CN112909273B - Pt-CuO-TiO 2 catalyst/C and synthesis method thereof - Google Patents

Pt-CuO-TiO 2 catalyst/C and synthesis method thereof Download PDF

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CN112909273B
CN112909273B CN202110086971.2A CN202110086971A CN112909273B CN 112909273 B CN112909273 B CN 112909273B CN 202110086971 A CN202110086971 A CN 202110086971A CN 112909273 B CN112909273 B CN 112909273B
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tio
cuo
catalyst
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CN112909273A (en
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马利
甘孟渝
谢菲
傅情
钟秀娟
詹旺
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Chongqing University
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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
    • 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
    • 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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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 invention relates to the technical field of catalysts, in particular to Pt-CuO-TiO 2 The synthesis method of the/C catalyst comprises the following steps: dissolving NaOH in ultrapure water, and adding TiO continuously 2 And Cu (NO) 3 ) 2 ·3H 2 Carrying out ultrasonic treatment after O; placing the mixture in a high-pressure reaction kettle for reaction; collecting and washing the product, and drying the product to obtain CuO-TiO 2 A composite carrier; preparing a slurry A, placing the prepared slurry A into a stirrer, and dropwise and uniformly adding a solution B prepared by trisodium citrate into the slurry A; then continuing stirring; then NaBH will be used 4 Continuously dropwise adding the prepared solution C, and stirring to obtain a reaction solution; finally, washing the product for 3 times, and drying to obtain the catalyst. The invention obviously improves the catalytic activity and stability of the Pt-based catalyst, obviously improves the charge transfer efficiency and the working efficiency of the direct methanol fuel cell, and promotes the commercialization of the direct methanol fuel cell.

Description

Pt-CuO-TiO 2 catalyst/C and synthesis method thereof
Technical Field
The invention relates to the technical field of fuel cells, in particular to Pt-CuO-TiO 2 a/C catalyst and a synthetic method thereof.
Background
As an anode active material of Direct Methanol Fuel Cells (DMFCs), fuel methanol has the characteristics of high energy density, wide and renewable sources, environmental friendliness, convenience in storage and transportation, and the like. Therefore, Direct Methanol Fuel Cells (DMFCs) are a promising energy device, and much research has been conducted thereon. Since the performance and development of current Direct Methanol Fuel Cells (DMFCs) is severely affected by the performance of the catalyst; at present, the anode catalyst of Direct Methanol Fuel Cells (DMFCs) generally adopts a Pt-based catalyst, but the Pt-based catalyst developed in the market at present has low catalytic activity and poor stability, which results in low charge transfer efficiency and working efficiency of Direct Methanol Fuel Cells (DMFCs), and the catalytic performance of the existing Pt-based catalyst is far from meeting the commercialization requirement of Direct Methanol Fuel Cells (DMFCs).
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides Pt-CuO-TiO 2 A/C catalyst and a synthesis method thereof aim to solve the technical problems that the current Pt-based catalyst has low catalytic activity and poor stability, so that the charge transfer efficiency and the working efficiency of a direct methanol fuel cell are low, the commercialization of the direct methanol fuel cell cannot be realized, and the like.
In order to achieve the above object, the present invention provides Pt-CuO-TiO 2 The synthesis method of the/C catalyst comprises the following steps:
1) dissolving NaOH in ultrapure water, and after the NaOH is completely dissolved, continuously adding TiO 2 And Cu (NO) 3 ) 2 ·3H 2 Ultrasonic treatment after O, wherein NaOH and TiO 2 And Cu (NO) 3 ) 2 ·3H 2 The molar ratio of O is 16: (1-2): (0.8 to 1.2); transferring the solution after ultrasonic treatment into a high-pressure reaction kettle, and reacting for 22-24 h at 140-160 ℃;
2) after the reaction in the step 1) is finished, collecting a brown product through a centrifugal device, washing the brown product with ethanol and distilled water respectively, and drying the finally obtained brown product at 50-60 ℃ for 11-13 h to obtain CuO-TiO 2 A composite carrier;
3) taking Vulcan XC-72R C and CuO-TiO obtained in the step 1) 2 Adding into ultrapure water for ultrasonic treatment, wherein Vulcan XC-72R C and CuO-TiO 2 The mass ratio of (A) to (B) is 3: (6-8); stopping ultrasonic treatment until uniform slurry A is formed;
4) dissolving 20-30 mg trisodium citrate in distilled water, and stirring until the trisodium citrate is dissolvedThen continuing to add H dropwise 2 PtCl 6 After the dropwise addition of the ethylene glycol solution, uniformly stirring to obtain a solution B;
5) 3 to 4mgNaBH 4 Adding the mixture into distilled water for ultrasonic treatment to form a uniform solution C;
6) placing the slurry A obtained in the step 3) into a magnetic stirrer, stirring at the rotating speed of 550-650 rmp, and then dropwise and uniformly adding the solution B obtained in the step 4) into the slurry A; after the dropwise adding is finished, continuously stirring for 50-70 min; then, in the stirring process, continuously dropwise adding the solution C obtained in the step 5), and continuously stirring for 24 hours after the addition is finished to obtain a reaction solution;
7) after the reaction is finished, filtering the reaction solution, washing the reaction solution with ethanol and distilled water for 3 times respectively, collecting black precipitates, and drying the black precipitates at the temperature of below 60 ℃ to obtain Pt-CuO-TiO 2 a/C catalyst.
