CN115084555A - Carbon-coated flower-shaped titanium oxide/titanium dioxide heterostructure supported ruthenium catalyst and preparation and application thereof - Google Patents

Carbon-coated flower-shaped titanium oxide/titanium dioxide heterostructure supported ruthenium catalyst and preparation and application thereof Download PDF

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CN115084555A
CN115084555A CN202210802359.5A CN202210802359A CN115084555A CN 115084555 A CN115084555 A CN 115084555A CN 202210802359 A CN202210802359 A CN 202210802359A CN 115084555 A CN115084555 A CN 115084555A
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tio
heterostructure
flower
nanoflower
titanium dioxide
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CN115084555B (en
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姜鲁华
高杰
刘静
崔学晶
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Qingdao University of Science and Technology
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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
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
    • 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
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • 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 provides a titanium oxide/titanium dioxide heterostructure nano flower for preparing carbon-coated load ruthenium nano particle, a preparation method and application thereof in fuel cell hydrogen oxidation reaction 2 Roasting the nanoflower precursor in argon atmosphere and ammonia atmosphere to obtain TiO/TiO 2 Loading ruthenium trichloride on the surface of the heterostructure nanoflower, polymerizing Dopamine (DA) in situ to form polydopamine, and coating the polydopamine on TiO/TiO containing ruthenium trichloride on the surface 2 The surface of the heterostructure nanoflower is subjected to hydrogen/argon reduction heat treatment to obtain carbon-coated ruthenium nanoparticle-loaded oxygenTitanium oxide/titanium dioxide heterostructure nanoflower Ru-TiO/TiO 2 @ NC. Ru-TiO/TiO obtained by the invention 2 The @ NC heterostructure nanoflower is good in conductivity and high in stability, and has good catalytic activity and stability for the fuel cell hydrogen oxidation reaction. The preparation method has the advantages of simple preparation process, easy scale-up production and good application prospect.

Description

Carbon-coated flower-shaped titanium oxide/titanium dioxide heterostructure supported ruthenium catalyst and preparation and application thereof
Technical Field
The invention relates to carbon-coated flower-shaped titanium oxide/titanium dioxide heterostructure loaded ruthenium, a preparation method thereof and application thereof in a fuel cell, and belongs to the technical field of new energy materials.
Background
The fuel cell directly converts chemical energy into electric energy through electrochemical reaction, has high energy conversion efficiency, is environment-friendly and has wide development prospect. Alkaline Anion Exchange Membrane Fuel Cells (AEMFCs) have attracted attention in recent years because their operating environments are alkaline, which enables the use of non-platinum catalysts, as compared to acidic Proton Exchange Membrane Fuel Cells (PEMFCs). However, both catalytic activity and stability of non-platinum catalysts to anodic Hydrogen Oxidation (HOR) in alkaline media are to be improved. In the aspect of catalytic activity, the performance of the non-platinum catalyst cannot be compared with that of platinum, particularly, the anode HOR dynamics is 2 to 3 orders of magnitude slower under an alkaline condition than under an acidic condition, and the improvement of the catalytic activity of the non-platinum catalyst is very important; in the aspect of catalyst stability, the non-platinum metal active component is easy to electrochemically oxidize and deactivate under the HOR potential; in addition, the traditional fuel cell catalyst adopts high specific surface active carbon as a carrier so as to ensure good conductivity and improve the dispersion degree of active components; however, under the condition that the fuel cell is started or stopped or the load of the fuel cell is changed to cause the reverse pole of the fuel cell, the activated carbon carrier can generate electrochemical oxidation corrosion due to the over-high potential of the anode, and further leads the loaded metal active substances to fall off and agglomerate. Therefore, the development of non-carbon supports and catalysts with high activity, high stability and high specific surface area is of great importance to the development of fuel cells.
