Solid hydrogen production composite catalyst carrier and preparation method thereof

Abstract

The application discloses a composite catalyst carrier for solid hydrogen production and a preparation method thereof. The composite catalyst carrier comprises lithium cobaltate and at least one metal oxide modifier selected from one or more of titanium dioxide, aluminum oxide, magnesium oxide and silicon dioxide, and is uniformly distributed in a lithium cobaltate matrix to form a composite structure. The preparation method only involves solid-phase mechanical mixing, is simple in process and suitable for large-scale production. The carrier has high specific surface area and strong synergistic effect, and is suitable for loading of non-noble metal catalysts.

Description

[0001] This application is a divisional application of the invention patent application filed by the applicant, Samara (Beijing) Technology Co., Ltd., on April 3, 2026, with application number 202610435397.X and invention title "A solid hydrogen storage material and its preparation method". Technical Field

[0002] This invention belongs to the field of hydrogen energy technology, specifically relating to a composite catalyst support for solid hydrogen production and its preparation method. Background Technology

[0003] Hydrogen energy, as a clean and efficient energy carrier, relies heavily on storage and release technologies for its application. The hydrolysis of chemical hydrides to produce hydrogen depends on catalysts. Currently, catalysts are often used in nanoparticle form, which suffers from problems such as easy aggregation, difficulty in recovery, and poor dispersibility. To address these issues, researchers have attempted to load catalysts onto porous supports. However, existing supports generally suffer from poor dispersibility, weak synergistic effects with the catalyst, and insufficient stability, limiting catalytic efficiency and material lifespan.

[0004] Therefore, developing a catalyst support that combines high dispersibility, strong synergistic catalytic effect, and good stability is of great significance for improving the overall performance of solid hydrogen production materials. Summary of the Invention

[0005] The composite catalyst support provided by this invention is particularly suitable for supporting non-precious metal catalysts (such as cobalt boride) for hydrogen production reactions via the hydrolysis of solid chemical hydrides (such as sodium borohydride). This support aims to solve the problems of catalyst agglomeration and poor synergistic effect with hydrogen-producing agents in existing technologies.

[0006] To achieve the above objectives, the present invention provides a composite catalyst support for solid hydrogen production, wherein the composite catalyst support comprises lithium cobalt oxide and at least one metal oxide modifier, wherein the metal oxide modifier is selected from one or more of titanium dioxide, aluminum oxide, magnesium oxide, and silicon dioxide; the metal oxide modifier is uniformly distributed in the lithium cobalt oxide matrix to form a composite structure.

[0007] Furthermore, the mass of the metal oxide modifier accounts for 1% to 40% of the total mass of the composite catalyst support.

[0008] This invention also provides a method for preparing the above-mentioned composite catalyst support, comprising the following steps: mixing lithium cobalt oxide powder and metal oxide modifier powder at a predetermined mass ratio, and mechanically mixing to uniformly disperse the metal oxide modifier in the lithium cobalt oxide matrix to obtain the composite catalyst support. The mechanical mixing can be performed using a ball mill, a V-type mixer, or a three-dimensional motion mixer.

[0009] Compared with the prior art, the present invention has the following significant advantages:

[0010] 1. Enhanced Synergistic Effect: This invention uses lithium cobalt oxide as the support matrix, which itself possesses potential catalytic active sites. By modifying its surface properties with metal oxide modifiers, it can form the expected synergistic effect with non-precious metal catalysts. Application verification experiments show that the solid hydrogen production material prepared using the support of this invention can achieve a hydrogen production rate of over 95%, far exceeding the 62% of the unmodified support.

[0011] 2. Improve dispersibility and stability: By introducing metal oxide modifiers (such as...) (etc.), effectively increasing the specific surface area and active sites of the support, preventing the agglomeration and deactivation of nanocatalysts, and extending the service life of the catalytic system.

[0012] 3. Enhanced structural stability: The composite catalyst support exhibits excellent chemical stability in alkaline reaction environments.

[0013] 4. Simple preparation process: The composite catalyst support of the present invention can be prepared by simple solid-phase mechanical mixing, which is simple, low-cost and easy to scale up. Detailed Implementation

[0014] The present invention provides a composite catalyst support for solid hydrogen production, which is a composite lithium cobalt oxide material in which a metal oxide modifier is uniformly composited in a lithium cobalt oxide matrix by a physical method.

[0015] The present invention will be further illustrated by specific embodiments below, but the present invention is not limited to the following embodiments. Unless otherwise stated, all "parts" mentioned in the following embodiments refer to parts by weight.

[0016] Disclaimer: The following embodiments involve hydrolysis hydrogen production tests of the carrier of the present invention in combination with a reference catalyst and a hydrogen-producing agent. These tests are only used to demonstrate the technical effects of the carrier of the present invention and do not constitute a limitation on the scope of protection of the present invention. The scope of protection of the present invention is determined only by the claims.

