WO2016206345A1 - 基于氮化物纳米粒子的低铂催化剂及其制备方法 - Google Patents

基于氮化物纳米粒子的低铂催化剂及其制备方法 Download PDF

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WO2016206345A1
WO2016206345A1 PCT/CN2015/100018 CN2015100018W WO2016206345A1 WO 2016206345 A1 WO2016206345 A1 WO 2016206345A1 CN 2015100018 W CN2015100018 W CN 2015100018W WO 2016206345 A1 WO2016206345 A1 WO 2016206345A1
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nitride
transition metal
catalyst
carbon
nanoparticles
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French (fr)
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廖世军
田新龙
罗俊明
陈容
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华南理工大学
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Priority to US15/739,755 priority Critical patent/US10549266B2/en
Publication of WO2016206345A1 publication Critical patent/WO2016206345A1/zh
Priority to US16/726,836 priority patent/US11524280B2/en

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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • 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
    • H01M4/8853—Electrodeposition
    • 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
    • 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

Definitions

  • the invention relates to the field of fuel cells, and relates to a nitride nanoparticle-based low platinum catalyst applicable to a fuel cell and a preparation method thereof.
  • Low-temperature fuel cells are regarded as one of the most promising industrial fuel cells due to their high energy conversion efficiency, fast start-up and no pollution.
  • Low-temperature fuel cells include proton exchange membrane fuel cells, direct alcohol fuel cells, and direct acid fuel cells. These fuel cell catalysts use expensive and resource-poor precious platinum as the main active component, resulting in high fuel cell costs. It has become an important factor restricting the commercialization of fuel cells.
  • the currently widely used commercial Pt/C catalysts have only weak adsorption between the supported metal particles and the carbon support, and the carbon support is easily corroded under the operating conditions of the fuel cell, causing the exfoliation and migration of the active metal nanoparticles. , seriously restricting the service life of fuel cells. Therefore, the preparation and research of low-cost, high-activity and high-stability catalysts is of great significance for the development and promotion of fuel cells.
  • the cathode arc deposition technique is firstly used to deposit a layer of titanium nitride on the stainless steel wire to prepare a working electrode, and then Pd or Pt metal is deposited by direct current deposition to prepare a titanium nitride-supported Pt or Pd catalyst.
  • the catalyst exhibited better catalytic activity and stability than Pt/C.
  • the preparation of the catalyst is complicated in that the average particle diameter of the prepared noble metal is 200 nm, and the increase in the activity per unit mass of platinum of the catalyst is very limited.
  • Chinese Patent Application No. 200610027287 discloses a corrosion-resistant fuel cell catalyst preparation technique in which Pt is supported on a nitride-supported metal oxide surface by hydrolysis or gas phase thermal decomposition.
  • the morphology of the prepared catalyst and the performance of the catalyst are not clearly stated. And provide relevant supporting materials.
  • the invention discloses a low-platinum catalyst based on nitride nanoparticles for a fuel cell and a pulse electrodeposition preparation method thereof, which can be used for a proton exchange membrane fuel cell and other processes requiring a noble metal catalyst.
  • a low-platinum catalyst based on nitride nanoparticles for a fuel cell and a pulse electrodeposition preparation method thereof, which can be used for a proton exchange membrane fuel cell and other processes requiring a noble metal catalyst.
  • the complicated preparation technology of low platinum catalyst and the vulnerability of carbon carrier to corrosion it provides a high-efficiency and low-cost method for preparing high performance and high stability low platinum loading catalyst.
  • the transition metal ammonia complex nanoparticles were first synthesized by non-aqueous ammonia gas complexation method, and then the transition metal nitride nanoparticles were prepared by high temperature nitridation; the active metal salt solution was used as the electrodeposition precursor, and the constant current pulsed electricity was used.
  • the deposition method uses different Ton/Toff ratios (0.1-100) to uniformly deposit active metal at the atomic layer level on the surface of the transition metal nitride nanoparticles to obtain a low platinum catalyst with high activity and high stability.
  • the active component of the catalyst is a platinum atomic layer coated nitride nanoparticle, and the active metal is directly coated on the surface of the nitride particle in the form of an ultrathin atomic layer or coated on the surface of the nitride particle supported by the carbon support.
  • the catalyst is based on a transition metal nitride or a carbon-supported transition metal nitride, and one or more of Pt, Ir, Pd, Ru or Au elements are used as a coating layer.
  • the preparation method includes preparation of a transition metal nitride or a carbon-supported transition metal nitride as a base material, fabrication of a pulse electrodeposited working electrode, and finally a catalyst obtained by pulse electrodeposition.
  • the catalyst can be used as an anode or a cathode catalyst for a low temperature fuel cell, and the catalyst has the advantages of high activity and good stability.
  • the preparation technology has the advantages of simple operation, no need of inert atmosphere protection, and controllable deposition amount, and is suitable for large-scale production.
  • the catalyst can greatly reduce the precious metal usage of the fuel cell, greatly reduce the cost of the fuel cell, and is of great significance for promoting the commercialization process of the fuel cell.
  • a method for preparing a low platinum catalyst based on nitride nanoparticles comprises the following steps:
  • nitride nanoparticles one or more transition metal salts are dissolved in a non-aqueous solvent, and then ammonia gas is introduced into 0.5 – After 1 hour, the solvent was evaporated in a vacuum drying oven at 50-90 ° C to obtain a transition metal ammonia complex; the transition metal ammonia complex was nitrided at a high temperature for 3-5 hours in an ammonia atmosphere to obtain a transition metal nitride nanometer.
  • the transition metal ammonia complex comprises Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, An ammonia complex formed by any one of Mo or Ta or a binary or ternary ammonia complex formed by two or more;
  • the high temperature nitriding temperature is 500-900 ° C;
  • the obtained transition metal nitride nanoparticles The diameter is 5-15 Nm;
  • the nonaqueous solvent is an alcohol, or a mixture of an alcohol and a ketone or an ester;
  • the salts of the transition metal include titanium tetrachloride, tetrabutyl titanate, chromium acetate, manganese chloride, iron nitrate, cobalt acetate, copper chloride, barium chloride, molybdenum chloride and barium chloride.
  • Preparation of carbon-loaded transition metal nitride nanoparticles except for the simultaneous addition of a transition metal salt and a pretreated carbon support to a solvent, the other steps are the same as those of the above-described nitride nanoparticles;
  • the carbon support includes XC- 72R carbon black, carbon nanotubes, carbon nanofibers or graphene; the loading of the nitride nanoparticles on the carbon support is 10wt%-40wt%;
  • Method a Weigh an appropriate amount of the nitride nanoparticles or carbon-supported transition metal nitride nanoparticles, and add 1-5 In the mL of the alcohol solution containing the binder, ultrasonically disperse into a slurry, and apply a proper amount of the slurry to the surface of the working electrode substrate with a micropipette.
  • the final loading of the substrate material is 0.1-0.5 mg/ Cm2
  • the binder comprises a polytetrafluoroethylene emulsion, a fluorocarbon resin emulsion or a perfluorosulfonic acid resin emulsion, and the mass percentage of the binder is used for dry polymerization.