TiO 2 Good stability, is a common carrier in thermal catalysis, but TiO 2 Poor conductivity and low specific surface area severely limit its application as a fuel cell catalyst support. When used as an electrocatalyst support, it is generally mixed with a conductive agent such as activated carbon or graphene to improve its conductivity. For increasing TiO content 2 The specific surface area of the composite material is improved by regulating the shape, such as preparing the composite material into a two-dimensional array or a three-dimensional sheet structure. For example, the literature (Nature Catalysis,2020,3, 454-462) reports a sea urchin-like TiO 2 Preparation method of carrier used as electrocatalystTo improve TiO 2 Conductivity of the resulting Ru/TiO 2 Mixing a catalyst with a conductive agent nitrogen-doped graphene, and improving Ru/TiO by means of the graphene 2 Exhibits good electrical conductivity and stability of the HOR electrocatalytic activity. However, it is difficult to improve TiO by physically mixing a catalyst and a conductive agent 2 The conductivity of the body; furthermore, TiO 2 The lower specific surface area is difficult to load more catalytic active components, so that the catalytic activity cannot meet the application requirements. To improve this problem, the patent publication (CN 112968181A) discloses in-situ coating of high specific surface area TiO with a carbon layer 2 Strategy of nanoflower, TiO 2 The nano flower structure increases the surface area, and the coating carbon layer enables TiO 2 The conductivity of the composite is improved, so that after the Pt nano catalyst is loaded, the carbon is coated with TiO 2 The nanoflower-supported Pt catalyst shows good catalytic activity and stability for oxygen reduction reaction. However, despite the TiO produced by this method 2 Surface conductivity is improved by the carbon layer, but TiO 2 The conductivity of the bulk is still not improved and electrons are in TiO 2 The bulk phase transmission is difficult, and the conduction of electrons in the bulk phase and the interface is influenced, so that the electrode reaction efficiency is influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the carbon-coated flower-shaped titanium oxide/titanium dioxide heterostructure with high conductivity, high activity and high stability and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following specific scheme to realize:
(1) dissolving n-butyl titanate in glacial acetic acid according to a certain proportion, and uniformly stirring to obtain a milky white solution; heating the mixed solution in a hydrothermal kettle to 100-180 ℃, preserving heat for 6-24 hours, after the hydrothermal kettle is naturally cooled, centrifugally washing the obtained product, and finally drying the product to obtain a titanium dioxide nanoflower precursor (p-TiO) 2 )；
Preferably, the volume ratio of the n-butyl titanate to the glacial acetic acid is 1: 10-1: 100.
(2) Subjecting the flower-shaped titanium dioxide precursor obtained in the step (1) to argon atmosphere at the temperature of 1-5 ℃ for min -1 Heating to 450 deg.C, maintaining for 0.5-3 hr, and heating at 1-5 deg.C for min in ammonia atmosphere -1 Heating to 600 ℃ and 800 ℃, preserving the heat for 0.1-4 hours, and naturally cooling to obtain the titanium oxide/titanium dioxide nano flower powder (TiO/TiO) 2 )；
(3) TiO/TiO obtained in the step (2) 2 Adding the nanometer flower into ethanol to form suspension by ultrasonic treatment, adding ruthenium trichloride aqueous solution, stirring at room temperature for 1-8 hr, filtering and drying to obtain ruthenium precursor-loaded titanium oxide/titanium dioxide nanometer flower powder (Ru-TiO/TiO) 2 )；
(4) Adding the titanium oxide/titanium dioxide nanoflower powder loaded with the ruthenium precursor obtained in the step (3) into a tris (hydroxymethyl) aminomethane-buffer solution (pH:8.5) solution, performing ultrasonic treatment to form a suspension, adding a dopamine hydrochloride solution into the suspension under stirring, stirring at room temperature to polymerize dopamine and coat the dopamine on the surface of the titanium oxide/titanium dioxide nanoflower, and finally performing centrifugal washing and drying on the suspension to obtain the polydopamine-coated ruthenium-loaded titanium oxide/titanium dioxide nanoflower;
(5) subjecting the sample obtained in step (4) to reaction in H 2 Heating to 350-700 ℃ in the Ar atmosphere, and preserving the heat for 0.5-6 hours to obtain the aza-carbon-coated ruthenium nanoparticle-loaded titanium oxide/titanium dioxide nanoflower (Ru-TiO/TiO) 2 -NC)；
Preferably, H 2 the/Ar atmosphere contains 1-5% hydrogen.
