CN114824319A - N-doped TiO 2-x Preparation method and application of supported PtCu alloy nano catalyst - Google Patents
N-doped TiO 2-x Preparation method and application of supported PtCu alloy nano catalyst Download PDFInfo
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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Abstract
The invention relates to N-doped TiO 2‑x A preparation method and application of a supported PtCu alloy nano catalyst. The method modifies oxide, takes carbon-free metal oxide as a PtCu alloy catalyst carrier, and obtains N-doped porous TiO by calcining titanium salt with a polymer template in air and ammonia gas 2‑x The carrier is subjected to ethylene glycol reduction on metal Pt and Cu to form N-doped TiO 2‑x A supported PtCu alloy nanocatalyst. The invention loads the PtCu catalyst on a carbon-free metal oxide carrier for an acidic ORR catalyst, and has high catalytic activity and long-term stability.
Description
Technical Field
The invention belongs to the field of electrocatalysis of fuel cells, and relates to N-doped TiO 2-x A preparation method of a supported PtCu alloy nano catalyst and application thereof in oxygen reduction (ORR) electrocatalytic reaction.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are a new energy technology with environmental friendliness, high energy density, abundant fuel sources, and high energy conversion efficiency. Among them, an Oxygen Reduction Reaction (ORR) in which the kinetic process is slow is extremely important as a cathode reaction of PEMFCs. Noble metal catalysts based on Pt-based metals are still the most effective electrocatalysts for promoting ORR. However, the expensive price and scarce reserves of Pt limit the commercial development of PEMFCs. The development of low Pt loading, high activity, high stability ORR electrocatalysts is a must-way for large-scale commercialization of PEMFCs.
In recent years, a great deal of work has been directed to reducing the Pt metal loading and improving the performance of Pt-based catalysts, one of the most classical approaches being alloying with other transition metals (M). The ORR activity of the PtM alloy nanocatalyst is significantly improved compared to the Pt catalyst, which can be attributed to the ligand effect caused by the interaction between Pt and M. This ligand effect can intentionally adjust the d-band center of PtM, altering the adsorption energy of ORR reaction intermediates. However, the durability of PtM cannot meet the commercialization requirements due to M dissolution and nanoparticle aggregation. Designing a suitable support material plays a crucial role in improving the catalytic activity and stability of PtM. A carbon material having a high surface area and high electrical conductivity is currently the most practical catalyst support, but it is susceptible to carbon corrosion at high potentials, resulting in migration and loss of PtM nanoparticles.
The metal oxide has excellent chemical stability in perchloric acid, and moreover, the interaction between the metal catalyst and the metal oxide support provides an anchoring effect in terms of suppressing migration and agglomeration of the catalyst nano-metal, so that the catalyst nano-particles are uniformly dispersed on the support in a smaller size. However, metal oxides have been greatly limited as supports for PtM catalysts due to their poor electrical conductivity and limited specific surface area.
Disclosure of Invention
The invention aims to provide an oxygen-rich vacancy N-doped porous TiO aiming at the current situations of high Pt load and poor durability of a carbon-based carrier in the current acidic ORR electrocatalyst research 2 The material is used as a conductive and electrochemical oxidation resistant catalyst carrier, and a preparation method and application of the high-performance PtCu alloy nano catalyst are loaded. The method modifies the oxide and uses carbon-free metal oxide as a PtCu alloy catalyst carrier. By means of a pair of tools in air and ammoniaCalcining the titanium salt with the polymer template to obtain the N-doped porous TiO 2-x Support (X represents an oxygen vacancy). Further, the metals Pt and Cu were reduced with ethylene glycol on the support to form N-doped TiO 2-x A supported PtCu alloy nanocatalyst. Due to the reasonable application of the polymer template, the oxide carrier is converted into macropores with the size of about 200nm and interconnected frameworks, and the rich specific surface area is favorable for the loading of PtCu nanoparticles and the permeation of molecular oxygen-containing electrolyte. Simultaneously, through NH 3 Treated TiO 2 The conductivity of the carrier is greatly improved. Under the strong interaction of the catalyst and the carrier, the PtCu alloy nano particles are evenly and stably anchored on the N-doped porous TiO 2-x On a carrier. The PtCu catalyst is loaded on a carbon-free metal oxide carrier and is used for an acidic ORR catalyst, so that the catalyst has high catalytic activity and long-term stability.
