CN111215056B - Preparation method and application of low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst - Google Patents
Preparation method and application of low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst Download PDFInfo
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B01J35/33—
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- B01J35/394—
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- B01J35/50—
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- 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
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- Y02E60/50—Fuel cells
Abstract
The application provides a preparation method and application of a low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst, wherein a high-molecular template agent and a carbon source precursor are subjected to self-assembly in a hydrothermal process to synthesize hollow polymer spheres, and a simple and convenient double-solvent impregnation method is adopted to successfully prepare PdCl 4 2‑ Loaded on a hollow polymer ball, finally placing the reactant in a programmable atmosphere tube furnace, and carbonizing at the high temperature of 500-900 ℃ to obtain the low-load Pd/hollow carbon ball oxygen reduction electrocatalyst (Pd-HCS) which can be used as an efficient ORR electrocatalyst in an alkaline environment. The low-load Pd-HCS oxygen reduction electrocatalyst obtained by the method has the advantages of higher specific surface area, good conductivity and enough active sites, and shows more excellent oxygen reduction electrocatalysis performance, good stability and excellent methanol poisoning resistance activity. The preparation method has the advantages of simple process, low cost and certain universality, and has certain guiding significance for designing and developing a novel fuel cell cathode oxygen reduction electrocatalyst.
Description
Technical Field
The invention belongs to the field of chemical energy materials, particularly relates to preparation of a hollow carbon sphere oxygen reduction electrocatalyst, and particularly relates to a preparation method and application of a low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst for catalyzing reduction of cathode oxygen of a fuel cell into water.
Background
In recent years, due to exhaustion of conventional fossil energy and increasing environmental pollution, research and development of novel efficient, low-cost, and clean and renewable energy conversion and storage technologies, such as fuel cells, zinc-air cells, and water decomposition technologies, are in great demand. The fuel cell is the most rapidly developed and is considered as an energy source star in the 21 st century, the fuel cell can directly convert chemical energy in fuel and oxidant into electric energy without the limitation of Carnot cycle, and the conversion efficiency is as high as more than 60%; and the product is water, so that the cleaning agent is high-efficiency and pollution-free.
The electrode of the fuel cell is an electrochemical reaction site where the fuel undergoes an oxidation reaction and the oxidant undergoes a reduction reaction, and the electrode can be mainly divided into two parts, one part is an Anode (Anode), the other part is a Cathode (Cathode), and the thickness is generally 200-500mm; the structure of the fuel cell is different from that of a plate electrode of a general cell in that the electrode of the fuel cell has a porous structure, so that most of fuel and oxidant (such as oxygen, hydrogen, etc.) can pass through the porous structure. The oxygen reduction reaction generated at the cathode of the fuel cell relates to a multi-electron reaction process, the dynamics is slow, so that the commercialization promotion process of the fuel cell is not stopped, so that the existence of an electrocatalyst is generally needed to greatly improve the oxygen reduction reaction rate of the fuel cell, and the current commonly used commercial electrocatalyst is still a noble metal Pt/C catalyst, but the large-scale use of the fuel cell is limited by the defects of rare metal Pt element, high price, easy poisoning and the like. In order to increase the power density of the fuel cell and reduce the development cost of the fuel cell, it is necessary to not only achieve mass production of key materials such as the electrocatalyst as soon as possible, but also reduce the amount of platinum in the electrocatalyst. In order to reduce the development cost of cathode oxygen reduction electrocatalysts, numerous researchers are devoted to developing and researching novel Pt-based and non-Pt-based electrocatalysts, and the catalytic activity and stability of the catalyst are ensured while the loading capacity of noble metals is reduced.
Pd has very similar properties to Pt (in the same group of the periodic table, with the same fcc crystal structure, similar atomic sizes), and is inexpensive compared to Pt, and its abundance on earth is at least 50 times that of Pt, and thus can be a good alternative to Pt catalysts in fuel cells. However, due to the inherent tendency of metal atoms to migrate and aggregate into nanoparticles, surface energy is reduced by aggregation, with the particle size increasing, directly resulting in a reduction in the activity of the nanoelectrocatalyst. Therefore, fine control of the dispersion of Pd nanoparticles is required to improve their electrocatalytic activity, which is a challenging problem. To solve this problem, a highly conductive carbon material is combined with Pd nanoparticles to achieve a desired uniform dispersion effect, which not only facilitates charge transport, but also provides abundant active sites to immobilize Pd nanoparticles. At present, a carbon carrier material which is commonly used is a carbon black material which has high conductivity, a higher specific surface area and low price, and a commercial Pt/C oxygen reduction electrocatalyst is prepared by loading precious metal Pt on the carbon black material. However, as the loading of the catalyst increases, the particle size of the metal particles increases rapidly on the surface of the carbon black, and the catalyst is agglomerated to lower the stability and activity of the catalyst, resulting in waste of precious metals. The novel carbon carrier materials (hollow carbon spheres and mesoporous carbon) have high specific surface area, good conductivity and good corrosion resistance, and become the key point of research.
