CN113457689A - Three-dimensional structure iron-doped cobalt-molybdenum oxide composite material and preparation method and application thereof - Google Patents
Three-dimensional structure iron-doped cobalt-molybdenum oxide composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- QUEGLSKBMHQYJU-UHFFFAOYSA-N cobalt;oxomolybdenum Chemical compound [Mo].[Co]=O QUEGLSKBMHQYJU-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000013535 sea water Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000004729 solvothermal method Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- 150000002505 iron Chemical class 0.000 claims abstract 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000000460 chlorine Substances 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000002135 nanosheet Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910018890 NaMoO4 Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 2
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910015607 MoO3-a Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- MQYRLAZBVBHGDU-UHFFFAOYSA-J iron(2+) nickel(2+) dicarbonate Chemical compound C([O-])([O-])=O.[Ni+2].[Fe+2].C([O-])([O-])=O MQYRLAZBVBHGDU-UHFFFAOYSA-J 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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Abstract
The invention relates to the technical field of nano materials, and provides an iron-doped cobalt-molybdenum oxide composite material with a three-dimensional structure and a preparation method thereof aiming at the problems of poor catalytic selectivity and insufficient stability of an electrolytic seawater catalyst, wherein a precursor material Co-MOF @ NF is prepared firstly; then in the mixed solution of molybdate and iron salt, the precursor material is further extractedCarrying out a solvothermal method to obtain a metal ion doped MOF derivative material after reaction; and then placing the MOF derivative material in a reducing atmosphere, and heating at two stages to obtain the iron-doped cobalt-molybdenum oxide composite material. The three-dimensional structure iron-doped cobalt-molybdenum oxide composite material has higher electrocatalytic activity and stability of hydrogen precipitation and oxygen precipitation under the condition of chlorine, and is far superior to commercial Pt/C and IrO2The catalyst and the preparation method have low cost. The invention also provides application of the catalyst in seawater electrocatalysis.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a three-dimensional structure iron-doped cobalt-molybdenum oxide composite material and a preparation method and application thereof.
Background
The energy problem has been widely noticed by society, and currently, non-renewable energy sources such as coal, petroleum, natural gas and the like are mainly used, and the non-renewable energy sources can cause serious harm to the environment, so that people are forced to find a renewable new energy source with rich reserves. The hydrogen gas is one of ideal energy sources capable of replacing the traditional fossil fuel due to the characteristics of high energy density (142MJ kg-1) and no pollution. Among the hydrogen production methods, the hydrogen production by electrolyzing water becomes an important means for realizing the industrial low-cost hydrogen production due to the advantages of high product purity, high conversion rate (close to 100 percent) and the like. However, large scale electrolysis of fresh water will place heavy pressure on important water resources.
Seawater is one of the most abundant natural resources on earth, and accounts for 96.5 percent of the total amount of water resources in the world. It is very important and promising to directly electrolyze seawater instead of fresh water, especially in arid areas. For example, patent CN112501647A discloses an oxygen evolution reaction catalyst, preparation, application, electrolysis device and seawater cracking method, the oxygen evolution reaction catalyst comprises a foamed nickel substrate and amorphous/nanocrystalline basic iron carbonate loaded on the foamed nickel substrate, the amorphous and nanocrystalline mixed structure of basic iron nickel carbonate (FeNiCH) contains more surface adsorbed oxygen and oxygen defects, which may adjust the electronic structure of fe (iii)/ni (ii), optimize the adsorption energy of OER intermediate, and the surface adsorbed oxygen and defect oxygen may be related to its chloride resistance and high corrosion resistance.
The most major challenge in the seawater cracking process occurs in the Chlorine Evolution Reaction (CER) at the anode, which competes with the Oxygen Evolution Reaction (OER), due to the presence of chloride ions in the seawater. CER is a simple two-electron process, so the kinetic rate of CER is much faster. In this regard, one of the greatest challenges is to make a stable anode, increase catalyst selectivity to suppress CER to facilitate seawater electrolysis to the best performance achievable with fresh water, and make it widely used for hydrogen production.
