Porous sodalite electronization and preparation method thereof, and catalyst

Abstract

The application discloses a kind of porous chabazite electronic and preparation method thereof, catalyst, the porous chabazite electronic exists in the form of Na6M2 [Al6Si6O 24 ](e ‑ )2, wherein electron is as one kind of anion of the porous chabazite electronic, M is alkali metal or alkaline earth metal.Method includes: providing the porous Na6 [Al6Si6O 24 ]·8H2O;In vacuum environment, the first calcination treatment is carried out to the porous Na6 [Al6Si6O 24 ]·8H2O, obtains Na6 [Al6Si6O 24 ];Alkali metal or alkaline earth metal M is deposited on the Na6 [Al6Si6O 24 ], obtains the porous chabazite electronic.The chabazite electronic provided by the application is porous structure, fills the blank of electronic in the prior art without porous structure.Because of having porous structure, can be used as the carrier of supported catalyst, suitable for a variety of catalytic hydrogenation reaction, electron anion in carrier has great promoting effect to reaction performance.Preparation method is simple, suitable for large-scale production, suitable for most loading methods to carry out catalyst loading, suitable for a variety of catalytic hydrogenation reaction.

Description

Technical Field

[0001] This invention relates to the field of catalyst preparation technology, and in particular to a porous sodalite electron compound, its preparation method, and a catalyst. Background Technology

[0002] Electron compounds, first discovered and named by James L. Dye, are a special type of compound in which some electrons exist as anions, attracting widespread attention. Because electron anions are typically highly reactive and can be substituted by other anions, such as H-, combined with their low work function, they exhibit a unique activation ability towards H. Currently, there are no commonly used porous materials made from electron compounds.

[0003] Therefore, the existing technology still needs further improvement and enhancement. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the present invention provides a porous sodalite electron compound, its preparation method and catalyst, aiming to solve the problem that existing electron compounds lack porous materials.

[0005] The technical solution adopted by the present invention to solve the above-mentioned technical problems is as follows:

[0006] In a first aspect, a porous sodalite electron compound, wherein the porous sodalite electron compound is in the form of Na6M2[Al6Si6O] 24 ](e - It exists in the form of )2, wherein electrons are an anion of the porous sodalite electron compound, and M is an alkali metal or an alkaline earth metal.

[0007] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0008] As a preferred technical solution, the porous sodalite electron compound, wherein the porous sodalite electron compound is Na8[Al6Si6O] 24 ]2e - It exists in the form of.

[0009] Secondly, a method for preparing the porous sodalite electron compound described above, comprising:

[0010] Provides porous Na6[Al6Si6O] 24 ·8H2O;

[0011] In a vacuum environment, the porous Na6[Al6Si6O] was subjected to... 24Na6[Al6Si6O24]·8H2O is obtained by a first calcination treatment. 24 ];

[0012] An alkali metal or an alkaline earth metal M is deposited on the Na6[Al6Si6O 24 ]·8H2O to obtain the porous sodalite electronide.

[0013] As a preferred technical solution, the preparation method of the porous sodalite electronide, wherein the preparation method of the porous Na6[Al6Si6O 24 ]·8H2O comprises:

[0014] Sodium aluminate, sodium silicate and a template agent are mixed to obtain a mixed solution;

[0015] The mixed solution is subjected to a hydrothermal treatment to obtain a mixture of the template agent and Na8[Al6Si6O 24 ](OH)2·nH2O;

[0016] The mixture of the template agent and Na8[Al6Si6O 24 ](OH)2·nH2O is subjected to an extraction treatment to obtain a mixture of Na6[Al6Si6O 24 ]·8H2O and the template agent;

[0017] The mixture is subjected to a second calcination treatment to obtain the porous Na6[Al6Si6O 24 ]·8H2O.

[0018] As a preferred technical solution, the preparation method of the porous sodalite electronide, wherein the template agent is selected from any one or more of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer and polypropylene glycol-ethylene oxide adduct.

[0019] As a preferred technical solution, the preparation method of the porous sodalite electronide, wherein the molar ratio of the sodium aluminate to the sodium silicate is 1:0.7-1.3.

[0020] As a preferred technical solution, the preparation method of the porous sodalite electronide, wherein the temperature of the first calcination treatment is greater than 500°C; and the temperature of the second calcination treatment is greater than 500°C.

[0021] As a preferred technical solution, the preparation method of the porous sodalite electronide, wherein the alkali metal M or the alkaline earth metal is selected from any one of Li, Na, K, Mg, Ca and Sr.

