CN110556547B - Noble metal nano cage catalyst and preparation method and application thereof - Google Patents

Noble metal nano cage catalyst and preparation method and application thereof Download PDF

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CN110556547B
CN110556547B CN201810537534.6A CN201810537534A CN110556547B CN 110556547 B CN110556547 B CN 110556547B CN 201810537534 A CN201810537534 A CN 201810537534A CN 110556547 B CN110556547 B CN 110556547B
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noble metal
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CN110556547A (en
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符显珠
盛家利
谢金麒
康佳慧
盛国庆
孙蓉
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Shenzhen Institute of Advanced Technology of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
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    • 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
    • Y02E60/50—Fuel cells

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Abstract

The invention provides a noble metal nanocage catalyst and a preparation method and application thereof, wherein the catalyst is in a hollow nanocage structure; the preparation method of the catalyst comprises the following steps: mixing the hollow nano cage template agent with a noble metal precursor solution, reacting to generate noble metal, and washing to obtain the noble metal nano cage catalyst. The hollow nano cage catalyst greatly reduces the use amount of noble metal, and has the advantages of large specific surface area, more active sites and shorter material transmission distance; the preparation method is simple, and the noble metal catalyst and the structure thereof are directly obtained from a transition metal precursor; the obtained catalyst has good stability and high electrocatalytic activity, and when the catalyst is used for catalytic oxidation of an ethanol fuel cell, the mass activity can reach 3900mA mg ‑1 About, the specific activity can reach 4.0mA cm ‑2 Left and right.

Description

Noble metal nano cage catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, relates to a noble metal catalyst and a preparation method and application thereof, and particularly relates to a noble metal nanocage catalyst and a preparation method and application thereof as an anode catalyst of a fuel cell.
Background
The energy problem is one of the major problems in the present society, and is closely related to the human survival, and with the increasing shortage of fossil energy, the development of renewable energy and the realization of effective utilization of energy are problems that need to be solved urgently. The fuel cell is a power generation device which directly converts chemical energy existing in an oxidant and fuel into electric energy, can realize effective utilization of resources, and is convenient for transportation and storage of energy.
The direct ethanol fuel cell is an important fuel cell, has the characteristics of high energy density, low toxicity and no pollution, has wide application prospect in the field of portable equipment such as electric automobiles and the like, and is widely researched by researchers. However, the normal operation of a fuel cell requires a catalyst for catalysis. At present, a lot of researches are carried out on direct ethanol fuel cell catalysts, most of high-efficiency catalysts are mainly concentrated on noble metal Pt, however, the Pt is expensive, the cost of the catalyst is too high, and the toxicity resistance is poor, so that a new Pt-free catalyst needs to be developed, and the novel catalyst needs to have the characteristics of low cost, strong toxicity resistance, difficult particle agglomeration, strong stability and the like. Therefore, it remains a great challenge to prepare efficient and inexpensive catalysts.
Aiming at the problems of the existing catalyst, a plurality of researchers also make improvements in the aspects of raw materials, structures, morphologies and the like. Compared with a solid metal catalyst, the hollow structure has the advantages of low density, high specific surface area, material saving and low cost; CN 1616165A discloses a method for preparing a hollow nano-metal sphere, which takes citric acid as a protective agent, sodium borohydride as a reducing agent and cobalt salt as a template to reduce noble metal salt to prepare a noble metal nano hollow structure with the particle size of 15-50 nm. CN 103050716A discloses a hollow palladium nanosphere which is prepared by a sacrificial template method, hollow sphere structures are formed by stacking palladium nanoparticles, but the catalyst is a hollow structure formed by stacking nanoparticles, and has poor stability, difficult control of morphology, harsh reaction conditions and still unsatisfactory catalytic performance.
In summary, the improvement of the catalyst for fuel cell needs to consider various influencing factors, start from aspects of morphology, structure, composition and the like, and simultaneously simplify the preparation process and reduce the cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a noble metal nanocage catalyst and a preparation method and application thereof, wherein the nanocage catalyst is of a hollow structure, so that the use amount of noble metal is greatly reduced, the specific surface area is large, and the material transmission distance is short; the preparation method is simple, and the noble metal catalyst and the structure thereof are directly obtained from a transition metal precursor; the obtained catalyst has good stability and high electrocatalytic activity.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a noble metal catalyst having a hollow nanocage structure.
