PEM electrolyzed water catalyst carrier as well as preparation method and application thereof

Abstract

The invention discloses a PEM electrolyzed water catalyst carrier and a preparation method and application thereof. The PEM electrolyzed water catalyst carrier is of a nano needle-shaped structure, the length of the nano needle-shaped structure is 50-200 nm, the diameter of the nano needle-shaped structure is 5-20 nm, and the length-diameter ratio of the nano needle-shaped structure is (10-20): 1; the molecular formula is AxTi (1-x) O2, x is 0.01-0.05, and A is a metal. The catalyst carrier disclosed by the invention is simple in process, low in cost and easy for large-scale production, and the nanostructure and crystalline phase composition of the carrier can be accurately controlled; the catalyst carrier is in a nanoneedle shape, and is high in conductivity, large in specific surface area and excellent in stability; the carrier has the advantages of high catalytic activity, low precious metal consumption and long service life when being applied to a PEM electrolyzed water catalyst.

Description

Technical Field

[0001] This invention relates to the field of water electrolysis catalyst technology, specifically to a PEM water electrolysis catalyst support, its preparation method, and its application. Background Technology

[0002] Proton exchange membrane (PEM) water electrolysis is a promising green hydrogen production technology. However, its commercialization is constrained by the anode oxygen evolution reaction (OER) catalyst. Currently, anode catalysts heavily rely on precious metals such as iridium (Ir), and their high cost and limited resource reserves have become bottlenecks for the large-scale application of PEM water electrolysis technology.

[0003] To reduce iridium usage and improve catalytic efficiency, a key technological direction is the development of high-performance catalyst supports. Traditional carbon black supports are highly susceptible to corrosion in the strongly acidic, high-potential environment of PEM water electrolysis anodes, leading to catalyst particle detachment and deactivation, severely impacting the lifespan of the equipment. Therefore, research has shifted towards metal oxides with better corrosion resistance, such as titanium dioxide (TiO2). Although titanium dioxide exhibits good chemical stability, it suffers from two significant drawbacks: firstly, its intrinsic electronic conductivity is low, hindering rapid electron transport during the reaction process; secondly, its specific surface area is typically limited, which is unfavorable for the high dispersion of noble metal active components and makes it difficult to form sufficient active sites.

[0004] While existing technologies have explored improving the performance of titanium dioxide through elemental doping or morphology control, shortcomings remain. For example, patent CN117403267A uses metal nitride (TiN) as a support, but its long-term operation suffers from oxidation, leading to decreased conductivity. Patent CN116397265A focuses on adding auxiliary components to the catalyst layer to improve proton transport, but it does not fundamentally address the structural and performance defects of the support material itself. Furthermore, existing methods for preparing titanium dioxide supports, such as hydrothermal methods and sol-gel methods, are often complex, costly, and difficult to precisely control the microstructure and crystal phase composition of the support.

[0005] Therefore, there is an urgent need in this field for a novel PEM water electrolysis catalyst support that combines high conductivity, high specific surface area, excellent stability, and simple preparation process with low cost, in order to promote the advancement and commercial application of PEM water electrolysis technology. Summary of the Invention

[0006] This invention addresses the shortcomings of existing technologies by providing a PEM electrolysis water catalyst support, its preparation method, and its application. The catalyst support is nanoneedle-shaped, exhibiting high conductivity, large specific surface area, and excellent stability. The catalyst support is simple to manufacture, low in cost, and easy to scale up, and its nanostructure and crystal phase composition can be precisely controlled. When applied to PEM electrolysis water catalysts, the catalyst support offers advantages such as high catalytic activity, low precious metal content, and long service life.

[0007] To address the aforementioned technical problems, the first aspect of this invention provides a PEM electrolysis water catalyst support, wherein the PEM electrolysis water catalyst support has a nanoneedle-like structure and a molecular formula of A. x Ti 1-x O2, where x is 0.01-0.05 and A is a metal.

[0008] Furthermore, A is selected from one or more of Al, Ni, Mn, and Co;

[0009] And / or, the length of the nanoneedle structure is 50-200 nm, the diameter is 5-20 nm, and the aspect ratio is (10-20):1;

[0010] And / or, the PEM water electrolysis catalyst support has a mixed crystalline phase of anatase and rutile.