[0022] In a third aspect, a catalyst comprises: a catalyst carrier and a transition metal supported on the catalyst carrier; the catalyst carrier is the porous chabazite electronide or the porous chabazite electronide obtained by the preparation method.

[0023] In a fourth aspect, the catalyst of the third aspect is applied in catalytic hydrogenation reaction.

[0024] Beneficial effects: compared with the prior art, the chabazite electronide provided by the application has a porous structure, which fills the gap of the electronide without a porous structure in the prior art. Due to the porous structure, the chabazite electronide can be used as a carrier of a supported catalyst and is suitable for various catalytic hydrogenation reactions. The electron anion in the carrier has a great promoting effect on the reaction performance. BRIEF DESCRIPTION OF DRAWINGS

[0025] Fig. 1 The electronide synthesized in Example 1 of the application with Na8[Al6Si6O 24 ](e - )2 as an example is a general electronide before adding a template agent and a porous electronide after adding the template agent.

[0026] Fig. 2 The crystal structure of the porous electronide synthesized in Example 1 of the application with Na8[Al6Si6O 24 ](e - )2 as an example changes slightly with the addition of a template agent.

[0027] Fig. 3 The porous characterization of the porous electronide synthesized in Example 1 of the application with Na8[Al6Si6O 24 ](e - )2 as an example shows that the pore volume is about 0.137476 cm3 / g.

[0028] Fig. 4 The electron spin resonance test of the porous electronide synthesized in Example 1 of the application with Na8[Al6Si6O 24 ](e - )2 as an example shows that the electronide has the characteristics of an electron anion.

[0029] Fig. 5 The porous electronide synthesized in Example 2 of the application with Na8[Al6Si6O 24 ](e - )2 as an example.

[0030] Fig. 6 The porous electronide synthesized in Example 2 of the application with Na8[Al6Si6O 24 ](e -Figure 2 is a chart showing the comparison of the performance of a synthesized porous sodalite electronide as an example with a conventional non-electronide catalyst supported with Ru as a catalyst for synthesizing ammonia. DETAILED DESCRIPTION

[0031] The present application provides a porous sodalite electronide and a preparation method thereof, and a catalyst. To make the purpose, technical solutions and effects of the present application clearer and more explicit, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and do not limit the present application.

[0032] In addition, the features, operations or characteristics described in the specification can be combined in any appropriate manner to form various embodiments. Meanwhile, the steps or actions in the method description can also be sequentially changed or adjusted in a manner that can be obviously seen by those skilled in the art. Therefore, the various sequences in the specification and the drawings are only for the purpose of clearly describing a certain embodiment and do not mean that the sequence is necessary. Unless otherwise stated, the sequence of some steps must be followed. The serial numbers of the components in this paper, such as "first", "second", etc., are only used to distinguish the described objects and do not have any sequence or technical meaning.

[0033] The present application provides a porous sodalite electronide, which exists in the form of Na6M2[Al6Si6O 24 ](e - )2, wherein the electron is a kind of anion of the porous sodalite electronide, and M is an alkali metal or an alkaline earth metal. The alkali metal or the alkaline earth metal can be lithium, sodium, potassium, magnesium, calcium, strontium, etc. If M is sodium, the porous sodalite electronide exists in the form of Na8[Al6Si6O 24 ]2e - .

[0034] The sodalite electronide in the present application has a porous structure, and therefore can be used as a carrier for loading a catalyst, such as loading a transition metal into the porous structure. Since the carrier has a porous structure, more catalysts can be loaded, the loading amount of the catalyst is increased, and the catalytic efficiency is improved.

[0035] Based on the same inventive concept, the present application also provides a preparation method of a porous sodalite electronide, which comprises the following steps:

[0036] S10, providing a porous Na6[Al6Si6O 24 ]·8H2O.

[0037] Specifically, a precursor Na6[Al6Si6O 24The precursor was calcined and bound water removed by 8H2O to obtain porous Na6[Al6Si6O] 24 ]

[0038] 8H2O.

[0039] In this invention, step S10 specifically includes the following steps:

[0040] S100. Sodium aluminate, sodium silicate and template agent are mixed to obtain a mixed solution;

[0041] S110. The mixed solution is subjected to hydrothermal treatment to obtain the template agent and Na8[Al6Si6O] 24 [(OH)2·nH2O mixture;]

[0042] S120, the template agent and Na8[Al6Si6O] 24 The mixture of (OH)2·nH2O was extracted to obtain Na6[Al6Si6O] 24 A mixture of 8H2O and template agent;

[0043] S130. The mixture is subjected to a second calcination treatment to obtain the porous Na6[Al6Si6O] 24 ]·8H2O.