Compared with the prior art, the invention has the following advantages and effects:
compared with titanium dioxide, the flower-shaped titanium oxide/titanium dioxide heterostructure electrocatalysis carrier prepared by the invention has good conductivity and is an excellent electrocatalysis carrier. The carrier has good electrocatalytic activity and stability for a hydrogen oxidation reaction after loading Ru nano particles. The preparation method is simple in preparation process, suitable for large-scale production and has a remarkable application prospect.
Description of the drawings:
FIG. 1 SEM pictures of samples prepared in example 1.
FIG. 2X-ray diffraction patterns of the samples prepared in comparative example 1, example 1 and example 2.
Figure 3 transmission electron micrograph of sample prepared in example 2.
FIG. 4 electrochemical impedance spectra of samples prepared in comparative example 2 and example 2.
Fig. 5 linear scan curves for HOR for samples prepared in comparative example 2 and example 2.
FIG. 6 chronoamperometric curves of samples prepared in comparative example 2 and example 2 versus HOR.
The specific implementation mode is as follows:
the invention is further illustrated below with reference to specific examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing description are intended to be included within the scope of the invention. The specific process parameters and the like of the following examples are also merely one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Comparative example 1
Dissolving 2ml of n-butyl titanate in 60ml of glacial acetic acid, and uniformly stirring to obtain a milky white solution; heating the mixed solution in a hydrothermal kettle to 140 ℃, and preserving heat for 12 hours; after the hydrothermal kettle is naturally cooled, centrifugally washing the obtained product by deionized water, and finally drying the product to obtain a white flower-shaped titanium dioxide precursor p-TiO 2 . Then adding p-TiO in air atmosphere 2 At 2 ℃ for min -1 Heating to 500 ℃ at the heating rate and preserving heat for 3 hours to obtain flower-shaped titanium dioxide powder (TiO) 2 )。
Comparative example 2
90mg of the flower-like titanium dioxide powder obtained in comparative example 1 was added to 30ml of ethanol and ultrasonically homogenized to form a suspension, and 2.72ml of ruthenium trichloride was addedAqueous solution (Ru concentration 3.67mg ml) -1 ) And stirred at room temperature for 5 hours. Then the solvent is removed by rotary evaporation to obtain flower-shaped titanium dioxide Ru-TiO loaded with ruthenium 2 And (3) powder. 90mg of dried Ru-TiO 2 The powder was added to 30ml of tris buffer (pH 8.5), dispersed by sonication, and then 90mg of dopamine hydrochloride was added and stirred at room temperature for 48 hours. And then centrifugally washing and drying the titanium dioxide to obtain the polydopamine-coated ruthenium-loaded flower-shaped titanium dioxide. Then again at H 2 In Ar atmosphere at 5 ℃ for min -1 Heating to 500 ℃ at the heating rate, and keeping the temperature for 2 hours to obtain the carbon-coated flower-shaped titanium dioxide Ru-TiO carrying ruthenium nano particles 2 @NC。
Example 1
Dissolving 2ml of n-butyl titanate in 60ml of glacial acetic acid, and uniformly stirring to obtain a milky white solution; heating the mixed solution in a hydrothermal kettle to 140 ℃, and preserving heat for 12 hours; after the hydrothermal kettle is naturally cooled, centrifugally washing the obtained product by deionized water, and finally drying the product to obtain a white flower-shaped titanium dioxide precursor p-TiO 2 . Then the titanium dioxide precursor p-TiO is added 2 Placing the mixture in a porcelain boat, placing the porcelain boat in a tubular furnace at the side close to outlet gas, and firstly, adding p-TiO in argon atmosphere 2 At 5 ℃ for min -1 Heating to 450 deg.C at a heating rate, maintaining the temperature for 0.25 hr, and converting the atmosphere to ammonia gas at 3 deg.C for 3 min -1 Heating to 800 deg.C at a heating rate, maintaining the temperature for 2 hr, and naturally cooling to obtain flower-like titanium oxide/titanium dioxide powder (TiO/TiO) 2 )。
As can be seen from the scanning electron micrograph of the sample prepared in example 1 of fig. 1, the sample prepared in example 1 has a spherical nanoflower structure. As can be seen from the X-ray diffraction pattern shown in FIG. 2, the X-ray diffraction patterns of comparative example 1 and example 1 are significantly different, the three-intensity peaks appear in comparative example 1 at diffraction angles of 25.28, 37.80 and 48.05 degrees, and the sample is anatase-phase TiO as seen by comparing with the X-ray diffraction pattern standard card 2 (JCPFD 21-1272); example 1 in addition to diffraction peaks at diffraction angles of 25.28, 37.80 and 48.05 degrees, diffraction peaks at 37.33, 43.36 and 62.96 degrees were observed for a comparative X-ray chart standard card, which corresponds to cubic phase TiO (JCPDF)08-0117). As a result, the sample prepared in example 1 contained TiO 2 And a TiO two-phase.
