CN113289620A - Monoatomic ruthenium catalyst, preparation method and application - Google Patents
Monoatomic ruthenium catalyst, preparation method and application Download PDFInfo
- Publication number
- CN113289620A CN113289620A CN202110698029.1A CN202110698029A CN113289620A CN 113289620 A CN113289620 A CN 113289620A CN 202110698029 A CN202110698029 A CN 202110698029A CN 113289620 A CN113289620 A CN 113289620A
- Authority
- CN
- China
- Prior art keywords
- ruthenium
- rare earth
- catalyst
- nitrate
- earth oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/047—Decomposition of ammonia
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a single atom ruthenium catalyst, a preparation method and application thereof, wherein the catalyst comprises a mesoporous rare earth oxide carrier and noble metal ruthenium atoms limited in the mesoporous rare earth oxide carrier, and the invention also provides the preparation method of the catalyst, which comprises the following steps: providing a precursor mixed solution, and removing a solvent from the mixed solution to obtain a light yellow gel; calcining the obtained xerogel at high temperature, and removing the polymer template to obtain a powder material; the invention further discloses the application of the monatomic ruthenium catalyst in preparing hydrogen by decomposing ammonia through solid phase catalysis.
Description
Technical Field
The invention relates to a single-atom ruthenium catalyst material with adjustable load (0.1-6 wt%) and a preparation method thereof.
Background
In recent years, due to the overuse of fossil fuels, the development of new energy has been receiving much attention from governments and researchers of various countries. Of which hydrogen energy has gained widespread attention in its unique potential and advantages of development. Ammonia (NH)3) Has higher energy density, is easy to store and transport, and does not produce toxic byproducts such as CO and the like when decomposing and producing hydrogen. Therefore, the ammonia decomposition on-line hydrogen production technology has wide application prospect and important research value. The temperature of the ammonia decomposition reaction is generally above 400 ℃, and extremely high requirements are provided for the sintering resistance stability of the catalyst. There is a need to develop a high-efficiency catalyst to achieve high activity and stability of ammonia decomposition. In recent years, monatomic catalytic materials have exhibited excellent catalytic performance in many reactions due to their 100% metal atom utilization efficiency and highly dispersed active sites at the atomic level. The use of such emerging catalytic materials in place of traditional metal particle catalysts has become a great trend in the development of many future catalytic industries. However, the lack of the preparation process results in a severe deficiency in the metal monatomic loading of the material itself, and thus the material itselfThe amount is greatly limited, and reports on such single-atom catalytic materials and methods for preparing the same are still less.
In view of the above, there is a need to provide a noble metal monatomic catalyst material with a tunable loading and a method for preparing the same.
Disclosure of Invention
The invention discloses a single-atom ruthenium catalyst material, which comprises a mesoporous rare earth oxide carrier and noble metal ruthenium atoms limited in the mesoporous rare earth oxide carrier, wherein the loading amount of ruthenium based on the total weight of the catalyst is 0.1-6 wt%, and in the mesoporous rare earth oxide carrier, rare earth oxide is selected from La2O3、Pr2O3、Nd2O3、Sm2O3、Eu2O3、Gd2O3Any one of, two of or a mixture of more of, the metallic ruthenium is anchored in the mesoporous mixed rare earth oxide in the form of a single atom.
Further, the mesoporous rare earth oxide carrier has an average pore size of 1-20nm, preferably 5-10nm, and is preferably fluorite structured cerium oxide or a cerium oxide-rare earth oxide mixture.
The catalyst is preferably Ru1-CeO2、Ru1-Eu2Ce2O7、Ru1-La2Ce2O7、Ru1-Pr2Ce2O7、Ru1-Nd2Ce2O7、Ru1-Sm2Ce2O7Or Ru1-Gd2Ce2O7Wherein, the metallic ruthenium is anchored in the mesoporous mixed rare earth oxide in the form of single atom; the ruthenium loading was 0.1 to 6 wt% based on the total weight of the catalyst.