[0044] Specifically, a suitable amount of template agent is added to a mixed solution of sodium aluminate and sodium silicate (e.g., molar ratio 0.7–1.3) to ensure that the final electron compound has the required structure and properties. The template agent can be a common surfactant such as dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, polypropylene glycol-ethylene oxide addition polymer (polyether), etc. The choice of template agent has a significant impact on the porosity characteristics of the final electron compound. After thorough stirring, the mixture is placed in a hydrothermal reactor and reacted at a temperature above 100 degrees Celsius for several hours to obtain the template agent and Na8[Al6Si6O] 24 A mixture of (OH)₂·nH₂O was obtained. The mixture was then subjected to Soxhlet extraction to yield Na₆[Al₆Si₆O₂]. 24 A mixture of 8H2O and template agent.

[0045] Na6[Al6Si6O] was calcined in air at temperatures above 500 degrees Celsius. 24 A mixture of 8H2O and a template agent was prepared for several hours to remove the template agent, yielding a pure-phase porous Na6[Al6Si6O] 24 ]·8H2O.

[0046] After the step S10, a step S20 is included, under vacuum environment, the Na6[Al6Si6O 24 ]·8H2O is subjected to a first calcination treatment, to obtain Na6[Al6Si6O 24 ]·8H2O.

[0047] Specifically, the obtained Na6[Al6Si6O 24 ]·8H2O is transferred into a vacuum environment, and is calcined at a temperature above 500 degrees Celsius for several hours to remove the combined water, so as to obtain Na6[Al6Si6O 24 ]·8H2O.

[0048] After the step S20, a step S30 is included, the alkali metal M is deposited on the Na6[Al6Si6O 24 ]·8H2O, to obtain the porous sodalite electronic product.

[0049] Specifically, under the protection of inert gas, the product obtained in the step S20 is placed in a stainless steel reaction container, and an appropriate amount of alkali metal or alkaline earth metal including but not limited to Li, Na, K, Mg, Ca, Sr, etc. is placed at the other end of the container, and the alkali metal or alkaline earth metal is heated to a vapor state under the protection of inert gas, and is deposited on the Na6[Al6Si6O 24 ]·8H2O, to completely react, to obtain the sodalite electronic product Na6M2[Al6Si6O 24 ](e - )2.

[0050] Based on the same inventive concept, the application also provides a catalyst, including: a catalyst carrier and a transition metal loaded on the catalyst carrier; the catalyst carrier is the porous sodalite electronic product described above. The loading method includes but is not limited to general, wet chemical method, photoreduction method, thermal reduction method, and solvent reduction method.

[0051] In the application, the catalyst provided can be applied in hydrogenation reactions, and the applied hydrogenation reactions include but are not limited to electrocatalytic hydrogen reduction, carbon dioxide reduction, nitrogen reduction, thermal synthesis of ammonia, nitrobenzene hydrogenation, acetylene semi-hydrogenation, and other organic hydrogenation reactions.

[0052] The porous sodalite electronic product and the preparation method thereof provided by the application are further explained and described below through specific examples.

[0053] Example 1

[0054] Na8[Al6Si6O24]·8H2O mixture (as shown in 24 ](OH)2·

[0055] nH2O mixture (as Figs. 1-2 shown, the difference between adding template and not adding is compared). The above obtained mixture is extracted by Soxhlet extraction method, thereby obtaining Na6[Al6Si6O 24 ]

[0056] 8H2O and template mixture. The Na6[Al6Si6O 24 ]·8H2O and template mixture is calcined at a high temperature of 550 degrees Celsius or above for several hours to remove the template, thereby obtaining pure phase porous Na6[Al6Si6O 24 ]·8H2O. The obtained Na6[Al6Si6O 24 ]·8H2O is transferred into a vacuum environment and calcined at 550 degrees Celsius for several hours to remove the combined water, thereby obtaining Na6[Al6Si6O 24 ]. The obtained product is placed in a stainless steel reaction container under inert gas protection, an appropriate amount of alkali metal Na is placed at the other end of the container, the Na metal is heated to vapor state at 1100 degrees Celsius under Ar gas protection, and is deposited on Na6[Al6Si6O 24 ], until complete reaction, thereby obtaining sodalite electronide Na8[Al6Si6O 24 ](e - )2 (as shown in Figs. 3-4 , the porous characteristics and electronic anion characteristics are characterized). The sample is washed with anhydrous ethanol for 6 times, dried in a vacuum drying box for 6 hours, and then stored in a glove box.