[0011] This invention constructs a nanoneedle-shaped catalyst support, which provides a huge specific surface area, which is beneficial to the high dispersion of active components. Element A is introduced into the crystal lattice of titanium dioxide, replacing some of the Ti atoms to form a mixed crystal phase of anatase and rutile. This generates lattice defects to synergistically improve the conductivity of the support, while maintaining the excellent corrosion resistance of titanium dioxide.

[0012] The second aspect of this invention provides a method for preparing the PEM electrolysis water catalyst support described in the first aspect, comprising the following steps:

[0013] S1. Melt metallic Ti and metallic A into an ATi alloy;

[0014] S2. The ATi alloy is placed in an acid solution for reaction;

[0015] S3. After the temperature drops to room temperature, the catalyst support is obtained by ultrasonic dispersion with ultrapure water, centrifugal washing, and drying.

[0016] This invention employs an "alloy smelting-selective corrosion" method. Acid selectively corrodes metal A, leaving only trace amounts of metal A in the corrosion product, with the main component being TiO2. The trace amounts of metal A regulate the TiO2 lattice: upon entering the acid, the alloy undergoes a typical dealloying reaction. Metal A is more reactive than metal Ti (or more readily soluble at its potential). In the acidic environment, A atoms act as a "sacrificial phase," preferentially oxidized into ions and entering the solution. The electrons released from the dissolution of metal A are immediately utilized by Ti atoms on the alloy surface. The Ti atoms do not simply dissolve but react with water molecules in the solution, directly generating TiO2 in situ.

[0017] Once corrosion begins, the metallic atom (A) within the alloy needs to diffuse to the alloy / solution interface to be dissolved. Simultaneously, the hydrogen (H) in the acid solution... + It also needs to diffuse to the reaction interface. Under specific corrosion conditions, this diffusion process is more advantageous in a certain direction. Reactants are transported inward more quickly along specific crystal orientations or channels of the initial corrosion pit, while reaction products (such as Al) are transported more rapidly. 3+ The corrosion reaction then diffuses outward. This anisotropy of the diffusion field causes the corrosion reaction to preferentially advance rapidly in certain directions, forming deep and narrow "channels" or "needle-like" structures, rather than eroding uniformly inward.

[0018] Doped elements A (such as Al) with different valence states and ionic radii 3+ Ni 2+ Co 2+ When element A enters the TiO2 lattice, it causes varying degrees of lattice distortion and strain. This lattice strain alters the relative stability of the anatase and rutile phases. By precisely designing the type and initial proportion of element A in the alloy (the value of x), the ratio of anatase to rutile phases in the final product can be "predicted" during the synthesis stage. The corrosion temperature directly affects the kinetics of atomic migration and crystal growth. Lower temperatures (e.g., 40-60℃): slower reaction and nucleation rates, favoring the formation of metastable anatase phases. Higher temperatures (e.g., 70-80℃): atoms possess higher energy, facilitating rearrangement and promoting the formation and growth of the thermodynamically more stable rutile phase. Furthermore, corrosion time affects the maturity of the crystal phases.

[0019] The process route of this invention is simple, requires no template agent or complex equipment, has mild reaction conditions, is easy to scale up, and has significant industrial advantages.

[0020] Furthermore, in S1, the molar ratio of the metal Ti to the metal A is 1:(3-8).

[0021] Furthermore, in S2, the acid solution is one or more of hydrochloric acid, sulfuric acid, and perchloric acid solutions;

[0022] And / or, the concentration of the acid solution is 0.5-1.5 mol / L;

[0023] And / or, the temperature of the reaction is 40-80°C.

[0024] Furthermore, in S3, the centrifugal cleaning speed is 6000-10000 rpm, the number of centrifugal cleaning cycles is 3-5, and the drying temperature is 60-80℃.

[0025] A third aspect of the present invention provides a PEM water electrolysis catalyst, comprising the PEM water electrolysis catalyst support described in the first aspect and an active component loaded on the support, wherein the mass ratio of the active component to the support is 1:(0.1-1).