Preferably, NaOH and TiO in the step 1) 2 And Cu (NO) 3 ) 2 ·3H 2 The molar ratio of O is 16: 1.5: 1; the solution after ultrasonic treatment is transferred to a high-pressure reaction kettle and reacted for 24 hours at the temperature of 150 ℃.
Preferably, the brown product obtained finally in step 2) is dried at 55 ℃ for 12h to obtain CuO-TiO 2 And (3) a composite carrier.
Preferably, Vulcan XC-72R C and CuO-TiO in the step 3) 2 The mass ratio of (A) to (B) is 3: 7; sonication for 30min resulted in a homogeneous slurry.
Preferably, in the step 4), 25mg of trisodium citrate is dissolved in 6mL of distilled water, stirred for 15min and then added dropwise with 0.525mL of 48.803mmol/LH 2 PtCl 6 And (4) after the dropwise addition of the ethylene glycol solution, stirring for 15min to obtain a solution B.
Preferably, 3.5mg NaBH will be used in said step 5) 4 Added to 8mL of distilled water and sonicated for 10min to form a homogeneous solution C.
Preferably, the slurry A obtained in the step 3) in the step 6) is placed in a magnetic stirrer and stirred at the rotating speed of 600rmp, and then the solution B obtained in the step 4) is uniformly added into the slurry A drop by drop; stirring was continued for another 60min after the addition was complete.
Preferably, it is prepared by any one of the methods of claims 1-7.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a method for preparing Pt-CuO-TiO 2 Method for preparing/C composite catalyst by doping TiO with CuO 2 Modified to strengthen metal oxide TiO 2 The conductive property of the Pt-based catalyst, the interaction between the Pt-based catalyst and the noble metal Pt, and the adsorption of-OH at a lower potential, thereby improving the catalytic activity and stability of the Pt-based catalyst; the charge transfer efficiency of Direct Methanol Fuel Cells (DMFCs) is obviously improved, so that the working efficiency of the cells is greatly improved, and the commercialization of the Direct Methanol Fuel Cells (DMFCs) is promoted gradually.
(2) In the invention, TiO is introduced into a catalyst carrier material 2 As cocatalyst, TiO 2 Has excellent stability, higher mechanical strength, low cost, good corrosion resistance in acid solution, TiO 2 Can generate rich OH, improves the CO poisoning resistance of the Pt nano-particles and is beneficial to improving the catalytic activity of the catalyst. Then doping TiO by CuO 2 Surface modification is carried out to shorten TiO 2 And modifying the electronic structure thereof; according to the related physical detection means, the CuO is successfully doped into the TiO 2 In the nanotube, electrochemical performance tests show that the Pt-CuO-TiO prepared in the invention 2 the/C catalyst has excellent methanol oxidation activity and stability, and is doped with CuO to TiO 2 Surface modification to TiO 2 The method lays a foundation for the wide application of the catalyst in methanol electrocatalysis materials, and provides a basis for the construction of other high-efficiency platinum-based catalysts.
(3) Pt-CuO-TiO prepared in the invention 2 the/C catalyst has rich pore structure and proper specific surface area, is beneficial to the dispersion of the noble metal Pt-based catalyst and can also promote the proton transmission in the cell reaction; also has good conductivity, and can accelerate the reaction kinetic rate of methanol oxidation, thereby Thereby improving the working efficiency of the battery; in addition, the Pt-CuO-TiO prepared by the invention 2 The corrosion resistance and stability of the/C catalyst in an acid solution or an acid electrolyte solution are good, and the interaction force between the catalyst and the carrier effectively avoids the phenomenon of catalyst agglomeration in an electrochemical test; therefore, the catalytic activity and the stability of the composite catalyst prepared by the method are greatly improved, the catalytic activity is improved by several times compared with the existing Pt-based catalyst, and the method can gradually meet the requirements of commercialization of methanol fuel cells (DMFCs).
