CN108754534B - Iron-based non-noble metal catalyst for synthesizing ammonia by electrocatalysis and preparation method thereof - Google Patents
Iron-based non-noble metal catalyst for synthesizing ammonia by electrocatalysis and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an iron-based non-noble metal catalyst for synthesizing ammonia by electrocatalysis and a preparation method thereof. Reducing divalent iron ions in a divalent iron salt solution by adopting an electrochemical deposition method and depositing the divalent iron ions on the surface of the conductive carrier, wherein the divalent iron salt solution contains divalent iron salt, a reducing agent, o-sulfonylbenzene imide and sodium dodecyl sulfate. The catalyst provided by the invention can be used for electrocatalytic synthesis of ammonia, and can obviously improve the Faraday efficiency of the electrocatalytic synthesis process of ammonia.
Description
Technical Field
The invention belongs to the technical field of preparation of catalysts in chemical engineering industry, and relates to an iron-based non-noble metal catalyst for synthesizing ammonia through electrocatalysis and a preparation method thereof.
Background
The synthetic ammonia industry is the backbone of chemical production. Through the development of hundreds of years, the technology for catalytically synthesizing ammonia makes great progress. In the Haber-Bosch nitrogen fixation process taking the heat energy of fossil fuel as the only driving force, raw materials and fuel for producing catalytic synthesis ammonia are energy sources, and certain byproducts (such as carbon dioxide) in the production process are regarded as sources of air pollution, the energy problem concerned globally nowadays is put in front of the ammonia synthesis industry, and energy conservation and emission reduction are the primary topics of the traditional ammonia synthesis process. The development of green high-efficiency catalysts as soon as possible plays a crucial role in reducing energy consumption and is imminent. At present, the catalytic efficiency of the catalyst in the ammonia synthesis industry reaches more than 90 percent at high temperature, and approaches the equilibrium ammonia concentration (different according to pressure). From a thermodynamic point of view, the positive reaction of ammonia synthesis belongs to an exothermic reaction of reduced volume. In order to increase the conversion per pass, it is only possible to increase the pressure and decrease the reaction temperature. It is suggested from the phenomenon that rhizobia of leguminous plants can fix nitrogen mildly in the atmosphere, and if a catalyst (e.g., nitrogenase) is suitable, the synthesis of ammonia at normal temperature and pressure is not remotely accessible. On the other hand, the technologist has reviewed the nature of the process for synthesizing ammonia by activating nitrogen, and the synthesis of ammonia can be realized by providing a proper electron and proton source, and the reaction equation is as follows:
N2+6H++6e→2NH3
based on such assumptions, schemes for electrocatalytic ammonia synthesis have been in force and rapidly become a research focus in the field of ammonia synthesis. The preparation of the electrode catalyst suitable for electro-catalysis ammonia synthesis is the first place to come. However, the faradaic efficiency of the existing electrocatalytic ammonia synthesis process is lower than 20%, and the catalytic efficiency is lower.
Disclosure of Invention
In order to solve the defects of the prior art, one of the purposes of the invention is to provide a preparation method of an iron-based non-noble metal catalyst for synthesizing ammonia by electrocatalysis, and the catalyst prepared by the method can obviously improve the Faraday efficiency of the ammonia synthesizing process by electrocatalysis.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of an iron-based non-noble metal catalyst for synthesizing ammonia through electrocatalysis comprises the step of reducing divalent iron ions in a divalent iron salt solution by an electrochemical deposition method and depositing the divalent iron ions on the surface of a conductive carrier, wherein the divalent iron salt solution contains divalent iron salt, a reducing agent, o-sulfonylbenzene imide and sodium dodecyl sulfate.
Firstly, the catalyst prepared by the method can improve the Faraday efficiency of the electrocatalytic synthesis of ammonia. Secondly, by adopting an electrochemical deposition method, the controllable preparation of the target catalyst can be realized through the electrifying time or the current density. Thirdly, an iron-based catalyst can be precipitated on the surface of a conductive electrode material such as graphite by adopting a chemical electrodeposition method, and loose iron species are distributed on the surface of an iron-based catalyst coating. The preparation method of the invention reduces the cost of the catalyst and improves the utilization rate of iron atoms.
