CN111349915A - CoSe with controllable appearance2/Ti composite material and preparation method thereof - Google Patents
CoSe with controllable appearance2/Ti composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 128
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 22
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 abstract description 17
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003837 high-temperature calcination Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- -1 transition metal chalcogenide Chemical class 0.000 abstract description 6
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000002905 metal composite material Substances 0.000 abstract 1
- 229960004011 methenamine Drugs 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 241000736199 Paeonia Species 0.000 description 7
- 235000006484 Paeonia officinalis Nutrition 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 240000008397 Ganoderma lucidum Species 0.000 description 5
- 235000001637 Ganoderma lucidum Nutrition 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 235000014653 Carica parviflora Nutrition 0.000 description 4
- 244000132059 Carica parviflora Species 0.000 description 4
- 241000222336 Ganoderma Species 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GAIMSHOTKWOMOB-UHFFFAOYSA-N [Se]=[Co]=[Se] Chemical compound [Se]=[Co]=[Se] GAIMSHOTKWOMOB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 150000004771 selenides Chemical class 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
- C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Ceramic Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides CoSe with controllable morphology2The preparation method of the/Ti composite material comprises the following steps: cobalt nitrate hexahydrate and NH4F and hexamethylenetetramine are sequentially added into a solvent, and the obtained mixed solution and a titanium sheet are subjected to hydrothermal reaction to obtain Co (OH)2a/Ti composite material; the resulting Co (OH)2Calcining the/Ti composite material at high temperature to obtain Co3O4a/Ti composite material; the obtained Co3O4the/Ti composite material and the selenium powder are mixed evenly and calcined at high temperature to obtain the CoSe2a/Ti composite material. The preparation method has the advantages of simple process, environmental protection, safety, low energy consumption and strong operability, and Co (OH) with various shapes can be obtained in the preparation process2/Ti and Co3O4a/Ti composite material. The method of the invention is used for preparing the transition metal chalcogenide/transition metal composite materialProvides a new idea.
Description
Technical Field
The invention relates to CoSe with controllable appearance2a/Ti composite material and a preparation method thereof, belonging to the technical field of synthesis of transition metal selenide composite materials.
Background
In order to solve the problem of limited fossil fuel resources and to pursue more environmentally friendly energy storage devices, researchers have been working on finding cell materials with high energy density and long life. Sodium ion batteries and lithium ion batteries have similar storage capacities and have been widely used in many fields in recent years. Heretofore, various anode materials have been studied and applied to lithium ion or sodium ion batteries such as metal oxides, metal sulfides, selenides, and the like. Among all negative electrode materials, the volume expansion of the metal oxide during charge/discharge causes structural damage thereof, thereby exhibiting low reversible capacity and poor cycle life; the metal sulfides are poor in cycle performance due to shuttle effect and generation of polysulfide ions. Therefore, it is important to search for a negative electrode material having excellent cycle stability and high reversible capacity. While metal selenides have higher theoretical capacity than metal oxides and longer-term cycling performance than metal sulfides, and are drawing much attention as negative electrode materials for lithium ion and sodium ion batteries.
Meanwhile, at present, where the energy problem is becoming more severe, the traditional energy sources such as coal and oil will generate larger pollution when in use, and face the serious problem of continuous exhaustion. As a new clean and renewable energy source, hydrogen has bright prospect in the aspect of replacing traditional energy sources such as petroleum in the future. The electrochemical method for decomposing water can generate hydrogen by utilizing clean and discontinuous energy sources such as solar energy, wind energy and the like, and provides a simple, energy-saving, high-efficiency and pollution-free method for producing high-purity hydrogen. However, in the process of electrochemically decomposing water, the Oxygen Evolution Reaction (OER) at the anode is a complex four-electron oxidation system, which is slow in kinetics, and generates a considerable overpotential, resulting in low overall efficiency, and therefore, it is imperative to find a high-performance Oxygen Evolution Reaction (OER) catalyst. In order to make the Hydrogen Evolution Reaction (HER) more energy-saving and efficient, the search for a high-performance Hydrogen Evolution Reaction (HER) catalyst is also of great significance.