NiO and Co have recently become the most useful materials3O4、MnO2The transition metal oxides have been widely studied in water electrolysis due to their advantages of high rare earth content, low cost, environmental friendliness, etc. However, the performance of the original metal oxide is often unsatisfactory due to its undesirable adsorption energy to the reaction intermediate, which is poor in conductivity. And the metal doping is an effective way for promoting the inter-ion synergistic effect and improving the intrinsic activity of the catalyst by adjusting the distribution of electrons. Molybdenum (Mo) element is considered to have good corrosion resistance, which is confirmed in corrosion resistant alloys and stainless steels containing Mo. Therefore, it is of great significance to develop an electrocatalytic material which can be adapted to work under chlorine-containing conditions and has good electrocatalytic performance.
Disclosure of Invention
The invention aims to overcome the problems of poor catalytic selectivity and insufficient stability of the existing seawater electrolysis catalyst, and provides a three-dimensional structure iron-doped cobalt-molybdenum oxide composite material and a preparation method thereof2The catalyst and the preparation method have low cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a three-dimensional structure iron-doped cobalt-molybdenum oxide composite material comprises the following steps:
1) preparing a precursor material: respectively preparing methanol solutions of cobalt nitrate hexahydrate and 2-methylimidazole, mixing, adding foamed nickel NF (NF) serving as a conductive substrate, standing, and growing a precursor on the foamed nickel to obtain a precursor material Co-MOF @ NF;
2) in a mixed solution of molybdate and ferric salt, further reacting the precursor material by adopting a solvothermal method to obtain a metal ion doped MOF derivative material;
3) and (3) placing the MOF derivative material obtained in the step 2) in a reducing atmosphere, heating to a first-stage temperature, then preserving heat for a period of time, then heating again for two steps, heating to a second-stage temperature, and preserving heat for a period of time to obtain the iron-doped cobalt-molybdenum oxide composite material.
In the synthesis process of the invention, firstly, a cobalt metal organic solution is prepared, and a two-dimensional sheet grows in situ on NF. The two-dimensional sheets growing on the surface of the conductive substrate are uniformly distributed and have uniform size, so that a good foundation is formed for the subsequent preparation of the composite material. And then in the solvothermal reaction, on the basis of keeping the original two-dimensional sheet, a smaller two-dimensional nano sheet is etched on the surface, so that the specific surface area of the whole material is improved. In the subsequent reduction and calcination process, part of the ligand is gradually eliminated in the one-step heating process, and the two-dimensional sheet is kept relatively stable when the temperature is kept at one stage. After the two-step temperature rise is started, iron compounds in the three metal components are gradually reduced to form elemental metal iron, the elemental metal iron is doped in situ, and the iron is uniformly distributed in the two-dimensional sheet, so that the aim of uniformly doping the reduced elemental metal iron can be directly fulfilled. In addition, part of the cobalt valence can react with gas components in the reducing atmosphere to form new cobaltous oxide, part of the molybdenum valence is not reduced to form molybdenum trioxide, and the other part of the cobalt valence and the molybdenum component form cobalt molybdate to form a cobaltous oxide/cobalt molybdate/molybdenum trioxide composite material two-dimensional sheet material. The material has excellent seawater electrolysis catalytic performance and excellent alkali resistance stability through the synergistic cooperation of the components and the structure.
Preferably, the molar ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate in the step 1) is (7-9): 1. As a further preference, the molar ratio of 2-methylimidazole to cobalt nitrate hexahydrate in step 1) is 8: 1. The optimal molar ratio of the 2-methylimidazole to the metal salt has the optimal proportion, and the change of the proportion can influence the crystallinity of the synthesized MOF and the stability of the material in subsequent operation.
Preferably, the growth time in the step 1) is 4h, and the morphology of the Co-MOF is a two-dimensional triangular structure.