In recent years, various noble metal/carbon composite materials have received attention from researchers due to their excellent oxygen reduction catalytic activity. For example, lorenzo et al have designed Pd/mesoporous carbon, pt/mesoporous carbon, pd/graphene and Pt/hollow carbon sphere composites ((1) Lorenzo Perini, christian Durante, et al, ACS appl. Mater. Interfaces 2015,7,1170-1179, (2) Sabina Yasmin, yuri Joo, seung Joon Jeon. Applied Surface Science,2017,406,226-234. (3) Guanghui Wang, et al, nature Materials,2014,13, 293-300), and found that there is a strong interaction force between the carbon material and the noble metal, which contributes to the dispersion of the metal particles and improves the electrocatalytic activity thereof. However, the preparation of the above catalyst has the following problems: (1) Various carbon materials need to be pretreated, and amino groups are additionally introduced to anchor metal particles, so that the acting force between the metal particles and a carrier is enhanced, and the dispersity of the Pd nanoparticles is improved; (2) Certain particle agglomeration phenomenon exists, the preparation process is complicated, the time consumption is long, the cost is high, and the industrial production is difficult. These problems are mainly due to the metal precursor ions being negatively charged noble metal ions (PtCl) in the same solution 4 2- 、PdCl 4 2- ) And a large amount of oxygen-containing functional groups with negative charges exist on the carbon precursor material, and electrostatic repulsive force exists, so that the loaded noble metal nano particles have a certain agglomeration phenomenon. If a simple double-solvent impregnation method is used for replacing single-solvent synthesis, pores have certain capillary action force in two solutions, noble metal ions are adsorbed to a carbon precursor by the capillary action force, electrostatic repulsion between a negatively charged carboxyl functionalized carbon sphere precursor and negatively charged ions can be overcome, and self-derived triple intercalation is utilized in a high-temperature processThe copolymer Pluronic P123, rich oxygen-containing functional groups of sodium oleate and DA and nitrogen-containing groups derived from HMT are anchored and promote the uniform dispersion of Pd nanoparticles, so that higher electrocatalytic activity and atom utilization rate are achieved.
Disclosure of Invention
In view of the above problems, the technical problem to be solved by the present invention is to provide a low-loaded Pd/hollow carbon sphere oxygen reduction electrocatalyst with low cost, high performance and high stability.
In order to solve the technical problems, the invention adopts the technical scheme that:
the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst has a diameter of about 130-180nm and a shell thickness of about 20-40nm.
Preferably, the diameter is about 150nm, the shell thickness is about 20nm, and the mass fraction of Pd is 1.7%.
The preparation method of the nano material comprises the following steps:
(a) A hydrothermal process: weighing a proper amount of template agent and a carbon source precursor, respectively preparing aqueous solutions A and B, stirring and mixing at room temperature to obtain a micelle solution C, then putting the solution C into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle into an oven, heating the polytetrafluoroethylene reaction kettle to a specific temperature from room temperature at a certain heating rate, carrying out heat preservation for a period of time, carrying out hydrothermal reaction, then naturally cooling to room temperature, centrifuging at a high rotating speed, taking out a solid at the bottom, washing the solid with deionized water and ethanol for multiple times, and drying the obtained precipitate to obtain a hollow polymer sphere precursor HPS;
(b) And (3) dipping: weighing a certain amount of hollow polymer sphere precursor HPS, dispersing in an organic solvent, performing ultrasonic treatment for a period of time, uniformly stirring to obtain dispersion liquid D, weighing a proper amount of Na 2 PdCl 4 Dissolving in deionized water, performing ultrasonic homogenization to obtain a solution E, gradually dripping the solution E into the dispersion D in the stirring process of the dispersion D to obtain a solution F, evaporating under the stirring condition, and then placing in a vacuum drying oven for vacuum drying to obtain a Pd/hollow polymer sphere precursor;
(c) And (3) calcining: and placing the porcelain boat containing the Pd/hollow polymer sphere precursor in a programmable atmosphere tube furnace, raising the temperature to a specific temperature at a certain heating rate, carrying out high-temperature calcination in an inert atmosphere, carrying out heat preservation for a period of time, and then naturally cooling to room temperature to obtain the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst Pd-HCS.