Example 2
Flower-like TiO/TiO obtained in example 1 was weighed 2 Adding 90mg of the powder into 30ml of ethanol, performing ultrasonic treatment to obtain a suspension, and adding 2.72ml of ruthenium trichloride aqueous solution (the concentration of Ru is 3.67mg ml) -1 ) The mixture was stirred at room temperature for 5 hours. Then the solvent is removed by rotary evaporation to obtain flower-shaped titanium oxide/titanium dioxide Ru-TiO/TiO loaded with ruthenium 2 And (3) powder. 90mg of dried Ru-TiO/TiO are taken 2 The powder was added to 30ml of a tris buffer solution (pH:8.5) and dispersed by sonication, and then 90mg of dopamine hydrochloride was added and stirred at room temperature for 48 hours. Then centrifugally washing and drying the mixture to obtain the poly-dopamine coated Ru-TiO/TiO 2 . Then, the mixture is heated at 5 ℃ for min in an H2/Ar atmosphere -1 Heating to 500 ℃ at the heating rate, preserving the heat for 2 hours, and naturally cooling to obtain the carbon-coated ruthenium-loaded titanium oxide/titanium dioxide nanoflowers Ru-TiO/TiO 2 @NC。
As can be seen from FIG. 3, which is a high-power transmission electron micrograph of the sample obtained in example 2, a substance having a lattice spacing of 0.209nm contained in the sample corresponds to a TiO (200) crystal plane; the substance adjacent thereto having a lattice spacing of 0.352nm corresponds to TiO 2 (002) crystal face of (1); furthermore, there are nanoparticles having a lattice spacing of 0.214nm, corresponding to the Ru (002) crystal plane. By combining the X-ray diffraction pattern of example 2 in FIG. 2, it can be confirmed that TiO/TiO formed in the sample obtained in example 2 2 And the surface of the heterostructure is loaded with Ru nano particles.
Effect example 1
The samples obtained in comparative example 2 and example 2 were used as catalysts, coated on the surface of a glassy carbon electrode, used as a working electrode, a graphite rod and a mercury/mercury oxide electrode were used as a counter electrode and a reference electrode, and a 1M aqueous solution of potassium hydroxide was used as an electrolyte, and the electrochemical impedance spectrum of the sample was measured in a three-electrode system, and the result is shown in fig. 4. After fitting, the charge transfer resistances of comparative example 2 and example 2 were 35.23 ohms and 16.54 ohms, respectively, and it can be seen that the example 2 sample was due to TiO/TiO 2 The formation of the heterostructure obviously reduces the charge transmission resistance in the electrochemical reaction process, thereby being beneficial to the implementation of the electrocatalytic reaction.
