CN115247271A - Transition metal heterogeneous catalyst with ultrahigh structural stability and preparation method thereof - Google Patents
Transition metal heterogeneous catalyst with ultrahigh structural stability and preparation method thereof Download PDFInfo
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- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 67
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 51
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- -1 nitrogen-containing anion Chemical class 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 37
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 239000004202 carbamide Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 150000001450 anions Chemical class 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- DZHMRSPXDUUJER-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;dihydrogen phosphate Chemical compound NC(N)=O.OP(O)(O)=O DZHMRSPXDUUJER-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008602 contraction Effects 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 28
- 229910052717 sulfur Inorganic materials 0.000 description 18
- 239000011593 sulfur Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 12
- 238000011056 performance test Methods 0.000 description 10
- 239000005864 Sulphur Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910003321 CoFe Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- ZMXPKUWNBXIACW-UHFFFAOYSA-N [Fe].[Co].[Mo] Chemical compound [Fe].[Co].[Mo] ZMXPKUWNBXIACW-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 1
- QRXDDLFGCDQOTA-UHFFFAOYSA-N cobalt(2+) iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Co+2].[O-2] QRXDDLFGCDQOTA-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- DMTIXTXDJGWVCO-UHFFFAOYSA-N iron(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Fe++].[Ni++] DMTIXTXDJGWVCO-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 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
- 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
-
- 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
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
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Abstract
The invention discloses a transition metal heterogeneous catalyst with ultrahigh structure stability and a preparation method thereof, wherein the transition metal heterogeneous catalyst is prepared by accurately controlling the dosage of a nitrogen-containing anion source and a transition metal oxide, converting partial oxides in the transition metal oxide into corresponding anion transition metal compounds, and simultaneously carrying out nitrogen doping on the anion transition metal compounds, thereby constructing a nitrogen-doped transition metal oxide/transition metal anion compound interface in a material. Compared with the traditional oxide/sulfide heterogeneous catalyst, the transition metal heterogeneous catalyst prepared by the invention has weaker hydroxide radical adsorption capacity and longer metal-oxygen bond, so that the transition metal heterogeneous catalyst has stronger resistance to hydroxide radical adsorption and bond length contraction in the phase transition process of oxyhydroxide, and can maintain a transition metal oxide/transition metal anion compound interface as an active site in an OER reaction, thereby having high conductivity and high OER catalytic activity.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a transition metal heterogeneous catalyst with ultrahigh structural stability and a preparation method thereof.
Background
The Oxygen Evolution Reaction (OER) of the water electrolysis anode often requires a large overpotential to drive the reaction due to its own complex reaction kinetics and four-electron transfer process, thereby reducing the hydrogen production efficiency of water electrolysis and increasing the application cost. Therefore, research and development of efficient and stable OER catalyst for reducing thermokinetic energy barrier are of great significance to the development of electrolytic aquaculture
The transition metal heterogeneous material is widely researched in the field of electrocatalysis in recent years, and by constructing a specific interface structure, strong electronic interaction can be generated between two phases of an interface, so that the conductivity of the catalyst can be remarkably improved, a new active site can be formed at the interface, and the catalyst has higher reaction activity, so that the transition metal heterogeneous catalyst can show excellent catalytic performance in electrocatalysis.
In OER catalysis, transition metal catalysts, including transition metal heterocatalysts, are inevitably oxidized to oxyhydroxides under the influence of their strong oxidizing environment and act as active sites to catalyze the progress of OER. Therefore, although the transition metal heterogeneous catalyst has many excellent characteristics, its specific interface structure cannot be maintained and used as an active site in the OER, which hinders further development in the OER catalytic field.
Disclosure of Invention
The present invention is directed to provide a transition metal heterogeneous catalyst having ultra-high structural stability in an Oxygen Evolution Reaction (OER) of an anode for electrolyzing water, which can maintain its specific interface structure and catalyze as an active site in the OER reaction, thereby enhancing its OER activity.