The technical scheme of the invention is as follows:
n-doped TiO 2-x The preparation method of the supported PtCu alloy nano catalyst comprises the following steps:
(1) mixing tetrabutyl titanate, absolute ethyl alcohol and concentrated hydrochloric acid, and stirring to prepare a precursor solution;
wherein the volume ratio of tetrabutyl titanate, absolute ethyl alcohol and concentrated hydrochloric acid is 5-10: 5-10: 1; the concentration range of the concentrated hydrochloric acid is 8-12M;
(2) under the condition of suction filtration, dropwise adding the precursor solution in the step (1) on a polymer template and drying;
wherein the polymer template is made of polyaniline microsphere template, polystyrene microsphere template or polymethyl methacrylate microsphere template; dripping 8-12 mL of precursor solution on each gram of template;
(3) putting the polymer template treated in the step (2) into a magnetic boat, putting the magnetic boat into a tube furnace, heating to 400-500 ℃, preserving the heat for 100-120 min, and cooling to room temperature to obtain porous TiO 2 A material; introducing Ar carrier gas into the tubular furnace, heating to 800-900 ℃, and then converting the atmosphere in the tubular furnace into NH 3 Keeping the temperature for 20-40 min to obtain N-doped porous TiO 2-x The material (X value is 0.4-1);
(4) putting chloroplatinic acid hexahydrate, copper chloride dihydrate and sodium citrate into a mixed solvent, and carrying out ultrasonic treatment to obtain a solution A; doping N with porous TiO 2-x Placing the materials in a mixed solvent, and stirring to obtain a solution B; mixing the solution A and the solution B, and shaking for 8-12 hours;
wherein the weight ratio of the substances of chloroplatinic acid hexahydrate, copper chloride dihydrate and sodium citrate is 1-3: 1: 1-3; the mixed solvent in the solution A and the mixed solvent in the solution B are the same and are both ethylene glycol and water solvent, and the volume ratio of the ethylene glycol to the water is (2-4): 1;
in the solution A, adding 0.03-0.05 mol of chloroplatinic acid hexahydrate into 10ml of mixed solvent; in the solution B, 20-80 mg of N-doped porous TiO is added into 10ml of mixed solvent 2-x A material; volume ratio, solution a: solution B is 0.5 to 2: 0.5 to 2;
(5) adjusting the pH value of the mixed solution in the step (4) to 9-11 with NaOH solution, reducing the mixed solution in an oil bath kettle at 140-160 ℃ for 2-3 hours under the protection of Ar, naturally cooling to room temperature, and continuously stirring for 8-12 hours;
the concentration of the NaOH solution is 0.5-2M;
(6) by H 2 SO 4 Adjusting the pH value of the mixture in the step (5) to 3-5, and standing for 6-10 h; centrifuging, washing and drying to finally obtain the N-doped TiO 2-x A supported PtCu alloy nanocatalyst;
said H 2 SO 4 The concentration of the solution is 0.5-2M;
the N-doped TiO prepared by the method 2-x The supported PtCu alloy nano catalyst is used for oxidation-reduction reaction under acidic conditions. In particular to a cathode catalyst of a proton exchange membrane fuel cell.
The raw materials involved are commercially available and the equipment used is well known to those skilled in the art.
The invention has the beneficial effects that:
(1) n-doped TiO in the invention 2-x The support retains the chemical stability of the metal oxide support and hasAbundant three-dimensional pore structure. The structure provides sufficient sites for the loading of the PtCu catalyst and is beneficial to the permeation of oxygen-containing molecular electrolyte.
(2) The material exhibits 0.1 to 10S cm as measured by a four-point probe resistor -1 High conductivity, N doping and the presence of oxygen vacancies for semiconductor TiO 2 Low electrical conductivity (<10 -10 S cm -1 ) Makes substantial changes.
(3) The material prepared by the invention realizes the electron transfer from the carrier to the PtCu, provides strong metal-carrier interaction between the carrier and the PtCu, ensures that the PtCu nano particles have high dispersibility and small size of about 3.41nm by the interaction, and improves the catalytic activity.
(4) The performance of the catalyst prepared by the invention can be compared with that of a commercial Pt/C catalyst, and the mass activity of the catalyst (1.09A mg) Pt -1 @0.9V) and specific surface area Activity (1.45mA cm Pt -1 @0.9V) far exceeds Pt/C catalyst (0.19A mg Pt -1 @0.9V；0.23mA cm Pt -1 @ 0.9V). And the catalyst maintains higher stability after 25000 CV cycles.
