A process for scaled-up synthesis of catalytic materials and optimization of noble metal valence state control

Abstract

This invention relates to the field of catalytic materials technology, and discloses a process for scaled-up synthesis of catalytic materials and optimization of noble metal valence state control, comprising the following steps: S1: calcining a noble metal-supported catalyst precursor once to obtain a first-calcined product; S2: calcining the first-calcined product a second time to obtain a noble metal-supported catalyst; the calcination parameters for the second calcination are determined based on a kinetic model. The process for scaled-up synthesis of catalytic materials and optimization of noble metal valence state control provided in this application establishes a quantitative correlation model of "atmosphere composition - reaction temperature - valence state transformation" through a kinetic model. This model allows for flexible control of the noble metal valence state according to the activation requirements of different stages of the catalytic reaction, effectively improving the multifunctional synergy of multi-component catalysts; enabling scientific design of calcination, accurate prediction of noble metal valence state distribution, reducing production energy consumption and cycle time, solving batch-to-batch performance deviation problems, and improving the controllability of the industrial-grade catalyst synthesis process.

Description

Technical Field

[0001] This invention relates to the field of catalytic materials technology, and in particular to a process for the scale-up synthesis of catalytic materials and the optimization of noble metal valence state control. Background Technology

[0002] Three-way catalysts (TWCs) are a core technology for purifying gasoline vehicle exhaust because they can simultaneously catalyze the conversion of incompletely burned carbon monoxide, hydrocarbons, and nitrogen oxides in automotive exhaust. With the rapid increase in vehicle ownership, industrial applications such as three-way catalysts place stringent demands on the large-scale production and performance stability of catalysts. As catalytic material preparation scales up from laboratory-scale (e.g., 500mL reactors) to industrial-scale (e.g., 100L reactors), the uniformity of heat conduction in large reaction vessels faces significant challenges. Uneven heat conduction causes abnormal oxidation state transformations of the precious metal active components in locally overheated areas, leading to instability in the oxidation state of the precious metal active components. This makes the catalyst synthesis process uncontrollable, becoming a major problem restricting the industrial scale-up of catalysts. Summary of the Invention

[0003] To address the aforementioned technical problems, this invention provides a process for the scaled-up synthesis of catalytic materials and the optimization of noble metal valence state control, comprising the following steps:

[0004] A noble metal supported catalyst precursor was calcined once to obtain a calcined product.

[0005] The product from the first calcination is subjected to a second calcination to obtain a noble metal supported catalyst; the calcination parameters for the second calcination are determined based on a kinetic model.

[0006] The dynamic model is shown in the following equation:

[0007] ;

[0008] in[ M 0 ]0 represents the percentage of elemental components in the product of the first calcination at the initial stage of the second calcination; [ M 0 ] t Indicates the calcination time in the secondary calcination. t The percentage of elemental components in the noble metal supported catalysts described later; A Pre-exponential factor, unit is h -1 ·atm -n ; E a R is the activation energy for oxidation, expressed in J / mol; T is the gas constant; and T is the calcination temperature, expressed in K. t is the partial pressure of oxygen; n is the oxygen reaction order; t is the calcination time, in hours.

[0009] Furthermore, the primary calcination of the noble metal supported catalyst precursor includes: calcining the noble metal supported catalyst precursor in an air atmosphere at 300-800°C.

[0010] Furthermore, the noble metal supported catalyst includes a support and a noble metal supported on the support.

[0011] Furthermore, the precious metal is selected from at least one of palladium, platinum, and rhodium.

[0012] Furthermore, the support is selected from at least one of molecular sieves, alumina, cerium oxide, and cerium-zirconium solid solutions.

[0013] Furthermore, the noble metal supported catalyst precursor is prepared by the following method: mixing the noble metal precursor, ligand, and water to obtain a noble metal complex solution; mixing the silicon source, template agent, the noble metal complex solution, and water to obtain a mixed liquid; transferring the mixed liquid into a closed reaction vessel for crystallization reaction to obtain the noble metal supported catalyst precursor.

[0014] Furthermore, the noble metal precursor is selected from at least one of palladium chloride, palladium nitrate, chloroplatinic acid, platinum nitrate, rhodium chloride, rhodium nitrate, and hexaamminerhodium trichloride.

[0015] Furthermore, the ligand is selected from at least one of ethylenediamine, tetraethylenepentamine, pentaethylenehexamine, and triethanolamine.

