CN114824319B - 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 PDF

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CN114824319B
CN114824319B CN202210563497.2A CN202210563497A CN114824319B CN 114824319 B CN114824319 B CN 114824319B CN 202210563497 A CN202210563497 A CN 202210563497A CN 114824319 B CN114824319 B CN 114824319B
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刘桂华
李敬德
王宏玉
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Hebei University of 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
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • 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
    • 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
    • H01M4/921—Alloys or mixtures with metallic elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to 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 PtCu alloy catalyst carrier, and obtains N doped porous TiO by calcining titanium salt with polymer template in air and ammonia gas 2‑x The carrier, and then the metal Pt and Cu are reduced by glycol on the carrier, thus forming N-doped TiO 2‑x Supported PtCu alloy nanocatalyst. The PtCu catalyst is loaded on a carbon-free metal oxide carrier and used for an acidic ORR catalyst, and has high catalytic activity and long-term stability.

Description

N-doped TiO 2-x Preparation method and application of supported PtCu alloy nano catalyst
Technical Field
The invention belongs to the field of fuel cell electrocatalysis, 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, rich fuel sources and high energy conversion efficiency. Among them, the Oxygen Reduction Reaction (ORR) whose kinetic process is slow is extremely important as a cathode reaction of the PEMFC. Noble metal catalysts based on Pt-based metals are currently still the most effective electrocatalysts for promoting ORR. However, the expensive price and scarce reserves of Pt limit the commercialization of PEMFCs. The development of ORR electrocatalysts with low Pt loading, high activity and high stability is a necessary way for large-scale commercialization of PEMFCs.
In recent years, a great deal of work has been directed to reducing Pt metal loading and improving Pt-based catalyst performance, one of the most classical methods being alloying with other transition metals (M). ORR activity of PtM alloy nanocatalysts is significantly improved compared to Pt catalysts, which can be attributed to ligand effects caused by interactions between Pt and M. This ligand effect can deliberately modulate the d-band center of PtM, altering the adsorption energy of the ORR reaction intermediate. However, durability of PtM cannot meet commercial requirements due to M dissolution and nanoparticle aggregation. The design of suitable support materials plays a critical role in improving the catalytic activity and stability of PtM. Carbon materials with high surface area and high conductivity are currently the most practical catalyst supports, but it is prone to carbon corrosion at high potential, leading to the 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 inhibiting migration and agglomeration of the catalyst nano-metals, so that the catalyst nano-particles are uniformly dispersed on the support in a smaller size. However, the metal oxide has poor conductivity and limited specific surface area, so that the metal oxide is greatly limited in being used as a carrier of PtM catalyst.
Disclosure of Invention
The invention aims at providing an oxygen-enriched vacancy N-doped porous TiO aiming at the current situation that Pt load is high and carbon-based carrier durability is poor in the current research of an acidic ORR electrocatalyst 2 The material is used as a conductive and electrochemical oxidation resistant catalyst carrier and is loaded with a preparation method and application of a PtCu alloy nano catalyst with high performance. The method modifies the oxide and takes the carbon-free metal oxide as a PtCu alloy catalyst carrier. Calcining titanium salt with polymer template in air and ammonia gas to obtain N doped porous TiO 2-x The carrier (X represents an oxygen vacancy). Further, the metals Pt and Cu are subjected to glycol reduction on the carrier to form N-doped TiO 2-x Supported PtCu alloy nanocatalyst. Due to reasonable application of the polymer template, the oxide carrier is converted into macropores with the diameter of about 200nm and interconnected skeletons, and the abundant specific surface area is favorable for loading PtCu nano particles and penetrating molecular oxygen-containing electrolyte. At the same time go through NH 3 Treated TiO 2 The conductivity of the carrier is greatly improved. PtCu alloy nano particles are uniformly and stably anchored on N-doped porous TiO under the strong interaction of catalyst-carrier 2-x And (3) on a carrier. The PtCu catalyst is loaded on a carbon-free metal oxide carrier and used for an acidic ORR catalyst, and 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, a step of; the concentration range of the concentrated hydrochloric acid is 8-12M;