In order to realize the purpose, the invention adopts the following technical scheme:
a transition metal heterogeneous catalyst with ultrahigh structure stability is prepared by the following steps:
(1) Respectively weighing a proper amount of nitrogen-containing anion source and transition metal oxide according to the molar ratio of the anion element to the transition metal element, and respectively filling the nitrogen-containing anion source and the transition metal oxide into two open quartz boats;
(2) Placing the quartz boat containing the nitrogen-containing anion source in an upper air inlet of the tube furnace, and placing the quartz boat containing the transition metal oxide in the center of the tube furnace;
(3) And carrying out chemical vapor deposition under an inert gas atmosphere to convert part of oxides in the transition metal oxide into corresponding transition metal anionic compounds, and carrying out nitrogen doping on the transition metal anionic compounds to obtain the nitrogen-doped transition metal oxide/transition metal anionic compound heterogeneous catalyst.
Wherein, the transition metal is any 1-3 of iron, cobalt, nickel and molybdenum, namely the transition metal can be iron, cobalt, nickel and molybdenum or binary and ternary alloys thereof, such as cobalt iron, nickel iron, cobalt iron molybdenum and the like.
The nitrogen-containing anion source is a substance capable of releasing ammonia gas and anion-containing gas-phase compounds in a high-temperature inert gas environment, and specifically comprises urea phosphate or a mixture of urea and any one of sublimed sulfur, sodium dihydrogen phosphate, red phosphorus, boron powder and boric acid; the molar ratio of the anion element to the nitrogen element in the nitrogen-containing anion source is 1.
When the molar ratio of the anionic element to the transition metal element is less than 10; when the molar ratio of the two is higher than 30. Therefore, when the molar ratio of the anion element to the transition metal element is controlled to be 10. When the molar ratio of the anion element to the transition metal element is preferably 20.
The reaction temperature of the chemical vapor deposition is 400-600 ℃, and the reaction time is 1 hour. When the temperature of the chemical vapor deposition is lower, the nitrogen-containing anion source is not completely decomposed and can not release ammonia gas, so that the nitrogen element is difficult to be doped into the catalyst; at higher temperature, the transition metal particles will agglomerate seriously, covering the active sites of the catalyst and reducing the activity of the catalyst.
In inert gas, nitrogen-containing anion source is used for carrying out vapor deposition on the transition metal oxide at high temperature, and only part of oxide in the transition metal oxide can be converted into corresponding transition metal anionic compound by accurately controlling the molar ratio of anion element to transition metal element, and the transition metal anionic compound is coupled with the rest oxide to form an interface structure. Meanwhile, nitrogen in the nitrogen-containing anion source can be simultaneously doped into the transition metal oxide and the transition metal anion compound in the vapor deposition process, so that the nitrogen-doped transition metal oxide/transition metal anion compound heterogeneous catalyst is obtained. The catalyst has weaker hydroxide radical adsorption capacity and longer metal-oxygen bonds, so that the catalyst has stronger resistance to hydroxide radical adsorption and bond length contraction in the phase transition process of oxyhydroxide, and the catalyst can maintain an interface structure and serve as an active site in OER catalysis, so that the transition metal heterogeneous catalyst can be used in oxygen evolution reaction of an electrolytic water anode.
The transition metal heterogeneous catalyst with ultrahigh structural stability for oxygen evolution reaction has the following benefits:
1) According to the invention, transition metal oxides such as iron, cobalt, nickel iron and the like react with a nitrogen-containing anion source according to a specific molar ratio to prepare the nitrogen-doped transition metal heterogeneous catalyst in one step, and the method is safe, convenient and fast and is easy for large-scale production.
2) The nitrogen element doped in the invention can effectively stretch the metal-oxygen bond of the oxide in the transition metal heterogeneous catalyst, so that the metal-oxygen bond has stronger resistance to bond length shrinkage in the formation process of oxyhydroxide, and the oxide phase in the transition metal heterogeneous catalyst can be retained in the OER process.
3) In the nitrogen-doped transition metal heterogeneous catalyst, the adsorption capacity of the material to hydroxide ions is weakened under the influence of nitrogen doping, so that the material is not easy to adsorb hydroxide ions in an OER process to form hydroxide oxides, and further the conversion of the material to the hydroxide oxides is inhibited.
4) The reservation of the nitrogen-doped transition metal oxide/transition metal anion compound heterostructure obtained by the invention enables the catalyst to have more excellent catalytic activity and conductivity in OER, thereby showing extremely high-efficiency OER performance.
Drawings
FIG. 1 is a graph showing the results of OER performance tests on the heterogeneous catalysts obtained in examples 1, 3 and 4.