Preferably, NaMoO is used as the molybdate and the ferric salt in the step 2) respectively4·2H2O and Fe (NO)3)3·9H2And O, wherein the solvent is a mixed solution of DMF and deionized water.
Preferably, the temperature of the solvothermal reaction in the step 2) is 100-200 ℃, and the reaction time is 2-24 h. If the temperature of the solvothermal reaction is too low, the two-dimensional nanosheet cannot be formed due to the fact that the thermodynamic temperature of the precursor is not reached, and the optimal solvothermal reaction temperature is 150 ℃.
Preferably, the reducing atmosphere in the step 2) is hydrogen and nitrogen atmosphere, wherein the hydrogen content is more than or equal to 10% VOL.
Preferably, the temperature rise rate of the one-step temperature rise in the step 3) is 1-10 ℃/min; the temperature of the first stage is 150-350 ℃, and the heat preservation time is 2-4 h; the temperature rise rate of the two-step temperature rise is 1-10 ℃/min; the temperature of the two stages is 400-700 ℃, and the heat preservation time is 2-4 h. Wherein, the second-order temperature is too high in the reducing atmosphere, so that the etching effect is further generated on the small nano-sheets in the sample, the two-dimensional nano-sheets on the surface are reduced into clusters, the specific surface area of the material is reduced, and the performance of the catalytic reaction is reduced.
The invention also provides a three-dimensional structure iron-doped cobalt-molybdenum oxide composite material prepared by the preparation method, and the structural formula is Fe-CoO/Co2Mo3O8/MoO3@NF。
The invention also provides application of the three-dimensional structure iron-doped cobalt-molybdenum oxide composite material prepared by the preparation method in seawater electrocatalysis.
Therefore, the beneficial effects of the invention are as follows: 1) the preparation is simple and efficient, the requirement on equipment is low, and the popularization is convenient to realize industrial production; 2) the hydrogen and oxygen evolution double functions are realized, the coating on the electrode is not needed, the self-supporting electrode can be directly used as a self-supporting electrode, and the universality is wide; 3) the prepared three-dimensional structure iron-doped cobalt-molybdenum oxide composite material has a stable microstructure, uniform size of a nano structure, uniform component distribution and good electro-catalytic performance and mechanical performance; 4) the electrocatalysis effect is better under the alkaline and seawater conditions; 5) the prepared three-dimensional structure iron-doped cobalt-molybdenum oxide composite material has higher electrocatalytic activity and stability of hydrogen precipitation and oxygen precipitation under the condition of chlorine, is far superior to commercial Pt/C and IrO2 catalysts, and has lower cost.
Drawings
FIG. 1 is Fe-CoO/Co prepared in example 12Mo3O8/MoO3The topographic structure group diagram of @ NF;
FIG. 2 shows Fe-CoO/Co prepared in example 12Mo3O8/MoO3The XRD spectrum of @ NF;
FIG. 3 shows Fe-CoO/Co prepared in example 12Mo3O8/MoO3The OER and HER performance test chart of @ NF in alkaline solution;
FIG. 4 shows Fe-CoO/Co prepared in example 12Mo3O8/MoO3@ NF A performance test chart under alkaline chlorine-containing conditions;
FIG. 5 shows Fe-CoO/Co prepared in example 22Mo3O8/MoO3-a topographic structure set of 0.4@ NF;
FIG. 6 is Fe-CoO/Co prepared in example 32Mo3O8/MoO3-2@ NF-150;
FIG. 7 shows Fe-CoO/Co prepared in example 32Mo3O8/MoO3The topographic structure group diagram of @ NF-130;
FIG. 8 is Fe-CoO/Co obtained in example 32Mo3O8/MoO3The topographic structure group diagram of @ NF-550.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
A preparation method of a three-dimensional structure iron-doped cobalt-molybdenum oxide composite material comprises the following steps:
