CN113526567A - Method for preparing oxygen vacancy type metal oxide with controllable acid etching effect - Google Patents
Method for preparing oxygen vacancy type metal oxide with controllable acid etching effect Download PDFInfo
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- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 54
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 37
- 239000001301 oxygen Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002253 acid Substances 0.000 title claims abstract description 28
- 238000005530 etching Methods 0.000 title claims abstract description 25
- 230000000694 effects Effects 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910000859 α-Fe Inorganic materials 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910003321 CoFe Inorganic materials 0.000 claims description 2
- 229910002521 CoMn Inorganic materials 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910002546 FeCo Inorganic materials 0.000 claims description 2
- 229910015136 FeMn Inorganic materials 0.000 claims description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 2
- 229910003266 NiCo Inorganic materials 0.000 claims description 2
- 229910003289 NiMn Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- CHZUADMGGDUUEF-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Co+2] Chemical compound [Mn](=O)(=O)([O-])[O-].[Co+2] CHZUADMGGDUUEF-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- UGPIGYYLADCIFW-UHFFFAOYSA-N dioxido(dioxo)manganese;nickel(2+) Chemical compound [Ni+2].[O-][Mn]([O-])(=O)=O UGPIGYYLADCIFW-UHFFFAOYSA-N 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 235000011044 succinic acid Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 9
- 238000002360 preparation method Methods 0.000 abstract description 6
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- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
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- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 1
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910021281 Co3O4In Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
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- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
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Abstract
The invention relates to the technical field of modification of functional metal compounds, in particular to a method for preparing oxygen vacancy type metal oxide with controllable acid etching effect, which has the following specific technical scheme: preparing inorganic acid or organic acid liquor with a certain concentration, adding a certain amount of original metal oxide into the acid liquor, carrying out acid etching reaction for 1-80 h at 25-50 ℃, carrying out centrifugation to realize solid-liquid separation, and then washing and drying with subsequent deionized water and absolute ethyl alcohol to obtain the oxygen vacancy type metal oxide, wherein the material preparation process is simple, the conditions are mild, the cost is low, the efficiency is high, and the material can be applied in a large scale; by selecting and adjusting the conditions such as acid liquor type, acid etching reaction temperature and time and the like, the oxygen vacancy concentration of the surface interface of the metal oxide can be effectively and accurately regulated and controlled; and the acid liquor after reaction can be recycled.
Description
Technical Field
The invention relates to the technical field of modification of functional metal compounds, in particular to a method for preparing oxygen vacancy type metal oxide with controllable acid etching effect.
Background
With the increasingly remarkable contradiction between the increasing consumption of non-renewable fossil fuels and the increasing energy use demand of people, the search and development of novel green renewable energy sources (such as wind energy, solar energy, tidal energy and the like) have great significance for the sustainable development of human beings. The rational utilization of energy storage and conversion devices based on electrochemical principles is the key to achieving efficient utilization of such renewable energy.
As a new generation of electrochemical energy storage technology with the most potential development, metal-air batteries are drawing attention due to their advantages of high theoretical energy density, environmental friendliness, and the like. As a core component of the metal-air battery, an Oxygen Evolution Reaction (OER) occurs in an air positive electrode during a battery charging process, but an actual OER process belongs to a multi-electron transfer and multi-phase reaction step, and the kinetics of the OER process is relatively slow and mass transfer is easily hindered, so that the working efficiency of the whole metal-air battery is not ideal.
Meanwhile, the water electrolysis device is taken as a representative of an electrochemical energy conversion technology, and can realize high-efficiency conversion between electric energy and hydrogen energy. The anode of the device mainly takes place the OER process, while the slow OER kinetics greatly retard the conversion efficiency of the electrolyzed water.
To achieve efficient operation of metal air cells and water electrolyzers, efficient electrocatalysts must be used to accelerate the OER reaction kinetics. Such as RuO2、IrO2Although noble metal oxides have high catalytic activity, the noble metal oxides have the defects of high price, scarce resources, poor stability and the like, and the large-scale commercial application of the noble metal oxides is greatly limited. The development of the non-noble metal OER catalyst which is low in cost, high in activity and good in stability is particularly important.