Preferably, in step (a), the templating agent is: the triblock copolymer Pluronic P123 and sodium oleate, wherein the molar ratio of the Pluronic P123 to the sodium oleate is 1.
Preferably, in step (a), the carbon source precursor is: hexamethylene tetramine (HMT) and 2, 4-Dihydroxybenzoic Acid (DA), the molar ratio of hexamethylene tetramine to 2, 4-dihydroxybenzoic acid being 1 to 1, 3, the molar ratio of triblock copolymer Pluronic P123 and hexamethylene tetramine (HMT) being 1.
Preferably, in the step (a), the heating rate is 1-4 ℃/min, the heat preservation temperature is 100-180 ℃, and the heat preservation time is 1-8 h.
Preferably, in step (b), the noble metal salt is: na (Na) 2 PdCl 4 The mass ratio of the noble metal salt to the hollow polymer ball precursor HPS is 1-1.
Preferably, in step (b), the organic solvent used to disperse the hollow polymer sphere precursor HPS is pentane.
Preferably, in the step (c), the heating rate is 1-10 ℃/min, the calcining temperature is 500-900 ℃, and the temperature is kept for 0.5-6 h under the inert atmosphere of nitrogen and argon.
The method for modifying the glassy carbon electrode by the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst comprises the following steps: ultrasonically dispersing a low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst in a Nafion solution to obtain 2mg/mL ink dispersion, uniformly dripping the ink dispersion on a glassy carbon electrode by using a micro-syringe, and baking under an infrared lamp, wherein the Nafion solution is a mixed solution of water, isopropanol and Nafion in a volume ratio of 4.
Compared with the prior art, the invention has the beneficial effects that:
(1) The low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst provided by the invention has the advantages of concentrated particle size distribution and uniform shell thickness, is expected to realize stable mass production, and has stable performance when being applied to fuel cell electrode materials.
(2) The low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst Pd nano-particles provided by the invention have good dispersibility, promote the adsorption of oxygen molecules in the oxygen reduction reaction process, reduce the overpotential of the oxygen reduction reaction, can quickly realize the adsorption of oxygen and reduce in an alkaline environment when being applied to the cathode oxygen reduction of a fuel cell, and show excellent electrochemical properties: has a half-wave potential and current density comparable to commercial Pt/C electrocatalysts; and has good stability under long-time cycle test and excellent methanol poisoning resistance.
(3) The invention adopts the hollow carbon spheres as the load matrix, and the hollow carbon spheres have the advantages of good conductivity, larger pore volume, higher specific surface area and the like. The abundant oxygen-containing functional groups derived from the triblock copolymer Pluronic P123, sodium oleate and DA and the nitrogen-containing functional groups derived from HMT favour anchoring and promote uniform dispersion of Pd nanoparticles. Due to the synergistic effect between the nitrogen-containing functional group and the oxygen-containing functional group, the aggregation and migration of the Pd nanoparticles are prevented in the pyrolysis process. So as to synthesize the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst with uniformly distributed Pd nano particles.
(4) The Pd nano-particles are successfully loaded on the hollow carbon spheres by adopting a simple double-solvent impregnation method, the double-solvent impregnation method is based on a hydrophobic solvent (pentane) and a hydrophilic solvent (water), the former solution disperses a large amount of HPS and plays a key role in smoothly carrying out the impregnation process, and the latter solution contains a metal precursor and can be adsorbed in pores by the capillary force of pores.
(5) The invention provides a low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst, wherein the mass fraction of Pd is 1.7%, the mass fraction of Pt in commercial Pt/C is 20%, the raw material reserves of the preparation method are rich, the price is relatively low, the preparation process is simple, the obtained low-load Pd-HCS electrocatalyst has the oxygen reduction catalytic performance equivalent to that of the commercial Pt/C, and the low-load Pd-HCS electrocatalyst has certain guiding significance for the commercial application of fuel cells.