[0017] Regarding the raw materials: The lithium cobalt oxide used in the following examples is a battery-grade product (purity ≥ 99.5%), but the present invention is not limited to this, and lithium cobalt oxide of other purities can also achieve the purpose of the present invention.

[0018] Preparation of the reference catalyst for comparison

[0019] The following reference catalyst preparation methods are existing technologies or conventional methods in the field, and are only used for performance comparison tests in conjunction with the support of the present invention.

[0020] To verify the performance of the support of this invention, a reference catalyst was prepared using the following method: a cobalt salt (such as cobalt chloride hexahydrate) was dissolved in deionized water, and an aqueous solution of sodium borohydride was added dropwise to the cobalt salt solution under stirring, resulting in a black precipitate. After centrifugation, washing, and drying, a cobalt boride catalyst powder was obtained. This catalyst was used only for testing the support performance.

[0021] Preparation of composite catalyst support

[0022] The composite catalyst support described in this invention is a composite lithium cobalt oxide. This support contains lithium cobalt oxide (…). It contains at least one metal oxide selected from titanium, aluminum, magnesium, and silicon as a modifying additive.

[0023] The preparation method of this composite lithium cobalt oxide support includes: mixing lithium cobalt oxide powder with one or more modifying additives (such as...) , , , Powders of (etc.) are processed by mechanical mixing (such as in a ball mill or mixer) to obtain modified composite lithium cobalt oxide carrier powder.

[0024] The content of the modified additive, based on the total mass of the carrier, shall not exceed 40%. This carrier primarily provides a high specific surface area and suitable pore structure to effectively disperse the nanocatalyst and prevent its aggregation and deactivation during the reaction; simultaneously, the modified additive (such as...) , (etc.) can adjust the hydrophilicity or hydrophobicity of the carrier surface, promote the diffusion of water molecules, and thus form a synergistic effect with the catalyst.

[0025] Application verification test methods

[0026] To verify the performance of the support of the present invention, the prepared composite catalyst support was mixed with a hydrogen-producing agent (sodium borohydride) and a reference catalyst according to the following steps and tested. The amounts of the hydrogen-producing agent and catalyst used were standard test amounts, intended to standardize the performance evaluation of the support, rather than limiting the usage ratio of the support of the present invention.

[0027] (1) Mixing: Weigh 2 grams of sodium borohydride ( 0.1 g of cobalt boron catalyst powder and 0.1 g of composite catalyst support were thoroughly mechanically mixed.

[0028] (2) Compression molding: The mixed powder is placed in a mold and compressed into a round disc (tablet) with a diameter of 13 mm under a pressure of about 50 MPa.

[0029] (3) Performance test: The tablet was placed in a 250 mL three-necked flask, and 10 mL of deionized water was added at room temperature (25℃) and atmospheric pressure. The mixture was left to stand without stirring, and the generated hydrogen gas was collected and measured. The hydrogen production rate was calculated based on the complete hydrolysis of sodium borohydride to produce 4 equivalents of hydrogen gas (theoretical hydrogen production of 5180 mL, 25℃, 101.3 kPa).

[0030] Example 1: Modified composite carrier (mechanical mixing method)

[0031] (1) Preparation of composite catalyst support: Weigh 76 parts by mass of battery-grade catalyst support. Powder and 24 parts by weight The powder was prepared into composite carrier A by mechanical mixing (V-type mixer, mixing for 1 hour).

[0032] (2) Characterization results: Observed by scanning electron microscopy, Particles are evenly distributed in Surface; X-ray diffraction analysis showed that carrier A simultaneously retained and anatase phase The characteristic diffraction peaks indicate that no new phase is formed.

[0033] (3) Application verification: Tablets were prepared and tested using composite carrier A according to the above application verification test method. Thanks to the composite carrier of the present invention, the prepared tablets exhibited excellent hydrogen production performance: the cumulative hydrogen production reached 4920 mL, the hydrogen production rate was about 95.0% of the theoretical value, and the reaction was completed within 12 minutes.

[0034] Example 2: Multi-component modified composite carrier ( (Mechanical mixing method)

[0035] (1) Preparation of composite catalyst support: Weigh 64 parts by mass of battery-grade catalyst support Powder, 24 parts by weight and 12 parts by weight Composite carrier B was prepared by mechanical mixing (three-dimensional motion mixer, mixing for 1.5 hours).

[0036] (2) Characterization results: Observed by scanning electron microscopy, and Evenly distributed in Energy dispersive spectroscopy (EDS) analysis confirmed that the components were uniformly distributed in the matrix, with no obvious segregation.

[0037] (3) Application verification: Following the application verification test method described above, composite carrier B was used instead of composite carrier A. Thanks to the composite carrier of the present invention, the prepared tablets exhibited excellent hydrogen production performance: the cumulative hydrogen production reached 4890 mL, and the hydrogen production rate was approximately 94.4% of the theoretical value.