In recent years, cobalt diselenide (CoSe)2) As a transition metal chalcogenide, the compound has proved to have higher activity in the field of electrocatalysis and has worthy application in the aspect of electrochemical energy storage. CoSe2Has high theoretical capacity and long cycle performance, and can be used as lithium ionNegative electrode materials for lithium ion and sodium ion batteries; at the same time, since CoSe2Co and Se are abundant in earth, the average content of Co in earth crust is 0.001%, the total content of Co in sea is about 23 hundred million tons, the content of Se in earth crust is 0.000005%, the price is low, the property is stable at room temperature, and CoSe is abundant2Is expected to become a substitute of expensive noble metal catalytic materials, and is used as a catalyst for oxygen evolution and hydrogen evolution reactions for water decomposition by an electrochemical method. But CoSe2The material has low conductivity, poor cycle stability and complex and various structure and appearance, and is difficult to control, so the structure and the synthesis method of the cobalt selenide material need to be designed and controlled.
As is well known, the catalytic activity of the material has a great relationship with the structure and the appearance of the material, so that a method with simple preparation process and low cost is developed to obtain CoSe with special appearance and structure2The material is a hot spot which is always concerned by the majority of researchers. For example: chinese patent document CN109046394A (application number: 201810879985.8) discloses a hollow tubular CoSe2Firstly, preparing a cobalt-based precursor material with a solid structure; further, cobalt-based precursor material with solid structure is selenized into orthorhombic CoSe in N, N-Dimethylformamide (DMF) liquid phase environment2Hollow tubular material of construction, but the CoSe2The material has a single shape and the organic solvent DMF used in the preparation process can have adverse effects on the environment and human body.
Titanium is a silvery white transition metal, is widely distributed in the natural world, is the seventh in the metal world, accounts for about 0.42 percent of the total weight in the earth crust, has good conductivity, can be compounded with metal chalcogenide to be commonly used as a battery cathode material, and has excellent cycle performance and good stability; the oxide titanium dioxide is commonly used in the field of catalysis and the like. Therefore, the cobalt diselenide and the transition metal titanium are combined, and the composite material which has controllable appearance and can be used for electrochemistry and electrocatalysis can be obtained by utilizing the advantages of the cobalt diselenide and the transition metal titanium. For example: chinese patent document CN10630438A provides a cobalt selenide/titanium mesh electrode used as an oxygen electrode for decomposing water, comprising a titanium mesh and cobalt selenide nanosheets grown on the mesh. However, the cobalt selenide obtained in the electrode has a single appearance.
Therefore, the CoSe with special and controllable appearance is prepared by a simple and low-cost method2the/Ti composite material has very important significance for realizing the application of the composite material in the field of electrocatalysis and the aspect of electrochemical energy storage.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides CoSe with controllable morphology2a/Ti composite material and a preparation method thereof. The composite material is synthesized by a two-step method, and firstly, cobalt nitrate hexahydrate, ammonium fluoride and hexamethylenetetramine are taken as raw materials to carry out hydrothermal reaction with a titanium sheet to prepare Co (OH)2The material/Ti composite material can obtain Co (OH) with different shapes by adjusting the proportion of raw materials and the type of solvent2the/Ti composite material is prepared by calcining to obtain Co with different shapes3O4a/Ti composite material, followed by the Co obtained3O4the/Ti composite material and the selenium powder are subjected to selenylation reaction to obtain CoSe with different shapes2a/Ti composite material. The preparation method disclosed by the invention is simple, safe in preparation process, low in energy consumption, strong in operability, environment-friendly and pollution-free, and the product appearance is controllable.
The technical scheme of the invention is as follows:
CoSe with controllable appearance2The composite material is cobalt nitrate hexahydrate and NH4F and hexamethylenetetramine are used as raw materials, and the hydrothermal reaction is carried out on the surface of a titanium sheet substrate to obtain Co (OH)2The precursor of the/Ti composite material is prepared by calcining and selenizing the obtained precursor.
According to the invention, the CoSe2The microscopic morphology of the/Ti composite material is glossy ganoderma sheet, peony or coral rod-shaped; the diameter of the ganoderma lucidum tablet is 5-15 μm; the diameter of the peony is 2-10 μm; the length of the coral stick is 0.5-2 μm.
According to the invention, the CoSe with controllable morphology is obtained2The preparation method of the/Ti composite material comprises the following steps：
(1) Cobalt nitrate hexahydrate and NH4Sequentially adding F and hexamethylenetetramine into a solvent, uniformly stirring to obtain a mixed solution, and carrying out hydrothermal reaction on the mixed solution and a titanium sheet; filtering, washing and drying to obtain Co (OH)2a/Ti composite material;
(2) the Co (OH) obtained in the step (1)2the/Ti composite material is calcined at high temperature in air atmosphere to obtain Co3O4a/Ti composite material;
(3) co obtained in the step (2)3O4the/Ti composite material and the selenium powder are mixed evenly and calcined at high temperature in the argon atmosphere to obtain CoSe2a/Ti composite material.