Drawings
FIG. 1 is a TEM photograph of low loading Pd/hollow carbon sphere oxygen reduction electrocatalysts prepared at different calcination temperatures in examples 2-4: a is Pd-HCS-500; TEM images with B being Pd-HCS-700 and C being Pd-HCS-900;
FIG. 2 is an XRD diffraction pattern of the hollow carbon sphere nanomaterial (HCS) prepared in example 1 and the low loading Pd/hollow carbon sphere oxygen reduction electrocatalyst in examples 2-4;
FIG. 3 is a linear scan plot of ORR catalytic activity of HCS-700 prepared in example 1, pd-HCS-700 prepared in example 3, and a commercial Pt/C catalyst;
FIG. 4 is a linear scan plot of ORR catalytic activity for Pd-HCS-500, pd-HCS-700, and Pd-HCS-900 catalysts prepared in examples 2-4;
FIG. 5 is a cyclic voltammogram of the Pd-HCS-700 modified glassy carbon electrode prepared in example 3 in 0.1M potassium hydroxide solution containing 1M methanol at a sweep rate of 10mV/s;
FIG. 6 is a linear plot of ORR catalytic activity of the Pd-HCS-700 catalyst prepared in example 2 after 1, 3500 and 10000 cyclic voltammetry scans;
figure 7 is a linear plot of ORR catalytic activity of commercial Pt/C catalysts after 1, 3500 and 10000 cyclic voltammetry scans.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the examples.
Example 1 preparation of hollow carbon sphere nanomaterial (HCS-700)
In order to compare the performance difference between the Pd-free hollow carbon sphere oxygen reduction electrocatalyst and the low-loaded Pd/hollow carbon sphere oxygen reduction electrocatalyst, a Hollow Carbon Sphere (HCS) was first prepared, and the specific preparation method included the following steps:
(a) A hydrothermal process: 54mg of the template Pluronic P123 and 90mg of sodium oleate were weighed out to give aqueous solutions A having concentrations of 0.375mmol/L and 12mmol/L, respectively. 231mg of 2, 4-Dihydroxybenzoic Acid (DA) and 88mg of Hexamethylenetetramine (HMT) are weighed to prepare aqueous solutions with the concentrations of 20mmol/L and 8.3mmol/L respectively, and the aqueous solutions are fully stirred and dissolved for 30min to obtain a solution B. And then slowly adding the solution A into the solution B in the stirring process, and continuously stirring for 30min to obtain a micelle solution C. And then transferring the solution C into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in an oven, carrying out temperature preservation for 2h at the temperature rising rate of 1 ℃/min to 160 ℃, then naturally cooling to room temperature, centrifuging for 20min at the rotating speed of 10000rpm, repeatedly carrying out deionized water/ethanol cleaning for 3 times, and placing the obtained reddish brown precipitate in a vacuum oven at the temperature of 50 ℃ for drying for 24h to obtain the hollow polymer sphere precursor HPS.
(b) And (3) calcining: placing the ceramic boat containing the hollow polymer ball precursor HPS in a programmable atmosphere tube furnace, and programming the temperature to 700 ℃ at the speed of 2 ℃/min in a N 2 Calcining at high temperature in the atmosphere, preserving the heat for 3 hours, and naturally cooling to room temperature to obtain the hollow carbon sphere nano material (HCS-700).
Example 2 preparation of Low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-500)
A preparation method of a low-load Pd/hollow carbon sphere nano material comprises the following steps:
(a) A hydrothermal process: 54mg of template Pluronic P123 and 90mg of sodium oleate are weighed out to prepare aqueous solution A with the concentrations of 0.375mmol/L and 12mmol/L respectively. 231mg of 2, 4-dihydroxy benzoic acid (DA) and 88mg of Hexamethylenetetramine (HMT) are weighed and prepared into aqueous solutions with the concentrations of 20mmol/L and 8.3mmol/L respectively, and the aqueous solutions are fully stirred and dissolved for 30min to obtain a solution B. And then slowly adding the solution A into the solution B in the stirring process, and continuously stirring for 30min to obtain a micelle solution C. And then transferring the solution C into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in an oven, carrying out temperature preservation for 2h at the temperature rising rate of 1 ℃/min to 160 ℃, then naturally cooling to room temperature, centrifuging for 20min at the rotating speed of 10000rpm, repeatedly carrying out deionized water/ethanol cleaning for 3 times, and placing the obtained reddish brown precipitate in a vacuum oven at the temperature of 50 ℃ for drying for 24h to obtain the hollow polymer sphere precursor HPS.