In recent years, metal oxides have been widely used and studied as active materials for energy storage and conversion due to their low price and abundant reserves. However, metal oxides are typical semiconductors, have wide band gaps and poor conductivity, and have slow electron conduction inside materials; and the effective active sites of the metal oxide are few, and the intrinsic catalytic activity is relatively low, so that the performance of the original metal oxide serving as an OER catalyst is often unsatisfactory.
To improve the OER performance of metal oxides, there are two modification strategies currently in use: firstly, metal oxide is compounded with high-conductivity materials (such as carbon materials, conductive polymers and the like) to improve the conductivity of the materials, so that the electron transfer is accelerated, and the kinetics of the OER reaction is improved. However, in fact, the introduction of the conductive agent can only improve the conductivity of the metal oxide interface contact, and cannot fundamentally improve the intrinsic conductivity. Thus, the problem of low intrinsic catalytic activity of metal oxides has not been effectively solved. Another modification method is to create defects (e.g., oxygen vacancies) in the metal oxide structure. By introducing a proper amount of oxygen vacancies to synthesize the oxygen vacancy type metal oxide, the electronic characteristics and the energy band structure of the metal oxide can be changed, the electrical conductivity and the intrinsic catalytic activity of the metal oxide are expected to be improved substantially, and the OER catalytic performance of the metal oxide is further greatly improved.
At present, many documents report methods for producing oxygen vacancies in materials, such as flame roasting, hydrogen heat treatment, ammonia heat treatment, plasma bombardment, active metal reduction, and the like. The adopted flame roasting method is usually operated under the conditions of high temperature and high energy consumption, and the treatment process is not easy to be accurately controlled; substances such as hydrogen, ammonia and the like are flammable and explosive, have high danger and poor controllability, and have certain difficulty in transportation and storage; the plasma bombardment and the active metal reduction method require high-end expensive equipment, and the operation conditions are harsh and difficult to control.
Patent CN107999076B discloses a composite metal oxide nanosheet rich in oxygen vacancy and a preparation method and use thereof, comprising the following steps: (1) adding an aqueous solution containing at least two metal salts and a nucleating agent and a clean substrate material into a reaction kettle and sealing the reaction kettle; (2) placing the closed reaction kettle at the temperature of 80-140 ℃, carrying out hydrothermal reaction on the contents of the closed reaction kettle for 0.5-24 hours under the autogenous pressure to generate a plurality of composite metal hydroxide nanosheets on the surface of the substrate, and washing and drying the nanosheets after solid-liquid separation; (3) and roasting the composite metal hydroxide nanosheets at high temperature by using reducing flame to obtain the composite metal oxide nanosheets with hexagonal cavities and oxygen vacancies.
However, the production process is relatively complex, the energy consumption is high, the danger is large, the processes of high-temperature high-pressure hydrothermal treatment, subsequent high-temperature flame roasting and the like are involved, waste materials in the production process are difficult to recycle, and the adopted high-temperature flame roasting process is difficult to effectively realize accurate regulation and control of the concentration of oxygen vacancies in the product.
Patent CN112939053A discloses a method for preparing transition metal oxide material containing oxygen vacancy, which is characterized by comprising the following steps: (1) heating metal sodium to a molten state in an inert atmosphere to obtain liquid metal sodium; (2) adding a transition metal oxide into the liquid metal sodium in an inert atmosphere, fully mixing, preserving heat for a certain time at the same temperature as that in the step 1), and naturally cooling to room temperature to obtain a mixture; (3) removing residual metallic sodium in the mixture by adopting absolute ethyl alcohol in an inert atmosphere; (4) and (3) washing the product obtained in the step (3) by using deionized water and absolute ethyl alcohol in sequence in an air atmosphere, and then filtering and drying to obtain the transition metal oxide containing oxygen vacancies.
However, it still has the following disadvantages: the synthesis process is complicated, the operation risk coefficient is high, and the processes of sodium addition and sodium removal are involved; the implementation conditions are harsh, and no water and no oxygen need to be ensured; the waste materials left in the reaction in each step are difficult to recycle, so that resource waste is easily caused; the concentration of oxygen vacancies created in the metal oxide structure is difficult to control efficiently and precisely.