According to the present invention, it is preferable that the ratio of the number of moles of cobalt nitrate hexahydrate to the volume of the solvent in step (1) is 0.5 to 1.5mmol:10 to 30mL, more preferably 0.5 to 1.5mmol: 20 mL.
According to the present invention, it is preferable that the cobalt nitrate hexahydrate and NH as described in the step (1)4The molar ratio of F is 0.5-1.5: 1; the molar ratio of the cobalt nitrate hexahydrate to the hexamethylenetetramine is 1: 0.5-7.
According to the present invention, it is preferable that the solvent in step (1) is distilled water, or a mixed solvent of distilled water and absolute ethyl alcohol; further preferably, the volume ratio of distilled water to absolute ethyl alcohol in the mixed solvent is 1: 1-2, more preferably 1: 1.5.
according to the invention, the titanium sheet in the step (1) has a thickness of 0.5-1.5mm and a diameter of 10-20 mm.
According to the present invention, it is preferable that the ratio of the volume of the mixed solution to the area of the titanium plate in the step (1) is 10 to 30mL: (1-4) π cm2。
According to the present invention, preferably, the hydrothermal reaction temperature in step (1) is 90 to 110 ℃, and more preferably 100 ℃; the hydrothermal reaction time is 6 to 24 hours, and more preferably 15 hours.
According to the present invention, it is preferable that the washing in the step (1) is washing with distilled water and absolute ethyl alcohol 2 to 4 times, respectively; the drying is vacuum drying at 50-80 deg.C for 12-36 h.
According to the present invention, preferably, the high-temperature calcination temperature in step (2) is 200-; the high-temperature calcination time is 1 to 10 hours, and more preferably 2 to 4 hours.
According to the present invention, it is preferable that Co described in the step (3)3O4Co in/Ti composite material3O4The mass ratio of the selenium powder to the selenium powder is 5-10: 1.
According to the present invention, it is preferred that the flow rate of argon gas in the step (3) is 50 to 70 mL/min.
According to the present invention, preferably, the high-temperature calcination temperature in step (3) is 500-; the high-temperature calcination time is 0.5 to 5 hours, and more preferably 1 to 3 hours.
According to the invention, when the solvent in the step (1) is distilled water, the molar ratio of the cobalt nitrate hexahydrate to the hexamethylenetetramine is preferably 1: 0.5 to 2.1, more preferably 1:2, obtaining ganoderma flake Co3O4the/Ti composite material is selenized to obtain the CoSe with glossy ganoderma sheet shape2The shape of the ganoderma lucidum sheet is that a plurality of small pieces are attached to a large sheet and stacked into a blocky structure, and the shape before and after selenization is basically unchanged; the molar ratio of the cobalt nitrate hexahydrate to the hexamethylenetetramine is preferably 1:2.5-7, and more preferably 1: 3, obtaining Co with a cylindrical shape stacked by sheets3O4Selenizing the/Ti composite material to obtain peony-shaped CoSe2the/Ti composite material is in a uniform columnar structure before selenization, and part of columns are broken after selenization to form a peony shape; when the solvent is a mixed solvent of distilled water and absolute ethyl alcohol, and the volume ratio of the distilled water to the absolute ethyl alcohol is 1: 1-2, preferably in a volume ratio of 1: 1.5, wherein the molar ratio of the cobalt nitrate hexahydrate to the hexamethylenetetramine is 1:2.5-7, preferably 1: 3, obtaining the Co with the more uniform cubic rod appearance3O4Selenizing the/Ti composite material to obtain coral-shaped CoSe rod2a/Ti composite material.
The invention has the following technical characteristics and beneficial effects:
1. CoSe of the invention2Firstly, cobalt nitrate hexahydrate, ammonium fluoride and hexamethylenetetramine are taken as raw materials to carry out hydrothermal reaction with titanium sheets to prepare Co (OH)2the/Ti composite material can obtain Co (OH) with different shapes by adjusting the proportion of cobalt nitrate hexahydrate and hexamethylenetetramine and the type of solvent2the/Ti composite material is prepared by calcining to obtain Co with different shapes3O4a/Ti composite material, followed by the Co obtained3O4the/Ti composite material and the selenium powder are subjected to selenylation reaction to obtain CoSe with different shapes2Experiments prove that the CoSe with different shapes obtained by the invention is prepared from the Ti/Ti composite material2The X-ray diffraction spectra of the/Ti composite material are the same, and CoSe with three morphologies is shown2The phases of the/Ti composite materials are consistent.
