CN114561651A - FeCo @ NC core-shell structure catalyst, preparation method and application thereof in seawater electrolytic hydrogen production - Google Patents
FeCo @ NC core-shell structure catalyst, preparation method and application thereof in seawater electrolytic hydrogen production Download PDFInfo
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- 229910002546 FeCo Inorganic materials 0.000 title claims abstract description 131
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 239000011258 core-shell material Substances 0.000 title claims abstract description 45
- 239000013535 sea water Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000001257 hydrogen Substances 0.000 title claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 16
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
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- 239000000956 alloy Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 abstract description 17
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- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
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- 230000001105 regulatory effect Effects 0.000 abstract description 5
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- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
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- 238000005979 thermal decomposition reaction Methods 0.000 description 6
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- 230000003321 amplification Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
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- 239000011261 inert gas Substances 0.000 description 4
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- 230000005469 synchrotron radiation Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention relates to a FeCo @ NC core-shell structure catalyst, a preparation method and application thereof in seawater electrolytic hydrogen production. According to the invention, the thickness of the outer nitrogen-doped carbon shell in the core-shell structure is effectively regulated and controlled by changing the addition of melamine, so that various performances of the catalyst are optimized, and the nitrogen-doped and non-nitrogen-doped core-shell structure catalyst is synthesized by changing the type of a carbon source, so that a coordination bond M-N-C formed among N, metal M and carbon atoms in the core-shell catalyst FeCo @ NC containing the nitrogen-doped carbon shell is beneficial to electron transfer and selective oxygen precipitation reaction, and an infinite number of rapid electron transfer channels are built in the carbon shell of the FeCo @ NC during catalytic reaction to promote the electron transfer between the inner metal core and the outer carbon shell. Used for the experiment of decomposing seawater completely, and is found to be at 30 ℃ and 1.0Acm‑2Under the high current density, the electrode voltage is only 1.98V, and the method has a good application prospect.
Description
Technical Field
The invention relates to a FeCo @ NC core-shell structure catalyst, a preparation method and application thereof in seawater electrolytic hydrogen production, and belongs to the technical field of water electrolytic hydrogen production.
Background
Hydrogen energy is regarded as a clean, efficient and sustainable secondary energy source with the most potential development in the 21 st century. The development of green 'hydrogen energy' is one of important measures for achieving 'carbon peak reaching' and 'carbon neutralization' targets, and is one of the key research and development directions of the country.
In recent years, the technology of electrolyzing water to prepare 'green hydrogen' is receiving wide attention. The seawater is used as a raw material, renewable resource power generation (such as wind energy, water energy, solar power generation and the like) is used as a driving force to form a hydrogen production route for electrolyzing seawater, so that the problem of an electrolyzed water source can be solved, and the problems of effective resource allocation, weak freshwater resource and the like can be solved.
However, in the electrolysis process, the precipitation reaction (CER) of a large amount of chloride ions in seawater not only competes with the oxygen precipitation reaction (OER), but also easily reacts with the metal current collector to dissolve out metal, so that corrosion occurs, and the service life of the system is limited. Therefore, there is an urgent need to develop an electrocatalyst having high OER selectivity, high stability and catalytic activity to accelerate the seawater decomposition process.
Despite the noble metal-based catalyst (e.g., RuO)2) The catalyst shows excellent catalytic activity and stability in electrolyzed water, but the cost is high, and resources are scarce, so that the catalyst cannot be applied on a large scale. And the OER selectivity and long-term stability of transition metal-based compounds (such as Fe, Co, Ni and the like) in high-salinity seawater are poor. Therefore, many researchers have made great efforts to improve the stability of transition metal catalysts.
Disclosure of Invention
The technical problems to be actually solved by the present invention are: in the process of producing hydrogen by seawater electrolysis, the existing catalytic material is generated by Cl existing in an electrolysis system-Resulting in a low selectivity of Oxygen Evolution Reaction (OER), anCl-The corrosion and the inactivation of the active metal caused by the existence of the (A) are also disclosed.