Therefore, the preparation method of the oxygen vacancy type metal oxide which is simple in process, low in cost, safe and environment-friendly, high in raw material utilization rate and easy to adjust and control the oxygen vacancy concentration is designed, and the preparation method has important significance for developing the high-performance OER catalyst.
Disclosure of Invention
The invention mainly aims to overcome the defects of the prior art and provide the method for preparing the oxygen vacancy type metal oxide with the controllable acid etching effect, and the method has a series of advantages of simple operation, low cost, environmental friendliness, reusable reaction raw materials, wide application range, easy regulation and control of oxygen vacancy concentration and the like.
In order to realize the purpose of the invention, the following technical scheme is provided:
a method for preparing oxygen vacancy type metal oxide with controllable acid etching effect comprises the following steps:
(1) preparing inorganic acid liquid or organic acid liquid with the quantity concentration of 1-12M and the volume of 20-100 mL;
(2) adding 20-2000 mg of original metal oxide into the acid liquor obtained in the step (1);
(3) stirring and reacting the mixed solution obtained in the step (2) at the temperature of 25-50 ℃ at the rotating speed of 50-400 r/min for 1-80 h;
(4) and (4) carrying out high-speed centrifugal separation on the reaction liquid obtained in the step (3) at a rotating speed of 2000-10000 r/min to obtain a solid component, repeatedly washing the solid component for 3-4 times by using water and ethanol, and finally carrying out vacuum drying for 5-12 h at the temperature of 50-100 ℃ to obtain the oxygen vacancy type metal oxide.
Preferably, the inorganic acid solution is one or more of hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid.
Preferably, the organic acid solution is one or more of formic acid, acetic acid, propionic acid or succinic acid.
Preferably, the original metal oxide comprises a single metal oxide, the original metal oxide being tricobalt tetraoxide (Co)3O4) Cobalt protoxide (CoO), nickel oxide (NiO), manganomanganic oxide (Mn)3O4) Manganese dioxide (MnO)2) Manganese oxide (MnO) and ferroferric oxide (Fe)3O4) Iron oxide (Fe)2O3) Ferrous oxide (FeO), copper oxide (CuO), cuprous oxide (Cu)2O), molybdenum trioxide (MoO)3) Molybdenum dioxide (MoO)2) Titanium dioxide (TiO)2) Titanium monoxide (TiO), ruthenium dioxide（RuO2) Indium oxide (In)2O3) Tin dioxide (SnO)2) Or stannous oxide (SnO).
Preferably, the primary metal oxide comprises a multi-component metal oxide, the primary metal oxide being manganese cobaltate (MnCo)2O4) Iron cobaltate (FeCo)2O4) Nickel cobaltate (NiCo)2O4) Manganese ferrite (MnFe)2O4) Cobalt ferrite (CoFe)2O4) Nickel ferrite (NiFe)2O4) Cobalt manganate (CoMn)2O4) Iron manganese (FeMn)2O4) Or nickel manganate (NiMn)2O4) One or more mixtures thereof.
The invention has the following beneficial effects:
(1) the preparation process of the material is simple, the cost is low, the safety coefficient is high, the reaction raw materials can be recycled, and the problems of resource waste, environmental pollution and the like are effectively reduced;
(2) the method has wide application range, can be used for large-scale macro preparation, can effectively and accurately regulate and control the concentration of oxygen vacancies in the metal oxide, and is expected to obtain the oxygen vacancy type metal oxide base OER catalyst with high activity and good stability.