[0057] Example 2

[0058] Na8[Al6Si6O24]·8H2O mixture (as shown in 24 ](OH)2·

[0059] Na6[Al6Si6O 24 ]·8H2O and template agent. The mixture of Na6[Al6Si6O 24 ]·8H2O and template agent was calcined in air at 550 °C for several hours to remove the template agent, and pure phase porous Na6[Al6Si6O 24 ]·8H2O was obtained. The obtained Na6[Al6Si6O 24 ]

[0060] 8H2O was transferred into a vacuum environment and calcined at 600 °C for several hours to remove the combined water, and Na6[Al6Si6O 24 ](SOD) was obtained. The obtained product was placed in a stainless steel reaction vessel under inert gas protection, 2 g (10 g) of alkali metal K was placed at the other end of the vessel, and the K metal was heated to vapor state at 1100 °C under Ar protection and deposited on Na6[Al6Si6O 24 ], to complete the reaction, and Na6K2[Al6Si6O 24 ](e - )2 (2 g and 10 g of alkali metal K correspond to product electronides e-SOD-brown and e-SOD-black, respectively) was obtained. The sample was washed with anhydrous ethanol for 6 times and dried in a vacuum drying box for 6 hours, and noble metal Pt was loaded on the sample by a general photoreduction method (under light protection, 1 g of sample was dispersed in 20 mL of aqueous solution, 1 mL of a chloroplatinic acid solution with a mass fraction of 1 wt% was added, and the mixture was exposed to a xenon lamp for 30 minutes under sufficient stirring), and Pt-e-SOD-brown and Pt-e-SOD-black were obtained. Subsequently, the obtained catalyst was applied to electrocatalytic hydrogen reduction in a 1M KOH solution (as shown in FIG. 1, it is shown that the electron anion has a great promotion effect on the reaction performance). Fig. 5

[0061] Example 3

[0062] Sodium aluminate and sodium silicate 18 g were mixed in an equimolar ratio, 27 g of sodium hydroxide, 27 mL of deionized water, and 2.5 mL of a template agent, a polyaddition product (polyether) of polypropylene glycol and ethylene oxide with a mass fraction of 45 wt% were added, the mixture was stirred uniformly, and then placed in a hydrothermal reaction kettle, and reacted at 180 °C for 7 hours, to obtain a mixture of template agent and Na8[Al6Si6O 24 ](OH)2·nH2O. The obtained mixture was subjected to Soxhlet extraction, and Na6[Al6Si6O 24 ] ​

[0063] 8H2O and a template. The mixture of Na6[Al6Si6O 24 ]·8H2O and a template is calcined at a high temperature of 550 degrees Celsius in air for several hours to remove the template, to obtain a pure phase porous Na6[Al6Si6O 24 ]·8H2O. The obtained Na6[Al6Si6O 24 ]·8H2O is transferred into a vacuum environment and calcined at 650 degrees Celsius for several hours to remove the combined water, to obtain Na6[Al6Si6O 24 ](SOD). The obtained product is placed in a stainless steel reaction container under inert gas protection, 2g (10g) of alkali metal Na is placed at the other end of the container, the Na metal is heated to a vapor state at 1200 degrees Celsius under Ar gas protection, and is deposited to the Na6[Al6Si6O 24 ]·8H2O, to completely react, to obtain sodalite electronide Na8[Al6Si6O 24 ](e - )2. The sample is washed with anhydrous ethanol for 6 times and dried in a vacuum drying box for 7 hours, to obtain a pure product. The obtained catalyst is subjected to ruthenium loading by chemical vapor deposition (CVD), and then is applied to a thermal catalytic synthesis of ammonia. (As shown in Fig. 6 , it is shown that the electronic anion greatly promotes the reaction performance).