Description of the drawings:
FIG. 1 shows N-doped TiO prepared in example 1 2-x SEM image of supported PtCu alloy nanocatalyst.
FIG. 2 shows N-doped TiO prepared in example 1 2-x EPR oxygen vacancy representation of the supported PtCu alloy nano-catalyst.
FIG. 3 shows N-doped TiO prepared in example 1 2-x O1S XPS plot of supported PtCu alloy nanocatalyst.
FIG. 4 shows N-doped TiO prepared in example 1 2-x TEM elemental mapping images of the supported PtCu alloy nanocatalyst.
FIG. 5 shows N-doped TiO prepared in example 1 2-x TEM images of supported PtCu alloy nanocatalysts.
FIG. 6 shows N-doped TiO compound obtained in example 1 2-x Ti 2p XPS plot of supported PtCu alloy nanocatalyst.
FIG. 7 is a schematic view ofN-doped TiO prepared in example 1 2-x Acidic ORR reaction LSV profile of supported PtCu alloy nanocatalysts with commercial Pt/C.
FIG. 8 shows N-doped TiO prepared in example 1 2-x LSV profiles of supported PtCu alloy nanocatalysts before and after accelerated durability reactions.
FIG. 9 shows N-doped TiO compound obtained in example 1 2-x Comparison of mass activity of the supported PtCu alloy nanocatalyst with commercial Pt/C before and after accelerated durability reactions.
FIG. 10 shows N-doped TiO compound obtained in example 1 2-x Specific surface area activity of the supported PtCu alloy nanocatalyst and commercial Pt/C before and after accelerated durability reaction are compared.
FIG. 11 shows the N-doped TiO obtained in examples 1 to 4 2-x Supported PtCu alloy nano catalyst, N-doped TiO 2-x Supported Pt nano catalyst, N-doped TiO 2-x Loaded PtNi alloy nano-catalyst and TiO 2 Acidic ORR reaction LSV profile of supported PtCu alloy nanocatalyst.
FIG. 12 shows N-doped TiO compounds obtained in examples 1 and 5 2-x Supported PtCu alloy nano catalyst and N-doped TiO 2-x Acidic ORR reaction LSV profile of supported 1.5PtCu alloy nanocatalyst.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention.
The invention is further illustrated with reference to the following figures and examples.
Example 1:
(1) the precursor solution is prepared by mixing tetrabutyl titanate, anhydrous ethanol and 12M hydrochloric acid in a volume ratio of 5:5:1 and stirring to obtain a titanium precursor solution;
(2) under vacuum filtration, 10mL of the titanium precursor solution was dropped drop-wise onto 1g of polystyrene sphere template (polystyrene spheres having a diameter of about 300 nm), and the treated template was dried overnight at 60 ℃;
(3) raising the temperature of the treated polystyrene template to 500 ℃ from room temperature in an air atmosphere,and maintained at 500 ℃ for 2 hours to obtain TiO 2 . Then TiO is added 2 N-doped TiO for preparing oxygen-rich vacancy as raw material 2 Material, heating to 800 deg.C under Ar atmosphere, and changing from Ar atmosphere to NH under 800 deg.C 3 Keeping for 30 min;
(4) 0.05mol of H 2 PtCl 6 ·6H 2 O、0.02mol CuCl 2 ·2H 2 O and 0.05mol sodium citrate were dissolved in 10mL of a solution containing H 2 And (3) carrying out ultrasonic treatment on the mixed solution of O and ethylene glycol (the volume ratio is 1: 2) for 30 minutes to obtain solution A. At the same time, 50mg of N-doped TiO 2-x Material addition to 10mL H 2 And (3) adding the mixed solution of O and ethylene glycol (the volume ratio is 1: 2) and stirring to obtain solution B. Mixing the A and B solutions and transferring the A and B solutions to a shaker, and shaking the A and B solutions overnight;
(5) adjusting the pH value of the mixed solution obtained in the step (4) to 10 by using a 1M NaOH solution, stirring the mixed solution in an oil bath kettle at 160 ℃ under Ar atmosphere for 2.5 hours, cooling the solution to room temperature, and continuing stirring the solution for 12 hours;
(6) use 0.5M H 2 SO 4 The pH was adjusted to 3 and left for a further 8 hours, centrifuged, washed with deionized water and ethanol and dried.