In the invention, the noble metal catalyst is of a hollow nano cage structure, the noble metal is less in use amount, the specific surface area is larger, the number of active sites is more, and the noble metal catalyst has higher stability and catalytic activity; the transition metal precursor is directly obtained by taking the transition metal precursor as a template, and the preparation method is simple and efficient and is suitable for large-scale production.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferred embodiment of the present invention, the noble metal in the noble metal catalyst comprises any one or a combination of at least two of palladium, ruthenium, platinum or gold, and the combination is exemplified by, but not limited to: a combination of palladium and ruthenium, a combination of ruthenium and platinum, a combination of palladium, platinum and gold, a combination of ruthenium, platinum and gold, and the like, with palladium being preferred.
Preferably, the catalyst is in an octahedral hollow nanocage structure.
Preferably, the catalyst has a particle size of 100 to 1050nm, for example 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm or 1050nm, but is not limited to the recited values, and other values not recited within this range are equally applicable, preferably 400 to 550nm.
Preferably, the catalyst has a wall thickness of 20 to 60nm, for example 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm or 60nm, but not limited to the recited values, and other values not recited within this range of values are equally applicable.
Preferably, the specific surface area of the catalyst is 20 to 60m 2 G, e.g. 20m 2 /g、25m 2 /g、30m 2 /g、35m 2 /g、40m 2 /g、45m 2 /g、50m 2 /g、55m 2 (ii)/g or 60m 2 G, etcHowever, the numerical values recited are not intended to be limiting, and other numerical values not recited within the numerical range may be equally applicable.
In the invention, the octahedral structure and the particle size of the catalyst are mainly determined by the template transition metal precursor, and if the particle size of the catalyst is too large, the specific surface area of the catalyst is smaller, which is not beneficial to the stability of a hollow structure; the particle size of the catalyst is too small, the morphology and the structure of the template agent are difficult to maintain in the preparation process, and the hollow structure is easy to collapse. The wall thickness of the catalyst is comprehensively regulated and controlled according to the particle size of the catalyst and the catalytic activity which can be achieved by the catalyst, so that the proper wall thickness is selected.
In a second aspect, the present invention provides a method for preparing the above noble metal catalyst, the method comprising: mixing the hollow nano cage template agent with a noble metal precursor solution, reacting to generate noble metal, and washing to obtain the noble metal nano cage catalyst.
In the invention, the hollow nano cage is used as a template agent and a reactant, and the hollow nano cage and a noble metal precursor are subjected to oxidation-reduction reaction to obtain the noble metal catalyst with the hollow nano cage structure.
As a preferable technical scheme of the invention, the hollow nano cage template in the step (1) comprises amorphous cobalt hydroxide.
In the invention, the cobalt hydroxide used as the template agent is in an amorphous structure, compared with a common crystalline material, the amorphous nano material has richer content and more diversified appearance in nature, and the noble metal catalyst synthesized by using the cobalt hydroxide as the template has diversified structures, improves the catalytic activity, and simultaneously can reduce the raw material and preparation cost.
Preferably, the cobalt hydroxide is in an octahedral hollow nanocage structure.
In the invention, the cobalt hydroxide used is prepared by using octahedral cuprous oxide and cobalt chloride as raw materials, reacting with a complexing agent under the action of a stabilizing agent, etching the cuprous oxide, and generating hydroxide ions and cobalt chloride to generate cobalt hydroxide to cover the surface, thereby finally generating the cobalt hydroxide with a hollow structure.
According to the invention, a small amount of cobalt ions dissociated from the cobalt hydroxide react with the noble metal salt adsorbed on the surface of the cobalt hydroxide to reduce the noble metal ions into simple substances, the simple substances are attached to the surface, the reaction is carried out quickly and is carried out from outside to inside, and finally the noble metal nanocage catalyst with the same structure as the cobalt hydroxide is obtained.