Aiming at the problems, the invention designs a novel core-shell structure catalyst, the shell layer of which is a nitrogen-doped carbon material, and the inner core of which is FeCo alloy; by nitrogen doping in the shell layer, on one hand, more active sites are provided, so that the catalytic activity and OER selectivity of the material are improved, and on the other hand, by regulating the thickness of the shell layer, the shell layer plays a role in protecting the internal active metal, so that Cl is avoided-Resulting in corrosion deactivation of the active metal.
The more specific technical scheme is as follows:
a FeCo @ NC core-shell structure catalyst comprises a core and a shell, wherein the core is made of FeCo alloy, and the shell is a carbon material doped with N elements.
The thickness of the shell is 7-30nm, preferably 10-15 nm.
The mol ratio of Fe to Co in the inner core is 1: 0.5-1.5.
A preparation method of a FeCo @ NC core-shell structure catalyst comprises the following steps:
dissolving a cobalt source, an iron source and a nitrogen-containing carbon source in a solvent, uniformly stirring, and evaporating the solvent to obtain a precursor;
and 2, roasting the precursor to obtain the catalyst.
The cobalt source is one or more of cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt citrate.
The iron source is one or more of ferric nitrate, ferric oxide, ferric sulfate and ferric citrate.
The nitrogen-containing carbon source is selected from melamine.
The molar ratio of the cobalt source to the iron source is 1: 0.5-1.5.
The addition amounts of the cobalt source, the iron source and the nitrogen-containing carbon source are as follows according to the total addition molar weight of cobalt and iron and the addition weight of the nitrogen-containing carbon source: 2-4 mmol: 10-60 g; preferably 2 to 4 mmol: 30 g.
The firing process is in an inert atmosphere.
Temperature rise rate control of the first stage in the calcination stepAt 1-2 deg.C for min-1To 350-500 ℃ for 1-1.5h, and controlling the second-stage heating rate to 4-6 ℃ for min-1Maintained at 800 ℃ for 1-2h to 700 ℃ and above.
The FeCo @ NC core-shell structure catalyst is used in the process of seawater electrolysis hydrogen production.
In the application, the loading capacity of the FeCo @ NC core-shell structure catalyst on the surface of an electrode is 2-2.5mg cm-2。
Advantageous effects
The invention obtains the catalyst with the core-shell structure of the nitrogen-containing carbon shell coated FeCo alloy by a one-step thermal decomposition technology. Firstly, the preparation process related by the invention is simple and is very easy for the large-scale production of the catalyst. Secondly, the nitrogen-doped carbon shell of the core-shell structure catalyst FeCo @ NC prepared by the invention not only has a protection effect on an internal metal structure and prevents metal from being oxidized and corroded in alkaline seawater electrolyte, thereby increasing the stability of the catalyst; more active sites Co/Fe-N-C are distributed in the carbon shell, thereby greatly accelerating the electron transfer rate and selectively catalyzing OH-Thereby increasing the OER selectivity of the catalyst. Therefore, the catalyst FeCo @ NC prepared in the invention has very good catalytic activity, oxygen precipitation selectivity and overlong stability in seawater electrolytic hydrogen production, basically meets the industrial requirement, and has very good industrial application prospect.
Drawings
FIG. 1 is a flow chart of the preparation process of the catalysts of examples 1, 2 and 3 and comparative example of the present invention
FIG. 2 is an XRD pattern of catalysts FeCo @ NC, FeCo @ NC-7, FeCo @ NC-30 and FeCo @ C in examples 1, 2, 3 and comparative examples of the present invention
FIG. 3 is a TEM image of catalysts FeCo @ NC, FeCo @ NC-7, FeCo @ NC-30 and FeCo @ C in examples 1, 2, 3 and comparative examples of the present invention
FIG. 4 shows XPS spectra (a) and N1s spectra (b) of FeCo @ NC catalyst in example 1 of the present invention
FIG. 5 is a synchrotron radiation pattern of catalysts FeCo @ NC and FeCo @ C of example 1 and comparative example of the present invention, N-K edge (a) and C-K edge (b)
FIG. 6 is a graph showing LSV performance detection of catalysts FeCo @ NC, FeCo @ NC-7, FeCo @ NC-30 and FeCo @ C in 0.1M KOH +0.6M NaCl solution
FIG. 7 shows the Faraday current efficiency measurements of the catalysts FeCo @ NC, FeCo @ NC-7, FeCo @ NC-30 and FeCo @ C in 0.1M KOH +0.6M NaCl solution under high voltage 2.46V vs Ag/AgCl for OER in accordance with the present invention
FIG. 8 shows the 10h stability test of the catalysts FeCo @ NC, FeCo @ NC-7, FeCo @ NC-30 and FeCo @ C in 0.1M KOH +0.6M NaCl solution in accordance with the present invention
FIG. 9 shows the long term stability measurements of catalysts FeCo @ NC, FeCo @ NC-7, FeCo @ NC-30 and FeCo @ C of the present invention in solutions of 0.1M KOH +0.6M NaCl (a) and 1.0M KOH +0.6M NaCl (b), respectively.