[0016] Furthermore, the silicon source is selected from at least one of tetraethyl orthosilicate and silica sol.

[0017] Furthermore, the template agent is selected from at least one of triethylamine, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide.

[0018] The embodiments of the present invention have the following technical effects:

[0019] The catalytic material scale-up synthesis and noble metal valence state control optimization process provided in this application establishes a quantitative correlation model of "atmosphere composition-reaction temperature-valence state transformation" through a kinetic model. It can flexibly control the valence state of noble metals according to the activation requirements of different stages of the catalytic reaction, effectively improving the multifunctional synergy of multi-component catalysts; realizing the scientific design of calcination, accurately predicting the valence state distribution of noble metals, reducing production energy consumption and cycle time, solving the problem of batch-to-batch performance deviation, and improving the controllability of industrial-grade catalyst synthesis process. Attached Figure Description

[0020] Figure 1 The conversion curves of CH4 in the three-way catalytic reaction process of the catalysts prepared in Example 1 and Comparative Examples 1-5;

[0021] Figure 2 The conversion curves of CO in the three-way catalytic reaction process for the catalysts prepared in Example 1 and Comparative Examples 1-5;

[0022] Figure 3 The conversion curves of NO in the three-way catalytic reaction process of the catalysts prepared in Example 1 and Comparative Examples 1-5. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are part of this invention.

[0024] In the large-scale production of catalysts, as the preparation of catalytic materials is scaled up from the laboratory level (e.g., 500mL reactor) to the industrial level (e.g., 100L reactor), the radial temperature difference of the material inside the reactor can reach more than 15℃. Furthermore, the increased material thickness leads to a further intensification of the axial temperature gradient. The uneven heat conduction directly causes a decrease in mass and heat transfer efficiency, resulting in abnormal oxidation state transformation of the noble metal active component in the local overheated area. This leads to instability of the oxidation state of the noble metal active component, which has a decisive influence on the catalytic performance of the three-way catalyst. Therefore, the instability of the oxidation state of the noble metal active component directly affects the catalytic performance of the three-way catalyst.

[0025] To regulate the valence state of precious metals, traditional industrial-scale production relies on empirically set parameters such as temperature and time for calcination processes. This leads to significant fluctuations in the valence state distribution of precious metals during the scale-up synthesis process, resulting in deviations in catalytic performance. To meet performance requirements, existing processes often require correction through 3-4 repeated calcinations, which not only increases energy costs but also significantly prolongs the research and development cycle.

[0026] To address the uncontrollable issues in the scale-up synthesis of existing three-way catalysts, this application provides a process for the scale-up synthesis of catalytic materials and the optimization of noble metal valence state control. This process includes the following steps:

[0027] S1: The precursor of the noble metal supported catalyst is calcined once to obtain the calcined product; in the process of this calcination, the support crystallization and organic matter removal are achieved.

[0028] S2: The product from the first calcination is subjected to a second calcination to obtain a noble metal supported catalyst; the calcination parameters for the second calcination are determined based on a kinetic model.

[0029] The dynamic model is shown in the following equation:

[0030] ;

[0031] in[ M 0 ]0 indicates the percentage of elemental substances in the product of the first calcination at the initial stage of the second calcination; [ M 0 ] t Indicates the calcination time during the second calcination. t The proportion of elemental components in post-precious metal supported catalysts; A Pre-exponential factor, unit is h -1 ·atm -n The frequency of the reaction collision; E a R is the activation energy for oxidation, expressed in J / mol, representing the energy barrier for valence state transition; R is the gas constant, specifically 8.314 J / (mol·K); T is the temperature during the isothermal calcination stage, expressed in K. t is the partial pressure of oxygen, such as 0.05 atm for a volume content of 5% O2; n is the oxygen reaction order, usually 1; t is the isothermal calcination time, in hours.

[0032] During calcination, the valence state transformation of noble metals (such as Pd, Pt, and Rh) is mainly controlled by redox reaction kinetics, and its core reaction can be represented as:

[0033] M 0 +x / 2O2→M x+ O x

[0034] Among them, M 0 M is a precious metal element. x+ The metal is in the oxidized state. The rate of this reaction depends on the partial pressure of oxygen, temperature, and time. The partial pressure of oxygen directly affects the driving force of the oxidation reaction; the higher the oxygen concentration, the stronger the tendency for the element to transform into a higher oxidation state. Temperature regulates the reaction rate through the Arrhenius relation; higher temperatures accelerate the oxidation or reduction process. Time determines the degree of oxidation state transformation.

