CN108878896B - Metal nano-cluster composite catalyst and preparation method and application thereof - Google Patents
Metal nano-cluster composite catalyst and preparation method and application thereof Download PDFInfo
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/33—
-
- B01J35/393—
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a supported metal nano-cluster composite catalyst and a preparation method and application thereof. The catalyst has the characteristics of high metal loading, small size of the metal nanocluster, high dispersity, high proportion of dominant crystal faces in the catalytic oxygen reduction reaction of the metal nanocluster, large electrochemical active area and hexagonal small-size metal nanocrystals with morphology projections, has high quality catalytic activity for reactions such as oxygen reduction and the like, and has wide application prospects in the aspect of chemical processes such as catalytic fuel cell reactions and the like.
Description
Technical Field
The invention relates to a metal nano-cluster composite catalyst, a preparation method thereof and application thereof in catalyzing fuel cell reaction.
Background
The fuel cell is a device capable of directly converting chemical energy into electric energy, and has the advantages of high energy conversion efficiency, quick start, environmental friendliness and the like. Catalysts are an important component in fuel cells. In order to improve the energy utilization efficiency of fuel and reduce the internal resistance of the cell, the catalyst in practical application needs to have high metal loading and good metal dispersion besides good catalytic property. However, as the metal loading increases, some of the primary particles approach each other and tend to aggregate and grow more readily between particles, which in turn leads to a decrease in catalytic performance of the catalyst.
Many studies have shown that for fuel cell catalysts, the metal nanoparticles should be smaller than 5nm in size, and larger metal nanoparticles have lower mass catalytic activity for fuel cell reactions (Shao M., et al., Nano Lett.,2011,11, 3714-.
Some research results show that some high-index crystal faces of Pt metal have higher catalytic activity per unit area (N.Tian, et al., Science,2007,316, 732-one 735; S.Liu, et al., J.Am.chem.Soc.,2016,138, 5753-one 5756), but the conventional catalyst synthesis method is difficult to prepare the regular-morphology Pt nano-cluster composite catalyst with small size, high metal loading and high catalytic oxygen reduction dominant crystal face ratio.
Therefore, how to prepare the high-performance fuel cell catalyst with high metal loading, small size of the metal nanocluster, high dispersion degree, high proportion of dominant crystal faces of the reaction such as catalytic oxygen reduction of the metal nanocluster and large electrochemical active area is a challenging subject.
We have invented a class of 'non-protective' noble metals and their alloy nanoclusters, which uses simple ions and organic solvent molecules as stabilizers, not only has small size and narrow particle size distribution, but also can conveniently deposit the nanoparticles on the surface of a carrier by adding acidic aqueous solution, heating and other methods to prepare the complex phase metal catalyst. (Wang Yuan et al, chem.Mater.2000,12,1622; Chinese Patent invention ZL 99100052.8; J.Catal.2004,222, 493-498; J.Catal.2005,229,114-118) such metal nanoclusters have been used in the synthesis of fuel cell catalytic electrodes (S.Mao, G.Mao, Supported nanoparticle catalyst. USA Patent, US 2003/0104936; W.ZHou, et al, App.Catal.B.2003,46,273).
Disclosure of Invention
The invention prepares the high-performance metal nano-cluster composite fuel cell catalyst with high metal loading, small size of the metal nano-cluster, high dispersion degree, high proportion of dominant crystal face of the metal nano-cluster catalytic oxygen reduction reaction and large electrochemical active area by controlled assembly of the metal nano-cluster, and provides a new way for solving the problems of the fuel cell catalyst.
The metal nano-cluster composite catalyst provided by the invention basically comprises metal nano-clusters and a conductive carrier, wherein the number average particle size of the metal nano-clusters is 1.5-3.5 nanometers, and the metal nano-clusters account for 10-50% of the catalyst by mass percent; the ratio of the (200) crystal face diffraction peak to the (111) crystal face diffraction peak area in the X-ray diffraction spectrum of the metal nanocluster is very small, and specifically, when the mass percentage content of the metal nanocluster in the catalyst is more than or equal to 10% and less than 30%, the value is less than 22%, preferably less than 20%; when the mass percentage of the metal nanoclusters in the catalyst is more than or equal to 30% and less than 50%, the value is less than 25%.
Further, in the catalyst of the present invention, the metal is Pt, and the conductive carrier is a carbon-based carrier.
Further, the carbon-based material is one or more of conductive carbon black, nitrogen-doped carbon nanohorns, carbon nanotubes and graphene.
Furthermore, the catalyst of the invention has a metal nanocluster with a hexagonal shape projection in a transmission electron microscope photo, and the length of the longest diagonal line of the hexagon is 1.2 to 4 nanometers.