The invention also aims to provide the iron-based non-noble metal catalyst obtained by the preparation method.
The invention also aims to provide the application of the iron-based non-noble metal catalyst in an ammonia synthesis process or a catalytic process taking an iron-based material as an active center.
The invention also provides a method for synthesizing ammonia by electrocatalysis, which takes the iron-based non-noble metal catalyst as a working electrode, and introduces nitrogen into electrolyte to prepare ammonia by electrocatalysis.
The invention has the beneficial effects that:
the method reduces the cost of the catalyst, improves the utilization rate of iron atoms, and is convenient and controllable. The prepared iron-based catalyst is used for synthesizing ammonia, and the electro-catalysis ammonia production amount can reach 100-400 mg.h at room temperature and normal pressure-1m-2The Faraday efficiency can reach 30-60%. The catalyst generally used in the ammonia synthesis industry generally requires high temperature and high pressure (400-500 ℃ and 20-30 MPa), and the faradaic efficiency of the electrochemical ammonia synthesis process reported in the literature is lower than 20%. The invention makes beneficial exploration for synthesizing ammonia at normal temperature and normal pressure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a schematic diagram of the preparation of an iron-based ammonia synthesis catalyst supported on a conductive material;
FIG. 2 is a diagram of an apparatus for preparing an iron-based ammonia synthesis catalyst of a conductive material;
FIG. 3 is a cyclic voltammogram of a preparation of a graphite rod-supported iron-based ammonia synthesis catalyst;
figure 4 is an XRD characterization pattern of a graphite rod-supported iron-based ammonia synthesis catalyst.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The ferrous salts described herein are compounds that are capable of ionizing ferrous cations in water.
The conductive carrier described herein refers to an object of any shape formed of a conductive material such as: graphite, metallic materials, etc., any shape such as: stick, sheet, block, etc.
As introduced in the background art, the prior art has the defect of low faraday efficiency of the electrocatalytic ammonia synthesis process, and in order to solve the technical problems, the application provides an iron-based non-noble metal catalyst for electrocatalytic ammonia synthesis and a preparation method thereof.
In one exemplary embodiment of the present application, a method for preparing an iron-based non-noble metal catalyst for ammonia electrocatalytic synthesis is provided, in which a ferrous ion in a ferrous salt solution is reduced by an electrochemical deposition method and deposited on the surface of a conductive carrier, and the ferrous salt solution contains a ferrous salt, a reducing agent, o-sulfonylbenzimide and sodium dodecyl sulfate.
Firstly, the catalyst prepared by the method can improve the Faraday efficiency of the electrocatalytic synthesis of ammonia. Secondly, by adopting an electrochemical deposition method, the controllable preparation of the target catalyst can be realized through the electrifying time or the current density. Thirdly, an iron-based catalyst can be precipitated on the surface of a conductive electrode material such as graphite by adopting a chemical electrodeposition method, and loose iron species are distributed on the surface of an iron-based catalyst coating. The preparation method reduces the cost of the catalyst and improves the utilization rate of iron atoms.
Preferably, in the electrochemical deposition method, the conductive carrier is used as a working electrode, and the platinum sheet is used as a counter electrode.
Preferably, the electrochemical deposition method is a direct current deposition method or cyclic voltammetry.
Preferably, the ferrous salt is ferrous chloride, ferrous sulfate or ferrous nitrate.
The purpose of the addition of the reducing agent is to stabilize the ferrous ions against oxidation. Preferably, the reducing agent is ascorbic acid. Experiments prove that the catalyst prepared by adopting the ascorbic acid has better catalytic effect.