2. CoSe of the invention2The preparation method of the/Ti composite material adopts a direct deposition method, namely Co (OH)2Directly depositing on a Ti sheet by a hydrothermal method, and further obtaining CoSe by calcining and selenizing2The preparation method of the/Ti composite material is simple and the product appearance is controllable.
3. CoSe in the invention2The synthesis process of the/Ti composite material is environment-friendly and pollution-free, and the used reagent is environment-friendly and has no harm to human bodies.
4. CoSe in the invention2The synthesis method of the/Ti composite material has important reference value for preparing the transition metal chalcogenide/transition metal simple substance composite material.
Drawings
FIG. 1 shows Co prepared in example 13O4Per Ti and CoSe2Scanning Electron Microscope (SEM) picture of/Ti composite material, wherein (a) is Co3O4Scanning Electron Microscope (SEM) pictures of the/Ti composite material; (b) is CoSe2Scanning Electron Microscope (SEM) picture of the/Ti composite material.
FIG. 2 shows Co prepared in example 23O4Per Ti and CoSe2Scanning Electron Microscope (SEM) photograph of/Ti composite materialA sheet wherein (a) is Co3O4Scanning Electron Microscope (SEM) pictures of the/Ti composite material; (b) is CoSe2Scanning Electron Microscope (SEM) picture of the/Ti composite material.
FIG. 3 shows Co prepared in example 33O4Per Ti and CoSe2Scanning Electron Microscope (SEM) picture of/Ti composite material, wherein (a) is Co3O4Scanning Electron Microscope (SEM) pictures of the/Ti composite material; (b) is CoSe2Scanning Electron Microscope (SEM) picture of the/Ti composite material.
FIG. 4 shows Co (OH) prepared in example 12X-ray diffraction (XRD) spectrum of the/Ti composite material.
FIG. 5 shows Co prepared in example 13O4X-ray diffraction (XRD) spectrum of the/Ti composite material.
FIG. 6 is CoSe prepared in example 12X-ray diffraction (XRD) spectrum of the/Ti composite material.
FIG. 7 is CoSe prepared in example 22X-ray diffraction (XRD) spectrum of the/Ti composite material.
FIG. 8 is CoSe prepared in example 32X-ray diffraction (XRD) spectrum of the/Ti composite material.
FIG. 9 shows two Co types prepared in example 43O4Scanning Electron Microscope (SEM) picture of/Ti composite material, wherein (a) is Co (NO)3)3·6H2The adding amount of O is 1.0 mmol; (b) is Co (NO)3)3·6H2The amount of O added was 0.5 mmol.
FIG. 10 shows three Co species prepared in example 53O4A Scanning Electron Microscope (SEM) picture of the/Ti composite material, wherein (a) the adding amount of the hexamethylenetetramine is 2.0 mmol; (b) the adding amount of the hexamethylene tetramine is 1.5 mmol; (c) the amount of hexamethylenetetramine added was 1.0 mmol.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
The equipment used in the examples is conventional equipment unless otherwise specified, and the chemical raw materials are conventional commercially available raw materials.
The titanium sheets used in the examples were produced by Guangzhou nonferrous metals research institute and were approximately 1mm in thickness.
Example 1
CoSe with controllable appearance2/The preparation method of the Ti composite material comprises the following steps:
(1) 1.5mmol of Co (NO)3)3·6H2O is added to 20mL of distilled water, magnetically stirred at room temperature until dissolved, and then 1.0mmol of NH is added4F, magnetically stirring at room temperature until the mixture is dissolved, then adding 3.0mmol of hexamethylenetetramine, and magnetically stirring at room temperature for 20min to obtain a light red clear transparent mixed solution; flatly paving a Ti wafer with the diameter of 1cm at the bottom of a high-pressure reaction kettle with a 55mL polytetrafluoroethylene lining; transferring the obtained light red clear transparent mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining and a titanium sheet, screwing the high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven, carrying out hydrothermal reaction for 15h at 100 ℃, naturally cooling the high-pressure reaction kettle to room temperature after the reaction is finished, filtering, washing the obtained dark red substance with distilled water and absolute ethyl alcohol for 3 times respectively, and drying in a vacuum drying oven for 12h at 60 ℃ to obtain Co (OH)2/A Ti composite material;
(2) the Co (OH) obtained in the step (1)2/Spreading Ti composite material in a porcelain boat, placing in a tube furnace, heating to 300 deg.C at a heating rate of 2 deg.C/min in air atmosphere, calcining at 300 deg.C for 1h, and cooling to obtain black Co3O4/A Ti composite material;
(3) black Co obtained in the step (2)3O4/Placing Ti in a long glass tube, adding selenium powder and Co3O4/Co in Ti composite material3O4The mass ratio of the selenium powder to the selenium powder is 8: 1, uniformly mixing the solid substances, placing the mixture in a tube furnace, heating to 600 ℃ at the heating rate of 5 ℃/min under the argon atmosphere with the argon flow rate of 70mL/min, calcining for 1h at 600 ℃, and cooling to obtain gray CoSe2/A Ti composite material.