[0026] Furthermore, the active component is iridium oxide nanoparticles with a particle size of 2-5 nm.

[0027] The unique nanoneedle-like structure of the PEM electrolysis water catalyst support in this invention and the strong interaction (electronic effect) between the support (A) x Ti 1-x O2 is in close contact with the supported iridium oxide nanoparticles, and the electronic structures of the two influence each other; geometric effect: the unique nanoneedle morphology of the support plays a role in stabilizing and fixing the metal particles, resulting in uniform distribution and strong bonding of iridium oxide nanoparticles; the mass activity of the catalyst can reach 3-5 times that of traditional catalysts, and the amount of precious metal iridium can be greatly reduced under the same performance requirements, effectively reducing costs.

[0028] A fourth aspect of this invention provides a method for preparing the PEM water electrolysis catalyst described in the third aspect, comprising the following steps:

[0029] (1) The PEM electrolysis catalyst carrier, the soluble inorganic salt of noble metal Ir, the complexing agent and ultrapure water are mixed to form a suspension;

[0030] (2) After evaporating and grinding the suspension, it is annealed in air to form iridium oxide supported on the support, thus obtaining the PEM water electrolysis catalyst Ir / A. x Ti 1-x O2.

[0031] Furthermore, the soluble inorganic salt of the noble metal Ir is selected from one or more of iridium trichloride hydrate, iridium tetrachloride hydrate, dodecyltetrairidium, potassium hexachloroiridate, and ammonium hexachloroiridate hydrate.

[0032] And / or, the complexing agent is selected from one or more of sodium nitrate, oxalic acid, ascorbic acid, and citric acid;

[0033] And / or, the annealing temperature is 300-500℃.

[0034] The fifth aspect of this invention provides the application of the PEM water electrolysis catalyst described in the third aspect in the fields of proton exchange membrane water electrolysis and fuel cells.

[0035] The PEM water electrolysis catalyst of this invention exhibits excellent stability under the harsh environment of PEM water electrolysis anode; accelerated aging tests show that its voltage decay rate is much lower than that of traditional commercial catalysts, which greatly extends the service life of membrane electrode.

[0036] The beneficial effects of this invention are:

[0037] This invention constructs a nanoneedle-shaped catalyst support with a huge aspect ratio. Those skilled in the art can reasonably expect that the support has a significantly higher specific surface area than conventional titanium dioxide nanoparticles, which is beneficial for the high dispersion of active components. Due to the doping of element A and the synergistic effect of the mixed crystal phase of anatase and rutile, the conductivity of the support is improved by generating lattice defects. The electronic conductivity of the support is expected to be significantly improved compared to pure titanium dioxide, while maintaining the excellent corrosion resistance of titanium dioxide.

[0038] This invention employs an "alloy smelting-selective corrosion" method, which has a simple process route, requires no template agents or complex equipment, has mild reaction conditions, is easy to scale up, and has significant industrial advantages.

[0039] The unique nanoneedle structure of the catalyst support in this invention and the strong interaction between it and the active components result in uniform distribution and strong bonding of iridium nanoparticles. The mass activity of the catalyst can reach 3-5 times that of traditional catalysts, and the amount of precious metal iridium can be significantly reduced under the same performance requirements, effectively reducing costs. The catalyst exhibits excellent stability under the harsh environment of PEM water electrolysis anode. Accelerated aging tests show that its voltage decay rate is much lower than that of traditional commercial catalysts, greatly extending the service life of the membrane electrode. Attached Figure Description

[0040] To more clearly illustrate the technical solution of the present invention, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0041] Figure 1 The Al obtained in Example 1 of the present invention 0.02 Ti 0.98 O2 carrier material scanning electron microscopy characterization;

[0042] Figure 2The Al obtained in Example 1 of the present invention 0.02 Ti 0.98 X-ray diffraction characterization of O2 carrier materials;

[0043] Figure 3 The Co obtained in Example 2 of this invention 0.04 Ti 0.96 O2 carrier material scanning electron microscopy characterization;

[0044] Figure 4 The Co obtained in Example 2 of this invention 0.04 Ti 0.96 X-ray diffraction characterization of O2 carrier materials;