Drawings
FIG. 1 shows Pt-CuO-TiO in the present invention 2 XRD pattern of/C catalyst;
FIG. 2 shows Pt-CuO-TiO in the present invention 2 TEM image of the/C catalyst;
FIG. 3 shows Pt-CuO-TiO in the present invention 2 /C、Pt-TiO 2 Catalyst concentration of/C, Pt/C-JM at 0.5M H 2 SO 4 +1M CH 3 Graph of CV test results performed in OH solution;
FIG. 4 shows Pt-CuO-TiO in the present invention 2 /C、Pt-TiO 2 Catalyst at N/C, Pt/C-JM 2 Saturated 0.5M H 2 SO 4 A CO stripping voltammetry test result graph is carried out in an acid solution;
FIG. 5 shows Pt-CuO-TiO in the present invention 2 /C、Pt-TiO 2 Catalyst at N/C, Pt/C-JM 2 Saturated 0.5M H 2 SO 4 +1M CH 3 Graph of results of 3600s Chronoamperometric (CA) tests in OH solution.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the invention. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
Pt-CuO-TiO 2 The synthesis method of the/C catalyst comprises the following steps:
1) dissolving NaOH in ultrapure water, and after the NaOH is completely dissolved, continuously adding TiO 2 And Cu (NO) 3 ) 2 ·3H 2 Ultrasonic treatment after O, wherein NaOH and TiO 2 And Cu (NO) 3 ) 2 ·3H 2 The molar ratio of O is 16: (1-2): (0.8 to 1.2); transferring the solution after ultrasonic treatment into a high-pressure reaction kettle, and reacting for 22-24 h at 140-160 ℃;
2) after the reaction in the step 1) is finished, collecting a brown product through a centrifugal device, washing the brown product with ethanol and distilled water respectively, and drying the finally obtained brown product at 50-60 ℃ for 11-13 h to obtain CuO-TiO 2 A composite carrier;
3) taking Vulcan XC-72R C and CuO-TiO obtained in the step 1) 2 Adding into ultrapure water for ultrasonic treatment, wherein Vulcan XC-72R C and CuO-TiO 2 The mass ratio of (A) to (B) is 3: (6-8); stopping ultrasonic treatment until uniform slurry A is formed;
4) dissolving 20-30 mg trisodium citrate in distilled water, stirring until the trisodium citrate is dissolved, and then continuously dropwise adding H 2 PtCl 6 After the dropwise addition of the ethylene glycol solution, uniformly stirring to obtain a solution B;
5) 3 to 4mgNaBH 4 Adding the mixture into distilled water for ultrasonic treatment to form a uniform solution C;
6) placing the slurry A obtained in the step 3) into a magnetic stirrer, stirring at the rotating speed of 550-650 rmp, and then dropwise and uniformly adding the solution B obtained in the step 4) into the slurry A; after the dropwise adding is finished, continuously stirring for 50-70 min; then, in the stirring process, continuously dropwise adding the solution C obtained in the step 5), and continuously stirring for 24 hours after the addition is finished to obtain a reaction solution;
7) after the reaction is finished, filtering the reaction solution, washing the reaction solution with ethanol and distilled water for 3 times respectively, collecting black precipitates, and drying the black precipitates at the temperature of below 60 ℃ to obtain Pt-CuO-TiO 2 a/C catalyst.