Preferably, the cobalt hydroxide has a particle size of 100 to 1000nm, for example 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000nm, but not limited to the recited values, and other values not recited within the range of the values are also applicable, preferably 400 to 500nm.
As the preferable technical scheme, the hollow nano cage template agent forms dispersion liquid firstly;
preferably, the solvent of the transition metal precursor dispersion liquid is water.
Preferably, the concentration of the dispersion of the hollow nanocage templating agent is from 0.01 to 1mg/mL, such as 0.01mg/mL, 0.02mg/mL, 0.05mg/mL, 0.1mg/mL, 0.2mg/mL, 0.4mg/mL, 0.6mg/mL, 0.8mg/mL, or 1mg/mL, but is not limited to the recited values, and other values within the range of values are equally applicable.
Preferably, the transition metal precursor dispersion is obtained by stirring.
Preferably, the stirring treatment time is 5 to 30min, for example, 5min, 10min, 15min, 20min, 25min, or 30min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred embodiment of the present invention, the noble metal precursor includes a noble metal salt.
Preferably, the noble metal salt comprises any one of or a combination of at least two of sodium chloropalladate, sodium chlorotruthenate, sodium chloroplatinate or sodium chloroaurate, typical but non-limiting examples of which are: the combination of sodium chloropalladate and sodium chloropalladate, the combination of sodium chloropalladate and sodium chloroaurate, the combination of sodium chloropalladate, sodium chloroplatinate and sodium chloroaurate, the combination of sodium chloropalladate, sodium chloropalladate and sodium chloroaurate and the like.
Preferably, the noble metal precursor solution has a concentration of 1 to 20mM, such as 1mM, 2mM, 5mM, 8mM, 10mM, 12mM, 15mM, 18mM, or 20mM, but not limited to the recited values, and other values not recited within this range are equally applicable, preferably 10mM.
Preferably, the molar ratio of the noble metal precursor to the hollow nanocage template is 3:1-6:1, such as 3:1, 3.5, 4:1, 4.5.
Preferably, the reaction temperature is 20 to 40 ℃, such as 20 ℃, 22 ℃, 25 ℃, 27 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃ or 40 ℃, but is not limited to the recited values, and other unrecited values within the range of values are equally applicable.
Preferably, the reaction time is 15 to 60min, such as 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the reaction is carried out under stirring conditions.
As a preferable technical scheme of the invention, the washing sequentially comprises acid washing and water washing;
in the present invention, the acid is added to remove the residue on the generated noble metal, the residue comprises cobalt hydroxide and cobalt oxyhydroxide, divalent cobalt in the cobalt hydroxide is oxidized into trivalent cobalt, part of the trivalent cobalt exists in the solution in the form of ions, and the other part forms cobalt oxyhydroxide which is precipitated on the surface of the generated noble metal.
Preferably, the acid comprises any one of hydrochloric acid, sulfuric acid or nitric acid, or a combination of at least two of these, typical but non-limiting examples being: combinations of hydrochloric acid and sulfuric acid, sulfuric acid and nitric acid, combinations of hydrochloric acid, sulfuric acid and nitric acid, and the like.
Preferably, the molar ratio of the acid to the hollow nanocage templating agent is 1:1-6:1, such as 1:1, 2:1, 3:1, 4:1, 5:1 or 6:1, and the like, but is not limited to the recited values, and other values not recited in this range of values are equally applicable.
Preferably, the acid addition treatment time is 20 to 120min, such as 20min, 30min, 40min, 50min, 60min, 70min, 80min, 100min, or 120min, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the washing with water is a centrifugal washing.
Preferably, the number of washing with water is at least 1, for example 1, 2, 3, 4 or 5, but not limited to the recited values, and other values not recited within the range of values are also applicable, preferably 3.
In a preferred embodiment of the present invention, the washing is followed by drying.