Pre-polishing a glassy carbon rotating disk electrode (S0.196 cm) with 0.1M perchloric acid as electrolyte -2 ) The test method is characterized in that the test method is a working electrode, a graphene rod is a counter electrode, a saturated calomel electrode is a reference electrode, and the performance of the test method is tested by using a Shanghai electrochemical workstation.
FIG. 1 shows that: the three-dimensional macroporous oxide carrier with high specific surface area of about 200nm is successfully prepared, and the reduction treatment of the PtCu metal has no influence on the appearance of the oxide carrier.
FIG. 2 shows that: the oxygen vacancy characterization showed a strong EPR signal, demonstrating the abundance of oxygen vacancies in the material.
FIG. 3 shows: the oxygen vacancy peak area accounted for about 0.4 in the total oxygen peak area, again demonstrating the abundance of oxygen vacancies in the material.
FIG. 4 shows that: TEM elemental mapping images show that Ti, N and O are present on the support frame, whereas Pt and Cu are present in smaller amounts and are uniformly distributed. Proves that TiO is doped with N 2-x Loaded PtCu alloyThe successful preparation of rice catalyst.
FIG. 5 shows that: the TEM image clearly shows the loading of PtCu nanoparticles with an average particle size of 3.41 nm.
FIG. 6 shows that: with N-doped TiO 2-x Compared with the carrier, the carrier has positive displacement of Ti peak after PtCu loading, which shows that electrons are transferred from Ti to PtCu, namely PtCu nano particles and the metal oxide carrier have interaction.
FIG. 7 shows that: n-doped TiO compared to Pt/C 2-x The supported PtCu alloy nanocatalyst shows high half-wave potential and onset potential, indicating high ORR activity of the material.
FIG. 8 shows that: after 25000-turn acceleration durability test, N-doped TiO 2-x The ORR performance of the supported PtCu alloy nano catalyst is only slightly reduced.
FIG. 9 shows that: n-doped TiO compared to Pt/C 2-x The supported PtCu alloy nano catalyst shows high mass specific activity and still shows high stability after 5000-turn accelerated durability tests.
FIG. 10 shows: n-doped TiO compared to Pt/C 2-x The supported PtCu alloy nano catalyst shows high specific surface area specific activity and still shows high stability after 5000-turn accelerated durability tests.
Example 2:
the other steps are the same as example 1 except that only chloroplatinic acid hexahydrate and sodium citrate are contained in the solution in step (4) A. To obtain N-doped TiO 2-x A supported Pt nanocatalyst.
Comparison of the LSV curves of fig. 11 shows that: n-doped TiO 2-x The ORR performance of the loaded PtCu alloy nano catalyst is higher than that of N-doped TiO 2-x A supported Pt nanocatalyst. The alloying of the noble metal Pt and the transition metal is an effective strategy for improving the catalytic performance of the ORR.
Example 3:
the other steps are the same as the example 1, except that the solution in the step (4) A contains chloroplatinic acid hexahydrate, nickel chloride and sodium citrate, and the molar weight ratio of the chloroplatinic acid hexahydrate to the nickel chloride is 1: 1. to obtain N-doped TiO 2-x A supported PtNi alloy nanocatalyst.
Comparison of the LSV curves of fig. 11 shows that: n-doped TiO 2-x The ORR performance of the loaded PtNi alloy nano catalyst is higher than that of N-doped TiO 2-x Supported Pt nanocatalyst but less than N-doped TiO 2-x A supported PtCu alloy nanocatalyst. It is shown that alloying Pt with Ni is also an effective strategy to improve ORR catalytic performance, but performance is lower than PtCu.
Example 4:
the other steps are the same as example 1 except that the polymer template treated with the Ti-based precursor solution in step (3) is treated only in air and not with NH 3 And (6) processing. To obtain TiO 2 A supported PtCu alloy nanocatalyst.
Comparison of the LSV curves of fig. 11 shows that: n-doped TiO 2-x The ORR performance of the loaded PtCu alloy nano catalyst is obviously higher than that of TiO 2 A supported PtCu alloy nanocatalyst. NH (NH) 3 The treatment process is to TiO 2 The key of modification can improve TiO 2 The conductivity of the catalyst promotes the strong interaction of the catalyst and the carrier, and the catalytic performance is improved.
Example 5:
the other steps are the same as example 1, except that the molar concentrations of chloroplatinic acid hexahydrate and copper chloride dihydrate in the solution in step (4) A are 1.5 times of those in example 1. To obtain N-doped TiO 2-x A supported 1.5PtCu nanocatalyst.