Drawings
FIG. 1 shows virgin Co from example 13O4 (a) And Co3O4–Vo-Scanning Electron Microscope (SEM) images of 4-24 (b); (wherein VoRepresents oxygen vacancy, 4 represents hydrochloric acid concentration 4M, 24 represents acid etching time 24 h, the same applies below)
FIG. 2 shows virgin Co in example 13O4And Co3O4–Vo-X-ray diffraction (XRD) (a) and Raman (Raman) spectra (b) of 4-24;
FIG. 3 shows virgin Co in example 13O4And Co3O4–Vo-Electron Paramagnetic Resonance (EPR) spectra of 4-24;
FIG. 4 shows virgin Co in example 13O4And Co3O4–Vo-linear scan curves (LSVs) (a) and Tafel (Tafel) plots (b) of 4-24;
FIG. 5 shows virgin Co in example 23O4、Co3O4–Vo6-6 and Co3O4–Vo-xrd (a) and raman (b) spectra of 6-54;
FIG. 6 shows virgin Co in example 23O4High resolution O1 ofs (a) And Co 2p (b) A spectrogram; co3O4–VoHigh resolution O1 of 6 to 6s (c) And Co 2p (d) Spectrogram and Co3O4–VoHigh resolution O1 of 6 to 54s (e) And Co 2p (f) A spectrogram;
FIG. 7 shows virgin Co in example 23O4、Co3O4–Vo6-6 and Co3O4–VoV of-6 to 54oPercentage and Co2+/Co3+The result of the ratio;
FIG. 8 shows virgin Co in example 23O4、Co3O4–Vo6-6 and Co3O4–VoLSV (a) and Tafel (b) of FIGS. 6-54.
Detailed Description
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings or the orientations or positional relationships that the products of the present invention are conventionally placed in when used, and are only used for convenience of describing the present invention and simplifying the description, but do not indicate or imply that the devices or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood, however, that the description herein of specific embodiments is only intended to illustrate the invention and not to limit the scope of the invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Example 1
A4M hydrochloric acid solution of 20 mL volume was prepared and 40 mg of commercial Co was added to the hydrochloric acid solution3O4 (purchased from Shanghai Michelin Biochemical technology Co., Ltd.), subjecting the obtained mixed solution to acid etching reaction at 25 deg.C for 24 h, subjecting the reaction solution to high-speed centrifugal separation at 4000 r/min to obtain solid component, repeatedly washing with deionized water and anhydrous ethanol for 3 times, and drying in a vacuum drying oven at 60 deg.C for 10 h to obtain oxygen vacancy type cobaltosic oxide (Co)3O4–Vo–4–24)。
Referring to FIG. 1, a commercial virgin Co is shown3O4And Co3O4–VoSEM pictures of 4-24. As can be seen, both samples exhibited spherical structures assembled from a large number of nanoparticles. Compared with original Co3O4，Co3O4–VoThe spherical structure of-4-24 is partially etched to form partial cavities (as shown by the white dashed box).
Referring to FIG. 2, a diagram of a commercial virgin Co is shown3O4And Co3O4–Vo-xrd (a) and raman (b) spectra of 4-24. As can be seen from FIG. (a), both samples were 2θTypical Co appears at = 31.3 °, 36.8 °, 44.8 °, 59.4 ° and 65.2 °3O4Diffraction signature peaks. With virgin Co3O4In contrast, Co3O4–VoThe phase structure of-4-24 still belongs to Co3O4However, the diffraction peak intensity is significantly reduced, indicating that the crystallinity is weakened, which is mainly associated with VoIs related to the formation of (1); graph (b) shows Raman spectra for samples at 189, 472, 509, 601 and 675 cm−1Is out ofNow 5 characteristic peaks, corresponding to Co respectively3O4F12 g, EgF22 g, F32 g and A1 g, also indicating that the acid etching treatment did not change Co3O4The phase structure of (1). At 189 and 675 cm–1The characteristic peak appears mainly from Co2+−O2−And Co3+−O2−The vibration of (2). Furthermore, we found that compared to virgin Co3O4，Co3O4–VoShift of the A1 g peak to a more positive position for-4-24, indicating VoSuccessful introduction of (1).
Referring to FIG. 3, a diagram of a commercial virgin Co is shown3O4And Co3O4–VoEPR plots of 4-24. It can be seen from the figure that3O4In contrast, Co3O4–Vo-4-24 are ingA typical EPR signal appears at =2.13, again demonstrating VoAnd (4) generating.