Preferably, the drying temperature is 24 to 65 ℃, for example 24 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, or 65 ℃, but not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the drying time is not less than 1 hour, such as 1 hour, 2 hours, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, and the like, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) Dispersing octahedral amorphous cobalt hydroxide hollow nanocages with the particle size of 100-1000 nm in water, stirring for 5-30 min, mixing the formed dispersion with a noble metal salt solution with the concentration of 1-20 mM, and reacting at the temperature of 20-40 ℃ for 15-60 min to obtain noble metal;
(2) And (2) adding acid into the noble metal obtained in the step (1) for washing, wherein the acid adding washing time is 20-120 min, then washing for at least 1 time by using water, and drying to obtain the noble metal nanocage catalyst.
In a third aspect, the present invention provides the use of the above-described noble metal catalyst as a fuel cell catalyst.
Preferably, the catalyst is used as an anode catalyst for a direct ethanol fuel cell.
Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst has a hollow structure, the use amount of noble metal is less, the specific surface area is larger, the number of active sites is more, the electron transmission speed is high, the stability and the catalytic activity are higher, and the mass activity can reach 3900mAmg -1 About, the specific activity can reach 4.0mAcm -2 Left and right;
(2) The catalyst is directly obtained by taking a transition metal precursor as a template, and the preparation method is simple, efficient, low in cost and suitable for large-scale production.
Drawings
FIG. 1 is a TEM image of a noble metal nanocage catalyst provided in example 1 of the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1:
the embodiment provides a noble metal nanocage catalyst and a preparation method thereof, wherein the catalyst comprises a noble metal element palladium; the catalyst is of an octahedral hollow nanometer cage structure, the particle size is 525nm, and the wall thickness is 40nm.
The preparation method of the catalyst comprises the following steps:
(1) Dispersing 1mg of octahedral amorphous cobalt hydroxide hollow nanocages with the particle size of 500nm in 15mL of water, stirring for 10min to form a dispersion, adding 4mL of 10mM sodium chloropalladate solution, and reacting at the temperature of 30 ℃ for 20min to obtain noble metal elemental palladium;
(2) And (2) adding 0.05mmol of hydrochloric acid to remove residues on the noble metal simple substance obtained in the step (1), treating for 20min, washing for 3 times with water, and drying to obtain the noble metal palladium nanocage catalyst.
The prepared noble metal palladium nanocage catalyst is characterized by a Transmission Electron Microscope (TEM), and a TEM image is shown in figure 1; the catalyst is used as an anode catalyst of an ethanol fuel cell, the catalytic performance of the catalyst is tested, and a three-electrode test is carried out in a mixed solution of 1M KOH and 1M ethanol saturated by nitrogen to characterize the activity of the catalyst. The catalytic activity includes mass activity normalized by the mass of the noble metal and specific activity normalized by the active area of the noble metal.
In this embodiment, as can be seen from fig. 1, the catalyst has an octahedral hollow nanocage structure, the particle size of which is about 525nm, and the wall thickness of which is about 40nm; the catalyst is used for anode catalysis of an ethanol fuel cell, and the mass activity can reach 3915mAmg -1 Pd The specific activity can reach 4.13mAcm -2 。
Example 2:
the embodiment provides a noble metal nanocage catalyst and a preparation method thereof, wherein the catalyst comprises a noble metal element ruthenium; the catalyst is in an octahedral hollow nanometer cage structure, the particle size is 110nm, and the wall thickness is 20nm.
The preparation method of the catalyst comprises the following steps:
(1) Dispersing 4mg of octahedral amorphous cobalt hydroxide hollow nanocages with the particle size of 100nm in 40mL of water, stirring for 15min to form a dispersion, adding 45mL of 5mM sodium chlororuthenate solution, and reacting at the temperature of 20 ℃ for 30min to obtain the noble metal elementary ruthenium;
(2) And (2) adding 0.125mmol of sulfuric acid to remove residues on the noble metal simple substance obtained in the step (1), treating for 50min, then washing for 1 time by using water, and drying to obtain the noble metal ruthenium nanometer cage catalyst.
The prepared noble metal ruthenium nanocage catalyst is used as an anode catalyst of an ethanol fuel cell, and the catalytic performance of the catalyst is tested, wherein the test conditions refer to example 1.
