CN114160065B - Preparation method of crystalline phase controllable delafossite AgFeO2 powder material - Google Patents
Preparation method of crystalline phase controllable delafossite AgFeO2 powder material Download PDFInfo
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- CN114160065B CN114160065B CN202111361509.5A CN202111361509A CN114160065B CN 114160065 B CN114160065 B CN 114160065B CN 202111361509 A CN202111361509 A CN 202111361509A CN 114160065 B CN114160065 B CN 114160065B
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- 239000000843 powder Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 53
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 46
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 23
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052683 pyrite Inorganic materials 0.000 claims description 2
- 239000011028 pyrite Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 93
- 238000000862 absorption spectrum Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
- B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a crystalline phase controllable delafossite AgFeO 2 A method of preparing a powder material comprising: (1) Mixing a silver nitrate solution and a ferric nitrate solution, and forming a suspension after strong stirring; (2) Adding a mineralizer into the suspension, and obtaining a mixed solution B after strong stirring; (3) Transferring the mixed solution B into an autoclave, heating to a certain temperature, and performing hydrothermal reaction for a certain time to obtain a reaction solution C after the reaction is finished; (4) Centrifuging the reaction solution C, washing to obtain a powder reaction product, and drying the powder reaction product to obtain the delafossite AgFeO with controllable crystalline phase 2 A powder material. The copper iron ore AgFeO prepared by the invention 2 The powder material has the advantages of controllable crystalline phase, good crystallinity, complete stoichiometric ratio, no obvious defects and impurities and the like; the preparation method has the advantages of simple method, easily controlled parameters, environmental protection, high yield and low costThe advantages of quick temperature, low cost and the like can be widely applied to the agalmatolite AgFeO 2 And (3) preparing the novel photoelectric functional material.
Description
Technical Field
The invention relates to the technical field of metal oxides, in particular to a crystalline phase controllable delafossite AgFeO 2 A method for preparing a powder material.
Background
Compared with a single metal compound, the multi-metal compound has a variety of compositions and structures, so that the multi-metal compound shows rich physicochemical properties such as optics, electricity, magnetism, mechanics, catalysis and the like. The rich components and structures and flexible and adjustable physicochemical properties lead the multi-element metal compound to be a hot spot and an emerging field in the research directions of solid chemistry, functional materials and the like. The synthesis and structure regulation of the multi-element metal compound not only can enrich the knowledge content of structural chemistry, but also can develop new materials with practical application value and specific functions. However, since the liquid phase synthesis of a multi-metal compound involves two or more cationic reactions, if the reactivity of these metal cation precursors is greatly different, a hetero-phase or polymorphism phenomenon of the binary compound is easy to occur, so that the synthesized sample is often a mixture of multiple phases with the same components. This has made the use of liquid phase synthesis to prepare multi-metal compound nanomaterials very limited.
Paigeite ABO 2 The crystal structure of the compound exhibits a natural layered quasi-two-dimensional superlattice structure, with each unit cell consisting of two structural units: hexagonal close-packed surface of A atoms and [ BO ] centered on B atoms 6 ]The two structural units are alternately stacked and arranged along the c-axis of the octahedron. Due to the different arrangement and stacking number of the two structural units, the delafossite crystal structure generally has two homeotropic phases: the rhombohedral 3R phase was formed with a … abcab c … stack and the hexagonal 2H phase was formed with a … ABAB … stack. Paigeite type ABO 2 The unique structure of the compound enables the compound to have excellent optical and electrical properties, so that the compound can be widely applied to the technical fields of high and new photoelectrons such as microelectronics, solar cells, lithium/sodium ion batteries, transparent conduction, photocatalysis, gas sensors, detectors and the like. ABO as paigeite 2 One member of the family of compounds, agFeO 2 With a suitable band gap (1.5-2.0 eV), it is readily excited by visible light to generate photo-generated electron-hole pairs. At the same time, the unique crystal structure enables the crystal structure to be provided with a proper carrier rapid transmission channel, so that photo-generated electrons or photo-generated holes can be rapidly migrated. Thus, the delafossite AgFeO 2 Has the potential advantages of ideal photoelectric functional materials, such as the photoelectric technologyRelated application reports are already reported in the technical field.