In this example, a Pt-CuO-TiO compound was prepared 2 The synthesis method of the/C catalyst comprises the following steps:
1) Dissolving 6g of NaOH in ultrapure water, and after the NaOH is completely dissolved, continuously adding 0.5g of TiO 2 And 2.265gCu (NO) 3 ) 2 ·3H 2 Carrying out ultrasonic treatment after O; transferring the solution after ultrasonic treatment into a high-pressure reaction kettle, and reacting for 24 hours at 150 ℃;
2) after the reaction in the step 1) is finished, collecting a brown product through a centrifugal device, washing the brown product for 3 times by using ethanol and distilled water respectively, and drying the finally obtained brown product at 55 ℃ for 12h to obtain CuO-TiO 2 A composite carrier;
3) taking 6mgVulcan XC-72R C and 14mgCuO-TiO obtained in the step 1) 2 Adding into ultrapure water, and performing ultrasonic treatment for 30min to form uniform slurry A;
4) dissolving 25mg trisodium citrate in 6mL distilled water, stirring for 15min until the trisodium citrate is dissolved, and then continuously dropwise adding 0.525mL 48.803mmol/LH 2 PtCl 6 After the dropwise addition of the ethylene glycol solution, stirring for 15min to obtain a solution B;
5) 3.5mg NaBH 4 Adding into 8mL distilled water for ultrasonic treatment for 10min to form a uniform solution C;
6) placing the slurry A obtained in the step 3) into a magnetic stirrer, stirring at the rotating speed of 600rmp, and then dropwise and uniformly adding the solution B obtained in the step 4) into the slurry A; after the dropwise addition is finished, stirring is continued for 60 min; then, in the stirring process, continuously dropwise adding the solution C obtained in the step 5), and continuously stirring for 24 hours after the addition is finished to obtain a reaction solution;
7) After the reaction, the reaction solution was filtered, washed with ethanol and distilled water for 3 times, respectively, and collected to obtain a black precipitateDrying the black precipitate at the temperature of below 60 ℃ to obtain Pt-CuO-TiO 2 a/C catalyst.
Pt-CuO-TiO prepared by the invention 2 The electrocatalytic performance test method of the/C catalyst comprises the following steps:
(1) and (4) preparing an electrode. Pt-CuO-TiO 2 /C、Pt-TiO 2 Electrocatalytic performance tests of/C, Pt/C-JM catalyst all take a Glassy Carbon Electrode (GCE) coated with the catalyst as a working electrode, Hg/Hg 2 Cl 2 The calomel electrode is a reference electrode, the platinum sheet (1cm multiplied by 1cm) is an auxiliary electrode, and a three-electrode system is assembled to be tested on an Shanghai Chenghua CHI 760E type electrochemical workstation.
(2) And (3) preparing the catalyst ink. Accurately weighing 2.0mgPt-CuO-TiO 2 /C or Pt-TiO 2 placing/C or Pt/C-JM catalyst in 2mL centrifuge tube, accurately transferring 475 μ L distilled water and 475 μ L anhydrous ethanol and 50 μ L5 wt% Nafion solution into the centrifuge tube, and ultrasonically dispersing for 30min to obtain the final product with concentration of 2mg mL -1 The catalyst ink of (1).
(3) And (6) coating the sample. The glassy carbon electrode surface of 4mm diameter was polished to a mirror surface on a chamois using 0.05 μm alumina powder and then ultrasonically cleaned with an appropriate amount of ethanol and water in sequence. After the surface of the electrode is dried, accurately transferring 5 mu L of catalyst ink, uniformly coating the catalyst ink on the surface of the glassy carbon electrode, and drying at 40 ℃ for later use.
(4) Methanol electrocatalytic activity test
The methanol electrocatalytic activity test is carried out at room temperature by using N 2 Saturated 0.5M H 2 SO 4 +1M CH 3 In OH solution, 50mV s is used in a potential range of-0.20-1.00V -1 Is subjected to Cyclic Voltammetry (CV) testing. And (3) activating the electrode, and performing CV test after the scanning curve is stable.
(5) CO stripping voltammetry test
CO stripping voltammetry is an important method to evaluate the resistance of a catalyst to CO poisoning. Assembling the working electrode into a three-electrode system and placing the three-electrode system in N 2 Saturated 0.5M H 2 SO 4 In solution. Activating the working electrode, introducing high-purity CO into the electrolyte to saturate for 20min, and thenPerforming cyclic voltammetry testing at a constant potential of 0.6V; finally, introducing N into the electrolyte again 2 Removing residual CO in the solution, and adding 50mV s -1 The CV test was performed.
(6) Chronoamperometric testing
The activated working electrode is placed in N under the constant voltage of 0.6V 2 Saturated 0.5M H 2 SO 4 +1M CH 3 3600s Chronoamperometric (CA) tests were performed in OH solution.