(2) Dropwise adding the precursor solution in the step (1) on a polymer template in a suction filtration state, and drying;
wherein the polymer template is made of polyaniline microsphere template, polystyrene microsphere template or polymethyl methacrylate microsphere template; dropwise adding 8-12 mL of precursor solution to each gram of template;
(3) Placing the polymer template treated in the step (2) into a magnetic boat, placing into a tubular furnace, heating to 400-500 ℃, preserving heat for 100-120 min, and cooling to room temperature to obtain porous TiO 2 A material; then Ar carrier gas is introduced into the tube furnace, the temperature is raised to 800-900 ℃, and then the atmosphere in the tube furnace is converted into NH 3 Preserving heat for 20-40 min to obtain N-doped porous TiO 2-x The value of the material (X) is 0.4-1);
(4) Placing chloroplatinic acid hexahydrate, cupric chloride dihydrate and sodium citrate in a mixed solvent, and carrying out ultrasonic treatment to obtain a solution A; n-doped porous TiO 2-x Placing the material 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 mass ratio of the hexa-hydrated chloroplatinic acid, the dihydrate cupric chloride and the sodium citrate is 1-3: 1:1 to 3; the mixed solvents in the solution A and the solution B are the same and are ethylene glycol and water solvent, and the volume ratio of the ethylene glycol to the water is 2-4: 1, a step of;
in the solution A, 0.03-0.05 mol of hexahydrated chloroplatinic acid is added into every 10ml of mixed solvent; in the solution B, 20 to 80mg of N-doped porous TiO is added into each 10ml of mixed solvent 2-x A material; the volume ratio is that solution A: solution b=0.5 to 2:0.5～2；
(5) Adjusting the pH=9-11 of the mixed solution in the step (4) by using NaOH solution, then reducing the mixed solution in an oil bath 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 Regulating 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 Supported PtCu alloy nanocatalyst;
said H 2 SO 4 The concentration of the solution is 0.5-2M;
n-doped TiO prepared by the method 2-x The supported PtCu alloy nano catalyst is used for oxidation-reduction reaction under an acidic condition. The catalyst is particularly applied to a proton exchange membrane fuel cell cathode catalyst.
The raw materials involved are all commercially available and the equipment used is well known to those skilled in the art.
The beneficial effects of the invention are as follows:
(1) In the invention, N is doped with TiO 2-x The carrier retains the chemical stability of the metal oxide carrier and has a rich three-dimensional pore structure. The structure provides sufficient sites for the loading of the PtCu catalyst and is beneficial to the permeation of the oxygen-containing molecular electrolyte.
(2) The material showed 0.1-10S cm by testing of four-point probe resistor -1 Semiconductor TiO with high conductivity, N-doping and oxygen vacancy presence 2 Low conductivity%<10 -10 S cm -1 ) Is essentially changed.
(3) The material prepared by the invention realizes electron transfer from the carrier to PtCu, provides strong metal-carrier interaction between the carrier and PtCu, ensures that PtCu nano particles have high dispersibility and small size of about 3.41nm, and improves the catalytic activity.
(4) The catalyst prepared by the invention has the performance which is comparable with that of a commercial Pt/C catalyst, and the mass activity (1.09)A mg Pt -1 @0.9V) and specific surface area Activity (1.45 mA cm Pt -1 @0.9V) all far exceeded the 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 characterization map of supported PtCu alloy nanocatalyst.
FIG. 3 is an 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 element map image of supported PtCu alloy nanocatalyst.
FIG. 5 is an N-doped TiO prepared in example 1 2-x TEM image of supported PtCu alloy nanocatalysts.
FIG. 6 shows N-doped TiO prepared in example 1 2-x Ti 2p XPS plot of supported PtCu alloy nanocatalyst.
FIG. 7 shows N-doped TiO prepared in example 1 2-x LSV profile of the acidic ORR reaction of supported PtCu alloy nanocatalyst with commercial Pt/C.
FIG. 8 shows N-doped TiO prepared in example 1 2-x LSV profile of supported PtCu alloy nanocatalyst before and after acceleration of the durability reaction.
FIG. 9 shows N-doped TiO prepared in example 1 2-x Comparison of mass activity of supported PtCu alloy nanocatalysts with commercial Pt/C before and after acceleration of the durability reaction.
FIG. 10 shows N-doped TiO prepared in example 1 2-x Comparison of specific surface area activity of supported PtCu alloy nanocatalysts versus commercial Pt/C before and after accelerating the durability reaction.
FIG. 11 shows N-doped TiO obtained in examples 1 to 4 2-x Supported PtCu alloy nano catalyst and N-doped TiO 2-x Supported Pt nanocatalyst, N-doped TiO 2-x Supported PtNi alloy nanocatalyst and TiO 2 Acidic ORR reaction LSV profile of supported PtCu alloy nanocatalyst.