In the embodiment, the catalyst is used for anode catalysis of the ethanol fuel cell, and the mass activity can reach 3901mAmg -1 Ru The specific activity may beTo reach 3.93mAcm -2 。
Example 3:
the embodiment provides a noble metal nanocage catalyst and a preparation method thereof, wherein the catalyst comprises noble metal elements of palladium and ruthenium; the catalyst is in an octahedral hollow nanometer cage structure, the particle size is 1050nm, and the wall thickness is 60nm.
The preparation method of the catalyst comprises the following steps:
(1) Dispersing 50mg of octahedral amorphous cobalt hydroxide hollow nanocages with the particle size of 1000nm in 200mL of water, stirring for 30min to form a dispersion solution, adding 108mL of a mixed solution of sodium chloropalladate and sodium chlororuthenate with the concentration of 15mM, wherein the volume ratio of the sodium chloropalladate to the sodium chlororuthenate is 1:1, and reacting at the temperature of 40 ℃ for 60min to obtain noble metal palladium and ruthenium;
(2) And (2) adding 1.2mmol of nitric acid to remove residues on the noble metal obtained in the step (1), treating for 100min, washing for 5 times with water, and drying to obtain the noble metal palladium rhodium nanocage catalyst.
The prepared noble metal palladium rhodium nanocage catalyst is used as an anode catalyst of an ethanol fuel cell, and the catalytic performance of the catalyst is tested, wherein the test conditions refer to example 1.
In the embodiment, the catalyst is used for anode catalysis of the ethanol fuel cell, and the mass activity can reach 3880mAmg -1 Pd-Ru The specific activity can reach 3.89mAcm -2 。
Example 4:
the embodiment provides a noble metal nanocage catalyst and a preparation method thereof, wherein the catalyst comprises a noble metal element platinum; the catalyst is in an octahedral hollow nanometer cage structure, the particle size is 320nm, and the wall thickness is 30nm.
The preparation method of the catalyst comprises the following steps:
(1) Dispersing 20mg of octahedral amorphous cobalt hydroxide hollow nanocages with the particle size of 300nm in 40mL of water, stirring for 20min to form a dispersion, adding 64mL of 20mM potassium chloroplatinate solution, and reacting at the temperature of 25 ℃ for 40min to obtain the noble metal simple substance platinum;
(2) And (2) adding 0.22mmol of hydrochloric acid to remove residues on the noble metal simple substance obtained in the step (1), treating for 70min, washing for 2 times with water, and drying to obtain the noble metal platinum nanocage catalyst.
The prepared noble metal platinum nanocage catalyst is used as an anode catalyst of an ethanol fuel cell, and the catalytic performance of the catalyst is tested, wherein the test conditions refer to example 1.
In the embodiment, the catalyst is used for catalyzing the anode of the ethanol fuel cell, and the mass activity can reach 3910mAmg -1 Pt The specific activity can reach 4.10mA cm -2 。
Example 5:
the embodiment provides a noble metal nanocage catalyst and a preparation method thereof, wherein the catalyst comprises noble metal elements of palladium and gold; the catalyst is in an octahedral hollow nanometer cage structure, the particle size is 780nm, and the wall thickness is 50nm.
The preparation method of the catalyst comprises the following steps:
(1) Dispersing 30mg of octahedral amorphous cobalt hydroxide hollow nanocages with the particle size of 750nm in 30mL of water, stirring for 25min to form a dispersion, adding 115mL of a mixed solution of 10mM sodium chloropalladate and sodium chloroaurate, wherein the volume ratio of the sodium chloropalladate to the sodium chloroaurate is 4:1, and reacting at 35 ℃ for 50min to obtain noble metals palladium and gold;
(2) And (2) adding 0.65mmol of sulfuric acid to remove residues on the noble metal obtained in the step (1), treating for 80min, washing for 4 times with water, and drying to obtain the noble metal palladium-gold nanocage catalyst.
The prepared noble metal palladium gold nanocage catalyst is used as an anode catalyst of an ethanol fuel cell, and the catalytic performance of the catalyst is tested, wherein the test conditions refer to example 1.