[0045] Figure 5 The Ir / Al obtained in Example 3 of this invention 0.02 Ti 0.98 Transmission electron microscopy characterization of O2 carrier materials;

[0046] Figure 6 These are battery performance test diagrams for Embodiment 4 and Comparative Example 1 of the present invention. Detailed Implementation

[0047] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0048] This embodiment relates to a PEM water electrolysis catalyst support, which has a nano-needle structure, a mixed crystalline phase of anatase and rutile, and a molecular formula of A. x Ti 1-x O2, where x is 0.01-0.05, and A is a metal selected from one or more of Al, Ni, Mn, and Co; the length of the nanoneedle structure is 50-200 nm, the diameter is 5-20 nm, and the aspect ratio is (10-20):1; this embodiment constructs a nanoneedle structure catalyst support, which provides a huge specific surface area, which is beneficial to the high dispersion of active components; element A is introduced into the crystal lattice of titanium dioxide, replacing some of the Ti atoms, forming a mixed crystal phase of anatase and rutile, which synergistically improves the conductivity of the support by generating lattice defects, while maintaining the excellent corrosion resistance of titanium dioxide.

[0049] Another embodiment provides a method for preparing the PEM electrolysis water catalyst support of the above embodiments, comprising the following steps:

[0050] S1. Melt metallic Ti and metallic A into an ATi alloy;

[0051] Wherein, the molar ratio of the metal Ti to the metal A is 1:(3-8);

[0052] S2. The ATi alloy is placed in an acid solution for reaction;

[0053] The acid solution is one or more of hydrochloric acid, sulfuric acid, and perchloric acid solutions; the concentration of the acid solution is 0.5-1.5 mol / L; and the reaction temperature is 40-80℃.

[0054] S3. After the temperature drops to room temperature, the catalyst support is obtained by ultrasonic dispersion in ultrapure water, centrifugal washing, and drying.

[0055] The centrifugal cleaning speed is 6000-10000 rpm, the number of centrifugal cleaning cycles is 3-5, and the drying temperature is 60-80℃.

[0056] This embodiment employs an "alloy smelting-selective corrosion" method, in which acid selectively corrodes metal A. The corrosion product contains only trace amounts of metal A, with the main component being TiO2. The TiO2 lattice is controlled by the trace amounts of metal A. The process route is simple, requiring no template agents or complex equipment. The reaction conditions are mild, making it easy to achieve large-scale production and demonstrating significant industrial advantages.

[0057] Another embodiment provides a PEM water electrolysis catalyst, comprising the PEM water electrolysis catalyst support described in the first aspect and an active component supported on the support, wherein the mass ratio of the active component to the support is 1:(0.1-1); the active component is iridium oxide nanoparticles with a particle size of 2-5 nm.

[0058] The unique nanoneedle-like structure of the PEM electrolysis water catalyst support in this invention and the strong interaction (electronic effect) between the support (A) x Ti 1-x O2 is in close contact with the supported iridium oxide nanoparticles, and the electronic structures of the two influence each other; geometric effect: the unique nanoneedle morphology of the support plays a role in stabilizing and fixing the metal particles, resulting in uniform distribution and strong bonding of iridium oxide nanoparticles; the mass activity of the catalyst can reach 3-5 times that of traditional catalysts, and the amount of precious metal iridium can be greatly reduced under the same performance requirements, effectively reducing costs.

[0059] Another embodiment provides a method for preparing the PEM water electrolysis catalyst described in the above embodiments, comprising the following steps:

[0060] (1) The PEM electrolysis catalyst carrier, the soluble inorganic salt of noble metal Ir, the complexing agent and ultrapure water are mixed to form a suspension;

[0061] (2) After evaporating and grinding the suspension, it is annealed in air to form iridium oxide supported on the support, thus obtaining the PEM water electrolysis catalyst Ir / A. x Ti 1-x O2.

[0062] In a preferred embodiment, the soluble inorganic salt of the noble metal Ir is selected from one or more of iridium trichloride hydrate, iridium tetrachloride hydrate, dodecyltetrairidium, potassium hexachloroiridate, and ammonium hexachloroiridate hydrate; the complexing agent is selected from one or more of sodium nitrate, oxalic acid, ascorbic acid, and citric acid; and the annealing temperature is 300-500℃.