FIG. 10 is an XRD representation of the scaled-up production of catalyst FeCo @ NC of the present invention.
FIG. 11 is a TEM representation of the magnified production of the catalyst FeCo @ NC of the present invention.
FIG. 12 is a diagram (a) and a performance detection diagram (b) of an experimental apparatus for full hydrolysis of catalyst FeCo @ NC in the present invention.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding the features and advantages of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention relates to a design preparation and large-scale production technology of a core-shell type nano catalyst FeCo @ NC formed by nitrogen-doped graphite carbon and FeCo alloy, and application thereof in seawater electrolytic hydrogen production. Firstly, the thickness of the outer nitrogen-doped carbon shell in the core-shell structure is effectively regulated and controlled by changing the addition of melamine, so that various performances of the catalyst are optimized. Secondly, the invention synthesizes nitrogen-doped and non-nitrogen-doped core-shell structure catalysts by changing the type of a carbon source, and researches the difference of the catalytic performance of the nitrogen-doped and non-nitrogen-doped core-shell structure catalysts to find that a coordination bond M-N-C formed among N, metal M and carbon atoms in the nitrogen-carbon shell-containing core-shell catalyst FeCo @ NC is favorable for electron transfer and selective oxygen evolutionAnd (3) an out-reaction (OER), compared with a non-nitrogen-doped core-shell structure catalyst FeCo @ C, when a catalytic reaction occurs, like an infinite number of rapid electron transfer channels are built in a carbon shell of FeCo @ NC, electron transfer is promoted between an inner metal core and an outer carbon shell. Secondly, the synthesis method is subjected to 100 times of amplification production to synthesize the catalyst with similar appearance structure and performance, and the method can be used for meeting the requirement of industrial amplification production. Finally, the catalyst was used in a full-scale seawater hydrolysis experiment and found to be 1.0Acm at 30 deg.C-2The electrode voltage was only 1.98V at high current density, indicating that this catalysis has practical application possibilities.
More specifically, the design idea and the preparation process of the material are as follows:
an infinite number of coordination bonds M-N-C are distributed in an N-doped carbon shell outside FeCo @ NC, so that the electron transfer capacity is increased, and the catalytic activity of OER is selectively enhanced. The invention is also characterized in that the thickness of the nitrogen-doped carbon shell outside the core-shell structure catalyst FeCo @ NC is controllable between 7 and 30nm, and the preferable thickness is 12 nm.
A core-shell structure catalyst FeCo @ NC of the nitrogen-doped carbon shell-coated FeCo alloy is synthesized by adopting a one-step thermal decomposition technology. The specific implementation steps are as follows:
In step 1 of the above scheme, the molar ratio of cobalt nitrate and ferric nitrate is controlled to be the same, the total metal content is kept at 2-4 millimoles, and the melamine content is controlled at 10-60 g.
In step 2 of the above scheme, the temperature rise rate of the first stage is controlled to be 1-2 ℃ for min-1To 350-500 ℃ for 1-1.5h, and controlling the second-stage heating rate to 4-6 ℃ for min-1Maintaining at 700-800 deg.c for 1-2 hr, and final naturally cooling to obtain the catalyst.