Ruthenium atoms in the catalyst are combined with the mixed rare earth oxide carrier through O coordination.
The invention discloses a monoatomic ruthenium catalyst material and a preparation method thereof, and the preparation method comprises the following steps:
s1: mixing soluble metal salt and a solvent to form a solution, and adding a template agent and a gel production agent;
s2: desolventizing the precursor solution to obtain xerogel;
s3: calcining at high temperature to obtain catalyst powder;
in step S1, the soluble ruthenium salt and the soluble rare earth salt of the soluble metal salt include an inorganic salt, an organic acid salt or a complex of soluble ruthenium, and an inorganic salt or an organic acid salt of rare earth metal. The soluble ruthenium salt is preferably nitrosyl ruthenium nitrate or ruthenium trichloride; the soluble rare earth salt is selected from any one or a mixture of two of cerium nitrate, europium nitrate, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, samarium nitrate and gadolinium nitrate; the gel forming agent is selected from citric acid or ethylene glycol; the template is selected from
Or
A triblock polymer. The solvent is dilute hydrochloric acid or dilute nitric acid with the concentration of 0.5-2mol/L, or C1-C4Alcohol compounds, preferably ethanol.
The total concentration of the metal precursor is 0.5-1 mol/L. According to different designed single atom ruthenium load, adding different amount of ruthenium salt.
In step S2, the solvent is removed by heating evaporation, vacuum heating evaporation, or freeze drying, such as heating the precursor solution to the solvent evaporation temperature, and removing the solvent to obtain a light yellow xerogel.
In step S3, the high-temperature calcination temperature is 400-800 ℃, the calcination atmosphere is an oxygen-containing atmosphere, such as air or oxygen, and the calcination time is preferably 4-8 hours. And (3) calcining the obtained xerogel in air at high temperature, and removing the polymer template to obtain catalyst powder.
The single-atom ruthenium catalyst material with adjustable load (0.1-6 wt%) is in a solid powder state. In the catalyst material, the mass percentage of the noble metal ruthenium is 0.1-6%.
The invention also protects the application of the catalyst or the catalyst prepared by the method in catalyzing ammonia decomposition to prepare hydrogen.
The invention further protects a gas-solid phase catalytic reaction for ammonia decomposition, wherein in the gas-solid phase catalytic reaction, the monatomic ruthenium catalyst material is used as a catalyst to catalytically decompose ammonia to prepare hydrogen.
Advantageous effects
The invention provides a load-adjustable monoatomic ruthenium catalyst material and a preparation method thereof, which uses a triblock polymer P123 as a template agent and citric acid as a gel generating agent, removes the template agent after high-temperature calcination, and synchronously generates the monoatomic ruthenium catalyst material limited in a mesoporous mixed rare earth oxide carrier. The method has the advantages of simple operation, flexible and adjustable components, enlargeable yield, low raw material cost, environmental protection, good repeatability and the like. In addition, the material fully utilizes the synergistic catalytic advantages of the noble metal single atom sites and the mixed rare earth oxide carrier, and a plurality of solid acid and alkali sites are constructed through rich oxygen vacancies on the surface of the rare earth oxide. Compared with the catalyst produced by the traditional impregnation method, the monatomic catalyst provided by the invention has excellent catalytic activity and structural stability, and has extremely high basic research value and industrial application prospect.
Drawings
FIG. 1: example 1 mesoporous mixed rare earth oxide (CeO)2-Eu2O3) High-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) photograph of limited-domain monoatomic ruthenium catalyst material (ruthenium content 5.7 wt.%)
FIG. 2: EXAMPLE 1 mesoporous mixed rare earth oxide (CeO)2-Eu2O3) Spherical aberration corrected high angle annular dark field scanning transmission electron microscopy (AC-HAADF-STEM) photographs of the domain-limited monatomic ruthenium catalyst material (ruthenium content 5.7 wt%).