1. For Pt-CuO-TiO 2 XRD detection of the/C catalyst can obtain the attached figure 1, and the figure can show that: many obvious peaks appear in the detection range of 20-90 degrees, and the comparison with the standard cards of all the materials shows that the peak of 2 theta at about 25 degrees corresponds to a C (002) crystal face, and the peak at about 28 degrees is TiO 2 The sharp peaks appearing at 39.8 °, 46.2 °, 67.4 ° and 81.3 ° are respectively assigned to the (111), (200), (220) and (311) crystal planes of face-centered cubic Pt, indicating that Pt Nanoparticles (NPs) are successfully loaded onto the composite material. In addition, no distinct separate CuO diffraction peak was observed, as was evident from the position and XRD diffraction pattern analysis of the standard card, probably due to the characteristic peaks of CuO with Pt or TiO 2 Partially overlap to form a wider diffraction peak, e.g. about 40 deg. between the (200) crystal plane of CuO and TiO 2 (200) The crystal planes of Pt (111) are overlapped. XRD detection results show that the CuO is successfully doped into the TiO by the method of the invention 2 In nanotubes, and the PtNPs are payload.
2. For Pt-CuO-TiO 2 The catalyst/C is detected by a transmission electron microscope to obtain the attached figure 2, and as shown in attached figures 2A and 2B, the product prepared by the method consists of carbon black particles and obvious nanotubes, and small-size nanoparticles are uniformly deposited on the surface of the composite carrier. From Pt-CuO-TiO 2 In the high-resolution TEM image of the/C catalyst (FIG. 2C), significant lattice fringes can be seen, which were measured to have a lattice spacing of 0.197nm and to correspond to the (200) plane of Pt, whereas the lattice fringes having a spacing of 0.2218nm are attributed to TiO 2 The (200) crystal face of (A) indicates that PtNPs and TiO exist in the composite catalyst 2 A nanotube. Further, from the element distribution image (FIG. 2D)It shows that Pt nano particles are mainly distributed on the surface of the nano tube, three elements of O, Cu and Ti are uniformly distributed, the result is consistent with the result of an XRD (X-ray diffraction) diagram, and effective doping of CuO and Pt-CuO-TiO are verified again 2 Successful preparation of the/C catalyst.
3. According to the test method of the electrocatalytic activity of the methanol, for Pt-CuO-TiO 2 /C、Pt-TiO 2 Catalyst concentration of/C, Pt/C-JM at 0.5M H 2 SO 4 +1M CH 3 CV testing in OH solution, the results are shown in FIG. 3. From the figure, it can be seen that Pt-CuO-TiO 2 The highest specific mass activity for methanol oxidation (1537.3mA mg/C) -1 Pt ) Is Pt-TiO respectively 2 /C(558.7mAmg -1 Pt ) And Pt/C-JM (256.2 mAmg) -1 Pt ) 2.75 times and 6 times; illustrating Pt-CuO-TiO 2 The catalytic activity of the catalyst/C is improved by times.
4. According to a CO stripping voltammetry test method, Pt-CuO-TiO is subjected to 2 /C、Pt-TiO 2 Catalyst at N/C, Pt/C-JM 2 Saturated 0.5M H 2 SO 4 The results of the CO stripping voltammetry tests in acidic solution are shown in FIG. 4, which shows that all catalysts tested compare to Pt-TiO 2 catalyst/C, Pt/C-JM, Pt-CuO-TiO 2 the/C has the lowest peak potential (0.575V) and peak oxidation potential (0.633V). The results described above show that Pt-CuO-TiO is superior to several other catalysts 2 the/C catalyst has higher CO resistance ads Poisoning ability, which facilitates re-exposure of active sites on the surface of the Pt-based catalyst. Pt-CuO-TiO 2 The enhanced CO poisoning resistance of the/C is attributed to Pt, CuO and TiO 2 Strong interactions between nanotubes.
5. For Pt-CuO-TiO 2 /C、Pt-TiO 2 Catalyst at N/C, Pt/C-JM 2 Saturated 0.5M H 2 SO 4 +1 M CH 3 3600s Chronoamperometric (CA) tests were performed in OH solution. The results are shown in FIG. 5, which shows that after 3600s chronoamperometric test, the results are compared with Pt-TiO 2 /C(16.5mAmg -1 Pt ) And Pt/C-JM (9.8 mA mg -1 Pt ) Catalyst, Pt-CuO-TiO 2 /CThe catalyst had the highest specific mass activity (70.6mA mg -1 Pt ). This means that the catalyst still retains a relatively rich active site, Pt-CuO-TiO, after testing 2 the/C catalyst has better stability compared with other catalysts.
In summary, Pt-CuO-TiO 2 The specific activity and stability of methanol oxidation quality of the/C catalyst are far superior to those of Pt-TiO 2 The research shows that the doping modification of CuO can effectively improve TiO by virtue of the doping modification of CuO and the enhanced interaction and synergistic effect among the components 2 The co-catalysis effect proves that the Pt-CuO-TiO prepared in the invention 2 The catalyst has better catalytic activity and stability, and can better meet the commercialization of Direct Methanol Fuel Cells (DMFCs).