The invention achieves the purpose of regulating the thickness of the outer carbon shell by regulating and controlling the mass ratio of the metal nitrate to the melamine, thereby optimizing the catalytic performance of the catalyst.
In the step 1) in the scheme 1), the ratio of the total molar amount of the metal ions to the mass of the melamine can be controlled within different ranges of 1: 2.5-3, 1: 5-5.5, 1: 7.5-8, 1: 10-10.5 and 1: 12.5-13, so that the core-shell structure catalyst with different carbon shell thicknesses can be prepared. In the specific examples, the total amount of the fixed metal moles was constant and the amount of melamine added was varied.
Preferably, the melamine is added in an amount of 20-30 g. In particular, the melamine mass is 30 g.
Preferably, the first stage calcination temperature is controlled at 350-. Specifically, the first stage calcination temperature is 500 ℃.
Preferably, the second stage calcination temperature is controlled at 700-800 ℃. Specifically, the second stage calcination temperature is 800 ℃.
Preferably, the temperature rising rate of the first stage calcination is controlled to be 1-2 ℃ for min-1. Specifically, the first-stage heating rate is 2 ℃ min-1。
Preferably, the temperature rising rate of the second-stage calcination is controlled to be 4-6 ℃ for min-1. Specifically, the second-stage heating rate is 5 ℃ min-1。
Preferably, the first period of calcination is controlled to be 1-1.5 h. Specifically, the first stage calcination time is 1 h.
Preferably, the second stage calcination time is controlled to be 1-2 h. Specifically, the second stage calcination time is controlled to be 2 h.
In a full-solution seawater simulation test experiment, a 1M KOH +0.6M NaCl solution is used as an electrolyte, Pt/C (40%) loaded foamed nickel is used as a cathode, FeCo @ NC loaded foamed nickel is used as an anode, wherein the loading amounts of Pt/C (40%) and FeCo @ NC are controlled to be 2-2.5mg cm-2。
Preferably, the total molar amount of metal ions is controlled to be 4-5 mmol. Specifically, the total molar amount of metal ions was controlled to 4mmol, and both iron nitrate and cobalt nitrate were 2 mmol.
The invention provides application of the catalyst prepared by the method in seawater electrolysis for hydrogen production.
Example 1 preparation of core-Shell catalyst FeCo @ NC having Nitrogen-containing carbon Shell thickness of 12nm
(1) Preparation of the precursor
Dissolving 2mmol of cobalt nitrate hexahydrate and 2mmol of ferric nitrate nonahydrate in deionized water, adding 30g of melamine into the solution, uniformly stirring, placing in an oil bath kettle at the temperature of 80 ℃, heating and stirring to form dry powder.
(2) Calcination Process for core-Shell structured catalyst FeCo @ NC
Putting the powder obtained in the step (1) into an alumina crucible, and putting the alumina crucible into a tube furnace and inert gas N2The thermal decomposition step is carried out in an atmosphere of (3). The first stage has a temperature rise rate of 2 deg.C for min-1Heating to 500 deg.C for 1 hr, and calcining at 5 deg.C for min-1And maintaining the temperature to 800 ℃ for 2 hours, and finally naturally cooling to obtain the core-shell structured catalyst FeCo @ NC. The synthetic scheme is shown in figure 1.
Example 2 preparation of core-Shell catalyst FeCo @ NC-7 having Nitrogen-containing carbon Shell thickness of 7nm
(1) Preparation of the precursor
Dissolving 2mmol of cobalt nitrate hexahydrate and 2mmol of ferric nitrate nonahydrate in deionized water, adding 15g of melamine into the solution, stirring uniformly, placing the solution in an oil bath kettle at the temperature of 80 ℃, heating and stirring the solution until the solution is dry and powdery
(2) Calcination process of core-shell structure catalyst FeCo @ NC-7
Putting the powder obtained in the step 2(1) into an alumina crucible, and putting the alumina crucible into a tube furnace and inert gas N2The thermal decomposition step is carried out in an atmosphere of (3). The first stage has a temperature rise rate of 2 deg.C for min-1Heating to 500 deg.C for 1 hr, and calcining at 5 deg.C for min-1And maintaining the temperature at 800 ℃ for 2 hours, and finally naturally cooling to obtain the core-shell structured catalyst FeCo @ NC-7.