[0063] Another embodiment provides the application of the PEM water electrolysis catalyst described in the above embodiments in the fields of proton exchange membrane water electrolysis and fuel cells. The PEM water electrolysis catalyst exhibits excellent stability under the harsh environment of PEM water electrolysis anode; accelerated aging tests show that its voltage decay rate is much lower than that of conventional commercial catalysts, greatly extending the service life of the membrane electrode.

[0064] Example 1

[0065] This embodiment relates to an Al 0.02 Ti 0.98 The preparation method of O2 nanoneedle-shaped PEM electrolysis water catalyst support includes the following steps:

[0066] Metallic Al particles and metallic Ti particles were uniformly mixed at a molar ratio of 3:1 and melted in a high-temperature furnace for 4 hours under argon protection to form a homogeneous Al3Ti alloy ingot. The resulting alloy ingot was mechanically pulverized into small particles with a width of approximately 10 mm. 10 g of the alloy particles were added to 250 mL of 1.5 mol / L hydrochloric acid aqueous solution and reacted in a constant temperature water bath at 60 °C for 8 hours. After the reaction was completed, the mixture was naturally cooled to room temperature, ultrasonically dispersed with ultrapure water for 30 minutes, and then centrifuged and washed 4 times at 10,000 rpm until the supernatant was neutral. The washed solid product was dried in a forced-air drying oven at 60 °C for 12 hours to obtain nano-needle-shaped Al. 0.02 Ti 0.98 O2 carrier material.

[0067] Figure 1 Al obtained in Example 1 0.02 Ti 0.98The O2 carrier material was characterized by scanning electron microscopy (SEM). The carrier material consists of uniform nanoneedle-like structures with a length of about 100-150 nm, a diameter of about 8-12 nm, and an aspect ratio of about 12:1. Figure 2 Al obtained in Example 1 0.02 Ti 0.98 X-ray diffraction (XRD) characterization of the O2-supported material revealed that it is a mixed crystalline phase of anatase and rutile. The chemical composition of the support consists of oxygen, titanium, and a small amount of residual aluminum. The weight percentage and atomic number percentage of these three components in the support are shown in Table 1.

[0068] Table 1

[0069] element Weight % Atomic % O 40.35 66.72 Ti 58.89 32.54 Al 0.75 0.74

[0070] Example 2

[0071] This embodiment relates to a Co 0.04 Ti 0.96 The preparation method of O2 nanoneedle-like carriers includes the following steps:

[0072] Metallic Co particles and metallic Ti particles were uniformly mixed at a molar ratio of 3:1 and melted in a high-temperature furnace for 3 hours under argon protection to form a homogeneous Co3Ti alloy ingot. The resulting alloy ingot was mechanically pulverized into small particles with a width of approximately 10 mm. 10 g of the alloy particles were added to 250 mL of 1 mol / L hydrochloric acid solution and reacted in a constant temperature water bath at 60 °C for 5 hours. After the reaction was completed, the mixture was naturally cooled to room temperature, ultrasonically dispersed with ultrapure water for 30 minutes, and then centrifuged and washed 5 times at 10,000 rpm until the supernatant was neutral. The washed solid product was dried in a forced-air drying oven at 60 °C for 12 hours to obtain nano-needle-shaped Co. 0.04 Ti 0.96 O2 carrier material.

[0073] through Figure 3 Scanning electron microscopy (SEM) characterization revealed that the carrier material consists of uniform nanoneedle-like structures with a length of approximately 80-120 nm, a diameter of approximately 8-10 nm, and an aspect ratio of approximately 12:1. Figure 4 X-ray diffraction (XRD) analysis showed that the material was a mixed crystalline phase of anatase and rutile. The chemical composition of the support was oxygen, titanium, and a small amount of residual cobalt. The weight percentage and atomic number percentage of the three components in the support are shown in Table 2.