Preferably, the concentration of the ferrous salt in the ferrous salt solution is 20-100 g/L, the concentration of the reducing agent is 0.5-5 g/L, the concentration of the o-sulfonylbenzene imide is 3-10 g/L, and the concentration of the sodium dodecyl sulfate is 0.1-105 g/L. Wherein, the o-sulfonylbenzene imide is used as an iron plating additive, and the lauryl sodium sulfate is used as a lubricant.
Preferably, before the electrochemical deposition method is adopted, inert gas is introduced into the ferrous salt solution to remove oxygen, and the pH value is adjusted to 3.0-5.0.
Preferably, the conductive carrier is a graphite electrode or a metal electrode. Further preferably, the metal electrode is a copper sheet or a stainless steel alloy rod. Still more preferably stainless steel alloy rods.
Preferably, the conditions of electrochemical deposition are: 10 to 15A/dm2The temperature is 25-50 ℃, the circulating voltage is-2.8-0.8V, the scanning is performed for 5-100 circles, and the time is 5-60 min.
In another embodiment of the present application, there is provided an iron-based non-noble metal catalyst obtained by the above-mentioned preparation method.
In a third embodiment of the present application, there is provided a use of the iron-based non-noble metal catalyst in an ammonia synthesis process or a catalytic process using an iron-based material as an active center.
In a fourth embodiment of the present application, a method for synthesizing ammonia by electrocatalysis is provided, wherein the iron-based non-noble metal catalyst is used as a working electrode, and nitrogen is introduced into an electrolyte to perform electrocatalysis to prepare ammonia.
Preferably, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and methanol is used as a proton source.
Preferably, the scan rate is 0.02 V.s-1The circulating potential is-1.6V to-0.8V, and the circulating times are 25 times.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
Example 1
Weighing FeSO4·7H2Adding 5.56g of O, 0.1g of ascorbic acid, 0.6g of O-sulfonylbenzimide and 0.3g of sodium dodecyl sulfate into a beaker, adding a proper amount of deionized water for dissolving, stirring until the solution is completely dissolved, transferring the solution into a 200mL volumetric flask, and continuously adding the deionized water to the scale mark; before electrodeposition, carrying out surface treatment on a graphite rod working electrode to increase surface smoothness or remove surface impurity ions; taking 50mL of FeSO prepared by taking a platinum electrode as a counter electrode, a saturated calomel electrode as a reference electrode and a graphite rod as a working electrode4Placing the solution in a conventional electrolytic cell (as shown in figure 2), adjusting pH to 3.0, performing electrodeposition by using cyclic voltammetry with a three-electrode system via a Gamry electrochemical workstation, and setting the scan rate to 0.02 V.s-1The preparation principle is shown in figure 1, and the structural representation is shown in figure 4, wherein the cycling potential is between-1.6V and-0.8V, the metal film generated on the graphite rod is the target catalyst after the cycle times are 5 times, the prepared catalyst electrode is put into a dryer for standby.
The performance test of the catalyst adopts trihexyltetradecyl phosphorus hexafluorophosphate ([ (C)6H13)3(C14H29)P]PF6) As a working solution, before the test, high-purity nitrogen is firstly introduced into the working solution to remove impurities such as oxygen in the working solution, methanol is used as a proton source, the iron-based graphite rod catalyst prepared in the step is used as a working electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and the scanning rate is set to be 0.02 V.s-1The circulating potential is between-1.6V and-0.8V, the circulating frequency is 25 times, high-purity nitrogen is continuously introduced at the speed of 0.5L/min in the experimental process, and a 0.005M dilute sulfuric acid solution is used as an absorption liquid. After the experiment was completed, the amount of ammonia generated in the working solution and the absorption solution was measured by colorimetry, and as shown in FIG. 3, the amount of ammonia produced by electrocatalysis was 166.8mg · h at room temperature and normal pressure-1m-2The Faraday efficiency can reach 48%.