  • the resin accounts for 0.5%-20% of the total amount of the catalyst base material;
  • the alcohol includes ethanol, isopropanol or ethylene glycol;
  • the working electrode substrate comprises glassy carbon, nickel foam, titanium flakes, and platinized titanium flakes. Or a platinum sheet;
  • the drying method comprises natural air drying, radiation drying under an infrared lamp or drying in an oven;
  • Method b directly adding the nitride nanoparticles or carbon-supported transition metal nitride nanoparticles as a base material to a catholyte solution containing a desired active metal for pulse electrodeposition, and stirring, continuously passing the particles through the cathode Contacting the conductor to form a working electrode; the catholyte is separated from the anolyte using a microporous medium;
  • Pulse electrodeposition The prepared working electrode was placed in a nitrogen-saturated 0.1-0.5 M H 2 SO 4 solution, and swept from an open circuit voltage to -0.25 to 0 V at a sweep speed of 5-50 mV/s, scanning The number of turns is 10-50 turns, and the substrate material is cleaned and activated; then the electrode is transferred under nitrogen to a nitrogen-saturated solution containing the desired active metal salt, complexing agent (or stabilizer) and conductive auxiliary agent.
  • the auxiliary electrode and the reference electrode are connected; the pulse frequency, the number of pulse deposition, the conduction and the disconnection time are set, and then the pulse electrodeposition process is started, and after the electrodeposition is completed, the catalyst is washed out from the electrode surface. That is, a low platinum catalyst based on nitride nanoparticles is prepared.
  • the transition metal ammonia complex in the non-aqueous solution is prepared by adding the transition metal precursor to a beaker containing a non-aqueous solvent, and after the dissolution is completed, transferring to a Meng's washing bottle and introducing ammonia gas.
  • ammonia gas flow control is 30-100 Ml/min, aeration time of 0.5-1 hour; transfer the resulting complex containing mixture to a crucible, vacuum drying in an oven at 50-90 ° C 8-24 h, obtaining a nitride ammonia complex; wherein the precursor comprises one or more of titanium tetrachloride, iron acetate, cobalt acetate, nickel acetate, vanadium chloride, chromium acetate, manganese chloride and barium chloride.
  • concentration of the precursor in the reaction system solution ranges from 0.1 to 3 Mg/mL;
  • the electrodeposition solution of the step (3) contains an active metal component comprising: one or more of Pt, Au, Pd, Ru, and Ir; and the active metal salt includes platinum tetraammine platinum, More than one of chloroplatinic acid, chloroauric acid, palladium dichloride, antimony trichloride and antimony trichloride; the complexing agent includes citric acid, EDTA or polyvinylpyrrolidone; the conductive auxiliary agent is sodium sulfate or potassium sulfate ; the concentration of the active metal component is 5-100 mM.
  • the method of depositing active metal in the step (3) adopts pulse electrodeposition, and the pulse frequency is 100 - 10000.
  • each pulse contains an on time and an off time
  • the on time (ton) is 0.00003 s to 0.001 s
  • the off time (toff) is 0.00015 – 0.01 s
  • the ratio of on-time to off-time (ton/toff) varies depending on the molar concentration of active metal in the electrolyte and the amount of active metal required. The value is between 0.1 and 100; the total number of pulses is 500-20000.
  • the pulse current density of the pulse electrodeposition in the step (3) is 1 to 50 mA/cm2.
  • the active component of the prepared catalyst is a transition metal nitride nanoparticle coated with an active metal atom layer, and the active metal is coated as a transition metal nitride as a substrate in the form of an ultrathin atomic layer.
  • the carbon carrier supports the surface of the transition metal nitride nanoparticle; wherein the transition metal nitride as the substrate comprises a mono-, binary or ternary transition metal nitride, and the average particle size of the nanoparticles is 5-15 Nm.
  • the active metals used for deposition include Pt, Ir, Pd, An alloy of one or two or more of Ru or Au; the carbon support includes carbon black particles, carbon nanotube fibers, carbon nanotubes or graphene.
  • the mass composition of the catalyst is: carbon carrier 50%-80%; transition metal nitride 10%-40%, active metal component 4%-10%;
  • the ultrathin atomic layer is composed of 1-5 atomic layers;
  • the transition metal nitride includes Ti, V, Cr, Mn, A binary or ternary transition metal nitride composed of one or more of Fe, Co, Ni, Cu, Nb, Mo or Ta.
  • the catalyst exhibits good activity for cathode oxygen reduction, methanol oxidation and formic acid oxidation reaction, and can be used as an anode and a cathode catalyst for a hydrogen-oxygen fuel cell, a direct methanol fuel cell, a direct formic acid fuel cell. Its precious metal usage is 4-5 times lower than that of the commercial Pt/C catalyst, and the mass activity and specific activity can be increased by 3-10 times compared with the commercial Pt/C catalyst; in addition, the catalyst can also be applied to a hydrogenation catalyst in the chemical industry.
  • the preparation technique of the present invention can also directly use commercial nitrides, carbides, oxides, sulfides, and phosphides as substrates for supporting active metals.
  • the nitride-based nanoparticle low platinum catalyst of the present invention Compared with the prior art, the nitride-based nanoparticle low platinum catalyst of the present invention and the preparation method thereof have the following advantages:
  • the present invention provides a method for preparing small particle nano-nitride particles with controllable particle size, and the prepared nitride nanoparticles have a particle diameter of less than 10 nm. Making it suitable for use in the preparation of fuel cell catalysts;
  • the nitride has better resistance to electrochemical corrosion; it can effectively solve the problem of carbon corrosion of the conventional carbon-supported catalyst and cause the fuel cell to decay.
  • the invention adopts pulse electrodeposition technology to realize atomic layer deposition of active components on the surface of nitride nanoparticles (usually thickness of 3-5 atomic layers), compared with conventional core-shell catalysts. It is not necessary to use a noble metal or a noble metal alloy as the core of the core-shell structure, and the cost of the catalyst can be effectively reduced while ensuring the high performance of the active component;
  • the catalyst prepared by the pulse electrodeposition technique of the present invention is comparable to the catalyst prepared by underpotential deposition; meanwhile, the pulse electrodeposition technique has a deposition amount. Controllable, easy to operate, no need for inert gas protection, etc.; easy to achieve industrial production and application;
  • the catalyst prepared by the invention has high catalytic performance for methanol, formic acid anodization and cathode reduction of oxygen, and the activity per unit mass of platinum is 2-10 times that of the commercial Pt/C catalyst, and the catalyst has a pole. High stability.
  • Example 1 is a TEM image of titanium nitride prepared in Example 1.
  • Example 2 is a TEM image of Pt@TiN prepared in Example 1.
  • Example 3 is a Pt@TiNiN transmission electron microscope (TEM) and a high-resolution transmission electron microscope (HR-TEM) diagram prepared in Example 2.
  • TEM transmission electron microscope
  • HR-TEM high-resolution transmission electron microscope
  • Figure 4 is an oxygen reduction polarization curve for Example 1, Example 2 and commercial Pt/C catalysts with the same Pt loading.
  • Figure 5 is a bar graph comparing the catalytic mass activity of Example 1, Example 2 and commercial Pt/C for oxygen reduction.
  • Figure 6 is a graph showing the oxidation performance of methanol of Example 1, Example 2 and commercial Pt/C.