Example 3 preparation of core-Shell catalyst FeCo @ NC-30 having Nitrogen-containing carbon Shell with a thickness of 30nm
(1) Preparation of the precursor
Dissolving 2mmol of cobalt nitrate hexahydrate and 2mmol of ferric nitrate nonahydrate in deionized water, adding 50g of melamine into the solution, stirring uniformly, placing the solution in an oil bath kettle at the temperature of 80 ℃, heating and stirring until the dried powder is obtained
(2) Calcination of core-shell catalyst FeCo @ NC-30
Putting the powder obtained in the step 3(1) into an alumina crucible, and putting the alumina crucible into a tube furnace and inert gas N2The thermal decomposition step is carried out in an atmosphere of (3). The first stage has a temperature rise rate of 2 deg.C for min-1Heating to 500 deg.C for 1 hr, and calcining at 5 deg.C for min-1And maintaining the temperature at 800 ℃ for 2 hours, and finally naturally cooling to obtain the core-shell structured catalyst FeCo @ NC-30.
Preparation of core-shell catalyst FeCo @ C formed by coating FeCo alloy with nitrogen-free carbon shell in comparative example
The difference from example 1 is that: melamine is replaced by polysaccharide. And the ratio of the total molar amount of metal ions to the mass of the polysaccharide is controlled to be 1: 7.5-8.
(1) Preparation of the precursor
Dissolving 2mmol cobalt nitrate hexahydrate and 2mmol ferric nitrate nonahydrate in deionized water, adding 30g polysaccharide into the solution, stirring, heating in 80 deg.C oil bath, and stirring to obtain dried powder
(2) Calcination of core-shell catalyst FeCo @ C
Putting the powder obtained in the step 4(1) into an alumina crucible, and putting the alumina crucible into a tube furnace and inert gas N2The thermal decomposition step is carried out in an atmosphere of (3). The first stage has a temperature rise rate of 2 deg.C for min-1Heating to 500 deg.C for 1 hr, and calcining at 5 deg.C for min-1And maintaining the temperature at 800 ℃ for 2 hours, and finally naturally cooling to obtain the core-shell catalyst FeCo @ C.
Characterization of materials
The catalysts FeCo @ NC, FeCo @ NC-7, FeCo @ NC-30 and FeCo @ C obtained above were subjected to X-ray diffraction analysis (XRD), and XRD patterns thereof are shown in FIG. 2. As can be seen from FIG. 2, the major peaks formed by FeCo @ NC, FeCo @ NC-7, FeCo @ NC-30 and FeCo @ C are the same and all show the crystal structure of FeCo alloys.
The catalysts FeCo @ NC, FeCo @ NC-7, FeCo @ NC-30 and FeCo @ C prepared above were subjected to transmission electron microscopy analysis (TEM), and their TEM images are shown in FIG. 3. From FIG. 3, it can be observed that the carbon shell thicknesses of FeCo @ NC, FeCo @ NC-7, FeCo @ NC-30 and FeCo @ C are 7, 12, 30 and 8.5nm, respectively.
The catalyst FeCo @ NC prepared above is subjected to X-ray photoelectron spectroscopy (XPS) detection, and the spectrogram is shown in FIG. 4. The area (a) of fig. 4 shows that the N element is indeed incorporated into the FeCo @ NC sample, and the area (b) of fig. 4 is an analysis of the N element in the catalyst FeCo @ NC, and the N and the metal Fe/Co form a covalent structure as shown by the N1s spectrum.
Cord characterization of C-K and N-K edges of synchrotron radiation of the catalysts FeCo @ NC and FeCo @ C prepared above is shown in FIG. 5. As shown in FIG. 5, characterization of the N-K edge revealed that the catalyst FeCo @ NC did form a Co/Fe-N covalent bond compared to the standard Boron Nitride (BN); and in the characterization of the C-K edge, FeCo @ NC and FeCo @ C are found to have no obvious change compared with the standard sample Highly Oriented Pyrolytic Graphene (HOPG), which indicates that no Co/Fe-C covalent bond is generated.