FIG. 3: example 1 mesoporous mixed rare earth oxides (CeO) at different loadings (ruthenium content 1.5-5.7 wt%)2-Eu2O3) K-edge Fourier transform extended absorption fine structure (EXAFS) spectrum of the limited-domain single-atom ruthenium catalyst material.
FIG. 4: mesoporous with different loading (ruthenium content 1.5-5.7 wt%) in example 1Mixed rare earth oxide (CeO)2-Eu2O3) A catalytic performance diagram of a limited-domain monoatomic ruthenium catalyst material for ammonia decomposition hydrogen production.
FIG. 5 shows the X-ray powder diffraction (XRD) results of the mesoporous mixed rare earth oxide supported monatomic ruthenium catalyst materials of examples 1, 3 to 6 according to the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Wherein
HAADF-STEM: high-angle annular dark field scanning transmission electron microscope
AC-HAADF-STEM: spherical aberration correction high-angle annular dark field scanning transmission electron microscope
EXAFS: x-ray absorption fine structure spectrum
Hereinafter, the method for preparing the monatomic ruthenium catalyst material according to the present invention will be described in detail with reference to specific examples.
Example 1Ru1-Eu2Ce2O7
A. Preparation of precursor mixture
a. Dissolving 0.5-0.7g of cerium nitrate, 0.03-0.1g of ruthenium nitrosyl nitrate and 0.7g of europium nitrate in 30mL of ethanol, and stirring for 5min until the cerium nitrate, the ruthenium nitrosyl nitrate and the europium nitrate are completely dissolved to form a precursor solution.
(Note: in 1.5% Ru1-Eu2Ce2O7During preparation, 0.66g of cerium nitrate, 0.03g of ruthenium nitrosyl nitrate and 0.7g of europium nitrate are added; at 2.7% Ru1-Eu2Ce2O7During preparation, 0.63g of cerium nitrate, 0.05g of ruthenium nitrosyl nitrate and 0.7g of europium nitrate are added; at 5.7% Ru1-Eu2Ce2O7During the preparation, 0.56g of cerium nitrate, 0.1g of ruthenium nitrosyl nitrate and 0.7g of europium nitrate are added
b. Adding 1g of the precursor solution
And stirring the triblock polymer and 0.5g of citric acid for 1 hour until the triblock polymer and the citric acid are completely dissolved to form a precursor mixed solution.
B.Ru1Synthesis of mesoporous mixed rare earth oxide
a. The precursor mixture is dried for 24h at 90 ℃ to form light yellow xerogel.
b. The pale yellow xerogel was heated to 400 ℃ at a rate of 10 ℃/min and then treated at 400 ℃ for 4 hours.
Three catalysts with different Ru loadings of 1.5%, 2.7% and 5.7% were prepared according to the same method, wherein a high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) photograph of a monoatomic Ru catalyst with a loading of 5.7% is shown in FIG. 1; a high-angle annular dark field scanning transmission electron microscope (AC-HAADF-STEM) photo corrected by spherical aberration is shown in FIG. 2, and a bright spot in FIG. 2 is a Ru monoatomic spot; the K-edge Fourier transform extended absorption fine structure (EXAFS) spectrum of Ru is shown in figure 3, and the catalytic performance of hydrogen production by ammonia decomposition is shown in figure 4.
Example 21.5% Ru1-La2Ce2O7
A. Preparation of precursor mixture
a. Dissolving 0.6g of cerium nitrate, 0.03g of ruthenium nitrosyl nitrate and 0.7g of lanthanum nitrate in 30mL of ethanol, and stirring for 5min until the cerium nitrate, the ruthenium nitrosyl nitrate and the lanthanum nitrate are completely dissolved to form a precursor solution.
b. Adding 1g of the precursor solution
And stirring the triblock polymer and 0.5g of citric acid for 1 hour until the triblock polymer and the citric acid are completely dissolved to form a precursor mixed solution.