Further, the longest diagonal of the hexagon has a length of 1.3 nm to 3.7 nm.
Further, the proportion of the number of the metal nanoclusters of which the shape projection is hexagonal in the number of all the metal nanoclusters is 1% to 40%.
Furthermore, the proportion of the metal nanoclusters with the hexagonal shape projection in the metal nanoclusters is 2% to 30%.
Further, the electrochemical active area of the catalyst obtained by calculating the hydrogen desorption peak on the cyclic voltammetry curve of the catalyst of the invention is large, and specifically, when the mass percentage content of the metal nanoclusters in the catalyst is more than or equal to 10% and less than 30%, the value is more than 75m2gPt and less than 120m2gPt; when the mass percentage of the metal nanoclusters in the catalyst is more than or equal to 30% and less than 50%, the mass percentage is more than 55m2gPt and less than 75m2/gPt。
Further, the electrochemical surface of the catalyst of the present inventionProduct greater than 90m2/gPt less than 120m2/gPt。
Further, the catalyst has a peak intensity at 0.177v (vs rhe) among hydrogen desorption peaks in cyclic voltammogram higher than a peak intensity at 0.122v (vs rhe).
Further, the catalyst contains a surfactant, and the mass percentage of the surfactant is 0.01-20%.
Further, the surfactant is at least one of a cationic surfactant, an anionic surfactant and an amphoteric surfactant.
Further, the surfactant is at least one of quaternary ammonium salt, carboxylic acid or carboxylate, betaine type surfactant and alkylbenzene sulfonic acid type surfactant.
Further, the structure of the quaternary ammonium salt is NR1R2R3R4Said R is1Is an alkyl group having 4 to 22 carbon atoms, R2、R3And R4Is alkyl with 1 to 4 carbon atoms; the anion in the quaternary ammonium salt is a halide ion.
The invention also provides a method for preparing the metal nano-cluster composite catalyst, which comprises the following steps:
1) mixing a surfactant solution with a conductive carrier to enable a surfactant to be adsorbed on the surface of the carrier to form a surfactant modified carrier;
2) mixing the product prepared in the step 1) with a metal nano-cluster colloidal solution prepared in advance, so that the metal nano-cluster is adsorbed on the surface of the carrier modified by the surfactant;
3) gradually expelling the surfactant in the product prepared in the step 2) by liquid, and assembling the metal nanoclusters on a carrier or a carrier modified by the surfactant to form a supported metal nanocluster catalyst;
4) drying the product prepared in the step 3).
Further, the surfactant in step 1) includes at least one of a cationic surfactant, an anionic surfactant and an amphoteric surfactant. The conductive carrier is a carbon-based carrier.
Further, the surfactant is at least one of quaternary ammonium salt, carboxylic acid or carboxylate, betaine type surfactant and alkylbenzene sulfonic acid type surfactant.
Further, the structure of the quaternary ammonium salt is NR1R2R3R4Said R is1Is an alkyl group having 4 to 22 carbon atoms, R2、R3And R4Is alkyl with 1 to 4 carbon atoms;
further, the metal nanocluster colloidal solution is a metal nanocluster colloidal solution using simple ions and a solvent as a stabilizer, or a metal nanocluster colloidal solution prepared by an alkali-ethylene glycol method.
Further, the metal nanocluster is a Pt metal nanocluster.
Further, in the mixture of the step 2), the mass ratio of the metal nanoclusters to the carrier is 1:9 to 3: 1.
Further, the metal nanocluster colloidal solution in the step 2) is prepared by the following method:
preparing a non-protective metal nano-cluster colloidal solution by adopting an alkali-polyol method: dissolving at least one of acid or soluble salt of transition metal in alcohol or alcohol-water mixed solution to obtain transition metal compound solution with concentration of 0.1-100g/L, mixing the transition metal compound solution with alcohol solution or water solution or alcohol-water solution of alkaline compound under stirring, and heating the system to prepare the metal nano cluster colloidal solution. The heating treatment mode comprises heat conduction heating or radiation heating, and the heating temperature is 333K-473K. The alkali compound is preferably at least one of hydroxide, acetate and carbonate of alkali metal.
Further, in the above preparation method, the adsorption of the surfactant, the adsorption of the metal nanoclusters, or the removal of the surfactant is performed in a solvent including at least one of water, alcohol, ketone, and halogenated alkane.
Further, the alcohol, ketone and halogenated alkane respectively refer to monohydric alcohol, dihydric alcohol and trihydric alcohol with the carbon atom number of 1-8, ketone with the carbon atom number of 3-6 and halogenated alkane with the carbon atom number of 1-6. Such as at least one of methanol, ethanol, propanol, butanol, cyclohexanol, acetone, butanone, cyclohexanone, ethylene glycol.