Experiment of electrolytic Hydrogen production
The catalysts FeCo @ NC, FeCo @ NC-7, FeCo @ NC-30 and FeCo @ C are used as electrode materials of the seawater electrolysis anode for electrochemical performance test and evaluation.
(1) Preparation of electrode materials and electrolytes
Respectively taking 10mg of FeCo @ NC (or FeCo @ NC-7, FeCo @ NC-30 and FeCo @ C) powder serving as catalysts and 10mg of graphite powder into a 2mL glass bottle, adding 1.0mL of absolute ethanol and 0.1mL of 5% Nafion solution (binder), and carrying out ultrasonic treatment on the mixed solution for 1 hour to obtain uniform slurry.
(2) Modification of electrodes
Firstly, 5 μ L of the slurry obtained in step (1) is uniformly dripped on a glassy carbon electrode (GCE, 5mm) by using a pipette gun and dried at room temperature.
(3) Detecting electrochemical performance of catalyst in simulated seawater solution
And (3) carrying out all electrochemical performance tests by adopting a rotatable three-electrode system, wherein the electrode modified in the step (2) is used as a working electrode, the carbon rod is used as a counter motor, and silver-silver chloride (saturated potassium chloride solution) is used as a reference electrode. The three-electrode system was placed in 0.1M KOH +0.6NaCl (alkaline simulated seawater) electrolyte and subjected to linear voltammetric sweep test at a sweep rate of 0.05V/s (FIG. 6).
The catalyst is produced by 100 times amplification, 200mM ferric nitrate and 200mM cobalt nitrate are weighed according to the material proportion of the step of the example 1 and dissolved in a 5L glass container, 3000g melamine is added to be heated and stirred uniformly until the solution is completely volatilized and dry blocky powder is presented, the powder is moved to a tubular furnace with a larger diameter to be calcined under the atmosphere of N2, the calcination step is the calcination step in the example 1, a product produced by 100 times amplification can be obtained, and the characterization test result is the same as that of the example 1.
The catalyst is subjected to full-hydrolytic seawater experimental detection, 2.5mg of catalyst FeCo @ NC, 1mL of ethanol solution and 0.1mL of ethanol solution are weighed and evenly ultrasonically treated in a 2mL glass bottle, and the catalyst is loaded on a foamed nickel substrate in a spraying mode to serve as a full-hydrolytic anode. Secondly, 2.5mg Pt/C (40 wt%), 1mL ethanol solution and 0.1mL Nafion solution are weighed and evenly ultrasonically sprayed on a foam nickel substrate in a 2mL glass bottle to serve as a cathode load for full hydrolysis. And finally, detecting the full-hydrolysis performance of the cathode and the anode to a 1.0MKOH +0.6NaCl solution.
As can be seen from FIG. 6, the FeCo @ NC modified electrode showed the lowest overpotential of 288mV (current density of 10mA cm)-2) While the overpotentials for FeCo @ NC-7, FeCo @ NC-30 and FeCo @ C exhibit overpotentials of 288, 318, 317 and 490mV, respectively.
The product (ClO) of the chloride ion evolution reaction (CER) of each electrode under the high voltage (2.46V vs Ag/AgCl) test condition was detected by a residual chlorine detector-) Concentration and calculating the Faraday current efficiency of the OER reaction according to Faraday's law, thereby further exploring the OER selectivity of each electrode (see FIG. 7)
As shown in FIG. 7, the electrodes FeCo @ NC, FeCo @ NC-7 and FeCo @ NC-30 all showed over 95% OER selectivity, while the selectivity of FeCo @ C was only about 89%.
The stability of each electrode in the simulated seawater solution is respectively tested by using a chronoamperometry (figure 8), after the operation is carried out for 10 hours, the current density of the electrodes FeCo @ NC, FeCo @ NC-30 and FeCo @ C is hardly changed obviously, while the current density of the electrodes FeCo @ NC-7 is reduced to 10 percent, which is mainly due to the fact that the shell layer is thin, so that the protection performance of internal metal in a Cl-containing environment is not high, and the integral catalytic activity is reduced.