In the embodiment, the catalyst is used for anode catalysis of the ethanol fuel cell, and the mass activity can reach 3911mA mg -1 Pd-Au The specific activity can reach 4.08mA cm -2 。
Comparative example 1:
the present comparative example provides a noble metal nanocage catalyst and a method of making the same, the catalyst comprising the noble metal element palladium; the catalyst is in an octahedral hollow nanometer cage structure.
The catalyst preparation is as described in example 1, with the only difference that: hydrochloric acid is not added in the step (2).
The prepared noble metal palladium nanocage catalyst is used as an anode catalyst of an ethanol fuel cell, and the catalytic performance of the catalyst is tested, wherein the test conditions refer to example 1.
In the comparative example, because acid treatment is not added after the reaction, residual cobalt hydroxide and generated cobalt oxyhydroxide in the product still exist, and the mass activity of the obtained catalyst for catalyzing and oxidizing the ethanol can only reach 3200mA mg -1 Pd The specific activity can only reach 3.10mA cm -2 。
Comparative example 2:
this comparative example provides a method for preparing a nanocatalyst, which is described with reference to example 1, except that: and (3) adding the sodium chloropalladate solution in the step (1) and the hydrochloric acid in the step (2) at the same time.
The prepared noble metal palladium nanocage catalyst is used as an anode catalyst of an ethanol fuel cell, and the catalytic performance of the catalyst is tested, wherein the test conditions refer to example 1.
In the comparative example, as the hydrochloric acid is added for a relatively early time, the cobalt hydroxide is etched under the acidic condition, and the nano cage structure of the cobalt hydroxide is destroyed as a template, the generated palladium nano cage structure is not as complete as the former appearance, and the activity of the obtained catalyst for catalyzing and oxidizing the ethanol can only reach 3150mA mg -1 Pd The specific activity only reaches 3.0mA cm -2 。
Comparative example 3:
the comparative example provides a nano metal hollow sphere catalyst, and a nano palladium hollow sphere is prepared according to example 3 in CN 1616165A.
The prepared nano-palladium hollow sphere catalyst is used as an anode catalyst of an ethanol fuel cell, and the catalytic performance of the catalyst is tested, wherein the test conditions are as in example 1.
Compared with the embodiment of the invention, the process for preparing the nano-palladium hollow sphere in the comparative example has more raw materials and steps and more rigorous condition control, and the catalytic activity under the same condition only reaches 3110mA mg -1 Pd The specific activity can reach 2.8mA cm -2 Inferior to the activity in the examples.
Comparative example 4:
this comparative example provides a palladium hollow nanosphere catalyst prepared according to example 1 of CN 103050716 a.
The prepared palladium hollow nanosphere catalyst was used as an anode catalyst of an ethanol fuel cell and tested for catalytic performance under the test conditions referred to in example 1.
Compared with the embodiment of the invention, the hollow structure of the catalyst obtained in the comparative example is formed by accumulating nano particles, and the stability is poor; meanwhile, the catalytic activity under the same condition only reaches 3115mA mg -1 Pd The specific activity can reach 2.88mA cm -2 Inferior to the activity in the examples.
It can be seen from the above examples and comparative examples that the catalyst of the present invention is directly obtained by using a transition metal precursor as a template, the preparation method is simple and efficient, the catalyst cost is low, and large-scale preparation can be realized; the obtained catalyst is of a hollow nano cage structure, the consumption of noble metal is less, the specific surface area is larger, the number of active sites is more, when the catalyst is used for catalytic oxidation of an ethanol fuel cell, the catalytic activity is higher, and the mass activity can reach 3900mA mg -1 About, the specific activity can reach 4.0mA cm -2 Left and right.
The applicant indicates that the present invention is illustrated by the above examples to describe the detailed application of the present invention, but the present invention is not limited to the above detailed application, i.e. it does not mean that the present invention must rely on the above detailed method to be carried out. It will be apparent to those skilled in the art that any modifications to the invention, equivalent variations of the materials used in the practice of the invention and the addition of additional components, specific conditions and manner of choice, etc., are deemed to be within the scope and disclosure of the invention.