B.Ru1Synthesis of mesoporous mixed rare earth oxide
a. The precursor mixture is dried for 24h at 90 ℃ to form light yellow xerogel.
b. The pale yellow xerogel was heated to 400 ℃ at a rate of 10 ℃/min and then treated at 400 ℃ for 4 hours.
Example 31.5% Ru1-Pr2Ce2O7
A. Preparation of precursor mixture
a. 0.6g of cerium nitrate, 0.03g of ruthenium nitrosyl nitrate and 0.7g of praseodymium nitrate are dissolved in 30mL of ethanol, and stirred for 5min until the cerium nitrate, the ruthenium nitrosyl nitrate and the praseodymium nitrate are completely dissolved to form a precursor solution.
b. Adding 1g of the precursor solution
And stirring the triblock polymer and 0.5g of citric acid for 1 hour until the triblock polymer and the citric acid are completely dissolved to form a precursor mixed solution.
B.Ru1Synthesis of mesoporous mixed rare earth oxide
a. The precursor mixture is dried for 24h at 90 ℃ to form light yellow xerogel.
b. The pale yellow xerogel was heated to 400 ℃ at a rate of 10 ℃/min and then treated at 400 ℃ for 4 hours.
Example 41.5% Ru1-Nd2Ce2O7
A. Preparation of precursor mixture
a. Dissolving 0.6g of cerium nitrate, 0.03g of ruthenium nitrosyl nitrate and 0.7g of neodymium nitrate in 30mL of ethanol, and stirring for 5min until the cerium nitrate, the ruthenium nitrosyl nitrate and the neodymium nitrate are completely dissolved to form a precursor solution.
b. Adding 1g of the precursor solution
And stirring the triblock polymer and 0.5g of citric acid for 1 hour until the triblock polymer and the citric acid are completely dissolved to form a precursor mixed solution.
B.Ru1Synthesis of mesoporous mixed rare earth oxide
a. The precursor mixture is dried for 24h at 90 ℃ to form light yellow xerogel.
b. The pale yellow xerogel was heated to 400 ℃ at a rate of 10 ℃/min and then treated at 400 ℃ for 4 hours.
Example 51.5% Ru1-Sm2Ce2O7
A. Preparation of precursor mixture
a. Dissolving 0.6g of cerium nitrate, 0.03g of ruthenium nitrosyl nitrate and 0.7g of samarium nitrate in 30mL of ethanol, and stirring for 5min until the cerium nitrate, the ruthenium nitrosyl nitrate and the samarium nitrate are completely dissolved to form a precursor solution.
b. Adding 1g of the precursor solution
And stirring the triblock polymer and 0.5g of citric acid for 1 hour until the triblock polymer and the citric acid are completely dissolved to form a precursor mixed solution.
B.Ru1Synthesis of mesoporous mixed rare earth oxide
a. The precursor mixture is dried for 24h at 90 ℃ to form light yellow xerogel.
b. The pale yellow xerogel was heated to 400 ℃ at a rate of 10 ℃/min and then treated at 400 ℃ for 4 hours.
Example 61.5% Ru1-Gd2Ce2O7
A. Preparation of precursor mixture
a. 0.6g of cerium nitrate, 0.03g of ruthenium nitrosyl nitrate and 0.7g of gadolinium nitrate are dissolved in 30mL of ethanol, and stirred for 5min until the cerium nitrate, the ruthenium nitrosyl nitrate and the gadolinium nitrate are completely dissolved to form a precursor solution.
b. Adding 1g of the precursor solution
And stirring the triblock polymer and 0.5g of citric acid for 1 hour until the triblock polymer and the citric acid are completely dissolved to form a precursor mixed solution.
B.Ru1Synthesis of mesoporous mixed rare earth oxide
a. The precursor mixture is dried for 24h at 90 ℃ to form light yellow xerogel.
b. The pale yellow xerogel was heated to 400 ℃ at a rate of 10 ℃/min and then treated at 400 ℃ for 4 hours.