The application of the catalyst of the present invention in catalyzing fuel cell reactions also falls within the scope of the present invention.
Effects of the invention
The catalyst has the characteristics of high metal loading, small size of the metal nanocluster, high dispersity, high proportion of dominant crystal faces in the catalytic oxygen reduction reaction of the metal nanocluster, large electrochemical active area and containing metal nanocrystals with the shape projection of hexagonal small size (1.3-3.7 nanometers), so that the metal nanocluster composite catalyst has high quality catalytic activity on reactions such as oxygen reduction and the like. For example, in the Pt metal nanocluster composite catalyst prepared in example 1 of the present invention, the nanoparticles having a hexagonal shape in a morphological projection account for 27% of the total particles, and the longest diagonal length of the nanoparticles having a hexagonal shape in a morphological projection is between 1.3 nm and 3.7 nm, which has not been reported in the past. The ratio of the (200) crystal face diffraction peak intensity to the (111) crystal face diffraction peak intensity of the catalyst is 14.5 percent, and the electrochemical active area of the catalyst is as high as 113m2and/gPt, the catalytic activity of the catalyst for catalyzing oxygen reduction reaction is as high as 380A/gPt, which is much higher than that of other supported Pt metal nanoclusters under the same conditions. The hydrogen absorption and desorption peak shape in the cyclic voltammetry curve of the metal nanocluster catalyst reflects the proportion of the exposed crystal face, the hydrogen absorption and desorption peak shape in the cyclic voltammetry curve of the supported Pt nanocluster catalyst prepared by the invention is different from the previously reported catalyst of the same kind, and the peak intensity at 0.177V (vs RHE) is higher than the intensity at 0.122V (vs RHE).
The above characteristics of the catalyst of the present invention reflect that the catalyst of the present invention has a specific structure different from that of the conventional catalyst.
The preparation method of the catalyst provided by the invention utilizes the controlled assembly of the metal nanoclusters on the surface of the carrier, and unexpectedly realizes the preparation of the catalyst containing the small-size nanoclusters (1.3-3.7 nanometers) with the hexagonal shape projection while obtaining high metal loading and high metal dispersity, thereby improving the effect of catalyzing the predominant crystal face proportion of the oxygen reduction reaction. The metal nano-cluster is controlled to be assembled, and the characteristic that the action of a certain crystal face or surface structure of the metal nano-cluster, particularly the stable metal nano-cluster consisting of a solvent and simple ions, is stronger than that of other crystal faces or surface structures is utilized to ensure that the crystal face or structure with stronger action of the surfactant preferentially acts with surfactant molecules or assemblies thereof adsorbed on the surface of the carrier, while the surfactant molecules on the crystal face or structure with weaker action are preferentially expelled, the metal nano-cluster is assembled with the carrier or other metal nano-clusters through the crystal face or part which does not adsorb the surfactant or has weaker action with the surfactant molecules under the special action, and the metal nano-cluster composite catalyst has unique appearance, controlled proportion of exposed crystal faces of the metal nano-cluster, high metal dispersion degree, large electrochemical active area and prominent performance of catalyzing the oxygen reduction reaction of the fuel cell.
None of the above features of the present invention can be inferred from the prior knowledge. The catalyst of the invention has wide application prospect in the aspects of catalyzing fuel cell reaction and the like.
Drawings
Fig. 1 is a high-resolution transmission electron micrograph of the Pt metal nanocluster composite catalyst prepared in example 1.
Fig. 2 is a particle size distribution diagram of the Pt metal nanocluster composite catalyst prepared in example 1.
Fig. 3 is an X-ray diffraction pattern of the Pt metal nanocluster composite catalyst prepared in example 1.
FIG. 4 is an overlay of polarization curves of the Pt metal nanocluster composite catalyst prepared in example 1 and the commercially available Pt/C-JM catalyst and the commercially available Pt/C-TKK catalyst catalyzing oxygen reduction reactions.
FIG. 5 is cyclic voltammograms under nitrogen for the Pt metal nanocluster composite catalyst prepared in example 1 along with a commercially available Pt/C-JM catalyst and a commercially available Pt/C-TKK catalyst.
FIG. 6 is an X-ray diffraction pattern of a commercially available Pt/C-JM catalyst.
FIG. 7 is an X-ray diffraction pattern of a commercially available Pt/C-TKK catalyst.
Fig. 8 is a polarization curve of the Pt metal nanocluster catalyst prepared in comparative example 1 catalyzing an oxygen reduction reaction.