[0064] In summary, the present application provides a porous sodalite electronide and a preparation method and a catalyst thereof, the porous sodalite electronide exists in the form of Na6M2[Al6Si6O 24 ](e - )2, wherein the electron is a kind of anion of the porous sodalite electronide, and M is an alkali metal or an alkaline earth metal. The preparation method comprises: providing porous Na6[Al6Si6O 24 ]·8H2O; performing a first calcination treatment on the porous Na6[Al6Si6O 24 ]

[0065] 8H2O in a vacuum environment, to obtain Na6[Al6Si6O 24 ]; depositing an alkali metal or an alkaline earth metal M to the Na6[Al6Si6O 24The porous chabazite electronides are obtained. The present application provides an electronide with a porous structure, which has not been reported in the prior art. The introduction of the porous structure greatly increases the specific surface area of the material, providing more active sites for the catalyst, thereby improving the catalytic efficiency. Since the electron anions in the porous chabazite electronide have high activity, they can effectively promote the progress of catalytic hydrogenation reactions. As a catalyst carrier, this material not only improves the reaction rate, but also can reduce the amount of catalyst required, thereby reducing the cost. This porous chabazite electronide is suitable for various catalytic hydrogenation reactions, including electrocatalytic hydrogen reduction, carbon dioxide reduction, nitrogen reduction, and organic hydrogenation reactions such as nitrobenzene hydrogenation and acetylene semi-hydrogenation. This makes it have wide application potential in the chemical industry. The preparation method of the present application is simple and efficient, and is suitable for large-scale production. By adjusting the type of template and calcination conditions, the characteristics of the porous structure can be easily controlled to adapt to different catalytic needs. Due to the high activity of the electronide, it can reduce the generation of harmful by-products in the catalytic reaction, thereby helping to achieve a more green and sustainable chemical process.

[0066] It should be understood that the application of the present application is not limited to the above examples, and those skilled in the art can make improvements or changes according to the above description, and all these improvements and changes shall belong to the protection scope of the appended claims of the present application.

Claims

1. A porous sodalite eletrochemical compound, characterized in that, said porous chabazite electronate is present in the form of Na6M2[Al6Si6O 24 ](e - )2, wherein the electron is a kind of anion of said porous chabazite electronate, M is an alkali metal or an alkaline earth metal.

2. The porous chabazite electronide of claim 1, wherein, The porous chabazite electronide is present in the form of Na8[Al6Si6O 24 ]2e - .

3. A method of preparing the porous sodalite e-lectronic according to claim 1, characterized in that, Comprising: Provided is a porous Na6[Al6Si6O 24 ]•8H2O; The porous Na6[Al6Si6O 24 ]•8H2O is subjected to a first calcination treatment in a vacuum environment to obtain Na6[Al6Si6O 24 ] depositing an alkali or alkaline earth metal M onto said Na6[Al6Si6O 24 ] to obtain said porous sodalite e- compound.

4. The method of claim 3, wherein the porous chabazite electronide is prepared by the steps of: A method for producing the porous Na6[Al6Si6O 24 ]•8H2O includes: mixing sodium aluminate, sodium silicate and a template agent to obtain a mixed solution; hydrothermally treating the mixed solution to obtain a template agent and a Na8[Al6Si6O 24 ](OH)2•nH2O mixture; The template and Na8[Al6Si6O 24 ]•8H2O and the template mixture is obtained by extraction treatment of the mixture of the template and Na8[Al6Si6O 24 ]•8H2O and the template mixture is obtained by extraction treatment of the mixture of the template and Na8[Al6Si6O subjecting the mixture to a second calcination process to obtain the porous Na6[Al6Si6O 24 ]•8H2O.

5. The method of claim 4, wherein the porous chabazite electronide is prepared by the steps of: the template agent is selected from any one or more of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer and polypropylene glycol-ethylene oxide adduct.

6. The method of claim 4, wherein the porous chabazite electronide is prepared by the steps of: the molar ratio of the sodium aluminate to the sodium silicate is 1:0.7-1.

3.

7. The method of claim 4, wherein the porous chabazite electronide is prepared by the steps of: the temperature of the first calcination treatment is greater than 500℃; the temperature of the second calcination treatment is greater than 500℃.

8. The method of claim 3, wherein the porous chabazite electronide is prepared by the steps of: the alkali metal or alkaline earth metal M is selected from any one of Li, Na, K, Mg, Ca and Sr.

9. A catalyst characterized by, Comprising: a catalyst carrier and a transition metal supported on the catalyst carrier; the catalyst carrier is the porous sodalite electronide according to claim 1 or 2, or is obtained by the preparation method according to any one of claims 3-8.

10. The catalyst according to claim 9, for use in catalytic hydrogenation reactions.

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