FIG. 2 is a graph showing the results of OER performance tests on the heterogeneous catalysts obtained in examples 1, 5, 7 and 8.
FIG. 3 is a graph showing the results of OER performance test of the heterogeneous catalysts obtained in example 1 and comparative example 1.
Fig. 4 is an X-ray photoelectron spectrum of examples 1 and 2 and comparative examples 1 and 2.
FIG. 5 is an X-ray diffraction pattern of example 1 and comparative example 5.
FIG. 6 is a graph showing the results of OER performance tests on the catalysts obtained in example 1 and comparative examples 3, 4 and 5.
FIG. 7 is a graph showing the results of OER performance test of the heterogeneous catalysts obtained in example 5 and comparative example 6.
FIG. 8 is an X-ray photoelectron spectrum of examples 5 and 6 and comparative examples 6 and 7.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1:
accurately weighing 100 mg of nickel oxide and a mixture consisting of 1.606g of urea and 0.856g of sulfur powder by using an electronic balance at normal temperature (wherein the molar ratio of sulfur to nickel is 20.
Example 2:
the heterogeneous catalyst I prepared in example 1 was subjected to a chronopotentiometric test (test potential 0.002V) in 1M KOH for 10 hours, and a sample after the test was collected to obtain a heterogeneous catalyst I after OER.
Example 3:
heterogeneous catalyst II was obtained by following the same procedure as in example 1 except that the mixture of 1.02g of urea and 0.272g of powdered sulfur in example 1 was replaced with a mixture of 0.803g of urea and 0.428g of powdered sulfur (wherein the molar ratio of sulfur/nickel was 10 and the molar ratio of sulfur/nitrogen was 1.
Example 4:
the same procedure as in example 1 was repeated except for replacing the mixture of 1.02g of urea and 0.272g of powdered sulfur in example 1 with a mixture of 2.409g of urea and 1.284g of powdered sulfur (the molar ratio of sulfur to nickel being 30 and the molar ratio of sulfur to nitrogen being 1).
FIG. 1 shows the results of OER performance tests of the heterogeneous catalysts obtained in examples 1, 3 and 4. As shown in the figure, the heterogeneous catalyst I has the most excellent OER catalytic performance, and the current density reaches 30 mA-cm -2 Its overpotential is only 270 mV, much lower than 318 mV for heterogeneous catalyst II and 303 mV for heterogeneous catalyst III, demonstrating a sulfur/nickel molar ratio of 20 in vapor deposition.
Example 5:
accurately weighing 100 mg of nickel-iron oxide (NiFe) by an electronic balance at normal temperature 2 O 4 ) And a mixture consisting of 0.519g of urea and 0.273g of sulfur powder (wherein the molar ratio of sulfur to transition metal atoms is 20, and the molar ratio of sulfur to nitrogen is 1.
Example 6:
the heterogeneous catalyst IV obtained in example 5 was subjected to a chronopotentiometric test (test potential of 0.002V) in 1M KOH for 10 hours, and a sample after the test was collected to obtain a heterogeneous catalyst IV after OER.
Example 7:
accurately weighing 100 mg of cobalt iron oxide (CoFe) by using an electronic balance at normal temperature 2 O 4 ) And a mixture consisting of 0.511 g of urea and 0.272g of sulfur powder (wherein the molar ratio of sulfur to transition metal atoms is 20.
Example 8:
accurately weighing 100 mg of cobalt-nickel oxide (CoNiO) by an electronic balance at normal temperature 2 ) And a mixture consisting of 0.802 g of urea and 0.428g of sulfur powder (wherein the molar ratio of sulfur to transition metal atoms is 20.
FIG. 2 is a graph showing the results of OER performance tests of examples 1, 5, 7 and 8. As shown, heterogeneous catalyst IV has the most excellent OER performance in all heterogeneous catalysts, demonstrating that nickel iron transition metal oxide is the optimal transition metal feedstock.
Comparative example 1:
heterogeneous catalyst VII was obtained by replacing the urea and sulphur powder mixture of example 1 with an equimolar amount of sublimed sulphur (molar ratio of sulphur to nickel of 20.
Comparative example 2:
the heterogeneous catalyst V obtained in comparative example 1 was subjected to a chronopotentiometric test (test potential 0.002V) in 1M KOH for 10 hours, and a sample after the test was collected to obtain a heterogeneous catalyst VII after OER.