1) 0.5g of Co (NO) is weighed3)2·6H2O, and 1.3g 2-methylimidazole were dissolved in 80mL deionized water to preparePreparing a metal organic solution, putting the foamed nickel into the solution, standing for 4h, taking out the foamed nickel with the grown precursor, washing with deionized water, and drying to obtain an MOF precursor material Co-MOF @ NF;
2) weighing 64mg NaMoO4·2H2O and 13mg Fe (NO)3)3·9H2Placing the Co-MOF @ NF prepared in the step 1) in a mixed solution of 14mL of DMF and 1mL of deionized water in a reaction kettle for hydrothermal reaction at 150 ℃ for 6h, and obtaining a metal doped MOF derivative material after the solvothermal reaction;
3) after the metal-doped MOF derivative material is naturally cooled to room temperature, placing the metal-doped MOF derivative material in hydrogen/nitrogen mixed gas with the hydrogen content of 10% VOL, carrying out one-step temperature rise at the temperature rise rate of 10 ℃/min to the first-stage temperature of 280 ℃, then carrying out heat preservation for 2h, then carrying out two-step temperature rise at the temperature rise rate of 10 ℃/min, carrying out heat preservation for 2h after the temperature rise to the second-stage temperature of 450 ℃, and cooling to room temperature to obtain the three-dimensional structure iron-doped cobalt-molybdenum oxide composite material, wherein the three-dimensional structure iron-doped cobalt-molybdenum oxide composite material prepared in the embodiment is marked as Fe-CoO/Co2Mo3O8/MoO3@ NF. FIG. 1(a) shows Fe-CoO/Co2Mo3O8/MoO3SEM picture of @ NF from which Fe-CoO/Co can be seen2Mo3O8/MoO3The @ NF two-dimensional sheet is vertically grown on a nickel foam substrate, the thickness of the two-dimensional sheet is about 500nm, and the thickness of the nano sheet on the surface is about 15 nm. FIG. 1(b) shows Fe-CoO/Co2Mo3O8/MoO3TEM image of @ NF, it can be seen that Fe-CoO/Co2Mo3O8/MoO3A nanosheet structure of @ NF surface; FIG. 1(c) shows Fe-CoO/Co2Mo3O8/MoO3The distribution diagram of the transmission element of @ NF shows that the Fe element is uniformly distributed in the nanosheet besides Co and Mo, and the composition is uniform. The resulting Fe-CoO/Co is shown in FIG. 22Mo3O8/MoO3The @ NF has good crystallinity, and the comparison of PDF cards shows that the @ NF respectively corresponds to CoO and Co2Mo3O8And MoO3Illustrates the successful synthesis of Fe-CoO/Co2Mo3O8/MoO3@ NF materials. The subsequent OER and HER performance tests are carried out, and as can be seen from FIG. 3(a), the OER performance test is carried out in 1M KOH, and the current density reaches 20mA/cm2In time of, Fe-CoO/Co2Mo3O8/MoO3The potential of @ NF is only 1.53V, which is far superior to that of commercial IrO2Exhibits excellent OER performance; FIG. 3(b) shows that HER performance tests were performed in 1M KOH and the current density reached-10 mA/cm2In time of, Fe-CoO/Co2Mo3O8/MoO3The potential of @ NF was only-0.087V, very close to that of the commercial Pt/C catalyst. FIG. 4(a) shows Fe-CoO/Co2Mo3O8/MoO3@NF||Fe-CoO/Co2Mo3O8/MoO3The polarization curves of the @ NF assembled catalyst in alkaline simulated seawater and alkaline seawater solution show that the current density is 10 mA-cm-2The cell voltages measured at that time were divided into 1.576V and 1.593V, indicating that the material maintained good performance under chlorine-containing conditions. Fig. 4(b) is a graph for detecting the hydrogen and oxygen yields of the catalyst under chlorine-containing conditions, and it can be seen that the actually measured gas volumes and theoretical values substantially coincide, indicating that our material has excellent selectivity. From the above characterization and testing, it is clear that Fe-CoO/Co prepared in this example2Mo3O8/MoO3The @ NF three-dimensional structure iron-doped cobalt-molybdenum oxide composite material has good electrocatalytic performance, good structural stability and good component uniformity. Can be used for seawater electrocatalysis.