Example 71.5% Ru1-CeO2
A. Preparation of precursor mixture
a. Dissolving 0.13g of cerium nitrate and 0.03g of ruthenium nitrosyl nitrate in 30mL of ethanol, and stirring for 5min until the cerium nitrate and the ruthenium nitrosyl nitrate are completely dissolved to form a precursor solution.
b. Adding 1g of the precursor solution
And stirring the triblock polymer and 0.5g of citric acid for 1 hour until the triblock polymer and the citric acid are completely dissolved to form a precursor mixed solution.
B.Ru1Synthesis of mesoporous rare earth oxide
a. The precursor mixture is dried for 24h at 90 ℃ to form light yellow xerogel.
b. The pale yellow xerogel was heated to 400 ℃ at a rate of 10 ℃/min and then treated at 400 ℃ for 4 hours.
Comparative example 81.5% Ru-CeO2IMPA synthesis of ruthenium-free mesoporous rare earth oxide
a. Dissolving 1.2g of cerium nitrate in 30mL of ethanol, and stirring for 5min until the cerium nitrate is completely dissolved to form a precursor solution.
b. Adding 1g of the precursor solution
And stirring the triblock polymer and 0.5g of citric acid for 1 hour until the triblock polymer and the citric acid are completely dissolved to form a precursor mixed solution.
c. The precursor mixture is dried for 24h at 90 ℃ to form light yellow xerogel.
d. Heating the light yellow xerogel to 400 ℃ at the speed of 10 ℃/min, and then processing the light yellow xerogel for 4 hours at 400 ℃ to obtain mesoporous CeO2。
B. Synthesis of reference Ru-mesoporous rare earth oxide
a. A certain amount of mesoporous CeO2And the ruthenium nitrosyl nitrate is dispersed in 5mL of deionized water, and the loading capacity of Ru is 1.5 percent of mass fraction. Heating to 60 deg.C, and stirring to dry to obtain black powder.
b. The black powder was heated to 400 ℃ at a rate of 10 ℃/min and then treated at 400 ℃ for 4 hours. Obtaining 1.5% Ru-CeO loaded by Impregnation (IMP)2Reference catalyst.
Comparative example 96% Ru-CeO2
A. Synthesis of ruthenium-free mesoporous rare earth oxide
a. Dissolving 1.2g of cerium nitrate in 30mL of ethanol, and stirring for 5min until the cerium nitrate is completely dissolved to form a precursor solution.
b. Adding 1g of the precursor solution
And stirring the triblock polymer and 0.5g of citric acid for 1 hour until the triblock polymer and the citric acid are completely dissolved to form a precursor mixed solution.
c. The precursor mixture is dried for 24h at 90 ℃ to form light yellow xerogel.
d. Heating the light yellow xerogel to 400 ℃ at the speed of 10 ℃/min, and then processing the light yellow xerogel for 4 hours at 400 ℃ to obtain mesoporous CeO2。
B. Synthesis of reference Ru-mesoporous rare earth oxide
a. A certain amount of mesoporous CeO2And the ruthenium nitrate and nitrosyl nitrate are dispersed in 5mL of deionized water, and the loading capacity of Ru is 6 percent by mass. Heating to 60 deg.C, and stirring to dry to obtain black powder.
b. The black powder was heated to 400 ℃ at a rate of 10 ℃/min and then treated at 400 ℃ for 4 hours. Obtaining 6 percent Ru-CeO loaded by an Impregnation Method (IMP)2Reference catalyst.
An X-ray powder diffraction (XRD) photograph of the monoatomic ruthenium catalyst material with a mass loading of 1.5% is shown in fig. 5.