Example 2
Weighing FeSO4·7H2Adding 8.58g of O, 0.2g of ascorbic acid, 0.8g of O-sulfonylbenzimide and 0.5g of sodium dodecyl sulfate into a beakerAdding a proper amount of deionized water for dissolving, stirring until the deionized water is completely dissolved, transferring the mixture into a 200mL volumetric flask, and continuously adding the deionized water to the scale mark; before electrodeposition, carrying out surface treatment on a graphite rod working electrode to increase surface smoothness or remove surface impurity ions; taking 50mL of FeSO prepared by taking a platinum electrode as a counter electrode, a saturated calomel electrode as a reference electrode and a graphite rod as a working electrode4The solution is placed in a conventional electrolytic cell, the pH is adjusted to 3.5, electrodeposition is carried out by means of a Gamry electrochemical workstation and a three-electrode system cyclic voltammetry, and the scanning rate is set to be 0.02 V.s-1The metal film generated on the graphite rod is the target catalyst after the circulation potential is between-1.6V and-0.8V and the circulation times is 15 times, and the prepared catalyst electrode is put into a dryer for standby.
The performance test of the catalyst adopts trihexyltetradecyl phosphorus hexafluorophosphate ([ (C)6H13)3(C14H29)P]PF6) As a working solution, before the test, high-purity nitrogen is firstly introduced into the working solution to remove impurities such as oxygen in the working solution, methanol is used as a proton source, the iron-based graphite rod catalyst prepared in the step is used as a working electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and the scanning rate is set to be 0.02 V.s-1The circulating potential is between-1.6V and-0.8V, the circulating frequency is 25 times, high-purity nitrogen is continuously introduced at the speed of 0.5L/min in the experimental process, and a 0.005M dilute sulfuric acid solution is used as an absorption liquid. After the experiment is finished, the amount of ammonia generated in the working solution and the absorption solution is detected by a colorimetric method, and the amount of the electro-catalytic ammonia production is 241.2 mg.h at room temperature and normal pressure-1m-2The Faraday efficiency can reach 54%.
Example 3
Weighing FeSO4·7H2Adding 5.56g of O, 0.1g of ascorbic acid, 0.6g of O-sulfonylbenzimide and 0.3g of sodium dodecyl sulfate into a beaker, adding a proper amount of deionized water for dissolving, stirring until the solution is completely dissolved, transferring the solution into a 200mL volumetric flask, and continuously adding the deionized water to the scale mark; before electrodeposition, carrying out surface treatment on a working electrode of a metal copper sheet to increase surface smoothness or remove surface impurity ions; using platinum electrode as counter electrodeTaking 50mL of FeSO prepared by using a saturated calomel electrode as a reference electrode and a copper sheet as a working electrode4The solution is placed in a conventional electrolytic cell, the pH is adjusted to 3.5, electrodeposition is carried out by means of a Gamry electrochemical workstation and a three-electrode system cyclic voltammetry, and the scanning rate is set to be 0.02 V.s-1The circulating potential is between-1.6V and-0.8V, the metal film generated on the copper sheet is the target catalyst after the circulating times is 15 times, and the prepared catalyst electrode is put into a dryer for standby.
The performance test of the catalyst adopts trihexyltetradecyl phosphorus hexafluorophosphate ([ (C)6H13)3(C14H29)P]PF6) As a working solution, before the test, high-purity nitrogen is firstly introduced into the working solution to remove impurities such as oxygen in the working solution, isopropanol is used as a proton source, the iron-based copper sheet catalyst prepared in the step is used as a working electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and the scanning rate is set to be 0.02 V.s-1The circulating potential is between-1.6V and-0.8V, the circulating frequency is 25 times, high-purity nitrogen is continuously introduced at the speed of 0.5L/min in the experimental process, and a 0.005M dilute sulfuric acid solution is used as an absorption liquid. After the experiment is finished, the amount of ammonia generated in the working solution and the absorption solution is detected by a colorimetric method, and the amount of the electrocatalytic ammonia production at room temperature and normal pressure is 216.4 mg.h-1m-2The Faraday efficiency can reach 52%.