[0074] Table 2

[0075] element Weight % Atomic % O 40.08 66.87 Ti 57.27 31.93 Co 2.65 1.2

[0076] Example 3:

[0077] This embodiment relates to an Ir / Al 0.02 Ti 0.98 The preparation method of O2 catalyst includes the following steps:

[0078] Take Al prepared in Example 1 0.02 Ti 0.98 1.0 g of O2 carrier powder, 1.0 g of iridium trichloride (IrCl3·3H2O), and 10.0 g of sodium nitrate were added to 250 mL of ultrapure water. After stirring for 2 h, the mixture was ultrasonically dispersed for 0.5 h to form a homogeneous suspension. The suspension was dried in an 80 °C drying oven. After thorough evaporation, the dried solid was ground into a fine powder and evenly placed in a ceramic boat. The powder was annealed in air at 400 °C for 2 h to form iridium oxide supported on the carrier. After annealing, the powder was dispersed in ultrapure water and then centrifuged and washed four times. The cleaned catalyst was dried in a 60 °C drying oven to obtain the final catalyst product, Ir / Al. 0.02 Ti 0.98 O2. Figure 5 Transmission electron microscopy (TEM) characterization showed that iridium nanoparticles were uniformly distributed on the surface of nanoneedles, with a particle size of 3-5 nanometers and a high distribution density. The Ir content in the catalyst was 52.5 wt.%.

[0079] Example 4:

[0080] This embodiment relates to an Ir / Al 0.02 Ti 0.98 The application test of O2 catalyst in PEM water electrolysis device includes the following steps:

[0081] The Ir / Al prepared in Example 3 0.02 Ti 0.98 O2 catalyst was used to prepare the anode catalyst layer of the PEM water electrolysis membrane electrode. Nafion 115 was used as the proton exchange membrane, and the catalyst slurry was coated onto both sides of the membrane using ultrasonic spraying. The iridium loading at the anode was 0.2 mg / cm², and the platinum loading at the cathode was 0.5 mg / cm². A single cell with an effective area of ​​4 cm² was assembled using a PEM water electrolysis anode plate structure, and performance testing was conducted.

[0082] Comparative Example 1

[0083] Using commercial anatase titanium dioxide as a support, an Ir / TiO2 catalyst was prepared by loading the same amount of iridium active component as in Example 3. 1.0 g of commercial TiO2 support, 1.0 g of iridium trichloride (IrCl3·3H2O), and 10.0 g of sodium nitrate were weighed, ultrasonically mixed, evaporated to dryness, dried, ground, and annealed at 400°C in air for 2 hours to form iridium oxide supported on the support. This catalyst was then used in the same PEM water electrolysis single-cell test as in Example 4.

[0084] The test conditions were: temperature 80℃, pressure 1 atm, and deionized water as feed water. Example 4 Test Results Figure 6 The display shows that Ir / Al is used. 0.02 Ti 0.98 The single cell of the O2 catalyst achieved a current density of 3.47 A / cm² at 1.8 V, while Comparative Example 1 only achieved a current density of 1.8 A / cm² at 1.8 V. Example 4 showed a 92% improvement over Comparative Example 1. The cell voltage of Example 4 at a current density of 3 A / cm² was 1.765 V, while the cell voltage of the Comparative Example was 1.900 V at the same current density. Example 4 showed a 135 mV reduction compared to Comparative Example 1 (1.900 V).

[0085] The catalyst support obtained in Example 1 and the commercial anatase titanium dioxide support in the comparative example were subjected to electrical performance tests. The resistivity of the materials was directly measured using the four-probe method: the powder sample was pressed into a dense disc under the same pressure, with the pressure set between 22.0 MPa and 30.0 MPa to eliminate the interference of porosity on the test results. The resistance was measured at room temperature using a four-probe resistivity meter, and the average resistivity ρ (Ω·cm) was calculated according to the formula ρ = 2πS(V / I) (where S is the probe spacing, V is the voltage, and I is the current). The conductivity (S / cm) was calculated from the reciprocal of the resistivity. The results are shown in Table 3. It can be seen that the catalyst support of Example 1 of the present invention has excellent electrical conductivity.