Application test example:
the ammonia decomposition activity test was performed on a fixed bed reactor. Firstly, 50mg (20-40 meshes) of catalyst to be detected is filled in a quartz reaction tube, and pure ammonia gas is introduced. Heating to 550 ℃ at a heating rate of 10 ℃/min, wherein the catalytic activity of the catalyst at 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ and 550 ℃ is detected, and each temperature point is kept constant for 1 h. The reaction space velocity is 22000cm3 g–1h–1. The activity test of each catalyst was performed twice in succession, the first test was taken as the activation process, and the results of the second test were taken for analysis. Real-time composition of gas by on-line gas chromatography (GC 9160)Detection (equipped with TCD detector, column Poraprak Q). And calculating the reaction conversion rate by using the integrated nitrogen peak area and ammonia peak area. The correlation results are shown in the following formula:
NH3 conversion(％)＝(S(o)N2*2)/S(i)NH3×100
S(o)N2and S (i)NH3The catalytic performance of the monatomic ruthenium catalyst prepared in the example on ammonia decomposition hydrogen production is shown in table 1, representing the peak areas of nitrogen gas and ammonia gas, respectively, which are generated by the reaction.
Table 1 application test data sheet
EX stands for example, CEX for comparative example
The test result shows that:
the monatomic ruthenium catalyst material prepared by the method has the hydrogen production effect by catalyzing ammonia decomposition far better than that of the catalyst material prepared by the traditional liquid phase impregnation method under the condition of the same ruthenium content. The mixed oxide carrier formed after the rare earth oxide is added has higher catalytic effect than the activity of the traditional catalyst by an impregnation method under the condition of the same ruthenium loading. At high temperature, rich in H2In the harsh reaction atmosphere, ruthenium in the catalyst material prepared by the invention can be always dispersed in a monoatomic form, and the catalyst material has excellent stability and sintering resistance.
In addition, other modifications within the spirit of the invention will occur to those skilled in the art, and it is understood that such modifications are included within the scope of the invention as claimed.
Claims (10)
1. A single-atom ruthenium catalyst comprises a mesoporous rare earth oxide carrier and noble metal ruthenium atoms confined in the mesoporous rare earth oxide carrier, wherein the catalyst is based onThe loading amount of ruthenium in the total weight of the catalyst is 0.1-6 wt%, and in the mesoporous rare earth oxide carrier, the rare earth oxide is selected from La2O3、Pr2O3、Nd2O3、Sm2O3、Eu2O3、Gd2O3Any one of, two of or a mixture of more of, the metallic ruthenium is anchored in the mesoporous mixed rare earth oxide in the form of a single atom.
2. The catalyst according to claim 1, wherein the mesoporous rare earth oxide support has an average pore size of 1-20nm, preferably 5-10nm, preferably a fluorite structured cerium oxide or cerium oxide-rare earth oxide mixture.
3. The catalyst of claim 1 or 2, which is Ru1-CeO2、Ru1-Eu2Ce2O7、Ru1-La2Ce2O7、Ru1-Pr2Ce2O7、Ru1-Nd2Ce2O7、Ru1-Sm2Ce2O7Or Ru1-Gd2Ce2O7Wherein the metal ruthenium is anchored in the mesoporous mixed rare earth oxide in a form of single atom, and the loading amount of the ruthenium is 0.1-6 wt% based on the total weight of the catalyst.
4. A preparation method of a monoatomic ruthenium catalyst comprises the following steps:
s1: mixing soluble metal salt and a solvent to form a solution, and adding a template agent and a gel production agent;
s2: desolventizing the precursor solution to obtain xerogel;
s3: calcining at high temperature to obtain catalyst powder,
wherein the soluble metal salt comprises soluble ruthenium salt and soluble rare earth salt, and comprises inorganic salt, organic acid salt or complex of soluble ruthenium, and inorganic salt or organic acid salt of soluble rare earth metal(ii) a The gel forming agent is selected from citric acid or ethylene glycol; the template is selected from
P123 or
F127 triblock polymer; the solvent is dilute hydrochloric acid or dilute nitric acid or C with the concentration of 0.5-2mol/L1-C4Alcohol compounds, preferably ethanol.