[0035] Based on the gas-solid phase reaction kinetics theory of the calcination process of noble metal supported catalysts, this application establishes the above-mentioned kinetic model to quantitatively describe the valence state transformation process of noble metals.

[0036] Based on this kinetic model, by fitting parameters with experimental data, the valence state distribution of precious metals under specific calcination conditions and parameters can be accurately predicted.

[0037] The calcination parameters in this application refer to calcination temperature, calcination time, and atmosphere composition.

[0038] Specifically, in the above dynamic model, [ M 0 [0] represents the percentage of elemental compounds in the primary calcination product, which can be obtained by detecting the primary calcination product; through two differentiated calcination experiments (e.g., calcination time is the same, but temperature and oxygen partial pressure are changed), the [M] obtained from the two experiments is compared. 0 ] t Substituting the data into the kinetic equations, a quantitative relationship between calcination conditions and the proportion of elemental components is established. Based on the target valence state distribution, the optimal combination of calcination temperature, time, and oxygen partial pressure is calculated in reverse.

[0039] The preferred secondary calcination process of this application is carried out as follows: the product from the primary calcination is ground to 50-200 mesh, placed in a calcination device with controllable oxygen partial pressure, heated to 300-650℃ at a heating rate of 1-10℃ / min, and kept at this temperature for 5-7 hours in an atmosphere with an oxygen volume concentration of 0%-50%. The valence state transformation is precisely controlled through a quantitative correlation model.

[0040] The catalytic material scale-up synthesis and noble metal valence state control optimization process provided in this application establishes a quantitative correlation model of "atmosphere composition-reaction temperature-valence state transformation" through a kinetic model. It can flexibly control the valence state of noble metals according to the activation requirements of different stages of the catalytic reaction, effectively improving the multifunctional synergy of multi-component catalysts; realizing the scientific design of calcination, accurately predicting the valence state distribution of noble metals, reducing production energy consumption and cycle time, solving the problem of batch-to-batch performance deviation, and improving the controllability of industrial-grade catalyst synthesis process.

[0041] It should be noted that for single-component catalysts, if the target valence state can be achieved through a single calcination, the second calcination can be omitted, and the single-stage calcination parameters optimized by the model can be used directly.

[0042] Based on the relationship between the oxidation state transformation of precious metals and calcination parameters during calcination, this application introduces a kinetic model to optimize and scale up the synthesis process without eliminating the temperature gradient inside the reactor. This reduces the impact of radial and axial temperature gradients inside the industrial-grade reactor on the valence state of precious metals, improves the controllability of industrial production, reduces the number of repeated calcinations, and allows for flexible adjustment of single-stage or two-stage calcination designs according to requirements. Compared with traditional processes, this reduces energy consumption, shortens the production cycle, and improves production efficiency.

[0043] The preferred method of this application for calcining the noble metal supported catalyst precursor includes calcining the noble metal supported catalyst precursor in an air atmosphere at 300-800°C, preferably for 1-24 hours, to achieve support crystallization and removal of organic matter.

[0044] The noble metal supported catalyst of this application includes a support and a noble metal supported on the support, and more preferably the noble metal is selected from at least one of palladium, platinum and rhodium, and the support is selected from at least one of molecular sieve, alumina, cerium oxide and cerium zirconium solid solution.

[0045] The noble metal supported catalyst precursor in this application can be prepared using any existing technology. Specifically, this application preferably prepares the noble metal supported catalyst precursor by the following method: mixing the noble metal precursor, ligand, and water to obtain a noble metal complex solution; mixing the silicon source, template agent, noble metal complex solution, and water to obtain a mixed solution; transferring the mixed solution to a closed reactor for crystallization reaction, preferably at a crystallization reaction temperature of 170 °C and a reaction time of 72 h; and performing membrane separation and washing on the product to obtain the precursor of the noble metal supported catalyst Pd@S-1.

[0046] The preferred noble metal precursor of this application is selected from at least one of palladium chloride, palladium nitrate, chloroplatinic acid, platinum nitrate, rhodium chloride, rhodium nitrate, and hexaamminerhodium trichloride; the preferred ligand is selected from at least one of ethylenediamine, tetraethylenepentamine, pentaethylenehexamine, and triethanolamine; the preferred silicon source is selected from at least one of tetraethyl orthosilicate and silica sol; and the preferred template agent is selected from at least one of triethylamine, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide.