Example 2
A preparation method of a three-dimensional structure iron-doped cobalt-molybdenum oxide composite material comprises the following preparation steps:
1) 0.5g of Co (NO) is weighed3)2·6H2Dissolving O and 1.3g of 2-methylimidazole in 80mL of deionized water to prepare a metal organic solution, putting the foamed nickel into the solution, standing for 4h, and after the foamed nickel with the precursor grown is taken out, washing and drying by using the deionized water to obtain an MOF precursor;
2) weighing 40mg NaMoO4·2H2O and 7.2mg Fe (NO)3)3·9H2O in a mixed solution of 14mL DMF and 5mL deionized water. Then placing the MOF precursor in a reaction kettle for hydrothermal reaction at 150 ℃ for 6 hours, and obtaining a metal doped MOF derivative material after the solvothermal reaction;
3) naturally cooling the metal-doped MOF derivative material to room temperature, placing the metal-doped MOF derivative material in hydrogen/nitrogen mixed gas with the hydrogen content of 10% VOL, carrying out one-step temperature rise at the temperature rise rate of 10 ℃/min to the first-stage temperature of 280 ℃, then carrying out heat preservation for 2h, then carrying out two-step temperature rise at the temperature rise rate of 10 ℃/min, carrying out heat preservation for 2h after the temperature rise to the second-stage temperature of 500 ℃, and cooling to room temperature to obtain the three-dimensional structure iron-doped cobalt molybdenum oxide composite material, wherein the three-dimensional structure iron-doped cobalt molybdenum oxide composite material prepared in the embodiment is marked as Fe-CoO/Co2Mo3O8/MoO3-0.4@ NF. Fe-CoO/Co obtained in example 22Mo3O8/MoO3SEM picture of-0.4 @ NF as shown in FIG. 5, Fe-CoO/Co2Mo3O8/MoO3The-0.4 @ NF two-dimensional sheet is vertically grown on a nickel foam substrate, the thickness of the two-dimensional sheet is about 500nm, and the surface of the two-dimensional sheet is provided with a large number of criss-cross nano sheets.
Example 3
A preparation method of a three-dimensional structure iron-doped cobalt-molybdenum oxide composite material comprises the following preparation steps:
1) 0.5g of Co (NO) is weighed3)2·6H2Dissolving O and 1.3g of 2-methylimidazole in 80mL of deionized water to prepare a metal organic solution, putting the foamed nickel into the solution, standing for 4h, and after the foamed nickel with the precursor grown is taken out, washing and drying by using the deionized water to obtain an MOF precursor;
2) weighing 120mg NaMoO4·2H2O and 21mg Fe (NO)3)3·9H2O in a mixed solution of 14mL DMF and 5mL deionized water. Then placing the MOF precursor in a reaction kettle for hydrothermal reaction at 150 ℃ for 6 hours, and obtaining a metal doped MOF derivative material after the solvothermal reaction;
3) after the metal-doped MOF derivative material is naturally cooled to room temperature, the metal-doped MOF derivative material is placed in a hydrogen gas content of 10 percentHeating up to a first-stage temperature of 280 ℃ at a heating rate of 10 ℃/min in hydrogen/nitrogen mixed gas of VOL, then preserving heat for 2h, then heating up to a second-stage temperature of 500 ℃ at a heating rate of 10 ℃/min, preserving heat for 2h, cooling to room temperature to obtain the three-dimensional structure iron-doped cobalt-molybdenum oxide composite material, and marking the three-dimensional structure iron-doped cobalt-molybdenum oxide composite material prepared by the embodiment as Fe-CoO/Co2Mo3O8/MoO3-2@ NF. Fe-CoO/Co obtained in example 32Mo3O8/MoO3SEM picture of-2 @ NF as shown in FIG. 6, Fe-CoO/Co2Mo3O8/MoO3The-2 @ NF two-dimensional sheet is vertically grown on a nickel foam substrate, the thickness of the two-dimensional sheet is about 500nm, and the surface of the two-dimensional sheet is provided with a large number of criss-cross nano sheets.