FIG. 12 is N-doped TiO obtained in example 1 and example 5 2-x Supported PtCu alloy nanocatalyst and N-doped TiO 2-x Acidic ORR reaction LSV profile of supported 1.5PtCu alloy nanocatalyst.
Detailed Description
The present invention is described in detail below by way of specific examples, but the scope of the present invention is not limited thereto.
The invention will be further described with reference to the drawings and examples.
Example 1:
(1) The precursor solution is prepared by mixing tetrabutyl titanate, absolute ethyl alcohol 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 sphere diameter about 300 nm), and the treated template was dried overnight at 60 ℃;
(3) Heating the treated polystyrene template from room temperature to 500 ℃ in an air atmosphere, and keeping the temperature at 500 ℃ for 2 hours to obtain TiO 2 . And then TiO 2 N-doped TiO for preparing oxygen-enriched vacancy by raw material 2 The material is heated to 800 ℃ in Ar atmosphere and then changed into NH from Ar atmosphere at 800 DEG C 3 Maintaining for 30min;
(4) Will 0.05mol H 2 PtCl 6 ·6H 2 O、0.02mol CuCl 2 ·2H 2 O and 0.05mol sodium citrate in 10mL containing H 2 And (3) in a mixed solution of O and ethylene glycol (volume ratio is 1:2), carrying out ultrasonic treatment for 30 minutes to obtain solution A. At the same time, 50mg of N-doped TiO 2-x Material was added to 10mL H 2 And (3) mixing the solution of O and glycol (volume ratio is 1:2) and stirring to obtain solution B. The solutions a and B were mixed and transferred to a shaker and shaken overnight;
(5) Adjusting the pH value of the mixed solution obtained in the step (4) to 10 by using a 1M NaOH solution, stirring for 2.5 hours in an oil bath at 160 ℃ under Ar atmosphere, and continuously stirring for 12 hours after the solution is cooled to room temperature;
(6) Using 0.5. 0.5M H 2 SO 4 Adjusted to ph=3 and left for an additional 8 hours, centrifuged, washed with deionized water and ethanol and dried.
Pre-polishing the vitreous carbon rotating disk electrode with 0.1M perchloric acid as electrolyte (s=0.196 cm -2 ) The graphene rod is used as a working electrode, the graphene rod is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, and the performances of the graphene rod are tested by using an Shanghai chemical 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 PtCu metal has no influence on the morphology of the oxide carrier.
Fig. 2 shows that: the oxygen vacancy characterization shows a strong EPR signal, proving the abundance of oxygen vacancies in the material.
Fig. 3 shows that: the oxygen vacancy peak area is about 0.4 in the total peak area of oxygen, 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 carrier frame, while the Pt and Cu content is low and uniformly distributed. It is demonstrated that N-doped TiO 2-x Successful preparation of supported PtCu alloy nanocatalyst.
Fig. 5 shows that: TEM images clearly show the loading of PtCu nanoparticles and an average particle diameter of 3.41nm.
Fig. 6 shows that: with N-doped TiO 2-x Compared with the carrier, the Ti peak of the carrier is positively displaced after PtCu loading, which indicates that electrons are transferred from Ti to PtCu, namely PtCu nano particles and a metal oxide carrier interact.
Fig. 7 shows: n-doped TiO compared to Pt/C 2-x The supported PtCu alloy nanocatalyst shows high half-wave potential and starting potential, indicating high ORR activity of the material.
Fig. 8 shows that: after 25000 cycles of accelerated durability experiments, N-doped TiO 2-x The ORR performance of the supported PtCu alloy nanocatalyst was only slightly reduced.
Fig. 9 shows that: compared with Pt/CN-doped TiO 2-x The supported PtCu alloy nano catalyst shows high mass specific activity and still shows high stability after 5000 circles of accelerated durability test.
Fig. 10 shows that: 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 circles of accelerated durability test.
Example 2:
the other steps are the same as in example 1 except that chloroplatinic acid hexahydrate and sodium citrate are only present in the solution of step (4) A. Obtaining N-doped TiO 2-x Supported Pt nanocatalyst.
Comparison of the LSV curves of fig. 11 shows that: n-doped TiO 2-x ORR performance of the supported PtCu alloy nano catalyst is higher than that of N-doped TiO 2-x Supported Pt nanocatalyst. It is explained that noble metal Pt alloying with transition metals is an effective strategy to improve ORR catalytic performance.
Example 3:
the other steps are the same as in example 1 except that chloroplatinic acid hexahydrate, nickel chloride and sodium citrate are present in the solution of step (4) a, and the molar ratio of chloroplatinic acid hexahydrate to nickel chloride is 1:1. obtaining N-doped TiO 2-x Supported PtNi alloy nanocatalyst.