(b) And (3) impregnation process: weighing 50mg HPS by double solvent immersion method, dispersing in pentane, ultrasonically stirring to obtain dispersion liquid D, weighing 2mg Na 2 PdCl 4 Dissolving in deionized water, and performing ultrasonic treatment to obtain solution E. Gradually dripping the solution E into the solution D in the stirring process of the solution D to obtain a solution F, stirring for 30min, opening a bottle cap, evaporating at room temperature for 2-24h, and then putting into a vacuum oven for drying at 50 ℃ for 12-48h to obtain the Pd/hollow polymer sphere precursor.
(c) And (3) calcining: placing the porcelain boat containing Pd/hollow polymer ball precursor in a programmable atmosphere tube furnace, programming the temperature to 500 ℃ at the speed of 2 ℃/min, and heating the ceramic boat in N 2 Calcining at high temperature in the atmosphere, preserving the heat for 3 hours, and then naturally cooling to room temperature to obtain the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-500).
Example 3 preparation of Low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-700)
A preparation method of a low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst comprises the following steps:
(a) A hydrothermal process: 54mg of template Pluronic P123 and 90mg of sodium oleate are weighed out to prepare aqueous solution A with the concentrations of 0.375mmol/L and 12mmol/L respectively. 231mg of 2, 4-dihydroxy benzoic acid (DA) and 88mg of Hexamethylenetetramine (HMT) are weighed and prepared into aqueous solutions with the concentrations of 20mmol/L and 8.3mmol/L respectively, and the aqueous solutions are fully stirred and dissolved for 30min to obtain a solution B. And then slowly adding the solution A into the solution B in the stirring process, and continuously stirring for 30min to obtain a micelle solution C. And then transferring the solution C into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in an oven, carrying out temperature preservation for 2h at the temperature rising rate of 1 ℃/min to 160 ℃, then naturally cooling to room temperature, centrifuging for 20min at the rotating speed of 10000rpm, repeatedly carrying out deionized water/ethanol cleaning for 3 times, and placing the obtained reddish brown precipitate in a vacuum oven at the temperature of 50 ℃ for drying for 24h to obtain the hollow polymer sphere precursor HPS.
(b) And (3) dipping: weighing 50mg HPS by double solvent immersion method, dispersing in pentane, ultrasonically stirring to obtain dispersion liquid D, weighing 2mg Na 2 PdCl 4 Dissolving in deionized water, and performing ultrasonic treatment to obtain solution E. Gradually dripping solution E into solution D while stirring solution D to obtain solution F, stirring for 30min, opening bottle cap, and evaporating at room temperature2-24h, then putting the mixture into a vacuum oven, and drying the mixture for 12-48h at the temperature of 50 ℃ to obtain the Pd/hollow polymer sphere precursor.
(c) And (3) calcining: placing the porcelain boat containing Pd/hollow polymer ball precursor in a programmable atmosphere tube furnace, programming the temperature to 700 ℃ at the speed of 2 ℃/min, and heating the ceramic boat to N 2 Calcining at high temperature in the atmosphere, preserving the heat for 3 hours, and then naturally cooling to room temperature to obtain the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-700).
Example 4 preparation of Low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-900)
A preparation method of a low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst comprises the following steps:
(a) A hydrothermal process: 54mg of the template Pluronic P123 and 90mg of sodium oleate were weighed out to give aqueous solutions A having concentrations of 0.375mmol/L and 12mmol/L, respectively. 231mg of 2, 4-Dihydroxybenzoic Acid (DA) and 88mg of Hexamethylenetetramine (HMT) are weighed to prepare aqueous solutions with the concentrations of 20mmol/L and 8.3mmol/L respectively, and the aqueous solutions are fully stirred and dissolved for 30min to obtain a solution B. And then slowly adding the solution A into the solution B in the stirring process, and continuously stirring for 30min to obtain a micelle solution C. And then transferring the solution C into a polytetrafluoroethylene reaction kettle, placing the reaction kettle in an oven, carrying out temperature preservation for 2h at the temperature rising rate of 1 ℃/min to 160 ℃, then naturally cooling to room temperature, centrifuging for 20min at the rotating speed of 10000rpm, repeatedly carrying out deionized water/ethanol cleaning for 3 times, and placing the obtained reddish brown precipitate in a vacuum oven at the temperature of 50 ℃ for drying for 24h to obtain the hollow polymer sphere precursor HPS.