  • Example 7 is Example 1, Example 2 and commercial Pt / C at room temperature, 0.5 M H 2 SO 4 in the electrochemically active surface area of the scan cycle (the ECSA) changes Comparative Embodiment FIG.
  • Figure 8 is a bar graph comparing the oxidation performance of methanol in Example 1, Example 2 and commercial Pt/C.
  • Example 9 is a (TEM) diagram of the synthesis of carbon nanotube-supported titanium nitride (TiN/CNTs) in Example 3.
  • the solid of the complex is placed in a quartz boat, placed in a quartz tube furnace, first introduced into the high-purity nitrogen to replace the air in the furnace tube, then introduced into the ammonia water and began to heat up; the ammonia flow rate is controlled at 10 ml / min, the heating rate is 5 °C /min; Warming up to 750 ° C and then nitriding at this temperature for two hours, then switching to high purity nitrogen and starting to cool down, cooling to room temperature and then taking out, using XRD
  • the product obtained was determined to be a pure face-cube structure of TiN (card number: JCPDS NO. 38-1420).
  • TiN 5 mg TiN was added to 1 mL of an ethanol solution containing 0.25 wt% of perfluorosulfonic acid resin (Nafion), sonicated for 15 min into an ink slurry, and 5 uL of the slurry was uniformly coated on the glass electrode as a working electrode. Naturally dry. The amount of TiN on the electrode was 75 ⁇ g/cm -2 .
  • the working electrode was placed in a nitrogen-saturated 0.5 MH 2 SO 4 solution and swept from the open circuit voltage to -0.2 V 20 turns at a sweep speed of 50 mV/s to remove Contaminants on the surface of nitride nanoparticles.
  • the actual composition of the catalyst can be obtained by inductively coupled plasma emission spectroscopy (ICP-OES) ) OK.
  • ICP-OES inductively coupled plasma emission spectroscopy
  • the specific method is as follows: the catalyst is washed out from the surface of the electrode with ethanol, then dissolved in aqua regia, the concentration is determined by ICP-OES spectroscopy, and finally the mass composition of the catalyst is converted to determine Pt. The actual load.
  • TEM transmission electron microscopy
  • the average particle size of titanium nitride prepared in this example was 8-11 nm. Evenly. It can be seen from Fig. 2 that the platinum deposited by pulse electrodeposition does not form particles on the surface of titanium nitride, and the lattice fringes of Pt and titanium nitride can be clearly seen by high-resolution transmission electron microscopy, and the two stripes are There are also significant differences between the two, demonstrating that Pt is deposited at the atomic layer thickness level.
  • the results of ICP analysis showed that the platinum loading of the catalyst prepared in this example was 5.3 wt%.
  • Cyclic voltammetry was performed using a three-electrode system in oxygen-saturated 0.1 M HClO 4 at a sweep rate of 10 mV/s and an electrode speed of 1600 r/min. The results are shown in Figure 3.
  • the catalytic activity of the catalyst for methanol anodization was measured by a three-electrode system in a 0.5 MH 2 SO 4 + 1 M CH 3 OH solution at a sweep speed of 50 mV/s. The results are shown in Fig. 6.
  • the activity of the catalyst prepared in this example for oxygen reduction and methanol oxidation was 2.8 for commercial Pt/C catalyst, respectively. Double and 1.7 times.
  • the catalysts of the present invention are the same as the above test methods for cathode oxygen reduction, anode methanol oxidation, and catalyst stability test methods.
  • the oxygen reduction and methanol oxidation performance of the catalyst prepared in this example were 4 times and 3.3 times that of the commercial Pt/C catalyst, respectively.
  • Example 2 Other preparations and test methods are identical to those of Example 2 except that cobalt acetate tetrahydrate is substituted for nickel acetate tetrahydrate. Similarly, the catalyst prepared in this example had an oxygen reduction performance of 3.3 times that of the commercial Pt/C catalyst.
  • Example 2 Other preparations and test methods are the same as in Example 2 except that molybdenum pentachloride is substituted for nickel acetate tetrahydrate.
  • the catalyst has an oxygen reduction performance of 3.1 times that of a commercial Pt/C catalyst.
  • Example 1 In a fume hood, add 60 mL of ethanol to the Mengshi wash bottle, then add 1 mL of TiCl 4 solution and 3.5 g of carbon nanotubes, stir them to mix well, and the carbon carrier accounts for 80% of the substrate mass ratio.
  • Example 1 In a fume hood, add 60 mL of ethanol to the Mengshi wash bottle, then add 1 mL of TiCl 4 solution and 3.5 g of carbon nanotubes, stir them to mix well, and the carbon carrier accounts for 80% of the substrate mass ratio.
  • Example 1 In a fume hood, add 60 mL of ethanol to the Mengshi wash bottle, then add 1 mL of TiCl 4 solution and 3.5 g of carbon nanotubes, stir them to mix well, and the carbon carrier accounts for 80% of the substrate mass ratio.
  • Active metal salt solution tetraammine platinum, concentration 5 mM, containing 0.1 M sodium sulfate, 0.125 M Sodium citrate
  • the pulse current is 10 mA/cm 2 , the conduction time is 0.3 ms, and the off time is 1.5 ms.
  • the catalyst prepared in this example has an oxygen reduction performance of 3.7 times that of the commercial Pt/C catalyst.
  • the catalyst prepared in this example had an oxygen reduction performance of 2.9 times that of the commercial Pt/C catalyst.
  • the catalyst prepared in this example had a methanol oxidation performance 2.5 times that of the commercial Pt/C catalyst.
  • NbN/CNTs are not taken out immediately after the tube furnace is cooled to room temperature. First pull out the exhaust port of the tube furnace, close to the side of the gas valve, continue to pass nitrogen, so that NbN/CNTs slowly contact the air to avoid oxidation of the tantalum nitride. After half an hour of continuous nitrogen gas, the sample was taken out.
  • the active metal salt solution is palladium dichloride, the concentration is 50 mM, containing 0.1 M sodium sulfate, 0.05 M Polyvinylpyrrolidone.
  • the catalyst prepared in this example had a methanol oxidation performance of 1.9 times that of a commercial Pt/C catalyst.
  • the active metal electrodeposition is carried out in two steps: firstly, Ru@TiN is prepared by the constant current pulse method, and the specific embodiment is the same as the first embodiment. Electrodeposited shell metal Pt part (just replace the plating solution with antimony trichloride solution; concentration 50 mM, containing 0.1 M sodium sulfate, 0.05 M Polyvinylpyrrolidone), and then PtRu@TiN was prepared by a constant current pulse method, and the Pt portion of the electrodeposited shell metal of Example 1 was specifically implemented.
  • the oxygen reduction performance and methanol oxidation performance of the catalyst prepared in this example are respectively 4.2 and 3.1 of commercial Pt/C catalysts. Times.
  • the catalyst prepared in this example had a methanol oxidation performance of 2.9 times that of a commercial Pt/C catalyst.
  • the low-platinum catalyst based on nitride nanoparticles prepared by pulse electrodeposition is superior to commercial Pt/C in both the methanol oxidation activity of the anode and the oxygen reduction activity of the cathode. Better catalytic activity and stability.