Example 4
Weighing FeSO4·7H2Adding 6.76g of O, 0.2g of ascorbic acid, 0.8g of O-sulfonylbenzimide and 0.5g of sodium dodecyl sulfate into a beaker, adding a proper amount of deionized water for dissolving, stirring until the solution is completely dissolved, transferring the solution into a 200mL volumetric flask, and continuously adding the deionized water to the scale mark; before electrodeposition, surface treatment is carried out on a working electrode of the stainless steel alloy rod to increase the surface smoothness or remove surface impurity ions; taking 50mL of FeSO prepared by taking a platinum electrode as a counter electrode, a saturated calomel electrode as a reference electrode and a stainless steel alloy rod as a working electrode4The solution is placed in a conventional electrolytic cell, the pH is adjusted to be 3.0, electrodeposition is carried out by adopting cyclic voltammetry of a three-electrode system by means of a Gamry electrochemical workstation, and scanning is setAt a rate of 0.02 V.s-1The circulating potential is between-1.6V and-0.8V, the metal film generated on the stainless steel alloy bar is the target catalyst after the circulating times is 10 times, and the prepared catalyst electrode is put into a dryer for standby.
The performance test of the catalyst adopts trihexyltetradecyl phosphorus hexafluorophosphate ([ (C)6H13)3(C14H29)P]PF6) As the working solution, before the test, high-purity nitrogen is firstly introduced into the working solution to remove impurities such as oxygen in the working solution, alcohols (such as methanol) are used as a proton source, the iron-based stainless steel alloy rod catalyst prepared in the step is used as a working electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and the scanning speed is set to be 0.02 V.s-1The circulating potential is between-1.6V and-0.8V, the circulating frequency is 25 times, high-purity nitrogen is continuously introduced at the speed of 0.5L/min in the experimental process, and a 0.005M dilute sulfuric acid solution is used as an absorption liquid. After the experiment is finished, the amount of ammonia generated in the working solution and the absorption solution is detected by a colorimetric method, and the amount of the electro-catalysis ammonia generation is 386.8 mg.h at room temperature and normal pressure-1m-2The Faraday efficiency can reach 60%.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (1)
1. An electrocatalytic ammonia synthesis method is characterized by comprising the following steps:
firstly, preparing an iron-based non-noble metal catalyst for synthesizing ammonia by electrocatalysis: reducing divalent iron ions in a divalent iron salt solution by adopting an electrochemical deposition method and depositing the divalent iron ions on the surface of a conductive carrier, wherein the divalent iron salt solution contains divalent iron salt, a reducing agent, o-sulfonylbenzene imide and sodium dodecyl sulfate; wherein:
in the electrochemical deposition method, a conductive carrier is used as a working electrode, and a platinum sheet is used as a counter electrode;
the electrochemical deposition method is cyclic voltammetry;
the conductive carrier is a stainless steel alloy rod;
the reducing agent is ascorbic acid; the concentration of a ferrous salt in the ferrous salt solution is 20-100 g/L, the concentration of a reducing agent is 0.5-5 g/L, the concentration of o-sulfonylbenzene imide is 3-10 g/L, and the concentration of sodium dodecyl sulfate is 0.1-105 g/L;
before an electrochemical deposition method is adopted, introducing inert gas into a ferrous salt solution to remove oxygen, and adjusting the pH value to 3.0-5.0; the conditions of electrochemical deposition were: the temperature is 25-50 ℃, the circulating voltage is-2.8-0.8V, the scanning is carried out for 5-100 circles, and the time is 5-60 min;
then, taking the iron-based non-noble metal catalyst as a working electrode, introducing nitrogen into the electrolyte, and carrying out electro-catalysis to prepare ammonia;
wherein, a platinum electrode is taken as a counter electrode, a saturated calomel electrode is taken as a reference electrode, trihexyltetradecyl phosphorus hexafluorophosphate is taken as an electrolyte, methanol is taken as a proton source, and the circulating potential is-1.6V to-0.8V.
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