Fig. 9 is an X-ray diffraction pattern of the Pt metal nanocluster composite catalyst prepared in example 2.
Fig. 10 is a polarization curve of the Pt metal nanocluster composite catalyst prepared in example 2 catalyzing an oxygen reduction reaction.
Fig. 11 is a cyclic voltammogram under nitrogen for the Pt metal nanocluster composite catalyst prepared in example 2.
Fig. 12 is a high-resolution transmission electron micrograph of the Pt metal nanocluster composite catalyst prepared in example 3.
Fig. 13 is a particle size distribution diagram of the Pt metal nanocluster composite catalyst prepared in example 3.
Fig. 14 is an X-ray diffraction pattern of the Pt metal nanocluster composite catalyst prepared in example 3.
Fig. 15 is a polarization curve of the Pt metal nanocluster composite catalyst prepared in example 3 catalyzing an oxygen reduction reaction.
Fig. 16 is an X-ray diffraction pattern of the Pt metal nanocluster composite catalyst prepared in example 4.
Fig. 17 is a polarization curve of the Pt metal nanocluster composite catalyst prepared in example 4 catalyzing an oxygen reduction reaction.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1 Synthesis and catalytic Performance of Pt Metal nanocluster composite catalyst (Pt content: 25 wt%)
1) Will be 1g H2PtCl6·6H2O was dissolved in 50mL of ethylene glycol, and the resulting solution was mixed with 50mL of NaOH in ethylene glycol (0.26 mol/L). In N2Stirring under atmosphereStirring the mixture, heating the mixture to 160 ℃ by microwave for reaction, and cooling to room temperature to prepare a Pt metal nano cluster colloidal solution with the Pt concentration of 3.7 g/L;
2) 0.1385g of trimethylhexadecylammonium bromide (CTAB) was dissolved in 10mL of n-propanol, and 59.4mg of conductive carbon black was added to the above mixture and subjected to ultrasonic treatment;
3) mixing 10mL of the Pt metal nano-cluster colloidal solution prepared in the step 1) with the dispersion system prepared in the step 2), stirring, and filtering to obtain a solid in a reaction mixture;
4) washing the solid obtained in the step 3) with hot water (90 ℃), and drying the solid in a vacuum drying oven at 60 ℃ to obtain the Pt metal nano cluster composite catalyst.
Inductively coupled plasma atomic emission spectrometry (ICP-AES) tests show that the mass percentage of the Pt metal nanoclusters in the prepared nano composite catalyst is 25 wt%; transmission electron microscope analysis (figure 1, figure 2) shows that the number average particle size of Pt metal nano-cluster in the catalyst is 1.9nm, and the standard deviation of the particle size distribution is 0.3 nm. The Pt nanoclusters with hexagonal morphology projection can be seen in a transmission electron microscope image. Statistical results show that the Pt nanoparticles with hexagonal morphology projection account for 27% of the total number of nanoparticles. The longest diagonal of the hexagon is 1.5nm to 3.6 nm.
Elemental analysis shows that the mass percent of nitrogen element in the prepared nano composite catalyst is 0.91 wt%, and the mass percent of CTAB (cetyltrimethyl ammonium bromide) in the catalyst is 14%.
The ratio of the diffraction peak area of the Pt (200) crystal plane to the diffraction peak area of the (111) crystal plane in the X-ray diffraction spectrum of the prepared catalyst was 14.5% (FIG. 3).
The performance of the catalyst in catalyzing oxygen reduction reaction is tested according to the following method:
ultrasonic treating 5mg of the prepared nano composite catalyst in 5mL of absolute ethyl alcohol for 30 minutes, and adding 100 mu L of the nano composite catalyst into the dispersion system
The solution was sonicated for an additional 30 minutes. Pipette 10. mu.L of the catalyst suspension into a glassAnd drying the sample on the surface of the carbon electrode at room temperature for 30 minutes, and then drying the sample in vacuum at 298K for 1 hour to obtain the catalytic electrode. The electrode is placed in perchloric acid (0.1M) electrolyte, and cyclic voltammetry scanning activation treatment is carried out in a potential interval of 0.05-1.2V (vs RHE).
The oxygen reduction reaction catalytic activity test was carried out in an oxygen-saturated perchloric acid solution (0.1M) at 333K, with a potential sweep rate of 5mV/s and a rotating disk electrode speed of 1600 revolutions.