FIG. 3 is a graph showing the results of OER performance tests on the heterogeneous catalysts obtained in example 1 and comparative example 1. As shown in the figure, the nitrogen-doped heterogeneous catalyst I has more excellent OER performance compared with the non-nitrogen-doped heterogeneous catalyst VII, and the current density reaches 30 mA-cm -2 When the catalyst is used, the overpotential is only 270 mV, which is far lower than 323 mV of the heterogeneous catalyst VII without nitrogen doping.
FIG. 4 is an X-ray photoelectron spectrum of examples 1 and 2 and comparative examples 2 and 3. As shown, example 1 and example 2 have similar signals in the Ni 2p orbital, demonstrating that nitrogen-doped heterogeneous catalyst I has excellent structural stability during OER; whereas for comparative example 1, which has a similar Ni 2p spectrum as example 1, it is demonstrated that nitrogen-doped heterogeneous catalyst I has a similar chemical structure as non-nitrogen-doped heterogeneous catalyst VII; for comparative example 2, the signal of the Ni 2p spectrum was significantly changed from that of comparative example 1, demonstrating that the non-nitrogen doped heterogeneous catalyst VII undergoes a significant phase structure transformation during the OER catalysis process and the heterostructure cannot be maintained in OER.
Comparative example 3:
the mixture of urea and sulfur powder in example 1 was replaced with 1.606g of urea, and the remaining procedure was the same as in example 1, to obtain nitrogen-doped oxide catalyst I.
Comparative example 4:
the heterogeneous catalyst VIII was obtained by replacing the urea and sulphur powder mixture of example 1 with 1.94g of thiourea (20 molar ratio of sulphur to nickel 1, 1 molar ratio of sulphur to nitrogen 2), and following the same procedure as in example 1.
Comparative example 5:
the same procedure as in example 1 was repeated except for replacing the urea and sulfur powder mixture of example 1 with 9.7 g of thiourea (sulfur/nickel molar ratio of 100:1 and sulfur/nitrogen molar ratio of 1: 2), to obtain nitrogen-doped sulfide catalyst I.
FIG. 5 is an X-ray diffraction pattern of example 1 and comparative example 5. As shown, comparative example 5 exhibited a pure-phase NiS crystal structure, demonstrating that when the sulfur/nickel molar ratio in vapor deposition is 100; while in XRD of example 1, two crystal phases of NiS and NiO exist simultaneously, which proves that example 1 is a heterogeneous catalyst of NiS/NiO heterostructure.
FIG. 6 is a graph showing the results of OER performance tests on the catalysts obtained in example 1 and comparative examples 3, 4 and 5. As shown in the figure, the heterogeneous catalyst I taking the mixture of urea and sulfur powder as the anion source has the most excellent catalytic activity, and the mixture of urea and sulfur powder as the optimal anion source for preparing the heterogeneous catalyst.
Comparative example 6
The heterogeneous catalyst IX was obtained by following the same procedure as in example 5, replacing the urea and sulfur powder mixture of example 5 with an equimolar amount of sublimed sulfur (wherein the molar ratio of sulfur to transition metal atoms was 20.
Comparative example 7:
the heterogeneous catalyst VI obtained in comparative example 6 was subjected to a chronopotentiometric test (test potential 0.002V) in 1M KOH for 10 hours, and a sample after the test was collected to obtain a heterogeneous catalyst IX after OER.
FIG. 7 is a graph showing the results of OER performance test of the heterogeneous catalysts obtained in example 5 and comparative example 6. As shown in the figure, nitrogen-doped heterogeneous catalyst IV has more excellent OER performance than non-nitrogen-doped heterogeneous catalyst IX, and the current density reaches 30 mA-cm -2 The overpotential is only 245 mV, much lower than 294 mV of heterogenous catalyst IX.