Comparison of the LSV curves of fig. 12 shows that: the catalytic performance is not greatly changed by increasing the concentration of the PtCu metal, and the PtCu metal has good ORR performance.
The invention is not the best known technology.
Claims (5)
1. N-doped TiO 2-x A preparation method of a supported PtCu alloy nano catalyst is characterized by comprising the following steps:
(1) mixing tetrabutyl titanate, absolute ethyl alcohol and concentrated hydrochloric acid, and stirring to prepare a precursor solution;
wherein the volume ratio of tetrabutyl titanate, absolute ethyl alcohol and concentrated hydrochloric acid is 5-10: 5-10: 1;
(2) under the condition of suction filtration, dropwise adding the precursor solution in the step (1) on a polymer template and drying;
wherein the polymer template is made of polyaniline microsphere template, polystyrene microsphere template or polymethyl methacrylate microsphere template; dripping 8-12 mL of precursor solution on each gram of template;
(3) putting the polymer template treated in the step (2) into a magnetic boat, putting the magnetic boat into a tube furnace, heating to 400-500 ℃, preserving the heat for 100-120 min, and cooling to room temperature to obtain porous TiO 2 A material; introducing Ar carrier gas into the tubular furnace, heating to 800-900 ℃, and then converting the atmosphere in the tubular furnace into NH 3 Keeping the temperature for 20-40 min to obtain N-doped porous TiO 2-x The material (X value is 0.4-1);
(4) putting chloroplatinic acid hexahydrate, copper chloride dihydrate and sodium citrate into a mixed solvent, and carrying out ultrasonic treatment to obtain a solution A; doping N with porous TiO 2-x Placing the materials in a mixed solvent, and stirring to obtain a solution B; mixing the solution A and the solution B, and shaking for 8-12 hours;
wherein the weight ratio of the substances of chloroplatinic acid hexahydrate, copper chloride dihydrate and sodium citrate is 1-3: 1: 1-3; the mixed solvent in the solution A and the mixed solvent in the solution B are the same and are both ethylene glycol and water solvent, and the volume ratio of the ethylene glycol to the water is (2-4): 1;
in the solution A, adding 0.03-0.05 mol of chloroplatinic acid hexahydrate into 10ml of mixed solvent; in the solution B, 20-80 mg of N-doped porous TiO is added into 10ml of mixed solvent 2-x A material; volume ratio, solution a: solution B is 0.5-2: 0.5 to 2;
(5) adjusting the pH value of the mixed solution in the step (4) to 9-11 by using a NaOH solution, reducing the mixed solution at 140-160 ℃ for 2-3 hours under the protection of Ar, naturally cooling the reduced solution to room temperature, and continuously stirring the cooled solution for 8-12 hours;
(6) adjusting the pH value of the mixture obtained in the step (5) to 3-5 by using sulfuric acid, and standing for 6-10 hours; centrifuging, washing and drying to finally obtain the N-doped TiO 2-x A supported PtCu alloy nanocatalyst.
2. The N-doped TiO of claim 1 2-x The preparation method of the supported PtCu alloy nano catalyst is characterized in that the concentration range of concentrated hydrochloric acid in the step (1) is 8-12M; the concentration of the sulfuric acid in the step (6) is 0.5-2M.
3. The N-doped TiO of claim 1 2-x The preparation method of the supported PtCu alloy nano catalyst is characterized in that the concentration of the NaOH solution in the step (5) is 0.5-2M.
4. N-doped TiO prepared by the process of claim 1 2-x A supported PtCu alloy nano catalyst is characterized by being used for oxidation-reduction reaction under acidic conditions.
5. N-doped TiO prepared by the method of claim 4 2-x A supported PtCu alloy nano catalyst is characterized by being specifically applied to a cathode catalyst of a proton exchange membrane fuel cell.
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| CN115784294A (en) * | 2022-11-22 | 2023-03-14 | 国家电投集团氢能科技发展有限公司 | Metal oxide carrier and preparation method and application thereof |
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| US20150246823A1 (en) * | 2012-09-29 | 2015-09-03 | Nanjing Tech University (Cn) | Anadium-titanium compound material with high thermal stability and high activity and preparation method thereof |
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| CN115784294A (en) * | 2022-11-22 | 2023-03-14 | 国家电投集团氢能科技发展有限公司 | Metal oxide carrier and preparation method and application thereof |
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