Referring to FIG. 4, a diagram of a commercial virgin Co is shown3O4And Co3O4–VoLSV (a) and Tafel (b) of 4-24. As can be seen, the comparison with the original Co3O4(overpotential)η=390 mV, Tafel slope 114 mV dec–1)，Co3O4–Vo4-24 at a current density of 10 mA cm–2Is corresponding toη=345 mV, Tafel slope 106 mV dec–1Showing more excellent OER catalytic activity, and the results also confirm VoThe presence of (A) is effective to enhance the OER performance of the metal oxide.
Example 2
Preparing two hydrochloric acid solutions with the concentration of 6M and the volume of 24 mL, and respectively adding 40 mg of commercial Co into the hydrochloric acid solutions3O4Respectively carrying out acid etching reaction on the obtained mixed solution for 6 h and 54 h at 25 ℃, then carrying out high-speed centrifugal separation on the obtained reaction solution at the rotating speed of 6000 r/min to obtain a solid component, repeatedly washing the solid component for 3 times by using deionized water and absolute ethyl alcohol, and drying the solid component for 12 h at 60 ℃ in a vacuum drying oven to obtain two different oxygen vacanciesType cobaltosic oxide (respectively marked as Co)3O4–Vo6-6 and Co3O4–Vo–6–54）。
Referring to FIG. 5, a diagram of a commercial virgin Co is shown3O4、Co3O4–Vo6-6 and Co3O4–Vo-xrd (a) and raman (b) spectra of 6-54. As can be seen from FIG. (a), the three samples are shown in FIG. 2θTypical Co appears at = 31.3 °, 36.8 °, 44.8 °, 59.4 ° and 65.2 °3O4Characteristic diffraction peaks indicating that the acid etching treatment did not change Co3O4The phase structure of (1). At the same time, it was found that3O4In contrast, Co3O4–Vo6-6 and Co3O4–VoThe diffraction peak intensities of-6 to 54 all became weaker and the longer the etching time, the weaker the diffraction peak intensities, which indicates that the etching treatment can be performed on Co3O4Oxygen vacancies are created in the structure and the longer the etch time, the higher the concentration of oxygen vacancies created. FIG. (b) is a Raman spectrum. As can be seen, all three samples were at 189, 472, 509, 601 and 675 cm−1There appear 5 characteristic peaks, respectively corresponding to Co3O4F12 g, EgF22 g, F32 g and A1 g, which shows that changing the acid etching time does not change Co3O4The phase structure of (1). At 189 and 675 cm–1The characteristic peak appearing at the position mainly corresponds to Co2+−O2−And Co3+−O2−The vibration mode of (1). Furthermore, we found that compared to virgin Co3O4，Co3O4–Vo6-6 and Co3O4–VoA1 g peak of-6-54 shifted positively, indicating VoIs performed. And it was found that as the acid etching time was increased from 6 h to 54 h, the amplitude of the positive shift of the A1 g peak was greater, indicating that V was generatedoThe concentration is higher.
Referring to FIG. 6, a diagram of a commercial virgin Co is shown3O4High resolution O1 ofs (a) And Co 2p (b)Spectrogram, Co3O4–VoHigh resolution O1 of 6 to 6s (c) And Co 2p (d) Spectrogram and Co3O4–VoHigh resolution O1 of 6 to 54s (e) And Co 2p (f) Spectra. As can be seen from the graphs (a, c and e), original Co3O4O1 of (A)sThere are only three different O configurations in the high resolution spectrum: Co-O (530.0 eV), O2 2–/O–(531.0 eV) and C-O (532.5-533.5 eV); in the presence of Co3O4–Vo6-6 and Co3O4–Vo6 to 54 of O1sIn the high-resolution spectrogram, a new partial peak (-532.0 eV) corresponding to V existsoIndicates VoThe successful formation of. As can be seen from the graphs (b, d and f), Co 2 of the three samplespThree different Co configurations exist in the high resolution spectrum: co3+、Co2+And satellite peak (labeled sat.).