(b) And (3) dipping: weighing 50mg HPS by double solvent immersion method, dispersing in pentane, ultrasonically stirring to obtain dispersion liquid D, weighing 2mgNa 2 PdCl 4 Dissolving in deionized water, and performing ultrasonic treatment uniformly to obtain a solution E. And gradually dripping the solution E into the solution D in the stirring process of the solution D to obtain a solution F, stirring for 30min, opening a bottle cap, evaporating at room temperature for 2-24h, and then putting into a vacuum oven for drying at 50 ℃ for 12-48h to obtain the Pd/hollow polymer sphere precursor.
(c) And (3) calcining: the porcelain containing Pd/hollow polymer ball precursorThe boat is placed in a programmable atmosphere tube furnace, and the temperature is programmed to 900 ℃ at the speed of 2 ℃/min under the condition of N 2 Calcining at high temperature in the atmosphere, preserving the heat for 3 hours, and then naturally cooling to room temperature to obtain the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-900).
Example 5 preparation of Low-Supported Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-5-700)
Samples were prepared in the same manner as in example 3, except that: HPS and Na in double-solvent impregnation process 2 PdCl 4 The amount of (c) added.
Example 6 preparation of Low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-6-700)
Samples were prepared in the same manner as in example 3, except that: HPS and Na in double-solvent impregnation process 2 PdCl 4 The amount of (c) added.
Example 7 preparation of Low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-7-700)
Samples were prepared in the same manner as in example 3, except that: HPS and Na in double-solvent impregnation process 2 PdCl 4 The amount of (2) added.
Example 8 preparation of Low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-8-700)
Samples were prepared in the same manner as in example 3, except that: HPS and Na in double-solvent impregnation process 2 PdCl 4 The amount of (2) added.
Example 9 preparation of Low-Supported Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-9-700)
Samples were prepared in the same manner as in example 3, except that: HPS and Na in double-solvent impregnation process 2 PdCl 4 The amount of (c) added.
Example 10 preparation of Low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-10-700)
Samples were prepared in the same manner as in example 3, except that: HPS and Na in double-solvent impregnation process 2 PdCl 4 The amount of (c) added.
Example 11 preparation of Low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-11-700)
Samples were prepared in the same manner as in example 3, except that: HPS and Na in double-solvent impregnation process 2 PdCl 4 The amount of (c) added.
Example 12 preparation of Low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-12-700)
Samples were prepared in the same manner as in example 3, except that: HPS and Na in double-solvent impregnation process 2 PdCl 4 The amount of (c) added.
Example 13 preparation of Low load Pd/hollow carbon sphere oxygen reduction electrocatalyst (Pd-HCS-13-700)
Samples were prepared in the same manner as in example 3, except that: HPS and Na in double-solvent impregnation process 2 PdCl 4 The amount of (c) added.
Table 1 shows Pluronic P123, sodium oleate, hexamethylenetetramine (HMT), 2, 4-dihydroxybenzoic acid, HPS, na in examples 1-13 2 PdCl 4 Summary of the amounts added and calcination temperatures.
TABLE 1
Example 14 method for modifying glassy carbon electrode with low Pd/hollow carbon sphere oxygen reduction electrocatalyst
Ultrasonically dispersing the prepared low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst catalyst in a Nafion solution to obtain 2mg/mL ink dispersion liquid, wherein the Nafion solution is a mixed solution of water, isopropanol and Nafion in a volume ratio of 4.
Example 15 test of oxygen reduction catalytic reaction Performance of a glassy carbon electrode modified by a Low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst
In 0.1M KOH electrolyte solution, a three-electrode system is adopted to carry out electrochemical test on the catalyst, a glassy carbon electrode modified by a low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst is used as a working electrode, a saturated Ag/AgCl electrode is used as a reference electrode, a Pt wire is used as a counter electrode, and an Shanghai Hua CHI-842D electrochemical workstation and a Japanese ALS RRDE-3A rotary disc device are adopted to carry out oxygen reduction catalytic reaction performance test on the catalyst modified electrode. The oxygen reduction catalytic activity was tested in 0.1M KOH solution saturated with oxygen.