[0086] Table 3

[0087] Vector group Resistivity (Ω·cm) Electrical conductivity (S / cm) Commercial titanium dioxide 3158900 <![CDATA[3.17×10 -7 ]]> Example 1 41624 <![CDATA[2.4×10 -5 ]]>

[0088] The specific surface area of ​​the catalyst support in Example 1 and the commercial titanium dioxide support in Comparative Example 1 was determined using the low-temperature nitrogen adsorption method (BET method). The samples were pretreated by vacuum degassing at 150°C to remove adsorbed moisture and impurities. Subsequently, nitrogen adsorption-desorption isotherms were measured using a specific surface area and pore size analyzer at a liquid nitrogen temperature of -196°C. The BET specific surface area was calculated using the Brunner-Emmet-Teller (BET) model within a linear range of 0.05–0.30 relative pressure (P / P0). The BET specific surface area of ​​the catalyst support in Example 1 was 79.61 m² / g, while the BET specific surface area of ​​the commercial titanium dioxide support used for comparison was only 14.61 m² / g, indicating that the catalyst support in Example 1 of this invention has a larger specific surface area.

[0089] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.

Claims

1. A PEM electrolysis water catalyst support, characterized in that, The PEM water electrolysis catalyst support has a nanoneedle-like structure and a molecular formula of A. x Ti 1-x O2, where x is 0.01-0.05 and A is a metal.

2. The PEM electrolysis water catalyst support as described in claim 1, characterized in that, The A is selected from one or more of Al, Ni, Mn, and Co; And / or, the length of the nanoneedle structure is 50-200 nm, the diameter is 5-20 nm, and the aspect ratio is (10-20):1; And / or, the PEM water electrolysis catalyst support has a mixed crystalline phase of anatase and rutile.

3. A method for preparing a PEM electrolysis water catalyst support according to any one of claims 1-2, characterized in that, Includes the following steps: S1. Melt metallic Ti and metallic A into an ATi alloy; S2. The ATi alloy is placed in an acid solution for reaction; S3. After the temperature drops to room temperature, the catalyst support is obtained by ultrasonic dispersion with ultrapure water, centrifugal washing, and drying.

4. The method for preparing the PEM electrolysis water catalyst support as described in claim 3, characterized in that, In S1, the molar ratio of metal Ti to metal A is 1:(3-8).

5. The method for preparing the PEM electrolysis water catalyst support as described in claim 3, characterized in that, In S2, the acid solution is one or more of hydrochloric acid, sulfuric acid, and perchloric acid solutions; And / or, the concentration of the acid solution is 0.5-1.5 mol / L; And / or, the temperature of the reaction is 40-80°C.

6. The method for preparing the PEM electrolysis water catalyst support as described in claim 3, characterized in that, In S3, the centrifugal cleaning speed is 6000-10000 rpm, the number of centrifugal cleaning cycles is 3-5, and the drying temperature is 60-80℃.

7. A PEM water electrolysis catalyst, characterized in that, It includes the PEM water electrolysis catalyst support according to any one of claims 1-2 and the active component loaded on the support, wherein the mass ratio of the active component to the support is 1:(0.1-1).

8. A method for preparing the PEM water electrolysis catalyst according to claim 7, characterized in that, Includes the following steps: (1) The PEM electrolysis catalyst carrier, the soluble inorganic salt of noble metal Ir, the complexing agent and ultrapure water are mixed to form a suspension; (2) After evaporating and grinding the suspension, it is annealed in air to form iridium oxide supported on the support, thus obtaining the PEM water electrolysis catalyst Ir / A. x Ti 1-x O2.

9. The preparation method of the PEM water electrolysis catalyst as described in claim 8, characterized in that, The soluble inorganic salt of the noble metal Ir is selected from one or more of iridium trichloride hydrate, iridium tetrachloride hydrate, dodecyltetrairidium, potassium hexachloroiridate, and ammonium hexachloroiridate hydrate. And / or, the complexing agent is selected from one or more of sodium nitrate, oxalic acid, ascorbic acid, and citric acid; And / or, the annealing temperature is 300-500℃.

10. The application of the PEM water electrolysis catalyst according to claim 7 in the fields of proton exchange membrane water electrolysis and fuel cells.

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