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.

Claims (8)

1. Pt-CuO-TiO 2 The synthesis method of the/C catalyst is characterized by comprising the following steps:
1) dissolving 6g of NaOH in ultrapure water, and after the NaOH is completely dissolved, continuously adding 0.5g of TiO 2 And 2.265gCu (NO) 3 ) 2 ·3H 2 Carrying out ultrasonic treatment after O; transferring the solution after ultrasonic treatment into a high-pressure reaction kettle, and reacting for 22-24 h at 140-160 ℃;
2) after the reaction in the step 1) is finished, collecting a brown product through a centrifugal device, washing the brown product with ethanol and distilled water respectively, and enabling the finally obtained brown product to be 50-60%Drying at the temperature of 11-13 h to obtain CuO-TiO 2 A composite carrier;
3) taking Vulcan XC-72R C and CuO-TiO obtained in the step 1) 2 Adding into ultrapure water for ultrasonic treatment, wherein Vulcan XC-72R C and CuO-TiO 2 The mass ratio of (A) to (B) is 3: (6-8); stopping ultrasonic treatment until uniform slurry A is formed;
4) dissolving 20-30 mg trisodium citrate in distilled water, stirring until the trisodium citrate is dissolved, and then continuously dropwise adding H 2 PtCl 6 After the dropwise addition of the ethylene glycol solution, uniformly stirring to obtain a solution B;
5) 3 to 4mgNaBH 4 Adding the mixture into distilled water for ultrasonic treatment to form a uniform solution C;
6) placing the slurry A obtained in the step 3) into a magnetic stirrer, stirring at the rotating speed of 550-650 rmp, and then dropwise and uniformly adding the solution B obtained in the step 4) into the slurry A; after the dropwise adding is finished, continuously stirring for 50-70 min; then, in the stirring process, continuously dropwise adding the solution C obtained in the step 5), and continuously stirring for 24 hours after the addition is finished to obtain a reaction solution;
7) after the reaction is finished, filtering the reaction solution, washing the reaction solution with ethanol and distilled water for 3 times respectively, collecting black precipitates, and drying the black precipitates at the temperature of below 60 ℃ to obtain Pt-CuO-TiO 2 a/C catalyst, said catalyst being applied to a methanol fuel cell.
2. Pt-CuO-TiO according to claim 1 2 The synthesis method of the/C catalyst is characterized in that the solution after ultrasonic treatment in the step 1) is transferred into a high-pressure reaction kettle and reacts for 24 hours at the temperature of 150 ℃.
3. Pt-CuO-TiO of claim 2 2 The method for synthesizing the/C catalyst is characterized in that the finally obtained brown product is dried for 12 hours at the temperature of 55 ℃ in the step 2) to obtain CuO-TiO 2 And (3) a composite carrier.
4. Pt-CuO-TiO of claim 3 2 The synthesis method of the/C catalyst is characterized in that Vulcan XC-72R C and CuO-TiO in the step 3) 2 The mass ratio of (A) to (B) is 3: 7; sonication for 30min resulted in a homogeneous slurry.
5. Pt-CuO-TiO of claim 4 2 The method for synthesizing the/C catalyst is characterized in that 25mg of trisodium citrate is dissolved in 6mL of distilled water in the step 4), and after the trisodium citrate is dissolved by stirring for 15min, 0.525 mL of 48.803 mmol/LH is continuously dripped 2 PtCl 6 And (4) after the dropwise addition of the ethylene glycol solution, stirring for 15min to obtain a solution B.
6. Pt-CuO-TiO of claim 5 2 The method for synthesizing the/C catalyst is characterized in that 3.5mgNaBH is added in the step 5) 4 Added to 8mL of distilled water and sonicated for 10min to form a homogeneous solution C.
7. Pt-CuO-TiO of claim 6 2 The method for synthesizing the/C catalyst is characterized in that the slurry A obtained in the step 3) in the step 6) is placed in a magnetic stirrer and stirred at the rotating speed of 600rmp, and then the solution B obtained in the step 4) is uniformly added into the slurry A drop by drop; stirring was continued for another 60min after the addition was complete.
8. Pt-CuO-TiO 2 A/C catalyst, characterized in that it is prepared by the synthesis method according to any one of claims 1 to 7.
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