The electrochemical catalytic experiment result shows that the activity of the catalyst in oxygen saturated perchloric acid solution (0.1M) for catalyzing the oxygen reduction reaction after the activation treatment is 380A/gPt (0.9V vs RHE), and the catalytic activity of the catalyst is superior to that of a commercial catalyst Pt/C-JM (Johnson Matthey company, platinum content: 20 wt%) for catalyzing the oxygen reduction reaction (162A/gPt (0.9V vs RHE)) under the same conditions; more superior to the catalytic activity of a commercially available catalyst Pt/C-TKK (noble metal Co., Takara, platinum content: 46 wt%) (132A/gPt (0.9V vs RHE)) (FIG. 4). The kinetic current value in the above experiment was calculated according to the Koutecky-Levich formula, and the 0.9V current value was taken from the oxygen reduction polarization curve.
Calculating the electrochemical active area of the catalyst from the hydrogen desorption peak of the catalyst in the cyclic voltammetry curve under nitrogen (figure 5), wherein the electrochemical active area of the catalyst after the activation treatment is 113m2/gPt, much larger than the electrochemically active area (60 m) of the above commercial Pt/C-JM catalyst measured under the same conditions2/gPt) and electrochemical active area of Pt/C-TKK catalyst (48 m)2/gPt)。
The current intensity of the hydrogen desorption peak of the catalyst after the activation treatment at 0.177v (vs rhe) is higher than that of the hydrogen desorption peak at 0.122v (vsrhe), which is different from the case of the conventional Pt/C catalyst. For example, of the hydrogen desorption peaks of the two commercial catalysts described above, the hydrogen desorption peak current intensity at 0.177v (vs rhe) was lower than the hydrogen desorption peak current intensity at 0.122v (vs rhe).
The ratio of the diffraction peak area of the Pt (200) crystal face to the diffraction peak area of the (111) crystal face in the X-ray diffraction spectrum of the commercially available catalyst Pt/C-JM is 43.1% (FIG. 6), and the ratio of the diffraction peak area of the Pt (200) crystal face to the diffraction peak area of the (111) crystal face in the X-ray diffraction spectrum of the Pt/C-TKK catalyst is 27.8% (FIG. 7), which is obviously larger than the corresponding value of the Pt metal nanocluster composite catalyst of the present invention.
Comparative example 1 preparation of Pt Metal nanocluster catalyst (Pt content 22 wt%) by uncontrolled Assembly
The uncontrolled assembly preparation of Pt metal nanocluster catalyst was prepared by synthesis under the procedure and conditions described in example 1 without CTAB.
ICP-AES tests show that in the catalyst prepared in the embodiment, the mass percentage content of the Pt metal nano cluster is 22 wt%, and the ratio of the diffraction peak area of the Pt (200) crystal face to the diffraction peak area of the (111) crystal face in the catalyst obtained by X-ray diffraction spectrum is 23.3%. The Pt metal nanoclusters of which the morphology is projected as a hexagon in the catalyst prepared in example 1 are not observed in the transmission electron microscope photograph thereof. In addition, in the electron micrograph of platinum nanoparticles of the Pt nanocluster metal colloid solution prepared as described in example 1, Pt metal nanoclusters whose morphology is projected as a hexagon as described above are also not observed.
The activity of catalyzing oxygen reduction reaction was tested by the method and conditions described in example 1 using the catalyst prepared in comparative example 1 instead of the nanocomposite catalyst prepared in example 1. The results showed that the catalyst prepared in comparative example 1 had a catalytic activity of 297A/gPt (0.9V vs RHE) for the oxygen reduction reaction (FIG. 8).
Example 2 Synthesis and catalytic Performance of Pt Metal nanocluster composite catalyst (Pt content: 37 wt%)
The mass of the conductive carbon black (EC-600) was changed to 40.1mg, and the Pt metal nanocluster catalyst was synthesized according to the procedure and conditions described in example 1.
ICP-AES test shows that the mass percentage of the Pt metal nano-cluster in the prepared nano-composite catalyst is 37 wt%. The element analysis shows that the mass percentage of the nitrogen element in the prepared nano composite catalyst is 0.75 wt%. The mass percentage content of the surfactant CTAB in the catalyst is 11%. The X-ray diffraction spectrum gave a catalyst having a ratio of the diffraction peak area for the Pt (200) face to the diffraction peak area for the (111) face of 19.7% (FIG. 9), which was smaller than the ratios of the commercially available Pt/C-JM and the commercially available Pt/C-TKK described in example 1. The results of electrochemical catalysis experiments show that the activity of the nanocomposite catalyst in catalyzing oxygen reduction reaction in oxygen saturated perchloric acid solution (0.1M) is 235A/gPt (0.9V vs RHE) (FIG. 10), and the catalytic activity is superior to that of the commercially available Pt/C-JM catalyst and the commercially available Pt/C-TKK catalyst described in example 1 and measured under the same conditions. The electrochemical active area calculated by the hydrogen desorption peak in the cyclic voltammetry curve of the nano composite catalyst under nitrogen is 63m2/gPt (FIG. 11) having an electrochemically active area greater than that of the commercially available Pt/C-JM catalyst and the commercially available Pt/C-TKK catalyst described in example 1, measured under the same conditions.