The specific operation is as follows: at the constant temperature of 25 ℃, introducing oxygen into the electrolyte for about 30min in advance to saturate the oxygen in the solution, and then scanning an oxygen reduction polarization curve from high potential 0V to low potential-0.5V at a scanning rate of 10 mV/s. The electrode modified by the hollow carbon sphere or the glassy carbon electrode modified by the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst, which is obtained by the invention, is placed in an oxygen-saturated 0.1M potassium hydroxide solution to carry out a cathode oxygen reduction reaction test of a fuel cell, and the activity parameters for representing the oxygen reduction reaction comprise the initial potential, half-wave potential and limiting current density of the oxygen reduction reaction.
Example 16 ICP Mass fraction test
Firstly carrying out acid dissolution digestion on a Pd-HCS-700 catalyst sample, then using a 5% nitric acid solution to fix the volume to 20mL, filtering, taking 10mL solution to dilute to 100mL, and carrying out ICP-OES: agilent 725 from Agilent, USA tests to obtain the Pd content in the solution.
FIG. 1 is a TEM photograph of oxygen reduction electrocatalysts of low-loaded Pd/hollow carbon spheres prepared at different calcination temperatures in examples 2-4. From FIG. 1, it can be seen that the three low-loaded Pd/hollow carbon spheres prepared in examples 2-4 have uniform size, diameter in the size range of 130-180nm, shell thickness of about 20-40nm, and from B, pd-HCS-700 nm carbon spheres have diameter of about 150nm and shell thickness of about 20nm. FIG. 2 is an XRD diffraction pattern of the four carbon sphere nano-materials prepared in examples 1-4, and it can be seen from the figure that at 500 ℃, the Pd-HCS-500 catalyst exists mainly in the form of PdO, when the temperature rises to 700 ℃ and 900 ℃, the PdO is converted into Pd elementary substance, and the existence of Pd is favorable for promoting the occurrence of ORR reaction.
To compare the difference in the noble metal content between the low-loaded Pd/hollow carbon sphere oxygen reduction electrocatalyst prepared according to the present invention and the commercial Pt/C electrocatalyst, the Pd-HCS-700 catalyst prepared in example 3 was subjected to the ICP test, and the mass fraction of Pd in the Pd-HCS-700 was 1.7%, while the mass fraction of Pt in the commercial Pt/C was 20%.
FIG. 3 shows the results of ORR catalytic activity tests for Pd-HCS-700, HCS-700 and commercial Pt/C catalysts. As can be seen from fig. 3, the modified electrode of the obtained Pd-HCS-700 catalyst has optimal catalytic activity for oxygen reduction, with a half-wave potential of 0.802V (vs. rhe), which is comparable to the performance of a commercial Pt/C catalyst with a half-wave potential of 0.804V (vs. rhe), and is of great significance for promoting the commercialization process of fuel cells.
FIG. 4 is a linear scanning curve of ORR catalytic activities of Pd-HCS-500, pd-HCS-700 and Pd-HCS-900 catalysts, and it can be seen from FIG. 4 that the oxygen reduction catalytic activity of Pd-HCS-500 is low, while the oxygen reduction catalytic activities of Pd-HCS-700 and Pd-HCS-900 are high, and it can be seen from the XRD diffraction pattern in FIG. 2 that Pd-HCS-500 mainly exists in the form of PdO, and PdO in Pd-HCS-700 and Pd-HCS-900 is converted into Pd, so that the catalytic activities are high.
Fig. 5 is a cyclic voltammogram of the Pd-HCS-700 catalyst modified glassy carbon electrode prepared in example 3 in 0.1M potassium hydroxide solution containing 1M methanol, and it can be seen from the cyclic voltammogram that the modified electrode of the Pd-HCS-700 catalyst obtained in example 2 has no obvious methanol oxidation peak after 1M methanol is added, and the oxygen reduction reaction peak is not substantially shifted negatively, which indicates that the low-loading Pd/hollow carbon sphere oxygen reduction electrocatalyst prepared by us possesses good methanol poisoning resistance.
FIGS. 6 and 7 are the ORR catalytic activity linear scan curves of Pd-HCS-700 and commercial Pt/C catalysts after 1, 3500 and 10000 cycles of cyclic voltammetry scan, respectively. It can be seen from the figure that the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst Pd-HCS-700 prepared in example 3 has no significant change in initial potential and half-wave potential after 10000 cycles of cycle, while the commercial Pt/C catalyst has significant negative shift in initial potential and half-wave potential after 10000 cycles of cycle, which indicates that the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst prepared by us has good stability.