[0047] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below.

[0048] Example 1

[0049] Preparation of the noble metal supported precursor: 39 g palladium chloride, 65.8 g ethylenediamine and 1000 g water were mixed evenly to obtain a noble metal complex solution; 15184 g tetraethyl orthosilicate, 23715 g tetrapropylammonium hydroxide (25% aqueous solution), the noble metal complex solution and 27131 g water were mixed and stirred to obtain a mixed solution; the mixed solution was transferred to a 100 L closed reactor and stirred for 6 h, and then the reactor was sealed for crystallization reaction at 170 ℃ for 72 h. The product was separated by membrane separation and washing to obtain the precursor of the noble metal supported catalyst Pd@S-1.

[0050] First calcination: The Pd@S-1 precursor was placed in an air atmosphere and heated to 550°C at a heating rate of 5°C / min for 3 hours to complete the crystallization of the support and the removal of impurities and organic matter, thus obtaining the first calcination product.

[0051] Secondary calcination: Calcination parameters were optimized based on a kinetic model.

[0052] After testing, the initial proportion of noble metal elements after one calcination was 35.7%. Two calcination experiments were then conducted on the sample after the first calcination. In the first calcination experiment, the temperature was increased to 700℃ at a rate of 5℃ / min and calcined for 12 hours with an oxygen volume concentration of 10%. After calcination, the initial proportion of noble metal elements in the sample was found to be 10.2%. In the second calcination experiment, the temperature was increased to 750℃ at a rate of 5℃ / min and calcined for 12 hours with an oxygen volume concentration of 15%. After calcination, the initial proportion of noble metal elements in the sample was found to be 1.9%. Substituting the above experimental data into the kinetic equation and solving the simultaneous equations, E was calculated. a It is 74 kJ / mol, and the pre-exponential factor A is 9.9 × 10⁻⁶. -3 h -1 ·atm -1 Based on the conditions for complete oxidation (the proportion of noble metal elements ≤ 0.1%), a suitable set of calcination parameters was determined as follows: 800℃, calcination time 12h, and oxygen concentration 20%.

[0053] A second calcination was performed based on the optimized calcination parameters: the product from the first calcination was thoroughly ground to 100 mesh and placed in a calcination device with controllable oxygen partial pressure and flowing air supply. The temperature was raised to 800°C at a rate of 5°C / min and kept at this temperature for 12 hours in an atmosphere with an oxygen volume concentration of 20%, thus obtaining a noble metal supported catalyst.

[0054] Comparative Example 1

[0055] Small-batch synthesis of catalyst samples:

[0056] A noble metal complex solution was obtained by uniformly mixing 0.0392 g palladium chloride, 0.0658 g ethylenediamine, and 5 g water. A mixed solution was obtained by mixing 15.18 g tetraethyl orthosilicate, 23.71 g tetrapropylammonium hydroxide (25% aqueous solution), the noble metal complex solution, and 23.13 g water. The mixture was then transferred to a 100 mL sealed reactor for crystallization at 170 °C for 72 h. The product was subjected to membrane separation and washing to obtain the precursor of the noble metal supported catalyst Pd@S-1. The Pd@S-1 precursor was placed in air and calcined at 550 °C for 3 h at a heating rate of 5 °C / min to complete the crystallization of the support and the removal of impurities and organic matter, yielding the catalyst sample.

[0057] Comparative Example 2

[0058] Preparation of the noble metal supported precursor: 39 g palladium chloride, 65.8 g ethylenediamine and 1000 g water were mixed evenly to obtain a noble metal complex solution; 15184 g tetraethyl orthosilicate, 23715 g tetrapropylammonium hydroxide (25% aqueous solution), the noble metal complex solution and 27131 g water were mixed and stirred to obtain a mixed solution; the mixed solution was transferred to a 100 L closed reactor and stirred for 6 h, and then the reactor was sealed for crystallization reaction at 170 ℃ for 72 h. The product was separated by membrane separation and washed to obtain the precursor of the noble metal supported catalyst Pd@S-1.