5. The production method according to claim 4, wherein the soluble ruthenium salt is preferably ruthenium nitrosylnitrate or ruthenium trichloride; the soluble rare earth salt is selected from any one or a mixture of two of cerium nitrate, europium nitrate, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, samarium nitrate and gadolinium nitrate; the solvent is ethanol.
6. The preparation method according to claim 4 or 5, wherein the total concentration of the metal precursor is 0.5 to 1mol/L, and different amounts of ruthenium salt are added according to different designed loading amounts of monoatomic ruthenium.
7. The method according to any one of claims 4 to 6, wherein the solvent is removed by a method selected from the group consisting of heating evaporation, vacuum heating and freeze-drying evaporation.
8. The preparation method according to any one of claims 4 to 7, wherein the high-temperature calcination temperature is 400-800 ℃, the calcination atmosphere is an oxygen-containing atmosphere, preferably air or oxygen, and the calcination time is preferably 4-8 hours.
9. Use of a catalyst according to any one of claims 1 to 3 for catalyzing the decomposition of ammonia to produce hydrogen.
10. A method for decomposing ammonia to produce hydrogen by catalytically decomposing ammonia using the monoatomic ruthenium catalyst according to any one of claims 1 to 3 as a solid-phase catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110698029.1A CN113289620A (en) | 2021-06-23 | 2021-06-23 | Monoatomic ruthenium catalyst, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110698029.1A CN113289620A (en) | 2021-06-23 | 2021-06-23 | Monoatomic ruthenium catalyst, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113289620A true CN113289620A (en) | 2021-08-24 |
Family
ID=77329399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110698029.1A Pending CN113289620A (en) | 2021-06-23 | 2021-06-23 | Monoatomic ruthenium catalyst, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113289620A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114917926A (en) * | 2022-04-24 | 2022-08-19 | 湖南大学 | LDH catalyst loaded with monoatomic ruthenium, preparation method thereof and application thereof in pathogen killing |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622227A (en) * | 2016-12-29 | 2017-05-10 | 天津大学 | Preparation method of monoatomic catalyst for indoor air purification |
| CN109954493A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | The rare-earth oxide supported ruthenium catalyst of preparing hydrogen by ammonia decomposition and preparation and application |
| CN110508278A (en) * | 2019-08-30 | 2019-11-29 | 浙江工业大学 | A kind of monatomic Pd/ mesoporous alumina catalyst in original position and the preparation method and application thereof |
| CN111036201A (en) * | 2019-12-04 | 2020-04-21 | 北京氦舶科技有限责任公司 | Supported monatomic Pt catalyst and preparation method and application thereof |
| CN111939907A (en) * | 2020-09-21 | 2020-11-17 | 浙江工业大学 | Catalyst for low-temperature ammonia decomposition hydrogen production and preparation method and application thereof |
| US20210016256A1 (en) * | 2019-07-19 | 2021-01-21 | Jingyue Liu | Functional nanoscale metal oxides for stable metal single atom and cluster catalysts |
| CN112774676A (en) * | 2019-11-11 | 2021-05-11 | 中国科学院大连化学物理研究所 | Rare earth oxide supported ruthenium catalyst and preparation method and application thereof |
-
2021
- 2021-06-23 CN CN202110698029.1A patent/CN113289620A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622227A (en) * | 2016-12-29 | 2017-05-10 | 天津大学 | Preparation method of monoatomic catalyst for indoor air purification |
| CN109954493A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | The rare-earth oxide supported ruthenium catalyst of preparing hydrogen by ammonia decomposition and preparation and application |
| US20210016256A1 (en) * | 2019-07-19 | 2021-01-21 | Jingyue Liu | Functional nanoscale metal oxides for stable metal single atom and cluster catalysts |
| CN110508278A (en) * | 2019-08-30 | 2019-11-29 | 浙江工业大学 | A kind of monatomic Pd/ mesoporous alumina catalyst in original position and the preparation method and application thereof |