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Abstract

本发明公开了基于氮化物纳米粒子的低铂催化剂及其制备方法。该催化剂的活性金属组分以超薄原子层的形式直接包覆在氮化物粒子表面或者碳载体负载的氮化物粒子的表面。制备步骤包括：先制得过渡金属的氨络合物，得到的氨络合物固体在氨气氛下氮化，得到氮化物纳米粒子；将氮化物纳米粒子负载在工作电极表面，采用脉冲沉积法在氮化物纳米粒子表面沉积活性组分，得到以氮化物为基底的低铂载量催化剂。该催化剂可用作低温燃料电池的阳极或者阴极催化剂，具有很高的催化活性和稳定性，可大幅度减少燃料电池的贵金属使用量，极大降低燃料电池的成本。本发明具有沉积量可控、操作简便、无需惰性气氛保护等重要特点，适合大规模工业化生产。

Description

基于氮化物纳米粒子的低铂催化剂及其制备方法
技术领域
本发明涉及燃料电池领域，为一种可应用于燃料电池的基于氮化物纳米粒子的低铂催化剂及其制备方法。
背景技术
大量燃烧矿物燃料所引起的能源短缺问题和环境问题日趋严峻，迫使人们越来越关注于探索新能源以及新的能源转换技术。低温燃料电池由于具有能量转换效率高、启动快和无污染等特点被誉为是最具大规模产业化前景的一类燃料电池。低温燃料电池包括质子交换膜燃料电池、直接醇燃料电池和直接酸燃料电池等，这些燃料电池催化剂均使用价格昂贵、资源稀缺的贵金属铂作为主要活性组分，由此造成的燃料电池成本高昂已成为制约燃料电池商业化进程的重要因素。同时，当前广泛使用的商业Pt/C催化剂由于负载的金属粒子和碳载体之间只存在弱的吸附作用，而且在燃料电池操作条件下碳载体容易被腐蚀，造成活性金属纳米粒子的脱落和迁移，严重制约了燃料电池的使用寿命。因此，制备和研究低成本，高活性和高稳定的催化剂对于燃料电池的开发和推广具有十分重要的意义。
过渡金属氮化物具有高熔点，高硬度，耐腐蚀和高导电性等特点，同时大量的研究表明，氮化物在一些加氢还原，氧还原的过程中表现出较高的活性，被称为“类铂催化剂”。Chen 等利用氮化碳作为硬模板合成了碳负载的氮化钛颗粒，直接利用氮化钛来催化氧化还原反应。（Ji Chen, Kazuhiro Takanabe, Ryohji Ohnishi, et al. Chem. Commun. , 2010, 46, 7492–7494.）通过该技术制备的碳负载氮化钛颗粒虽然表现出一定的氧还原活性，然而，其活性离实际应用的要求尚存在很大的距离。
DiSalvo等在1350 ℃下，首先将氧化锌和二氧化钛的混合物处理3h，冷却以后取样品在800-900℃下通入氨气，得到了粒径为25-45纳米的氮化钛颗粒。利用氮化钛颗粒代替碳粉负载Pt制备的催化剂，发现比商业Pt/C具有更好的甲醇氧化性能和稳定性。（Minghui Yang, Zhimin Cui and Francis J. DiSalvo, Phys . Chem . Chem . Phys., 2013, 15, 1088）同时，在该课题组利用相同的合成手段制得了粒径在30-50纳米的氮化铬颗粒，利用氮化铬颗粒负载的Pt催化剂，在表现出了比传统Pt/C催化剂更高的稳定性，同时，在相同电位下，氧还原活性和甲醇氧化活性分别是是Pt/C的1.8倍和1.4倍。（Minghui Yang, Rohiverth Guarecuco, and Francis J. DiSalvo, Chem. Mater., 2013, 25, 1783 −1787; Minghui Yang, Zhimin g Cui and Franc is J. DiSalvo, Phys . Chem . Chem . Phys., 2013,1 5, 7041.）但这种方法的对设备的要求较高，制备样品需要极高的温度，能耗高，同时Pt的负载量并没有有效降低。
Thotiyl 等利用阴极电弧沉积技术首先在不锈钢丝上沉积一层氮化钛制备工作电极，然后利用直流沉积法沉积Pd或者Pt金属，从而制备氮化钛负载的Pt或者Pd催化剂。在乙醇氧化实验中，该催化剂表现出了比Pt/C更好的催化活性和稳定性。（M.M.O. Thotiyl, T. Ravi Kumar, and S. Sampath, J. Phys. Chem. C, 2010, 114, 17934–17941; M.M.O. Thotiyl , S. Sampath, Electrochim. Acta, 2011, 56, 3549–3554.）该制备催化剂的方式复杂，制备得到的贵金属平均粒径在200nm，而且催化剂的单位质量铂的活性增加的幅度非常有限。
中国专利申请200610027287公开了一种抗腐蚀燃料电池催化剂制备技术，采用水解或气相热分解在氮化物负载的金属氧化物表面负载Pt，然而制备的催化剂的形貌以及催化剂的性能并没有明确的说明和提供相关证明材料。
总而言之，尽管人们在利用氮化物直接作为燃料电池催化剂以及用作燃料电池催化剂的载体方面做了许多的努力，但是尚存在这样或者那样的不足。现有技术中，尚未发现使用脉冲电沉积方法直接在廉价的过渡金属氮化物纳米粒子表面沉积活性金属薄层，制备粒径在10 nm以内的可适用于燃料电池催化剂的相关报道。
发明内容
本发明公开了一种燃料电池用基于氮化物纳米粒子的低铂催化剂及其脉冲电沉积制备方法，该新型催化剂可用于质子交换膜燃料电池以及其它需要使用贵金属催化剂的过程。针对当前Pt的负载量高，低铂催化剂制备技术复杂和碳载体易受腐蚀等不足之处，提供一种高效、低成本制备高性能和高稳定性低铂载量催化剂的方法。
采用非水溶液氨气络合方法首先合成过渡金属氨络合物纳米粒子，然后通过高温氮化的方式制备过渡金属氮化物纳米粒子；以活性金属盐溶液为电沉积前驱体，通过恒电流脉冲电沉积的方法，采用不同的Ton/Toff比值（0.1—100），将原子层级别厚度的活性金属均匀沉积在过渡金属氮化物纳米粒子的表面，得到具有高活性和高稳定性的低铂催化剂。
该催化剂的活性组分为铂原子层包覆的氮化物纳米粒子，活性金属以超薄原子层的形式直接包覆在氮化物粒子表面或者包覆在被碳载体负载的氮化物粒子的表面。该催化剂以过渡金属氮化物或者碳负载的过渡金属氮化物为基底，以Pt、Ir、Pd、Ru或Au元素一种以上作为覆盖层。制备方法包括：作为基底材料的过渡金属氮化物或者碳负载过渡金属氮化物的制备，脉冲电沉积的工作电极的制作，最终通过脉冲电沉积方式得到催化剂。该催化剂可用作低温燃料电池的阳极或者阴极催化剂，催化剂具有活性高、稳定性好的优点。 制备技术具有操作简便、无需惰性气氛保护、沉积量可控等优点，适合大规模的生产。该催化剂可大幅度减少燃料电池的贵金属使用量，极大降低燃料电池的成本，对促进燃料电池的商业化进程具有重要意义。
一种基于氮化物纳米粒子的低铂催化剂的制备方法，包括以下几个步骤：
（1）氮化物纳米粒子的制备：一种或者多种过渡金属的盐溶于非水溶剂，然后通入氨气0.5 – 1小时，在真空干燥箱中50-90℃蒸发溶剂，得到过渡金属的氨络合物；过渡金属氨络合物在氨气气氛下高温氮化3-5小时，制得过渡金属氮化物纳米粒子；所述过渡金属氨络合物包括 Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo或Ta任意一种形成的氨络合物或二种以上形成的二元或三元氨络合物；所述高温氮化的温度为500-900℃；制得的过渡金属氮化物纳米粒子的直径为5-15 nm；所述非水溶剂为醇类，或者醇类与酮或酯形成的混合物； 所述过渡金属的盐包括四氯化钛、钛酸四丁酯、乙酸铬、氯化锰、硝酸铁，乙酸钴、氯化铜、氯化铌、氯化钼和氯化钽。
碳负载过渡金属氮化物纳米粒子的制备：除向溶剂中同时加入过渡金属的盐类和经过预处理的碳载体外，其它步骤与上述氮化物纳米粒子的制备相同；所述碳载体包括XC-72R碳黑，碳纳米管，碳纳米纤维或石墨烯；氮化物纳米粒子在碳载体上的负载量为10wt%-40wt%；
（2）用于脉冲电沉积的工作电极的制作，采用如下方法a或方法b，
方法a：称取适量所述氮化物纳米粒子或碳负载过渡金属氮化物纳米粒子，加入1-5 mL的含有粘合剂的醇类溶液中，超声分散制成浆料，用微量移液管取适量浆料均匀涂覆在所用工作电极基体的表面，基底材料最终负载量为0.1-0.5 mg/cm2, 干燥后即制得用于脉冲电沉积的工作电极；所述粘合剂包括聚四氟乙烯乳液、氟碳树脂乳液或者全氟磺酸树脂乳液，粘合剂的使用量质量百分数为以干聚合物树脂计占催化剂基底材料总量的0.5%-20%；所述醇类包括乙醇、异丙醇或乙二醇；所述工作电极基体包括玻璃碳、泡沫镍、钛片、镀铂钛片或铂片；所述干燥的方式包括自然风干干燥、红外灯下辐射干燥或放入烘箱中干燥；
方法b：将作为基底材料的所述氮化物纳米粒子或碳负载过渡金属氮化物纳米粒子直接加入用于脉冲电沉积的含有所需活性金属的阴极电解质溶液中，并搅拌，通过粒子不断对阴极导体的接触而形成工作电极；阴极电解液与阳极电解液使用微孔介质隔离；
（3）脉冲电沉积：将制作好的工作电极置于氮气饱和的0.1-0.5 M H2SO4 溶液中，以5-50 mV/s的扫速从开路电压扫到-0.25~0 V，扫描圈数为10-50圈，实现基底材料的洁净化和活化处理；然后将电极在氮气保护下转入氮气饱和的含有所需活性金属盐、络合剂（或稳定剂）和导电助剂的电沉积溶液中，连接好辅助电极与参比电极；设定脉冲频率、脉冲沉积次数、通导及断开时间，然后开启脉冲电沉积程序，待电沉积完成，将催化剂从电极表面洗出，即制得基于氮化物纳米粒子的低铂催化剂。
上述制备方法中，所述将碳载体进行预处理具体方法为：称取5-20 g 碳载体，加入200-1000 mL烧杯中，注入烧杯3/5体积的丙酮，于室温下搅拌2-12 h，过滤，洗涤，然后在50-80℃下真空烘干；将干燥后的碳载体在高纯氩气氛保护下200-500℃焙烧2-3 h，然后在HNO3和H2SO4（摩尔百分比为1:1-1:5，溶液浓度为2-5 mol/L）混合溶液中加热回流6-10 h，保持温度在在70-80℃，最后将碳载体过滤并用二次水洗涤至中性后，在50-90℃烘箱中真空干燥8-24 h，，得到预处理过的碳载体;
上述制备方法中，所述非水溶液中过渡金属氨络合物制备具体方法为：将过渡金属前驱体加入含有非水溶剂的烧杯中，溶解完成后转移到孟氏洗瓶中，通入氨气进行络合反应，氨气气流量控制为30-100 ml/min, 通气时间为0.5-1 小时；将所得含有络合物的混合物转移到坩埚中，在50-90℃烘箱中真空干燥8-24 h，得到氮化物氨络合物；其中前驱体包括四氯化钛、醋酸铁、醋酸钴、醋酸镍、氯化钒、醋酸铬、氯化锰和氯化铌中的一种以上三种以下；所述前驱体在反应体系溶液中的浓度范围为0.1-3 mg/mL;
上述制备方法中，步骤（3）所述电沉积溶液含有的活性金属组分包括：Pt、Au、Pd、Ru和Ir中的一种以上；所述活性金属盐包括二氯四氨合铂、氯铂酸、氯金酸、二氯化钯、三氯化钌和三氯化铱中的一种以上；络合剂包括柠檬酸、EDTA或聚乙烯吡咯烷酮；导电助剂为硫酸钠或硫酸钾；活性金属组分的浓度为5-100 mM。
上述制备方法中，所述步骤（3）中活性金属沉积的方式采用的是脉冲电沉积，所述脉冲频率为100 – 10000 s-1, 每一个脉冲都包含一个导通时间和断开时间，导通时间（ton）为0.00003 s到0.001 s, 断开时间（toff）为0.00015 – 0.01 s, 导通时间与断开时间之比（ton/toff）根据电解液中活性金属摩尔浓度和所需活性金属负载量的不同而有所差异，其值在0.1—100之间；总的脉冲次数为500-20000.
上述制备方法中，步骤（3）中脉冲电沉积的脉冲电流密度为1-50 mA/cm2。
上述制备方法中，所制备的催化剂的活性组分为一种具有活性金属原子层包覆的过渡金属氮化物纳米粒子，活性金属以超薄原子层的形式包覆在作为基底的过渡金属氮化物或者碳载体负载过渡金属氮化物纳米粒子表面；其中，作为基底的过渡金属氮化物包括一元，二元或三元过渡金属氮化物,纳米粒子的平均粒径大小在5-15 nm。用来沉积的活性金属包括Pt、Ir、Pd, Ru或Au中的一种或两种以上组成的合金；所述碳载体包括炭黑颗粒、碳纳米管纤维、碳纳米管或石墨烯。所述催化剂的质量组成为：碳载体 50%-80%；过渡金属氮化物10%-40%， 活性金属组分4%-10%；
上述制备方法中，所述超薄原子层是由1-5个原子层组成；所述过渡金属氮化物包括Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo或Ta中的一种或两种以上组成的二元和三元过渡金属氮化物。
上述制备方法中，所述催化剂对阴极氧还原、甲醇氧化和甲酸氧化反应均表现出了良好的活性，可用作氢氧燃料电池、直接甲醇燃料电池、直接甲酸燃料电池的阳极和阴极催化剂。其贵金属使用量较商业Pt/C催化剂降低4-5倍，而质量活性和比活性可比商业Pt/C催化剂提高3-10倍；此外，该催化剂还可应用于化学工业中的加氢催化剂。
本发明的制备技术还可以直接使用商业的氮化物、碳化物、氧化物、硫化物和磷化物等作为负载活性金属的基底。
与现有技术相比较，本发明的基于氮化物纳米粒子低铂催化剂及其制备方法具有如下优点：
（1）本发明提出了一种制备颗粒度可控的小颗粒纳米氮化物粒子的制备方法，制备的氮化物纳米粒子的粒径低于10nm, 使得其适合用于制备燃料电池催化剂；
（2）与通常的碳载体比较，氮化物具有更好的耐电化学腐蚀稳定性；可有效解决传统的碳负载催化剂的碳腐蚀而导致燃料电池活性衰减的问题；
（3）本发明采用脉冲电沉积技术，可实现活性组分在氮化物纳米粒子表面的原子层级别的沉积（通常为3-5个原子层的厚度），与传统的核壳结构催化剂比较，无需使用贵金属或者贵金属的合金作为核壳结构的核，在保证了活性组分的高性能的同时，可有效降低催化剂的成本；
（4）与传统的制备核壳结构催化剂的欠电位沉积技术比较，本发明提出的脉冲电沉积技术制得的催化剂的活性可媲美欠电位沉积制备的催化剂；同时，脉冲电沉积技术具有沉积量可控、操作简便、无需惰性气体保护等；容易实现工业化生产及应用；
（5）本发明所制得的催化剂对于甲醇、甲酸阳极氧化以及氧气的阴极还原反应均具有较高催化性能，单位质量铂的活性是商品Pt/C催化剂的2-10倍，同时催化剂具有极高的稳定性。
附图说明
图1为实施例1所制得的氮化钛的TEM图。
图2为实施例1所制得的Pt@TiN 的TEM图。
图3为实施例2所制得的Pt@TiNiN透射电镜（TEM）和高分辨透射电镜（HR-TEM）图。
图4为在相同Pt负载量的情况下，实施例1、实施例2和商业Pt/C催化剂氧还原极化曲线。
图5为实施例1、实施例2和商业Pt/C对氧还原催化质量活性对比柱状图。
图6为实施例1、实施例2和商业Pt/C对甲醇氧化性能曲线图。
图7为实施例1、实施例2和商业Pt/C在室温，0.5 M H2SO4中循环扫描电化学活性表面积（ECSA）变化的对比图。
图8为实施例1、实施例2和商业Pt/C对甲醇氧化性能对比柱状图。
图9为实施例3中合成碳纳米管负载氮化钛（TiN/CNTs）的（TEM）图。
具体实施方式
下面结合附图和实施例对本发明作进一步的说明，以下实施例仅仅是为了更加清楚地阐述本发明，但本发明要求保护的范围并不局限于以下实施例表述的范围，本发明内容中所述的方案和效果均可参照如下实例实现。
实施例 1 ： Pt@TiN 催化剂
（ 1 ）用作基底的 TiN 纳米粒子的制备
在通风橱中，将 60 mL 绝对无水乙醇加入到孟氏洗瓶中，然后加入 2 mL TiCl4 。震荡（搅拌）均匀后，通入干燥氨气，直到形成的沉淀物数量不再增加，有氨气气泡冒出为止；断开氨气，将洗瓶盖好后，转入真空干燥箱，打开瓶盖，在 70 ℃ 烘箱中真空干燥蒸发溶剂 16h ，得到钛的氨络合物固体；
取 3g 络合物固体放入石英舟中，放入石英管石炉，先通入高纯氮置换炉管中的空气，然后通入氨水并开始升温；氨水流速控制在 10ml/min ， 升温速率为 5 ℃ /min; 升温到 750 ℃ 然后在此温度下恒温氮化两小时，然后切换为高纯氮气并开始降温，降温至室温后取出，用 XRD 测定，制得的产物为纯净的面立方体结构的 TiN （卡片号： JCPDS NO. 38-1420 ）。
（ 2 ）采用恒电流脉冲法制备 Pt@TiN
5 mg TiN 加入 1mL 含有 0.25 wt% 的全氟磺酸树脂（ Nafion ）的乙醇溶液中，超声 15 min 成墨汁状浆料后，取 5 uL 浆料均匀涂覆在作为工作电极玻碳电极上，自然干燥。 电极上 TiN 的量为 75 μg/cm-2 ， 将工作电极置于氮气饱和的 0.5 M H2SO4 溶液中，以 50 mV/s 的扫速从开路电压扫到 -0.2 V 20 圈，以除去氮化物纳米粒子表面的污染物。 随后将工作电极转入氮气饱和的氯铂酸盐溶液中（六水氯铂酸，浓度为 50 mM ，含 0.1 M 的硫酸钠， 50 mM 的聚乙烯吡咯烷酮），采用铂丝和 Ag/AgCl 电极分别作为对电极和参比电极，按照预先设定的恒电流脉冲沉积程序（峰值电流密度为 5 mA/cm2 ，通导时间为 3 ms ，关断时间为 15 ms ，脉冲数为 5200 ，电沉积温度为室温），得到 Pt@TiN 催化剂。
催化剂的实际组成可通过电感耦合等离子体发射光谱（ ICP-OES ）确定。具体做法为：将催化剂用乙醇从电极表面洗出，然后加入王水溶解，用 ICP-OES 光谱确定其浓度，最后换算得到催化剂的质量组成，确定 Pt 的实际负载量。
（ 3 ）催化剂的结构形貌表征及性能测试。
（ A ）催化剂的结构形貌表征：
采用透射电镜（TEM）观察了氮化物纳米粒子及负载铂的氮化物纳米粒子的形貌（图1），本实施例制得的氮化钛的平均粒径为8-11nm，粒径分布较为均匀。从图2可以看出，脉冲电沉积法沉积的铂在氮化钛表面并没有形成颗粒，而利用高分辨透射电镜图可以清晰的看到Pt和氮化钛的晶格条纹，两种条纹之间也存在着明显的差异，证明Pt以原子层厚度级别沉积。ICP分析的结果测得本实施例制得的催化剂的铂载量为 5.3 wt%。
（ B ）阴极氧还原催化性能测试：
采用三电极体系，在氧气饱和的 0.1 M HClO4 中，以 10 mV/s 的扫速， 1600 r/min 的电极转速进行循环伏安扫描，结果见图 3 。
（ C ）甲醇阳极氧化催化性能测试：
采用三电极体系，在 0.5 M H2SO4+ 1 M CH3OH 溶液中，以 50 mV/s 的扫速进行循环伏安扫描 , 测定了催化剂对于甲醇阳极氧化的催化活性，结果见图 6 。
（ D ）催化剂稳定性能测试：
采用三电极体系，在 0.5 M H2SO4 溶液中，以 50 mV/s 的扫速进行循环伏安扫描，扫描范围为 0.3-0.75V （ 0.6-1.05 Vs RHE ），扫描每 2000 圈记录一次电化学活性表面积（ ECSA ）的变化。具体操作为，以 50 mV/s 的扫速扫描，扫描范围为 -0.2-1.0V ，待曲线稳定后停止操作，记录扫描曲线。然后重新将扫描范围调整为 0.3-0.75V （ 0.6-1.05 Vs RHE ），进行下一次 2000 圈的扫描。催化剂电化学活性表面积变化见图 7 。
本实施例制得的催化剂对于氧还原和甲醇氧化的活性（单位质量铂的活性）分别是商业 Pt/C 催化剂的 2.8 倍和 1.7 倍。
除特别说明外，本发明所涉及的催化剂对于阴极氧还原、阳极甲醇氧化和催化剂稳定性测试方法均与以上测试方法相同。
实施例 2: Pt@TiNiN 催化剂
（ 1 ）双金属氮化镍钛（ TiNiN ）的制备：在通风橱中，将 60 mL 乙醇加入到孟氏洗瓶中，然后加入 2 mL TiCl4 溶液及 169.7 mg 四水合乙酸镍，搅拌使其充分溶解， Ti 和 Ni 的原子比为 19:1 ，其他制备流程与实施例 1 相同 ;
（ 2 ）采用恒电流脉冲法制备 Pt@TiNiN, 同实施例 1 。
（ 3 ）催化剂结构形貌见图 3 。
（ 4 ）催化剂氧还原性能测试和甲醇氧化性能测试分别见图 4 和图 6 （横坐标为电位，纵坐标为电流密度）。
（ 5 ）催化剂稳定性测试见图 7 。
本实施例制得的催化剂的氧还原和甲醇氧化性能分别是商业 Pt/C 催化剂的 4 倍和 3.3 倍。
实施例 3 ： Pt@TiCoN 催化剂
除以四水合乙酸钴取代四水合乙酸镍外，其它制备及测试方法完全与实施例 2 相同，本实施例制得的催化剂的氧还原性能是商业 Pt/C 催化剂的 3.3 倍。
实施例 4 ： Pt@TiMoN 催化剂
除以五氯化钼取代四水合乙酸镍外，其它制备及测试方法完全与实施例 2 相同，
该催化剂的氧还原性能是商业 Pt/C 催化剂的 3.1 倍。
实施例 5 ： Pt@TiN/CNTs 催化剂
（ 1 ）用作基底的 TiN/CNTs 的制备
在通风橱中，将 60 mL 乙醇加入到孟氏洗瓶中，然后加入 1 mL TiCl4 溶液和 3.5 g 碳纳米管 , 搅拌使其充分混合，碳载体占基底质量比为 80%. 其他过程同实施例 1 。
（ 2 ）采用恒电流脉冲法制备 Pt@TiN/CNTs ：除如下几点不同外，其它同实施例 1
（ A ）活性金属盐溶液（二氯四氨合铂，浓度 5 mM , 含 0.1 M 硫酸钠， 0.125 M 柠檬酸钠）；
（ B ）脉冲电流为 10 mA/cm2, 通导时间为 0.3 ms, 断开时间为 1.5 ms 本实施例制得的催化剂的氧还原性能是商业 Pt/C 催化剂的 3.7 倍。
实施例 6 ： Pt@TiCrN/G 催化剂
除以下几点不同外，其它同实施例 2
  1. （1） 使用六水合氯化铬取代四水合乙酸镍。
（ 2 ）在混合溶液中加入石墨烯，石墨烯占基底总质量比为 80%.
（ 3 ）采用恒电流脉冲法制备 Pt@TiCrN/CNTs ，同实施例 1
本实施例制得的催化剂的氧还原性能是商业 Pt/C 催化剂的 2.9 倍。
实施例 7 ： Pd@TiN 催化剂
除如下一点不同外，其它同实施例 1
（ 1 ）采用恒电流脉冲法制备 Pd@TiN
将氯铂酸溶液换成二氯化钯溶液，金属粒子浓度 100 mM , 含 0.2 M 硫酸钠， 0.05 M 聚乙烯吡咯烷酮，然后继续采用恒电流脉冲方法制备 Pd@TiN 催化剂。
本实施例制得的催化剂的甲醇氧化性能是商业 Pt/C 催化剂的 2.5 倍。
实施例 8 ： Pd@NbN/CNTs 催化剂
除如下几点不同外，其它同实施例 5
（ 1 ）作为基底的 NbN/CNTs 制备：以五氯化铌代替四氯化钛作为金属前驱体。
（ 2 ）管式炉冷却到室温后，不立刻取出 NbN/CNTs, 先拔下管式炉的尾气端口，靠近气体阀门一侧，继续通入氮气，使 NbN/CNTs 缓慢接触空气，避免氮化铌被氧化。连续通氮气气半个小时后，再取出样品。
（ 3 ）活性金属盐溶液为二氯化钯，浓度 50 mM , 含 0.1 M 硫酸钠， 0.05 M 聚乙烯吡咯烷酮。
本实施例制得的催化剂的甲醇氧化性能是商业 Pt/C 催化剂的 2.6 倍。
实施例 9 ： Ru@TiN 催化剂
除如下几点不同外，其它同实施例 1
（ 1 ）将沉积的活性金属溶液替换为三氯化钌溶液。
（ 2 ）采用将粘合剂用聚四氟乙烯乳液替换全氟磺酸树脂，溶剂用乙醇替换异丙醇，树脂的浓度改为 0.15%.
本实施例制得的催化剂的甲醇氧化性能是商业 Pt/C 催化剂的 1.9 倍。
实施例 10 ： PtRu@TiN 催化剂
除如下一点不同外，其它同实施例 1
（ 1 ）采用恒电流脉冲法制备 PtRu@TiN ：
活性金属电沉积分两步实施：首先采用恒电流脉冲方法制备 Ru@TiN ，具体实施同实施例 1 的电沉积壳层金属 Pt 部分（只是将电镀液换为三氯化钌溶液；浓度 50 mM , 含 0.1 M 硫酸钠， 0.05 M 聚乙烯吡咯烷酮），然后继续采用恒电流脉冲方法制备 PtRu@TiN ，具体实施同实施例 1 的电沉积壳层金属 Pt 部分。
本实施例制得的催化剂的氧还原性能和甲醇氧化性能分别是是商业 Pt/C 催化剂的 4.2 和 3.1 倍。
实施例 11 ： Pd@TiN/G 催化剂
除如下两点不同外，其它同实施例 1
（ 1 ）用作基底的 TiN/G 的制备
在通风橱中，将 60 mL 乙醇加入孟氏洗瓶中，然后将 1 mL TiCl4 溶液缓慢注入乙醇溶液中，然后向混合溶液中加入 200 mg 石墨烯 , 充分搅拌混合。
（ 2 ）采用恒电流脉冲法制备 Pd@TiN/G
将电镀液换为由氯铂酸溶液替换为二氯化钯溶液；浓度 100 mM , 含 0.1 M 硫酸钠， 0.1 M 聚乙烯吡咯烷酮
本实施例制得的催化剂的甲醇氧化性能是商业 Pt/C 催化剂的 2.9 倍。
从以上数据可以看出，采用脉冲电沉积法制备的基于氮化物纳米粒子的低铂催化剂无论在阳极的甲醇氧化活性还是在阴极的氧还原活性上都比商业 Pt/C 更好的催化活性以及稳定性。
本领域普通技术人员通过阅读本发明说明书而对本发明技术方案而使用的任何等效变换实施方式，均为本发明的权利所涵盖。

Claims (9)