Co prepared in this example3O4Per Ti and CoSe2Scanning Electron Microscope (SEM) pictures of the/Ti composite materials such asAs shown in FIG. 1, it can be seen from FIG. 1 that the obtained Co3O4Per Ti and CoSe2the/Ti composite material is in a shape of a ganoderma lucidum sheet, the diameter of the ganoderma lucidum sheet is 5-15 mu m, a plurality of small sheets are attached to a large sheet and stacked into a blocky structure, and the shapes of the small sheets before and after selenization are basically unchanged.
Co (OH) prepared in this example2/Ti、Co3O4/Ti and CoSe2The X-ray diffraction (XRD) patterns of the/Ti composite material are respectively shown in figures 4-6.
Example 2
CoSe with controllable appearance2/A Ti composite material was prepared as described in example 1, except that: co (NO)3)3·6H2The amount of O added was 0.5mmol, NH4The amount of F added was 1.0mmol, and the amount of hexamethylenetetramine added was 1.5 mmol.
Co prepared in this example3O4Per Ti and CoSe2A Scanning Electron Microscope (SEM) photograph of the/Ti composite material is shown in FIG. 2, and it can be seen from FIG. 2 that the obtained Co3O4/The Ti composite material is in a cylindrical shape formed by stacking sheets, and CoSe is obtained after selenization2/The Ti composite material is in a peony shape, and the diameter is 2-10 mu m; it can be seen from fig. 2 that the selenization solution is in a relatively uniform columnar structure before selenization, and after selenization, part of the columnar is broken, the shape of the columnar is relatively irregular, and the columnar is in a peony shape.
Example 3
CoSe with controllable appearance2/The Ti composite was prepared as described in example 1, except that: co (NO)3)3·6H2The amount of O added was 0.5mmol, NH4The adding amount of F is 1.0mmol, the adding amount of hexamethylenetetramine is 1.5mmol, and the volume ratio of the solvent to the absolute ethyl alcohol is 1: 1.5 of a mixed solvent.
Co prepared in this example3O4Per Ti and CoSe2A Scanning Electron Microscope (SEM) photograph of the/Ti composite material is shown in FIG. 3, and it can be seen from FIG. 3 that the obtained Co3O4/The Ti composite material is in a cubic rod shape, and CoSe is obtained after selenization2/The Ti composite material is coral stickShape, length 0.5-2 μm; as can be seen from FIG. 3, the product before selenization is in a more uniform cubic rod shape, is in a cross arrangement combination, and becomes a coral rod shape after selenization.
CoSe obtained from examples 1-32/The X-ray diffraction (XRD) spectra of the Ti composite materials are respectively shown in FIGS. 6-8, and it can be seen from FIGS. 6-8 that CoSe with different morphologies2/The Ti composite materials have the same X-ray diffraction (XRD) patterns, i.e., they have the same composition.
Example 4
Co with controllable appearance3O4The preparation of the/Ti composite material was as described in example 1, steps (1) to (2), except that: co (NO)3)3·6H2The addition amounts of O and NH were 1.0mmol and 0.5mmol, respectively4The amount of F added was 1.0mmol, and the amount of hexamethylenetetramine added was 2.5 mmol.
Two kinds of Co prepared in this example3O4A Scanning Electron Microscope (SEM) photograph of the/Ti composite material is shown in FIG. 9, and it can be seen from FIG. 9 that various amounts of Co (NO) were added3)3·6H2O, obtained Co3O4the/Ti composite material is in the shape of peony, and is accompanied by Co (NO)3)3·6H2The addition of O is reduced, and the number of peony layers tends to increase.