[0059] First calcination: The Pd@S-1 precursor is placed in an air atmosphere and heated to 550°C at a heating rate of 5°C / min for 3 hours to complete the crystallization of the support and the removal of impurities and organic matter, thus obtaining the first calcination product, namely the noble metal supported catalyst.

[0060] Comparative Example 3

[0061] Preparation of the noble metal supported precursor: 39 g palladium chloride, 65.8 g ethylenediamine and 1000 g water were mixed evenly to obtain a noble metal complex solution; 15184 g tetraethyl orthosilicate, 23715 g tetrapropylammonium hydroxide (25% aqueous solution), the noble metal complex solution and 27131 g water were mixed and stirred to obtain a mixed solution; the mixed solution was transferred to a 100 L closed reactor and stirred for 6 h, and then the reactor was sealed for crystallization reaction at 170 ℃ for 72 h. The product was separated by membrane separation and washed to obtain the precursor of the noble metal supported catalyst Pd@S-1.

[0062] First calcination: The Pd@S-1 precursor was placed in an air atmosphere and heated to 550°C at a heating rate of 5°C / min for 3 hours to complete the crystallization of the support and the removal of impurities and organic matter, thus obtaining the first calcination product.

[0063] Secondary calcination: The product from the primary calcination is thoroughly ground to 100 mesh and placed in a calcination device with controllable oxygen partial pressure and flowing air supply. The temperature is raised to 600°C at a rate of 5°C / min and held at this temperature for 6 hours in an atmosphere with an oxygen volume concentration of 20% to obtain a noble metal supported catalyst.

[0064] Comparative Example 4

[0065] Preparation of the noble metal supported precursor: 39 g palladium chloride, 65.8 g ethylenediamine and 1000 g water were mixed evenly to obtain a noble metal complex solution; 15184 g tetraethyl orthosilicate, 23715 g tetrapropylammonium hydroxide (25% aqueous solution), the noble metal complex solution and 27131 g water were mixed and stirred to obtain a mixed solution; the mixed solution was transferred to a 100 L closed reactor and stirred for 6 h, and then the reactor was sealed for crystallization reaction at 170 ℃ for 72 h. The product was separated by membrane separation and washed to obtain the precursor of the noble metal supported catalyst Pd@S-1.

[0066] First calcination: The Pd@S-1 precursor was placed in an air atmosphere and heated to 550°C at a heating rate of 5°C / min for 3 hours to complete the crystallization of the support and the removal of impurities and organic matter, thus obtaining the first calcination product.

[0067] Secondary calcination: The product from the primary calcination is thoroughly ground to 100 mesh and placed in a calcination device with controllable oxygen partial pressure and flowing air supply. The temperature is raised to 800°C at a rate of 5°C / min and held at this temperature for 6 hours in an atmosphere with an oxygen volume concentration of 20% to obtain a noble metal supported catalyst.

[0068] Comparative Example 5

[0069] Preparation of the noble metal supported precursor: 39 g palladium chloride, 65.8 g ethylenediamine and 1000 g water were mixed evenly to obtain a noble metal complex solution; 15184 g tetraethyl orthosilicate, 23715 g tetrapropylammonium hydroxide (25% aqueous solution), the noble metal complex solution and 27131 g water were mixed and stirred to obtain a mixed solution; the mixed solution was transferred to a 100 L closed reactor and stirred for 6 h, and then the reactor was sealed for crystallization reaction at 170 ℃ for 72 h. The product was separated by membrane separation and washed to obtain the precursor of the noble metal supported catalyst Pd@S-1.

[0070] First calcination: The Pd@S-1 precursor was placed in an air atmosphere and heated to 550°C at a heating rate of 5°C / min for 3 hours to complete the crystallization of the support and the removal of impurities and organic matter, thus obtaining the first calcination product.

[0071] Secondary calcination: The product from the primary calcination is thoroughly ground to 100 mesh and placed in a calcination apparatus with controllable oxygen partial pressure and a flowing air supply. The temperature is increased to 800℃ at a rate of 5℃ / min and held at this temperature for 18 hours in an atmosphere with an oxygen volume concentration of 20% to obtain a noble metal supported catalyst.