  1. 一种基于氮化物纳米粒子的低铂催化剂的制备方法， 其特征在于，包括以下步骤：
    （ 1 ）氮化物纳米粒子的制备：一种或者多种过渡金属的化合物溶于非水溶剂，然后通入氨气 0.5 - 1 小时，在真空干燥箱中 50-90℃蒸发溶剂，得到过渡金属的氨络合物；过渡金属氨络合物在氨气气氛下高温氮化3-5 小时，制得过渡金属氮化物纳米粒子；所述过渡金属氨络合物包括 Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo 或 Ta 任意一种形成的氨络合物或二种以上形成的二元或三元氨络合物；所述高温氮化的温度为 500-900℃；制得的过渡金属氮化物纳米粒子的直径为5-15 nm ；所述非水溶剂为醇类，或者醇类与酮或酯形成的混合物； 所述过渡金属的化合物包括四氯化钛、钛酸四丁酯、乙酸铬、氯化锰、硝酸铁，乙酸钴、氯化铜、氯化铌、氯化钼和氯化钽；
    碳负载过渡金属氮化物纳米粒子的制备：除向非水溶剂中同时加入过渡金属的化合物和经过预处理的碳载体外，其它步骤与上述氮化物纳米粒子的制备相同；所述碳载体包括 XC-72R 碳黑，碳纳米管，碳纳米纤维或石墨烯；氮化物纳米粒子在碳载体上的负载量为 10wt%-40wt% ；
    （ 2 ）用于脉冲电沉积的工作电极的制作，采用如下方法 a 或方法 b ，
    方法 a ：称取适量所述氮化物纳米粒子或碳负载过渡金属氮化物纳米粒子，加入 1-5 mL 的含有粘合剂的醇类溶液中，超声分散制成浆料，用微量移液管取适量浆料均匀涂覆在所用工作电极基体的表面，催化剂基底材料最终负载量为 0.1-0.5 mg/cm2, 干燥后即制得用于脉冲电沉积的工作电极；所述粘合剂包括聚四氟乙烯乳液、氟碳树脂乳液或者全氟磺酸树脂乳液，粘合剂的使用量质量百分数为以干聚合物树脂计占催化剂基底材料总量的 0.5%-20% ；所述醇类包括乙醇、异丙醇或乙二醇；所述工作电极基体包括玻璃碳、泡沫镍、钛片、镀铂钛片或铂片；所述干燥的方式包括自然风干干燥、红外灯下辐射干燥或放入烘箱中干燥；
    方法 b ：将作为基底材料的所述氮化物纳米粒子或碳负载过渡金属氮化物纳米粒子直接加入用于脉冲电沉积的含有所需活性金属的阴极电解质溶液中，并搅拌，通过粒子不断对阴极导体的接触而形成工作电极；阴极电解液与阳极电解液使用微孔介质隔离；
    （ 3 ）脉冲电沉积：将制作好的工作电极置于氮气饱和的 0.1-0.5 M H2SO4 溶液中，以 5-50 mV/s 的扫速从开路电压扫到 -0.25~0 V ，扫描圈数为 10-50 圈，实现基底材料的洁净化和活化处理；然后将电极在氮气保护下转入氮气饱和的含有所需活性金属的盐、络合剂和导电助剂的电沉积溶液中，连接好辅助电极与参比电极；设定脉冲频率、脉冲沉积次数、通导及断开时间，然后开启脉冲电沉积程序，待电沉积完成，将催化剂从电极表面洗出，即制得 基于氮化物纳米粒子的低铂催化剂 。
  2. 根据权利要求1所述的基于氮化物纳米粒子的低铂催化剂的制备方法，其特征在于，碳载体的所述预处理为：称取5-20 g 碳载体，加入200-1000 mL烧杯中，注入烧杯3/5体积的丙酮，于室温下搅拌2-12 h，过滤，洗涤，然后在50-80℃下真空烘干；将干燥后的碳载体在高纯氩气氛保护下200-500℃焙烧2-3 h，然后在摩尔比为1:1-1:5的HNO3和H2SO4混合溶液中加热回流6-10 h，保持温度在在70-80℃，混合溶液浓度为2-5 mol/L，最后将碳载体过滤并用二次水洗涤至中性后，在50-90℃烘箱中真空干燥8-24 h，得到预处理过的碳载体。
  3. 根据权利要求1所述的基于氮化物纳米粒子的低铂催化剂的制备方法，其特征在于，步骤（1）所述过渡金属的氨络合物的具体制备过程为：将过渡金属前驱体加入含有非水溶剂的烧杯中，溶解完成后转移到孟氏洗瓶中，通入氨气进行络合反应，氨气气流量控制为30-100 ml/min, 通气时间为0.5-1 小时；将所得含有络合物的混合物转移到坩埚中，在50-90℃烘箱中真空干燥8-24 h，得到氮化物氨络合物；其中前驱体包括四氯化钛、醋酸铁、醋酸钴、醋酸镍、氯化钒、醋酸铬、氯化锰和氯化铌中的一种以上三种以下；所述前驱体在反应体系溶液中的浓度范围为0.1-3 mg/mL。
  4. 根据权利要求1所述的基于氮化物纳米粒子的低铂催化剂的制备方法，其特征在于，步骤（3）中，所述活性金属包括：Pt、Au、Pd、Ru和Ir中的一种以上；所述活性金属的盐包括二氯四氨合铂、氯铂酸、氯金酸、二氯化钯、三氯化钌和三氯化铱中的一种以上；所述络合剂包括柠檬酸、EDTA或聚乙烯吡咯烷酮；所述导电助剂为硫酸钠或硫酸钾；活性金属组分在电沉积溶液中的浓度为5-100 mM。
  5. 根据权利要求1所述的基于氮化物纳米粒子的低铂催化剂的制备方法，其特征在于，步骤（3）中活性金属沉积的方式采用的是脉冲电沉积，所述脉冲频率为100 – 10000 s-1, 每一个脉冲都包含一个导通时间和断开时间，导通时间（ton）为0.00003 s到0.001 s, 断开时间（toff）为0.00015 – 0.01 s, 导通时间与断开时间之比（ton/toff）根据电解液中活性金属摩尔浓度和所需活性金属负载量的不同而有所差异，其值在0.1—100之间；总的脉冲次数为500-20000。
  6. 根据权利要求1所述的基于氮化物纳米粒子的低铂催化剂的制备方法，其特征在于，其特征在于步骤（3）中脉冲电沉积的脉冲电流密度为1-50 mA/cm2。
  7. 根据权利要求1所述的基于氮化物纳米粒子的低铂催化剂的制备方法，其特征在于所述非水溶剂包括乙醇或异丙醇溶液。
  8. 由权利要求1~7任一项所述的制备方法制备得到的基于氮化物纳米粒子的低铂催化剂，其特征在于：该催化剂的活性组分为具有活性金属原子层包覆的过渡金属氮化物纳米粒子，活性金属以超薄原子层的形式包覆在作为基底的过渡金属氮化物或者碳载体负载过渡金属氮化物纳米粒子表面；其中，作为基底的过渡金属氮化物或者碳载体负载过渡金属氮化物包括一元，二元或三元过渡金属氮化物,纳米粒子的平均粒径大小在5-15 nm；所述催化剂的质量组成为：碳载体 50%-80%；过渡金属氮化物10%-40%， 活性金属组分4%-10%。
  9. 根据权利要求8所述的低铂催化剂，其特征在于：所述超薄原子层是由1-5个原子层组成；所述过渡金属氮化物包括Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo或Ta中的一种或两种以上组成的二元和三元过渡金属氮化物。
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