Claims (30)

1. The preparation method of the noble metal catalyst is characterized in that the noble metal catalyst is in a hollow nano cage structure, and the noble metal in the noble metal catalyst comprises any one or the combination of at least two of palladium, ruthenium, platinum or gold; the wall thickness of the catalyst is 20-60 nm, and the specific surface area is 30-60 m 2 /g；
The preparation method comprises the following steps: mixing a hollow nano cage template agent with a noble metal precursor solution and then reacting, wherein the hollow nano cage template agent comprises amorphous cobalt hydroxide, the noble metal precursor comprises noble metal salt, the noble metal salt comprises any one or the combination of at least two of sodium chloropalladate, sodium chlororuthenate, sodium chloroplatinate and sodium chloroaurate, the molar ratio of the noble metal precursor to the hollow nano cage template agent is 3:1-6:1, generating noble metal, then washing, and the washing sequentially comprises acid washing and water washing to obtain the noble metal nano cage catalyst.
2. The method according to claim 1, wherein the noble metal in the noble metal catalyst is palladium.
3. The preparation method of claim 1, wherein the catalyst is in an octahedral hollow nanocage structure.
4. The method according to claim 1, wherein the catalyst has a particle size of 100 to 1050nm.
5. The method according to claim 4, wherein the catalyst has a particle size of 400 to 550nm.
6. The method of claim 1, wherein the cobalt hydroxide has an octahedral hollow nanocage structure.
7. The method according to claim 1, wherein the cobalt hydroxide has a particle size of 100 to 1000nm.
8. The method according to claim 7, wherein the cobalt hydroxide has a particle size of 400 to 500nm.
9. The method of claim 1, wherein the hollow nanocage template is reacted after forming a dispersion.
10. The method according to claim 9, wherein the solvent of the dispersion of the hollow nanocage template is water.
11. The method according to claim 9, wherein the concentration of the hollow nanocage template dispersion is 0.01 to 1mg/mL.
12. The preparation method according to claim 9, wherein the dispersion liquid of the hollow nanocage template is obtained by stirring.
13. The production method according to claim 12, wherein the stirring treatment time is 5 to 30min.
14. The method according to claim 1, wherein the concentration of the noble metal precursor solution is 1 to 20mM.
15. The method of claim 14, wherein the noble metal precursor solution has a concentration of 10mM.
16. The method according to claim 1, wherein the reaction temperature is 20 to 40 ℃.
17. The method according to claim 1, wherein the reaction time is 15 to 60min.
18. The method according to claim 1, wherein the reaction is carried out under stirring.
19. The method of claim 1, wherein the acid comprises any one of hydrochloric acid, sulfuric acid, or nitric acid, or a combination of at least two thereof.
20. The preparation method of claim 1, wherein the molar ratio of the acid to the hollow nanocage template is 1:1-6:1.
21. The method according to claim 1, wherein the time for the acid washing is 20 to 120min.
22. The method according to claim 1, wherein the washing with water is centrifugal washing.
23. The method according to claim 1, wherein the number of washing with water is at least 1 washing.
24. The method according to claim 23, wherein the number of washing with water is 3.
25. The method according to claim 1, wherein the washing is followed by drying.
26. The method of claim 25, wherein the drying temperature is 24 to 65 ℃.
27. The method of claim 25, wherein the drying time is not less than 1 hour.
28. The method for preparing according to claim 1, characterized in that it comprises the following steps:
(1) Dispersing octahedral amorphous cobalt hydroxide hollow nanocages with the particle size of 100-1000 nm in water, stirring for 5-30 min, mixing the formed dispersion with a noble metal salt solution with the concentration of 1-20 mM, and reacting at the temperature of 20-40 ℃ for 15-60 min to obtain noble metal;
(2) And (2) adding acid into the noble metal obtained in the step (1) for washing, wherein the acid adding washing time is 20-120 min, then washing for at least 1 time by using water, and drying to obtain the noble metal nano cage catalyst.
29. Use of a noble metal catalyst obtained by the production method according to any one of claims 1 to 28 as a fuel cell catalyst.
30. Use according to claim 29, wherein the catalyst is used as an anode catalyst for a direct ethanol fuel cell.
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