| CN112774676A (en) * | 2019-11-11 | 2021-05-11 | 中国科学院大连化学物理研究所 | Rare earth oxide supported ruthenium catalyst and preparation method and application thereof |
| CN111036201A (en) * | 2019-12-04 | 2020-04-21 | 北京氦舶科技有限责任公司 | Supported monatomic Pt catalyst and preparation method and application thereof |
| CN111939907A (en) * | 2020-09-21 | 2020-11-17 | 浙江工业大学 | Catalyst for low-temperature ammonia decomposition hydrogen production and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| HAIDI XU ET AL.: "Entropy-stabilized single-atom Pd catalysts via high-entropy fluorite oxide supports" * |
| 中国科学技术协会, 北京：中国科学技术出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114917926A (en) * | 2022-04-24 | 2022-08-19 | 湖南大学 | LDH catalyst loaded with monoatomic ruthenium, preparation method thereof and application thereof in pathogen killing |
| CN114917926B (en) * | 2022-04-24 | 2023-10-20 | 湖南大学 | LDH catalyst loaded with monoatomic ruthenium, preparation method thereof and application thereof in pathogen disinfection |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109746022B (en) | Preparation method and use method of high-dispersion copper-zinc catalyst for carbon dioxide reduction | |
| CN112121863B (en) | Catalyst for catalytic transfer hydrogenation and preparation method and application thereof | |
| CN112108148A (en) | Supported copper-based catalyst for hydrogen production by methanol steam reforming, and preparation method and application thereof | |
| JP2022114919A (en) | Ammonia decomposition catalyst and ammonia decomposition method using the same | |
| CN113856730B (en) | Copper monoatomic material, preparation method thereof and photocatalytic CO (carbon monoxide) 2 Application in reduction | |
| CN113351251A (en) | Core-shell catalyst, preparation method and application thereof | |
| CN112023934B (en) | Preparation method of copper-indium bimetallic monatomic catalyst | |
| CN111939907A (en) | Catalyst for low-temperature ammonia decomposition hydrogen production and preparation method and application thereof | |
| CN111454462A (en) | Preparation method of Zn-Cu-ZIF bimetal organic framework compound | |
| CN111229213A (en) | Preparation method of ruthenium-based catalyst | |
| CN111686774A (en) | High-stability monatomic platinum-based catalytic material, preparation method and application in purification of oxygen-containing volatile hydrocarbon | |
| CN113289620A (en) | Monoatomic ruthenium catalyst, preparation method and application | |
| CN113368861B (en) | Catalyst for synthesizing methanol by carbon dioxide hydrogenation and preparation method and application thereof | |
| CN113145122B (en) | Composite metal oxide catalyst, preparation method thereof and application thereof in catalyzing direct decomposition of nitrogen oxide | |
| CN104645983A (en) | Catalyst for cycling gas purification in process for producing glyoxal by air oxidation of ethylene glycol as well as preparation method and application thereof | |
| CN111167443A (en) | Novel ruthenium-based catalyst and preparation method and application thereof | |
| CN110548545A (en) | Application of titanium-based metal organic framework material in photocatalytic nitrogen fixation | |
| Rattan et al. | Effect of preparation methods on Al2O3 supported CuO-CeO2-ZrO2 catalysts for CO oxidation | |
| CN112892570B (en) | Hierarchical pore Co-N-C composite material and preparation method and application thereof | |
| CN105642290A (en) | Preparation method of catalyst for reforming of methane and carbon dioxide to prepare syngas | |
| CN112921342B (en) | CeO loaded2Hollow MnCo of nanoparticles2O4Preparation method of catalyst, obtained material and application | |
| CN115646510A (en) | Catalyst for CO selective oxidation reaction and preparation method thereof | |
| CN115155582A (en) | Active carbon-loaded methanol reforming hydrogen production catalyst and preparation method and application thereof | |
| JPH1099694A (en) | Photocatalyst and its preparation | |
| CN113398968A (en) | MOF-derived TiO2Porous g-C3N4Composite photocatalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |