickel palladium catalyst 2 The composite hydrogen storage system shows more excellent hydrogen release efficiency, wherein MgH 2 -Ni 0.9 Pd 0.1 The effect of the @ CC composite material is optimal, and only 7 minutes is needed for releasing hydrogen at 573K by 5.69wt%, which indicates that the doping of the nickel target catalyst reduces MgH 2 The dehydrogenation speed is accelerated, and the dehydrogenation efficiency is improved.
FIG. 8 shows MgH rapidly prepared by thermal shock with carbon in examples 1 to 4 2 -Ni x Pd 1-x Constant temperature hydrogen absorption curves of the composite hydrogen storage systems of @ CC (x=0.25, 0.5, 0.75, 0.90) and comparative examples 1 to 3, the results show that MgH doped with nickel palladium catalyst 2 The composite hydrogen storage system greatly improves the hydrogen absorption capacity at low temperature, wherein MgH 2 -Ni 0.9 Pd 0.1 The @ CC composite material has the best effect and can rapidly absorb 3.10wt% even at 373KIs a hydrogen gas of (a).
FIG. 9 shows MgH rapidly prepared by thermal shock with carbon in examples 1 to 4 2 -Ni x Pd 1-x JMAK curves and Arrhenius curves for @ CC (x=0.25, 0.5, 0.75, 0.90). The results show that MgH doped with nickel-palladium catalyst 2 The composite hydrogen storage system has low hydrogen release activation energy, wherein MgH 2 -Ni 0.9 Pd 0.1 The @ CC composite was reduced to 76.9kJ/mol.
FIGS. 10 to 11 are respectively the MgH rapidly prepared by thermal shock with carbon in example 1 2 -Ni 0.9 Pd 0.1 @ CC with MgH in comparative example 3 2 The results of the cyclic stability graph of (2) show that MgH 2 -Ni 0.9 Pd 0.1 The cycle stability of the @ CC composite material is most excellent, the hydrogen absorption amount and the hydrogen release amount after thirty cycles are carried out at 300 ℃ are 5.59 weight percent and 5.38 weight percent respectively, the hydrogen absorption capacity and the hydrogen release capacity retention rate are 97.7 percent and 95.6 percent respectively, and compared with MgH 2 The hydrogen absorption amount and the hydrogen release amount of the catalyst are only 4.06 percent and 4.03 percent, and the hydrogen absorption capacity and the hydrogen release capacity retention rate are only 65.5 percent and 62.5 percent, so that the composite material doped with the nickel target catalyst is obviously improved in cycle performance.
The composite hydrogen storage system of the invention shows excellent hydrogen storage performance, wherein MgH 2 -Ni 0.9 Pd 0.1 The performance of the @ CC system is optimal, and the initial hydrogen release temperature is compared with MgH 2 Reduces 577K of (2) to 486K, and can reach 5.69wt% of hydrogen release amount only in 7min at 573K, and simultaneously, the apparent dehydrogenation activation energy is 76.9kJ/mol, thereby remarkably reducing MgH 2 The dynamic barrier in the hydrogen release reaction improves the hydrogen release performance; mgH (MgH) 2 -Ni 0.9 Pd 0.1 The hydrogen absorption capacity and the hydrogen release capacity retention rate of the @ CC composite hydrogen storage system after thirty cycles are respectively 97.7% and 95.6%, compared with MgH 2 Is significantly improved by 65.5% and 62.5%.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.

Claims (10)

1. The preparation method of the carbon cloth supported nickel-palladium nano catalyst is characterized by comprising the following steps of:
and (3) immersing the carbon cloth in a nickel-palladium bimetallic salt precursor solution, drying after the immersion is finished, carrying out electrifying treatment on the obtained carbon cloth in a protective atmosphere, and carrying out heat treatment and cooling in sequence while carrying out electrifying treatment to obtain the carbon cloth supported nickel-palladium nano catalyst.
2. The method of claim 1, wherein the total concentration of nickel-palladium bimetal in the nickel-palladium bimetal salt precursor solution is 0.05mol/L and the molar ratio of nickel to palladium is 0.9:0.1-0.25:0.75.
3. The method according to claim 1, wherein the impregnation density is 300 to 500. Mu.L/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The heat treatment mode is as follows: maintaining at 1300-1500 deg.c for 30-120 s; the cooling mode is as follows: cooling from 1300-1500 ℃ to room temperature within 5 s.
4. The method according to claim 1, wherein the energizing is performed with a direct current having a current intensity of 375A, a pulse period of 100ms, and a duty cycle of 50%.
5. The method of claim 1, wherein the carbon cloth is pretreated; the step of preprocessing comprises the following steps: and (3) treating the carbon cloth for 0.5-1h at the temperature of 100-300 ℃ under the condition of hydrogen pressure.
6. The method of claim 1, wherein the drying temperature is 80 ℃.
7. The carbon cloth supported nickel palladium nano catalyst prepared by the preparation method of any one of claims 1 to 6.
8. The use of the carbon cloth supported nickel palladium nano catalyst according to claim 7 in catalyzing hydrogen storage performance of magnesium hydride.
9. A composite hydrogen storage system, characterized by comprising the carbon cloth supported nickel palladium nano catalyst and magnesium hydride according to claim 7.
10. The composite hydrogen storage system according to claim 9, wherein the composite hydrogen storage system comprises the carbon cloth supported nickel-palladium nano catalyst and magnesium hydride according to a mass ratio of 25:75, mixing and ball milling under a protective atmosphere.
CN202311502449.3A 2023-11-13 2023-11-13 Preparation method of carbon cloth supported nickel-palladium nano catalyst and solid hydrogen storage application thereof Pending CN117463363A (en)

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