Comparative example 1
Compared with the embodiment 1, the preparation method of the three-dimensional structure iron-doped cobalt-molybdenum oxide composite material has the advantages that the hydrothermal reaction temperature of the step 2) is changed from 150 ℃ to 130 ℃, and the rest is kept unchanged. From fig. 7, it can be seen that no two-dimensional nanoplatelets appear on the surface thereof.
Comparative example 2
Compared with the embodiment 1, the preparation method of the iron-doped cobalt-molybdenum oxide composite material with the three-dimensional structure has the advantages that only the second-order temperature in the step 3) is changed from 450 ℃ to 550 ℃, and the rest is kept unchanged. From fig. 8, it can be seen that the two-dimensional nanoplatelets on the surface thereof are destroyed due to an excessively high temperature.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a three-dimensional structure iron-doped cobalt-molybdenum oxide composite material is characterized by comprising the following steps:
1) preparing a precursor material: respectively preparing methanol solutions of cobalt nitrate hexahydrate and 2-methylimidazole, mixing, adding foamed nickel NF (NF) serving as a conductive substrate, standing, and growing a precursor on the foamed nickel to obtain a precursor material Co-MOF @ NF;
2) in a mixed solution of molybdate and ferric salt, further reacting the precursor material by adopting a solvothermal method to obtain a metal ion doped MOF derivative material;
3) and (3) placing the MOF derivative material obtained in the step 2) in a reducing atmosphere, heating to a first-stage temperature, then preserving heat for a period of time, then heating again for two steps, heating to a second-stage temperature, and preserving heat for a period of time to obtain the iron-doped cobalt-molybdenum oxide composite material.
2. The method for preparing the three-dimensional structure iron-doped cobalt molybdenum oxide composite material according to claim 1, wherein the molar ratio of the 2-methylimidazole to the cobalt nitrate hexahydrate in the step 1) is (7-9): 1.
3. The method for preparing the three-dimensional structure iron-doped cobalt-molybdenum oxide composite material according to claim 1, wherein NaMoO is used as the molybdate and the iron salt in the step 2), respectively4·2H2O and Fe (NO)3)3·9H2O。
4. The method for preparing the three-dimensional structure iron-doped cobalt molybdenum oxide composite material according to claim 1, wherein the temperature of the solvothermal reaction in the step 2) is 100-200 ℃, and the reaction time is 2-24 hours.
5. The method for preparing the three-dimensional structure iron-doped cobalt molybdenum oxide composite material according to claim 1, 3 or 4, wherein the reducing atmosphere in the step 2) is a hydrogen and nitrogen atmosphere, wherein the hydrogen content is not less than 10% VOL.
6. The preparation method of the three-dimensional structure iron-doped cobalt molybdenum oxide composite material according to claim 1, wherein the temperature rise rate of the one-step temperature rise in the step 3) is 1-10 ℃/min; the temperature of the first stage is 150-350 ℃, and the heat preservation time is 2-4 h; the temperature rise rate of the two-step temperature rise is 1-10 ℃/min; the temperature of the two stages is 400-700 ℃, and the heat preservation time is 2-4 h.
7. The three-dimensional structure iron-doped cobalt-molybdenum oxide composite material prepared by the preparation method of any one of claims 1 to 6, wherein the structural formula is Fe-CoO/Co2Mo3O8/MoO3@NF。
8. The application of the iron-doped cobalt molybdenum oxide composite material with the three-dimensional structure prepared by the preparation method of any one of claims 1 to 6 in seawater electrocatalysis.
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