Example 3 Synthesis and catalytic Performance of Pt Metal nanocluster composite catalyst (Pt content: 41 wt%)
The mass of the conductive carbon black was changed to 29.7mg, and the Pt metal nanocluster catalyst was synthesized according to the procedure and conditions described in example 1.
ICP-AES test shows that the mass percentage of the Pt metal nano-cluster in the prepared nano-composite catalyst is 41 wt%. Transmission electron microscopy analysis (FIG. 12, FIG. 13) shows that the number average particle size of Pt metal nanoclusters in the catalyst is 2.5nm, and the standard deviation of the particle size distribution is 0.5 nm. The Pt nanoclusters with hexagonal morphology projection can be seen in a transmission electron microscope image. Statistical results show that the Pt nanoparticles with hexagonal morphology projection account for 6% of the total number of nanoparticles. The longest diagonal of the hexagon is 2.0nm to 3.2 nm. The element analysis shows that the mass percentage of the nitrogen element in the prepared nano composite catalyst is 0.75 wt%. The mass percentage content of the surfactant CTAB in the catalyst is 12%. The X-ray diffraction pattern gave a catalyst having a diffraction peak area for the Pt (200) face to a diffraction peak area for the (111) face of 24.4% (FIG. 14), which was less than the corresponding values for the commercially available Pt/C-JM and Pt/C-TKK catalysts described in example 1. The results of electrochemical catalysis experiments show that the activity of the nanocomposite catalyst in catalyzing oxygen reduction reaction in oxygen saturated perchloric acid solution (0.1M) is 176A/gPt (0.9Vvs RHE) (FIG. 15), and the catalytic activity is superior to that of the commercially available Pt/C-JM catalyst and the commercially available Pt/C-TKK catalyst described in example 1 and measured under the same conditions. Cyclic voltammograms from catalysts under nitrogenCalculating the electrochemical active area of the catalyst by hydrogen desorption peak in the line to obtain the electrochemical active area of the catalyst of 57m2/gPt。
Example 4 Synthesis of Pt Metal nanocluster composite catalyst (Pt content: 26 wt%)
The n-propanol in example 1 was changed to cyclohexanol, and synthesized according to the procedure and conditions described in example 1, to obtain a Pt metal nanocluster catalyst.
ICP-AES test shows that the mass percentage of the Pt metal nano-cluster in the prepared nano-composite catalyst is 26 wt%. The element analysis shows that the mass percentage of the nitrogen element in the prepared nano composite catalyst is 0.95 wt%. The mass percentage content of the surfactant CTAB in the catalyst is 15%. The X-ray diffraction spectrum gave a ratio of the diffraction peak area of the Pt (200) crystal plane to the diffraction peak area of the (111) crystal plane in the catalyst of 22.6% (FIG. 16), which was smaller than the corresponding values of the commercially available Pt/C-JM catalyst and the commercially available Pt/C-TKK catalyst described in example 1. The results of electrochemical catalysis experiments show that the activity of the nanocomposite catalyst in catalyzing oxygen reduction reaction in oxygen saturated perchloric acid solution (0.1M) is 259A/gPt (0.9V vsRhE) (FIG. 17), and the catalytic activity is superior to that of the Pt/C-JM catalyst and the Pt/C-TKK catalyst described in example 1 and measured under the same conditions.
Example 5 Synthesis of Pt Metal nanocluster composite catalyst (Pt content: 46 wt%)
The quality of the conductive carbon black was changed to a multiwall carbon nanotube, and synthesized according to the procedure and conditions described in example 3, to obtain a Pt metal nanocluster catalyst.
ICP-AES test shows that the mass percentage of the Pt metal nano-cluster in the prepared nano-composite catalyst is 46 wt%. The electrochemical catalysis experiment result shows that the activity of the nano composite catalyst in the oxygen saturated perchloric acid solution (0.1M) for catalyzing the oxygen reduction reaction is 105A/gPt (0.9V vs RHE).
Example 6 Synthesis of Pt Metal nanocluster composite catalyst (Pt content: 40 wt%)
1) A3.7 g/L Pt metal nanocluster colloidal solution was prepared as in example 1.
2) 0.2761g of trimethyldecaHexaalkylammonium bromide (CTAB) was dissolved in 20mL of n-propanol, and 30mg of nitrogen-doped carbon nanohorns (specific surface area 800 m) were added to the above mixture2/g) sonication for 1.5 hours;
3) adding 20mL of Pt metal nano-cluster colloidal solution prepared in the step 1), stirring the obtained mixture in a water bath, and filtering and separating solids in the mixture;
4) and washing the solid with water and drying the solid in a vacuum drying oven at the temperature of 60 ℃ to obtain the Pt metal nano-cluster composite catalyst.
ICP-AES test shows that the mass percentage of the Pt metal nano-cluster in the prepared nano-composite catalyst is 40 wt%.
Example 7 Synthesis of Pt Metal nanocluster composite catalyst (Pt content: 11 wt%)
1) Will be 1g H2PtCl6·6H2O was dissolved in 50mL of ethylene glycol, and the resulting solution was mixed with 50mL of NaOH in ethylene glycol (0.26 mol/L). In N2Stirring the mixture in the atmosphere, heating the mixture to 160 ℃ by microwave for reaction for 15 minutes, and cooling to room temperature to prepare a Pt metal nano-cluster colloidal solution with the Pt concentration of 3.7 g/L;
2) 4.5mg of trimethyldecaalkylammonium bromide, 3.2mg of trimethyloctadecylammonium bromide, 6.9mg of sodium stearate, and 3.3mg of betaine were dissolved in a mixture of 15mL of acetone, 5mL of butanone, and 2.5mL of methanol. To the above mixture was added 86.7mg of conductive carbon black (EC-600JD) and sonicated for 0.5 hours;
3) mixing 10mL of the Pt metal nano-cluster colloidal solution prepared in the step 1) with the dispersion system prepared in the step 2), stirring for 18 hours, and filtering to separate solids in the mixture;
4) and washing the solid with water and drying the solid in vacuum at the temperature of 60 ℃ to obtain the Pt metal nano-cluster composite catalyst.
ICP-AES test shows that the mass percentage of the Pt metal nano-cluster in the prepared nano-composite catalyst is 11 wt%. Elemental analysis shows that the mass percent of nitrogen element in the prepared nano composite catalyst is 0.59 wt%.
Claims (28)
1. A metal nanocluster composite catalyst, characterized in that the catalyst consists essentially of metal nanoclusters and a conductive carrier, the metal nanoclusters being platinum-based metal nanoclusters having an average particle diameter of 1.5 to 3.5 nm; the mass percentage content of the metal nanocluster is 10-50%; the ratio of the (200) crystal face diffraction peak to the (111) crystal face diffraction peak area in the X-ray diffraction spectrum of the metal nanocluster is very small, and specifically, when the mass percentage content of the metal nanocluster in the catalyst is more than or equal to 10% and less than 30%, the value is less than 22%; when the mass percentage of the metal nanoclusters in the catalyst is more than or equal to 30% and less than or equal to 50%, the value is less than 25%.
2. The catalyst according to claim 1, wherein when the mass percentage of the metal nanoclusters in the catalyst is greater than or equal to 10% and less than 30%, the ratio of the diffraction peak area of the (200) crystal plane to the diffraction peak area of the (111) crystal plane in the X-ray diffraction spectrum of the metal nanoclusters is less than 20%.
3. The catalyst according to claim 1, wherein the metal constituting the metal nanocluster is Pt, and the conductive support is a carbon-based support.
4. The catalyst of claim 3, wherein the carbon-based support is one or more of conductive carbon black, nitrogen-doped carbon nanohorns, carbon nanotubes, and graphene.
5. The catalyst according to claim 1, wherein the catalyst has metal nanoclusters whose morphological projections are hexagons in a transmission electron micrograph, and the longest diagonal of the hexagons has a length of 1.2 nm to 4 nm.
6. The catalyst of claim 5 wherein the longest diagonal of the hexagon is between 1.3 nanometers and 3.7 nanometers in length.
7. The catalyst according to claim 5, wherein the number of metal nanoclusters whose topographical projection is hexagonal accounts for 1% to 40% of the number of all metal nanoclusters.
8. The catalyst according to claim 7, wherein the number of metal nanoclusters whose topographical projection is hexagonal accounts for 2% to 30% of the number of all metal nanoclusters.