From the above results of LSV, OER selectivity and stability tests, electrode FeCo @ NC showed the best OER catalytic performance (with the lowest overpotential), OER selectivity (99.9%) and stability (-99.9%). The characterization by combining XRD, TEM, XPS and synchrotron radiation XAS shows that the nitrogen-containing carbon shell is rich in Co/Fe-N-C coordination structure, so that the pair OH is increased-Selective oxidation of ions. The active sites will be substantially reduced when the outer carbon shell is thin (e.g., catalyst FeCo @ NC-7) or thicker (e.g., FeCo @ NC-30) hinders electron transport between the inner metal and the outer carbon layer. Therefore, the FeCo @ NC has Co/Fe-N-C coordination bonds and a nitrogen-doped carbon shell with proper thickness, so that the performance of the catalyst in the anode of seawater electrolysis water is improved.
FeCo @ NC catalysts were tested for long term stability, with electrode pastes drop-coated onto carbon paper and placed in a 0.1M KOH +0.6NaCl solution (as in panel (a) of FIG. 9) exhibiting an overlength stability of 700h and a stability of over 1500h in a 1.0M KOH +0.6NaCl solution (as in panel (b) of FIG. 9).
The catalyst modified foam nickel was used as the anode in combination with commercial Pt/C (40 wt%) modified foam nickel as the cathode to perform a full hydrolysis experiment on a 1.0M KOH +0.6NaCl solution. Reaching 1.0A cm at 30 DEG C-2The current density of the electrode only needs 1.98V (as shown in figure 12), and the electrode shows the prospect of industrial application.
Claims (10)
1. A FeCo @ NC core-shell structure catalyst comprises an inner core and an outer shell, and is characterized in that the inner core is FeCo alloy, and the outer shell is a carbon material doped with N elements.
2. FeCo @ NC core-shell structured catalyst according to claim 1, characterized in that the thickness of the shell is 7-30nm, preferably 10-15 nm.
3. The FeCo @ NC core-shell structured catalyst according to claim 1, wherein the molar ratio of Fe to Co in the core is 1: 0.5-1.5.
4. A preparation method of a FeCo @ NC core-shell structure catalyst is characterized by comprising the following steps:
dissolving a cobalt source, an iron source and a nitrogen-containing carbon source in a solvent, uniformly stirring, and evaporating the solvent to obtain a precursor;
and 2, roasting the precursor to obtain the catalyst.
5. The preparation method of the FeCo @ NC core-shell structure catalyst according to claim 4, characterized in that the cobalt source is one or a mixture of cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt citrate; the iron source is one or a mixture of ferric nitrate, ferric oxide, ferric sulfate and ferric citrate; the nitrogen-containing carbon source is selected from melamine.
6. The preparation method of the FeCo @ NC core-shell structure catalyst according to claim 4, wherein the molar ratio of the cobalt source to the iron source is 1: 0.5-1.5; the addition amounts of the cobalt source, the iron source and the nitrogen-containing carbon source are as follows according to the total addition molar weight of cobalt and iron and the addition weight of the nitrogen-containing carbon source: 2-4 mmol: 10-60 g; preferably 2 to 4 mmol: 30 g.
7. The method for preparing FeCo @ NC core-shell structured catalyst according to claim 4, characterized in that the calcination process is in inert atmosphere.
8. The method for preparing FeCo @ NC core-shell structured catalyst according to claim 4, wherein in the calcining step, the temperature rise rate of the first stage is controlled to be 1-2 ℃ for min-1To 350-500 ℃ for 1-1.5h, and controlling the second-stage heating rate to 4-6 ℃ for min-1Maintaining at 800 ℃ for 1-2h to 700-.
9. Use of a FeCo @ NC core-shell structured catalyst according to claim 1 in a process for the electrolytic production of hydrogen from seawater.
10. The use according to claim 9, wherein the FeCo @ NC core-shell structured catalyst has a loading on the electrode surface of 2-2.5mg cm-2。
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