Due to precursor oxide Ag 2 O is decomposed in an open system, thus synthesizing delafossite AgFeO 2 Special process conditions (e.g., closed systems, high pressure, high temperature, ultra high vacuum, etc.) are required. Therefore, is suitable for synthesizing pure-phase paigeite AgFeO 2 The number of processes is limited. In the literature published today, the synthesis of delafossite AgFeO has been reported 2 The process method of (1) comprises: high temperature solid state reaction, metathesis reaction, co-precipitation, hydrothermal synthesis, pulsed laser deposition, radio frequency sputtering, and the like. To our knowledge, the cupronite AgFeO synthesized by these processes 2 The samples have problems of impure crystal phase, obvious impurity/impurity phase, nonstoichiometric ratio and the like to a greater or lesser extent. Wherein, only coprecipitation method can relatively easily synthesize the paigeite AgFeO with relatively pure crystalline phase 2 And (3) a sample. However, improvements in the coprecipitation process are needed depending on reagents, reaction medium, mineralizer type, reaction conditions and post-synthesis treatments. It should be noted in particular that: due to the delafossite AgFeO 2 The difference in energy and stability between the two phases of (a) is very small, and the rhombohedral 3R phase is always accompanied by a small amount of hexagonal 2H phase in the synthesized sample. This was useful for the study of pure phase copper iron ore AgFeO 2 Is quite disadvantageous.
In view of the above, there is a need to develop a crystalline phase-controllable delafossite AgFeO 2 The preparation method of the powder material solves the technical problems.
Disclosure of Invention
The invention aims to provide a copper iron ore AgFeO with controllable crystalline phase 2 The preparation method of the powder material aims at obtaining the powder material of pure rhombohedral 3R phase, pure hexagonal 2H phase or 3R-2H mixed phase by regulating the preparation conditions.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a crystalline phase controllable delafossite AgFeO 2 The preparation method of the powder material, the crystal phase is rhombohedral 3R phase, hexagonal 2H phase or mixed phase 3R-2H of rhombohedral 3R phase and hexagonal 2H phase,the method is characterized by comprising the following specific steps:
(1) Weighing silver nitrate and ferric nitrate powder, and respectively dissolving the silver nitrate and the ferric nitrate powder in deionized water to obtain a silver nitrate solution and a ferric nitrate solution; mixing the silver nitrate solution and the ferric nitrate solution, stirring to obtain a mixed solution A, and strongly stirring the mixed solution A to form a suspension;
(2) Adding mineralizer into the suspension in the step (1) under the condition of strong stirring, continuing strong stirring for 4-8 hours, and obtaining a mixed solution B through coprecipitation reaction;
(3) Transferring the mixed solution B in the step (2) into an autoclave, sealing the autoclave body, then putting the autoclave body into an oven, heating to a certain temperature, and performing hydrothermal reaction for a certain time until the hydrothermal reaction is finished, thereby obtaining a reaction solution C;
(4) After the reaction solution C in the step (3) is naturally cooled to room temperature in an autoclave, opening the autoclave body to take out the reaction solution C, centrifuging the reaction solution C, alternately washing the reaction solution C with deionized water and absolute ethyl alcohol for a plurality of times to obtain a powder reaction product, and drying the powder reaction product to obtain the pyrite AgFeO with controllable crystalline phase 2 A powder material.
Preferably, the concentration of the silver nitrate solution and the ferric nitrate solution in the step (1) is 0.1-0.3mol/L; the molar ratio of the silver nitrate solution to the ferric nitrate solution in the mixed solution A is 1:1-2.
Preferably, the intensive stirring in step (1) and step (2) is preferably magnetic stirring at a rotational speed of 300 rpm.
Preferably, the magnetic stirring time in the step (1) is 1 to 3 hours.
Preferably, the mineralizer in the step (2) is one or a mixture of sodium hydroxide and potassium hydroxide.
Preferably, the mineralizer is added in step (2) in an amount of 10-50% by volume of the suspension.
Preferably, the autoclave in the step (3) is preferably a stainless steel autoclave with a polytetrafluoroethylene lining, the filling ratio of the mixed solution B in the lining is 40-80%, the hydrothermal reaction temperature is 70-200 ℃, and the hydrothermal reaction time is 10-20 hours.
Preferably, in step (4), the washing with deionized water and absolute ethanol is performed alternately a plurality of times, preferably 3 to 6 times; the drying temperature is 50-80 ℃, and the drying time is 10-15 hours.
Preferably, the crystalline phase controllable goethite AgFeO in step (4) 2 The particle size distribution range of the powder material is 30 nanometers to 2 micrometers.
Preferably, the hydrothermal reaction temperature is preferably 80 ℃, 170 ℃ and 190 ℃; when the hydrothermal reaction temperature is 80 ℃, the obtained paigeite AgFeO 2 The powder material is hexagonal 2H phase, and when the hydrothermal reaction temperature is 170 ℃, the obtained delafossite AgFeO 2 The powder material is mixed phase 3R-2H of rhombohedral 3R phase and hexagonal 2H phase, and when the hydrothermal reaction temperature is 190 ℃, the obtained delafossite AgFeO 2 The powder material is rhombohedral 3R phase.
In summary, compared with the prior art, the invention has the following advantages:
1. the invention controls the crystal phase of the synthesized sample by strictly controlling the hydrothermal reaction condition and utilizing the shear phase transition between the hexagonal 2H phase and the rhombohedral 3R phase, thereby obtaining the delafossite AgFeO with controllable crystal phase 2 Powder material, overcomes the defect of preparing the delafossite AgFeO in the prior art 2 And the crystal phase of the powder material is uncontrollable.