Example 5
Co with controllable appearance3O4The preparation of the/Ti composite material was as described in example 1, steps (1) to (2), except that: co (NO)3)3·6H2The amount of O added was 1.5mmol, NH4The amount of F added was 1.0mmol, and the amounts of hexamethylenetetramine added were 2.0mmol, 1.5mmol and 1.0mmol, respectively.
Three kinds of Co prepared in this example3O4The Scanning Electron Microscope (SEM) picture of the/Ti composite material is shown in FIG. 10, and it can be seen from FIG. 10 that Co obtained by adding different amounts of hexamethylenetetramine3O4the/Ti composite material is in a ganoderma shape, and the ganoderma lucidum sheets gradually have obvious accumulation along with the reduction of the addition of the hexamethylenetetramine.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (10)
1. CoSe with controllable appearance2the/Ti composite material is characterized in that the composite material is cobalt nitrate hexahydrate and NH4F and hexamethylenetetramine are used as raw materials, and the hydrothermal reaction is carried out on the surface of a titanium sheet substrate to obtain Co (OH)2The precursor of the/Ti composite material is prepared by calcining and selenizing the obtained precursor.
2. The topographically controllable CoSe of claim 12The preparation method of the/Ti composite material comprises the following steps:
(1) cobalt nitrate hexahydrate and NH4Sequentially adding F and hexamethylenetetramine into a solvent, uniformly stirring to obtain a mixed solution, and carrying out hydrothermal reaction on the mixed solution and a titanium sheet; filtering, washing and drying to obtain Co (OH)2a/Ti composite material;
(2) the Co (OH) obtained in the step (1)2the/Ti composite material is calcined at high temperature in air atmosphere to obtain Co3O4a/Ti composite material;
(3) co obtained in the step (2)3O4the/Ti composite material and the selenium powder are mixed evenly and calcined at high temperature in the argon atmosphere to obtain CoSe2a/Ti composite material.
3. The CoSe of claim 22The preparation method of the/Ti composite material is characterized in that the volume ratio of the mole number of the cobalt nitrate hexahydrate in the step (1) to the solvent is 0.5-1.5mmol:10-30mL, preferably 0.5-1.5mmol: 20 mL; the cobalt nitrate hexahydrate and NH4The molar ratio of F is 0.5-1.5: 1; the mole of the cobalt nitrate hexahydrate and the hexamethylenetetramineThe ratio is 1: 0.5-7.
4. The CoSe of claim 22The preparation method of the/Ti composite material is characterized in that the solvent in the step (1) is distilled water; or a mixed solvent of distilled water and absolute ethyl alcohol, wherein the volume ratio of the distilled water to the absolute ethyl alcohol in the mixed solvent is 1: 1-2, preferably 1: 1.5.
5. the CoSe of claim 22The preparation method of the/Ti composite material is characterized in that the thickness of the titanium sheet in the step (1) is 0.5-1.5mm, and the diameter is 10-20 mm; the ratio of the volume of the mixed solution to the area of the titanium sheet is 10-30mL (1-4) pi cm2。
6. The CoSe of claim 22The preparation method of the/Ti composite material is characterized in that the hydrothermal reaction temperature in the step (1) is 90-110 ℃, and preferably 100 ℃; the hydrothermal reaction time is 6-24h, preferably 15 h.
7. The CoSe of claim 22The preparation method of the/Ti composite material is characterized in that the washing in the step (1) is respectively washing for 2-4 times by using distilled water and absolute ethyl alcohol; the drying is vacuum drying at 50-80 deg.C for 12-36 h.
8. The CoSe of claim 22The preparation method of the/Ti composite material is characterized in that the high-temperature calcination temperature in the step (2) is 200-600 ℃, preferably 200-400 ℃, and the heating rate is 1-3 ℃/min; the high-temperature calcination time is 1-10h, preferably 2-4 h.
9. The CoSe of claim 22The preparation method of the/Ti composite material is characterized in that the Co in the step (3)3O4Co in/Ti composite material3O4The mass ratio of the selenium powder to the selenium powder is 5-10: 1.
10. the CoSe of claim 22The preparation method of the/Ti composite material is characterized in that the flow rate of the argon in the step (3) is 50-70 mL/min;
preferably, the high-temperature calcination temperature is 500-1000 ℃, more preferably 500-700 ℃, and the temperature rise rate is 5-10 ℃/min; the high-temperature calcination time is 0.5 to 5 hours, and more preferably 1 to 3 hours.
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