9. The catalyst according to claim 1, characterized in that the electrochemically active area of the catalyst calculated from the hydrogen desorption peak in its cyclic voltammetry curve is large, in particular greater than 75m when the mass percentage of metal nanoclusters in the catalyst is greater than or equal to 10% and less than 30%2gPt and less than 120m2gPt; when the mass percentage of the metal nanoclusters in the catalyst is more than or equal to 30% and less than 50%, the mass percentage is more than 55m2gPt and less than 75m2/gPt。
10. The catalyst according to claim 9, wherein when the mass percentage of the metal nanoclusters in the catalyst is greater than or equal to 10% and less than 30%, the electrochemical active area of the catalyst calculated from the hydrogen desorption peak in the cyclic voltammetry curve is greater than 90m2/gPt less than 120m2/gPt。
11. The catalyst of claim 1, wherein the catalyst has a peak intensity at 0.177v (vs rhe) of the hydrogen desorption peaks in the cyclic voltammogram higher than the peak intensity at 0.122v (vs rhe).
12. The catalyst according to claim 1, wherein the catalyst contains a surfactant, and the surfactant is contained in an amount of 0.01 to 20% by mass.
13. The catalyst of claim 12, wherein the surfactant is at least one of a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.
14. The catalyst of claim 13 wherein the surfactant is at least one of a quaternary ammonium salt, a carboxylic acid or carboxylate salt, a betaine-type surfactant, and an alkylbenzene sulfonic surfactant.
15. The catalyst of claim 14 wherein the quaternary ammonium salt has the structure NR1R2R3R4Wherein R is1Is an alkyl group having 4 to 22 carbon atoms, R2、R3And R4Is alkyl with 1 to 4 carbon atoms; the anion in the quaternary ammonium salt is a halide ion.
16. A process for preparing a catalyst as claimed in any one of claims 1 to 15, comprising the steps of:
1) mixing a surfactant solution with a conductive carrier to enable a surfactant to be adsorbed on the surface of the carrier to form a surfactant modified carrier;
2) mixing the product prepared in the step 1) with a metal nano-cluster colloidal solution prepared in advance, so that the metal nano-cluster is adsorbed on the surface of the carrier modified by the surfactant;
3) gradually expelling the surfactant in the product prepared in the step 2) by liquid, and assembling the metal nanoclusters on a carrier or a carrier modified by the surfactant to form a supported metal nanocluster catalyst;
4) drying the product prepared in the step 3).
17. The method according to claim 16, wherein the surfactant in step 1) is at least one of a cationic surfactant, an anionic surfactant and an amphoteric surfactant; the conductive carrier is a carbon-based carrier.
18. The method of claim 17, wherein the surfactant is at least one of a quaternary ammonium salt, a carboxylic acid or carboxylate salt, a betaine-type surfactant, and an alkylbenzene sulfonic surfactant.
19. The method of claim 18, wherein the quaternary ammonium salt has the structure NR1R2R3R4Wherein R is1Is an alkyl group having 4 to 22 carbon atoms, R2、R3And R4Is an alkyl group having 1 to 4 carbon atoms.
20. The method of claim 16, wherein the metal nanocluster colloid solution is a simple ion and solvent stable metal nanocluster colloid solution.
21. The method of claim 20, wherein the metal nanocluster colloid solution is a metal nanocluster colloid solution prepared by an alkali-ethylene glycol method.
22. The method of claim 16, wherein the mass ratio of the metal nanoclusters to the support in the mixed solution of step 2) is 1:9 to 3: 1.
23. The method as claimed in claim 16, wherein the metal nanocluster colloid solution of step 2) is prepared as follows: dissolving at least one of acid or soluble salt of transition metal in alcohol or alcohol-water mixed solution to prepare transition metal compound solution with the concentration of 0.1-100g/L, mixing the transition metal compound solution with alcohol solution or water solution or alcohol-water solution of alkaline compound under stirring, and heating the system to prepare the metal nano-cluster colloidal solution.
24. The method according to claim 23, wherein the heating treatment is performed by microwave heating, and the basic compound is at least one selected from the group consisting of hydroxides, acetates, and carbonates of alkali metals.
25. The method of claim 16, wherein the step 1) of adsorbing the surfactant, the step 2) of adsorbing the metal nanoclusters, and the step 3) of repelling the surfactant are performed in a solvent comprising at least one of water, an alcohol, a ketone, and a halogenated alkane.
26. The method of claim 25, wherein the alcohol is a monohydric alcohol, a dihydric alcohol, or a trihydric alcohol having 1 to 8 carbon atoms; the ketone is a ketone with 3-6 carbon atoms; the halogenated alkane is halogenated alkane with 1-6 carbon atoms.
27. The method of claim 26, wherein the solvent is at least one of water, methanol, ethanol, propanol, butanol, cyclohexanol, acetone, butanone, cyclohexanone, and ethylene glycol.
28. Use of a catalyst as claimed in any one of claims 1 to 15 in catalysing a fuel cell reaction.
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