Effect example 2
The samples obtained in comparative example 2 and example 2 were used as catalysts, respectively, and coated on the surface of a glassy carbon electrode as a working electrode, a graphite rod and a mercury/mercury oxide electrode as a counter electrode and a reference electrode, and a hydrogen-saturated 0.1M aqueous solution of potassium hydroxide as an electrolyte, and the catalytic activity of the samples on the hydrogen oxidation reaction was tested in a three-electrode system. The test conditions were: the electrolyte is hydrogen saturated 0.1M potassium hydroxide, the electrode rotation speed is 2500rpm, the sweep rate is as follows: 10mV s -1 . As shown in FIG. 5, the HOR currents at 100mV VS.RHE for the samples obtained in comparative example 2 and example 2 were 2.46 and 0.24mA cm, respectively -2 Showing a phase contrast of Ru-TiO 2 @ NC, Ru-TiO/TiO obtained in example 2 2 The catalytic activity of @ NC on HOR is obviously improved.
Effect example 3
The samples obtained in comparative example 2 and example 2 were used as catalysts, respectively, and coated on the surface of a glassy carbon electrode as a working electrode, a graphite rod and a mercury/mercury oxide electrode as a counter electrode and a reference electrode, and a hydrogen-saturated 0.1M aqueous solution of potassium hydroxide as an electrolyte, and the catalytic activity of the samples on the hydrogen oxidation reaction was tested in a three-electrode system. The catalytic stability to HOR was tested for the comparative example 2 and example 2 samples, respectively, in a three-electrode system using chronoamperometry. The test conditions were: the electrolyte is hydrogen saturated 0.1M KOH, the electrode rotation speed is 400rpm, and the potential is set to be 0.1V RHE The test time was 3600 seconds. As shown in FIG. 6, Ru-TiO/TiO obtained in example 2 2 The activity and stability of @ NC are both obviously superior to those of Ru-TiO obtained in comparative example 2 2 @ NC, and still maintained 68.7% of the initial current density after the test, no significant attenuation occurred, indicating Ru-TiO/TiO 2 @ NC is a catalyst with good stability.

Claims (4)

1. A preparation method of a carbon-coated titanium oxide/titanium dioxide heterostructure nanoflower supported ruthenium nanocatalyst is characterized by comprising the following steps of:
(1) the glacial acetic acid and the titanic acid n-butyl ester generate flower-shaped TiO through hydrothermal reaction 2 A precursor;
(2) flower-shaped TiO obtained in the step (1) 2 The precursor is heated from room temperature to 450 ℃ in an argon atmosphere and is kept warm for a certain time, then heated to 600-800 ℃ in an ammonia atmosphere and is kept warm for a certain time, and the titanium oxide/titanium dioxide TiO/TiO is obtained after cooling 2 A heterostructure nanoflower;
(3) TiO/TiO obtained in the step (2) 2 The nanometer flower and the ruthenium trichloride solution are mixed evenly and dried to obtain the compound Ru-TiO/TiO of the loaded metal salt ion 2 A nanoflower powder;
(4) Ru-TiO/TiO obtained in the step (3) 2 Adding the nanometer flower powder and Dopamine (DA) into trihydroxymethyl aminomethane-buffer solution to make the Ru-TiO/TiO coated with polydopamine 2 A nanoflower;
(5) coating the polydopamine obtained in the step (4) with Ru-TiO/TiO 2 Nanometer flower on H 2 Carrying out heat treatment in a/Ar atmosphere to obtain the carbon-coated titanium oxide/titanium dioxide heterostructure nano flower Ru-TiO/TiO of the load Ru nano particle 2 @NC。
2. The method according to claim 1, wherein the TiO/TiO in the step (2) 2 The heterostructure nanometer flower is made of flower-shaped TiO 2 The precursor is heated to 450 ℃ in the argon atmosphere and kept for 0.5-3 hours, and then the precursor is heated for 1-5 ℃ min in the ammonia atmosphere -1 Heating to 600-800 ℃, preserving heat for 0.5-4 hours, and naturally cooling to obtain the product.
3. The method according to claim 1, wherein the sample is flower-like TiO/TiO 2 And the surface of the heterostructure is loaded with Ru nano particles.
4. Use of a sample obtained by the preparation method according to claim 1 in a hydrogen oxidation reaction of a fuel cell.
CN202210802359.5A 2022-07-07 2022-07-07 Carbon-coated flower-like titanium oxide/titanium dioxide heterostructure supported ruthenium catalyst and preparation and application thereof Active CN115084555B (en)

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