Comparison of the LSV curves of fig. 11 shows that: n-doped TiO 2-x ORR performance of the supported PtNi alloy nano catalyst is higher than that of N-doped TiO 2-x Supported Pt nanocatalyst but lower than N-doped TiO 2-x Supported PtCu alloy nanocatalyst. Pt alloying with Ni is also an effective strategy to improve ORR catalytic performance, but performance is lower than PtCu.
Example 4:
other steps are the same as in example 1 except that the Ti-based precursor solution treated polymer template in step (3) is treated in air only without NH 3 And (5) processing. Obtaining TiO 2 Supported PtCu alloy nanocatalyst.
Comparison of the LSV curves of fig. 11 shows that: n-doped TiO 2-x Loaded PtCu alloyThe ORR performance of the nano catalyst is obviously higher than that of TiO 2 Supported PtCu alloy nanocatalyst. NH (NH) 3 The treatment process is to TiO 2 Key to modification, can improve TiO 2 Promotes the strong interaction of the catalyst-carrier and improves the catalytic performance.
Example 5:
the other steps are the same as in example 1 except that the molar concentration of chloroplatinic acid hexahydrate and copper chloride dihydrate in the solution of step (4) A is 1.5 times that of example 1. Obtaining N-doped TiO 2-x Supported 1.5PtCu nanocatalyst.
Comparison of the LSV curves of fig. 12 shows that: increasing PtCu metal concentration does not change the catalytic performance much, and has good ORR performance.
The invention is not a matter of the known technology.

Claims (5)

1. N-doped TiO 2-x The preparation method of the 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, a step of;
(2) Dropwise adding the precursor solution in the step (1) on a polymer template in a suction filtration state, and drying;
wherein the polymer template is made of polyaniline microsphere template, polystyrene microsphere template or polymethyl methacrylate microsphere template; dropwise adding 8-12 mL of precursor solution to each gram of template;
(3) Placing the polymer template treated in the step (2) into a magnetic boat, placing into a tubular furnace, heating to 400-500 ℃, preserving heat for 100-120 min, and cooling to room temperature to obtain porous TiO 2 A material; then Ar carrier gas is introduced into the tube furnace, the temperature is raised to 800-900 ℃, and then the atmosphere in the tube furnace is converted into NH 3 Preserving heat for 20-40 min to obtain N-doped porous TiO 2-x The value of the material (X) is 0.4-1);
(4) Placing chloroplatinic acid hexahydrate, cupric chloride dihydrate and sodium citrate in a mixed solvent, and carrying out ultrasonic treatment to obtain a solution A; n-doped porous TiO 2-x Placing the material 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 mass ratio of the hexa-hydrated chloroplatinic acid, the dihydrate cupric chloride and the sodium citrate is 1-3: 1:1 to 3; the mixed solvents in the solution A and the solution B are the same and are ethylene glycol and water solvents, and the volume ratio of the ethylene glycol to the water is 2-4: 1, a step of;
in the solution A, 0.03-0.05 mol of hexahydrated chloroplatinic acid is added into every 10ml of mixed solvent; in the solution B, 20 to 80mg of N-doped porous TiO is added into each 10ml of mixed solvent 2-x A material; the volume ratio is that solution A: solution b=0.5 to 2:0.5 to 2;
(5) Adjusting the pH=9-11 of the mixed solution in the step (4) by using NaOH solution, then reducing for 2-3 hours at 140-160 ℃ under Ar protection, naturally cooling to room temperature, and continuously stirring for 8-12 hours;
(6) Regulating the pH value of the mixture in the step (5) to 3-5 by sulfuric acid, and standing for 6-10 h; centrifuging, washing and drying to finally obtain the N-doped TiO 2-x 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 the concentrated hydrochloric acid in the step (1) is 8-12M; the concentration of 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. An N-doped TiO prepared according to the method of claim 1 2-x The supported PtCu alloy nano catalyst is characterized by being used for oxidation-reduction reaction under an acidic condition.
5. An N-doped TiO prepared by the method of claim 4 2-x The supported PtCu alloy nano catalyst is characterized by being specifically applied to a proton exchange membrane fuel cell cathode catalyst.
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CN108539219A (en) * 2018-05-07 2018-09-14 广西师范大学 A kind of sulfur and nitrogen co-doped carbon nanotube carries PtCu alloy catalysts and the preparation method and application thereof
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