FIG. 8 is an X-ray photoelectron spectrum of examples 5 and 6 and comparative examples 6 and 7. As shown, example 5 and example 6 have similar signals in both Ni 2p and Fe 2p orbitals, demonstrating the excellent structural stability of nitrogen-doped heterogeneous catalyst IV during OER; whereas for comparative example 6, which has similar Ni 2p and Fe 2p spectra as example 5, it is demonstrated that nitrogen-doped heterogeneous catalyst IV has a similar chemical structure as non-nitrogen-doped heterogeneous catalyst IX; in contrast, in comparative example 7, the signal of the Ni 2p spectrum was significantly changed from that in comparative example 6, which demonstrates that the non-nitrogen-doped heterogeneous catalyst VI undergoes a significant phase structure transformation during the OER catalysis process, and the heterogeneous structure cannot be maintained in the OER.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. A preparation method of a transition metal heterogeneous catalyst with ultrahigh structure stability is characterized by comprising the following steps: the method comprises the following steps:
(1) Respectively arranging a transition metal oxide and a nitrogen-containing anion source in two quartz boats with openings;
(2) Placing the quartz boat containing the nitrogen-containing anion source in an upper air inlet of the tube furnace, and placing the quartz boat containing the transition metal oxide in the center of the tube furnace;
(3) And carrying out chemical vapor deposition under an inert gas atmosphere to convert part of oxides in the transition metal oxide into corresponding transition metal anionic compounds, and carrying out nitrogen doping on the transition metal anionic compounds to obtain the nitrogen-doped transition metal oxide/transition metal anionic compound heterogeneous catalyst.
2. The method of preparing a transition metal heterogeneous catalyst according to claim 1, wherein: the transition metal is any 1-3 of iron, cobalt, nickel and molybdenum.
3. The method of preparing a transition metal heterogeneous catalyst according to claim 1, wherein: the nitrogen-containing anion source is a substance capable of releasing ammonia gas and anion-containing gas-phase compounds in a high-temperature inert gas environment, and specifically comprises urea phosphate or a mixture of urea and any one of sublimed sulfur, sodium dihydrogen phosphate, red phosphorus, boron powder and boric acid.
4. The method of preparing a transition metal heterogeneous catalyst according to claim 1, wherein: the dosage of the nitrogen-containing anion source and the transition metal oxide is converted according to the molar ratio of the anion element to the transition metal element of 10;
the molar ratio of the anion element to the nitrogen element in the nitrogen-containing anion source is 1.
5. The method of preparing a transition metal heterogeneous catalyst according to claim 1, wherein: the reaction temperature of the chemical vapor deposition is 400-600 ℃, and the reaction time is 1 hour.
6. A transition metal heterogeneous catalyst made by the process of claim 1.
7. Use of a transition metal heterogenous catalyst according to claim 6 in an oxygen evolution reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110201697A (en) * | 2019-05-29 | 2019-09-06 | 浙江大学 | A kind of three-dimensional N doping transition metal oxide/vulcanization nickel composite catalyst and preparation method and application |
| CN112795946A (en) * | 2020-12-08 | 2021-05-14 | 广西大学 | Preparation method of transition metal oxyhydroxide coated tungsten-based oxygen evolution catalyst |
| CN114016053A (en) * | 2021-12-10 | 2022-02-08 | 福州大学 | Method for improving stability of transition metal sulfide catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110201697A (en) * | 2019-05-29 | 2019-09-06 | 浙江大学 | A kind of three-dimensional N doping transition metal oxide/vulcanization nickel composite catalyst and preparation method and application |
| CN112795946A (en) * | 2020-12-08 | 2021-05-14 | 广西大学 | Preparation method of transition metal oxyhydroxide coated tungsten-based oxygen evolution catalyst |
| CN114016053A (en) * | 2021-12-10 | 2022-02-08 | 福州大学 | Method for improving stability of transition metal sulfide catalyst |
Non-Patent Citations (3)
| Title |
|---|
| TONGFEI LI: "Interfacial engineering-induced electronic regulation drastically enhances the electrocatalytic oxygen evolution: Immobilization of Janus-structured NiS/NiO nanoparticles onto carbon nanotubes/ nanofiber-integrated superstructures", CHEMICAL ENGINEERING JOURNAL, vol. 428, 2 July 2021 (2021-07-02) * |
| 李鑫: "几种过渡金属基异质结材料的电/光催化性能增强研究", 硕士电子期刊, 15 January 2022 (2022-01-15) * |
| 赵静;欧阳艳;: "富含缺陷的(Ni-Co)O_x-NiCo_2S_4三维异质纳米片的制备及氧析出性能研究", 电子元件与材料, no. 07, 5 July 2020 (2020-07-05) * |
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