[0072] The catalytic activity of the noble metal supported catalysts prepared in the above embodiments and comparative examples was tested using the following methods:

[0073] The catalysts prepared in each example and comparative example were evaluated for their catalytic activity using a simulated atmosphere evaluation system. The activity test atmosphere consisted of 1000 ppm CH4, 1000 ppm NO, 5000 ppm CO, 3500 ppm O2, 10 vol.% H2O, and 10 vol.% CO2, with N2 used as the balance gas and a space velocity of 50000 h⁻¹. -1 The activity test results are shown in Table 1, with some test results as follows: Figures 1-3 As shown.

[0074] Table 1

[0075]

[0076] The catalyst activity test results show that Example 1, prepared by the method of this invention, exhibits highly efficient three-way catalytic performance, comparable to Comparative Example 1 synthesized using a 100mL reactor. Comparative Examples 2-4, which did not optimize the secondary calcination parameters using a kinetic model, resulted in poorer catalytic performance. While Comparative Example 5, which also did not optimize the secondary calcination parameters using a kinetic model, achieved a three-way catalytic performance comparable to Example 1 by increasing the calcination time, this increased calcination time not only extended the production cycle but also increased energy consumption. Therefore, Example 1 simultaneously achieved optimal catalytic performance, lowest energy consumption, and shortest production cycle.

[0077] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the technical solutions of the embodiments of the present invention.

Claims

1. A process for the scaled-up synthesis of catalytic materials and the optimization of noble metal valence state control, characterized in that, Includes the following steps: A noble metal supported catalyst precursor was calcined once to obtain a calcined product. The product from the first calcination is subjected to a second calcination to obtain a noble metal supported catalyst; the calcination parameters for the second calcination are determined based on a kinetic model. The dynamic model is shown in the following equation: ； in[ M 0 ]0 represents the percentage of elemental components in the product of the first calcination at the initial stage of the second calcination; [ M 0 ] t Indicates the calcination time in the secondary calcination. t The percentage of elemental components in the noble metal supported catalysts described later; A Pre-exponential factor, unit is h -1 ·atm -n ; E a R is the activation energy for oxidation, expressed in J / mol; T is the gas constant; and T is the calcination temperature, expressed in K. t is the partial pressure of oxygen; n is the oxygen reaction order; t is the calcination time, in hours.

2. The process for scaled-up synthesis of catalytic materials and optimization of noble metal valence state control as described in claim 1, characterized in that, The first calcination of the noble metal supported catalyst precursor includes: calcining the noble metal supported catalyst precursor in an air atmosphere at 300-800℃.

3. The process for scaled-up synthesis of catalytic materials and optimization of noble metal valence state control as described in claim 1, characterized in that, The noble metal supported catalyst includes a support and a noble metal supported on the support.

4. The process for scaled-up synthesis of catalytic materials and optimization of noble metal valence state control as described in claim 3, characterized in that, The precious metal is selected from at least one of palladium, platinum, and rhodium.

5. The process for scaled-up synthesis of catalytic materials and optimization of noble metal valence state control as described in claim 3, characterized in that, The carrier is selected from at least one of molecular sieves, alumina, cerium oxide, and cerium-zirconium solid solutions.

6. The process for scaled-up synthesis of catalytic materials and optimization of noble metal valence state control as described in any one of claims 1-5, characterized in that, The noble metal supported catalyst precursor is prepared by the following method: mixing the noble metal precursor, ligand, and water to obtain a noble metal complex solution; mixing the silicon source, template agent, the noble metal complex solution, and water to obtain a mixed liquid; transferring the mixed liquid into a closed reactor for crystallization reaction to obtain the noble metal supported catalyst precursor.

7. The process for scaled-up synthesis of catalytic materials and optimization of noble metal valence state control as described in claim 6, characterized in that, The noble metal precursor is selected from at least one of palladium chloride, palladium nitrate, chloroplatinic acid, platinum nitrate, rhodium chloride, rhodium nitrate, and hexaamminerhodium trichloride.

8. The process for scaled-up synthesis of catalytic materials and optimization of noble metal valence state control as described in claim 6, characterized in that, The ligand is selected from at least one of ethylenediamine, tetraethylenepentamine, pentaethylenehexamine, and triethanolamine.

9. The process for scaled-up synthesis of catalytic materials and optimization of noble metal valence state control as described in claim 6, characterized in that, The silicon source is selected from at least one of tetraethyl orthosilicate and silica sol.

10. The process for scaled-up synthesis of catalytic materials and optimization of noble metal valence state control as described in claim 6, characterized in that, The template agent is selected from at least one of triethylamine, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide.

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