[0038] Example 3: Modified composite carrier (mechanical mixing method)

[0039] (1) Preparation of composite catalyst support: Weigh 75 parts by mass of battery-grade catalyst support Powder and 25 parts by weight Composite carrier C was prepared by mechanical mixing (ball mill, 300 rpm, mixing for 30 minutes).

[0040] (2) Characterization results: X-ray diffraction analysis showed that the carrier C simultaneously retained and The characteristic diffraction peaks were observed, and no new phase was formed. Specific surface area tests showed that the modified support had a higher specific surface area than the purer one. Significant improvement.

[0041] (3) Application verification: Following the application verification test method described above, composite carrier C was used instead of composite carrier A. Thanks to the composite carrier of the present invention, the prepared tablets exhibited excellent hydrogen production performance: the cumulative hydrogen production reached 4865 mL, and the hydrogen production rate was approximately 93.9% of the theoretical value.

[0042] Example 4: Modified composite carrier (mechanical mixing method)

[0043] (1) Preparation of composite catalyst support: Weigh 80 parts by mass of battery-grade Powder and 20 parts by weight The powder was mixed with a V-type mixer for 1 hour to obtain composite carrier D.

[0044] (2) Characterization results: Observations showed that Uniformly distributed at the nanoscale A coating structure is formed on the surface of the particles.

[0045] (3) Application verification: Following the application verification test method described above, composite carrier D was used instead of composite carrier A. Thanks to the composite carrier of the present invention, the prepared tablets exhibited excellent hydrogen production performance: the cumulative hydrogen production was approximately 4850 mL, and the hydrogen production rate was approximately 93.6% of the theoretical value.

[0046] Example 5: Broad-spectrum water source adaptability test

[0047] The tablets prepared in Example 1 (using composite carrier A) were tested at room temperature using different water sources (10 mL each), without stirring.

[0048] (1) Rainwater: The hydrogen production is about 4680 mL, and the hydrogen production rate is about 90.3% of the theoretical value.

[0049] (2) Tap water: The hydrogen production is about 4800 mL, and the hydrogen production rate is about 92.7% of the theoretical value.

[0050] (3) Simulated seawater (3.5%) (Solution): Hydrogen production is approximately 4640 mL, and the hydrogen production rate is approximately 89.6% of the theoretical value.

[0051] The results show that the solid hydrogen production material using the composite catalyst support of the present invention has good adaptability to various water sources.

[0052] Comparative Example 1: Unmodified Carrier

[0053] Use pure (Without adding any metal oxide modifier) ​​as the carrier, the other conditions are the same as in Example 1.

[0054] Results: The cumulative hydrogen production was only 3210 mL, with a hydrogen production rate of approximately 62.0% of the theoretical value, significantly lower than the 95.0% in Example 1. This indicates that the unmodified support has poor synergistic catalytic effect.

[0055] Comparative Example 2: Single metal oxide support (without )

[0056] Use pure The powder was used as a carrier, and the other conditions were the same as in Example 1.

[0057] Results: The cumulative hydrogen production was only 4030 mL, with a hydrogen production rate of approximately 77.8% of the theoretical value, and catalyst agglomeration occurred after the reaction. This indicates that a single metal oxide support cannot provide a synergistic effect.

[0058] The above examples and comparative examples demonstrate that the composite catalyst support for solid hydrogen production provided by this invention significantly improves the specific surface area, structural stability, and catalytic synergistic effect of the support by uniformly incorporating a metal oxide modifier into a lithium cobalt oxide matrix. Application verification experiments show that the solid hydrogen production material using the support of this invention can achieve a hydrogen production rate of over 95%, far superior to unmodified supports (62.0%) and single oxide supports (77.8%). This composite catalyst support has the advantages of simple preparation process and strong environmental adaptability, making it suitable for the field of solid hydrogen production.

Claims

1. A composite catalyst support for solid hydrogen production, characterized in that, The composite catalyst support comprises lithium cobalt oxide and at least one metal oxide modifier, wherein the metal oxide modifier is selected from one or more of titanium dioxide, aluminum oxide, magnesium oxide, and silicon dioxide; the metal oxide modifier is uniformly distributed in the lithium cobalt oxide matrix to form a composite structure.

2. The composite catalyst support for solid hydrogen production according to claim 1, characterized in that, The mass of the metal oxide modifier accounts for 1% to 40% of the total mass of the composite catalyst support.

3. A method for preparing the solid hydrogen production composite catalyst support as described in claim 1 or 2, characterized in that, The process includes the following steps: mixing lithium cobalt oxide powder and metal oxide modifier powder at a predetermined mass ratio, and using mechanical mixing to uniformly disperse the metal oxide modifier in the lithium cobalt oxide matrix to obtain a composite catalyst support.

4. The method according to claim 3, characterized in that, The mechanical mixing is carried out using a ball mill, a V-type mixer, or a three-dimensional motion mixer.