Referring to FIG. 7, raw Co is shown3O4，Co3O4–Vo6-6 and Co3O4–VoV of-6 to 54oPercentage and Co2+/Co3+And (4) a ratio map. As can be seen from the graph, V is observed as the acid etching time is prolongedoPercentage and Co2+/Co3+The ratio also increased, indicating that acid etching induced VoThe concentration is increased, so that the acid etching time is adjusted, and V in the metal oxide can be treatedoAnd (4) effectively regulating and controlling the concentration.
Referring to FIG. 8, raw Co is shown3O4，Co3O4–Vo6-6 and Co3O4–VoLSV (a) and Tafel (b) of FIGS. 6-54. As can be seen, the comparison with the original Co3O4 (η=390 mV, Tafel slope 114 mV dec–1)，Co3O4–Vo6-6 and Co3O4–Vo6-54 electrodes at a current density of 10 mA cm–2The overpotential under the condition is respectively reduced to 370 mV and 350 mV, and simultaneously the Tafel slopes of the overpotential and the Tafel slopes are respectively reduced to 95 mV and 89 mV dec–1Indicating its significantly improved OER catalytic activity. Furthermore, the above results also indicate VoThe increase of the concentration is favorable for further improving Co3O4OER performance of (d).
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein, or by using equivalent structures or equivalent processes performed in the content of the present specification and the attached drawings, which are included in the scope of the present patent.
Claims (5)
1. A method for preparing oxygen vacancy type metal oxide with controllable acid etching effect is characterized in that: the method comprises the following steps:
(1) preparing inorganic acid liquid or organic acid liquid with the quantity concentration of 1-12M and the volume of 20-100 mL;
(2) adding 20-2000 mg of original metal oxide into the acid liquor obtained in the step (1);
(3) stirring and reacting the mixed solution obtained in the step (2) at the temperature of 25-50 ℃ at the rotating speed of 50-400 r/min for 1-80 h;
(4) and (4) carrying out high-speed centrifugal separation on the reaction liquid obtained in the step (3) at a rotating speed of 2000-10000 r/min to obtain a solid component, repeatedly washing the solid component for 3-4 times by using deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying for 5-12 h at the temperature of 50-100 ℃ to obtain the oxygen vacancy type metal oxide.
2. The method for preparing the oxygen vacancy type metal oxide with controllable acid etching effect according to claim 1, wherein: the inorganic acid solution is one or a mixture of more of hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid.
3. The method for preparing the oxygen vacancy type metal oxide with controllable acid etching effect according to claim 1, wherein: the organic acid solution is one or a mixture of more of formic acid, acetic acid, propionic acid or succinic acid.
4. The method for preparing the oxygen vacancy type metal oxide with controllable acid etching effect according to claim 1, wherein: the primary metal oxide comprises a single metal oxide, and the primary metal oxide is cobaltosic oxide (Co)3O4) Cobalt protoxide (CoO), nickel oxide (NiO), manganomanganic oxide (Mn)3O4) Manganese dioxide (MnO)2) Manganese oxide (MnO) and ferroferric oxide (Fe)3O4) Iron oxide (Fe)2O3) Ferrous oxide (FeO), copper oxide (CuO), cuprous oxide (Cu)2O), molybdenum trioxide (MoO)3) Molybdenum dioxide (MoO)2) Titanium dioxide (TiO)2) Titanium monoxide (TiO), ruthenium dioxide (RuO)2) Indium oxide (In)2O3) Tin dioxide (SnO)2) Or stannous oxide (SnO).
5. The method for preparing the oxygen vacancy type metal oxide with controllable acid etching effect according to claim 1, wherein: the primary metal oxide comprises a multi-component metal oxide, and the primary metal oxide is manganese cobaltate (MnCo)2O4) Iron cobaltate (FeCo)2O4) Nickel cobaltate (NiCo)2O4) Manganese ferrite (MnFe)2O4) Cobalt ferrite (CoFe)2O4) Nickel ferrite (NiFe)2O4) Cobalt manganate (CoMn)2O4) Iron manganese (FeMn)2O4) Or nickel manganate (NiMn)2O4) One or more mixtures thereof.
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