Combining the above examples and test results, the low-loading Pd/hollow carbon sphere oxygen reduction electrocatalyst provided by the invention has uniform outer diameter and wall thickness and narrow particle size distribution, and has comparable oxygen reduction catalytic activity compared with the commercial Pt/C catalyst, but has higher methanol poisoning resistance and stability than the commercial Pt/C catalyst. In addition, the preparation process is simple, and the mass fraction of the metal in the obtained low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst is much lower than that of a commercial Pt/C catalyst, so that the preparation and application costs of the catalyst are undoubtedly greatly reduced, and the preparation method has an immeasurable promotion effect on the popularization and the application of a fuel cell.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be understood by those skilled in the art that the invention is not limited by the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (5)
1. A preparation method of a low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst is characterized by comprising the following steps:
(a) A hydrothermal process: weighing a proper amount of template agent and a proper amount of carbon source precursor, respectively preparing aqueous solutions A and B, stirring and mixing at room temperature to obtain a micellar solution C, then putting the solution C into a polytetrafluoroethylene reaction kettle, placing the polytetrafluoroethylene reaction kettle into an oven, heating the solution C to 100-180 ℃ from room temperature at a heating rate of 1-4 ℃/min, carrying out heat preservation for 1-8 h, carrying out hydrothermal reaction, then naturally cooling the solution C to room temperature, centrifuging the solution at a high rotating speed, taking out a solid at the bottom, washing the solid with deionized water and ethanol for multiple times, and drying the obtained precipitate to obtain a hollow polymer sphere precursor HPS; (b) impregnation process: weighing a certain amount of hollow polymer sphere precursor HPS, dispersing in an organic solvent, performing ultrasonic treatment for a period of time, uniformly stirring to obtain a dispersion solution D, weighing a proper amount of Na2PdCl4, dissolving in deionized water, performing ultrasonic treatment uniformly to obtain a solution E, gradually dripping the solution E into the dispersion solution D in the stirring process of the dispersion solution D to obtain a solution F, evaporating under the stirring condition, and then placing in a vacuum drying oven for vacuum drying to obtain a Pd/hollow polymer sphere precursor;
(c) And (3) calcining: placing the ceramic boat containing the Pd/hollow polymer ball precursor in a programmable atmosphere tube furnace, raising the temperature to 500-900 ℃ at the heating rate of 1-10 ℃/min, carrying out high-temperature calcination under the inert atmosphere, carrying out heat preservation for a period of time, and then naturally cooling to room temperature to obtain the low-load Pd/hollow carbon ball oxygen reduction electrocatalyst Pd-HCS;
in step (a), the templating agent is: the triblock copolymer Pluronic P123 and sodium oleate, wherein the molar ratio of Pluronic P123 to sodium oleate is 1; the precursor of the carbon source is as follows: hexamethylenetetramine (HMT) and 2, 4-Dihydroxybenzoic Acid (DA), the molar ratio of hexamethylenetetramine to 2, 4-dihydroxybenzoic acid being 1 to 1, 3, the molar ratio of triblock copolymer Pluronic P123 to Hexamethylenetetramine (HMT) being 1;
in step (b), the noble metal salt is: na (Na) 2 PdCl 4 The mass ratio of the noble metal salt to the hollow polymer sphere precursor HPS is (1-1);
in the step (c), the temperature is kept for 0.5 to 6 hours under the inert atmosphere of nitrogen and argon.
2. The method for preparing the low-loading Pd/hollow carbon sphere oxygen reduction electrocatalyst according to claim 1, characterized in that: the diameter of the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst is 130-180nm, and the shell thickness is 20-40nm.
3. The method for preparing the low-loading Pd/hollow carbon sphere oxygen reduction electrocatalyst according to claim 2, characterized in that: the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst has the diameter of 150nm and the shell thickness of 20nm, wherein the mass fraction of Pd is 1.7%.
4. The method for preparing the low-loading Pd/hollow carbon sphere oxygen reduction electrocatalyst according to claim 1, characterized in that: in step (b), the organic solvent used to disperse the hollow polymer sphere precursor HPS is pentane.
5. The method for modifying the glassy carbon electrode by the low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst prepared by the preparation method according to claim 1 is characterized by comprising the following steps of: ultrasonically dispersing a low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst in a Nafion solution to obtain 2mg/mL ink dispersion, uniformly dripping the ink dispersion on a glassy carbon electrode by using a micro-syringe, and baking under an infrared lamp, wherein the Nafion solution is a mixed solution of water, isopropanol and Nafion in a volume ratio of 4.
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