2. The method prepares the delafossite AgFeO by controlling the temperature and time of the hydrothermal reaction 2 The powder material has the characteristics of controllable crystalline phase (3R phase, 2H phase and 3R-2H mixed phase), good crystallinity, complete stoichiometric ratio, no obvious defects, no impurities and the like.
3. The preparation process provided by the invention has the advantages of simple operation, easily controlled parameters, environmental protection, high yield, quick low temperature, low cost and the like, and can be widely used for the delafossite AgFeO 2 The preparation of the novel photoelectric functional material is beneficial to the development and industrialization development of the novel photoelectric functional material.
Drawings
FIG. 1 shows the preparation of 3R-phase copper-iron ore AgF according to example 1 of the present inventioneO 2 Powder X-ray crystal diffraction pattern of (c).
FIG. 2 shows the preparation of 3R-phase copper-iron ore AgFeO according to example 1 of the present invention 2 Is a scanning electron microscope image of (c).
FIG. 3 shows the preparation of 3R-phase copper-iron ore AgFeO according to example 1 of the present invention 2 Is a diffuse reflection absorption spectrum of ultraviolet-visible light.
FIG. 4 shows the preparation of 2H-phase copper-iron ore AgFeO according to example 2 of the present invention 2 Powder X-ray crystal diffraction pattern of (c).
FIG. 5 shows the preparation of 2H-phase copper-iron ore AgFeO according to example 2 of the present invention 2 Is a scanning electron microscope image of (c).
FIG. 6 shows the preparation of 2H-phase copper-iron ore AgFeO according to example 2 of the present invention 2 Is a diffuse reflection absorption spectrum of ultraviolet-visible light.
FIG. 7 shows the preparation of 3R-2H mixed phase delafossite AgFeO according to example 3 of the present invention 2 Powder X-ray crystal diffraction pattern of (c).
FIG. 8 shows the preparation of 3R-2H mixed phase delafossite AgFeO according to example 3 of the present invention 2 Is a scanning electron microscope image of (c).
FIG. 9 shows the preparation of 3R-2H mixed phase delafossite AgFeO according to example 3 of the present invention 2 Is a diffuse reflection absorption spectrum of ultraviolet-visible light.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
Example 1
The specific embodiment provides rhombohedral 3R-phase copper-iron ore AgFeO 2 The preparation method of the powder material comprises the following specific steps:
step (1): 4mmol Fe (NO) 3 ) 3 ·9H 2 O was dissolved in 25mL deionized water, 4mmolAgNO 3 Dissolving in 25mL deionized water to obtain 0.16mol/L silver nitrate solution and ferric nitrate solution, mixingMixing the silver nitrate solution and the ferric nitrate solution according to the proportion of 1:1, continuously stirring to obtain a mixed solution A, and strongly stirring for 1 hour to form a suspension, wherein the stirring speed is 300 revolutions per minute;
step (2): adding 20mL of sodium hydroxide with the concentration of 1.6mol/L into the suspension under strong stirring, and continuing strong stirring for 5 hours at the stirring speed of 300 rpm to obtain a mixed solution B;
step (3): transferring the mixed solution B in the step (2) into a 100mL stainless steel autoclave with polytetrafluoroethylene lining, wherein the filling ratio is 45%, and reacting for 12 hours at 190 ℃ after sealing the autoclave body; after the reaction is finished, naturally cooling the kettle body to room temperature, opening the kettle body to take out a reaction solution, alternately washing the reaction product with deionized water and absolute ethyl alcohol, centrifuging for 6 times to obtain the reaction product, centrifuging for 10 minutes each time at a rotational speed of 7000 rpm, and drying at 60 ℃ for 12 hours to obtain 3R-phase paigeite AgFeO 2 A powder material.
3R-phase delafossite AgFeO prepared in this embodiment 2 The powder X-ray crystal diffraction pattern is shown in figure 1. As can be seen from FIG. 1, 3R-phase delafossite AgFeO 2 The characteristic diffraction peak of (2) completely corresponds to the 3R phase standard PDF card JCPDS#75-2147, which shows that the 3R phase copper iron ore AgFeO is successfully prepared 2 . No other diffraction peaks were found, indicating that the samples had high purity and crystallinity.
3R-phase delafossite AgFeO prepared in this embodiment 2 A scanning electron microscope image of (2) is shown in fig. 2. As can be seen from FIG. 2, 3R-phase delafossite AgFeO 2 In a polyhedral structure, most of which are fully grown cubes and a few of which are incompletely grown small cubes. And 3R phase paigeite AgFeO 2 The grain size distribution of (2) is about 1 micron.
The specific embodiment prepares the 3R-phase copper-iron ore AgFeO 2 The ultraviolet-visible diffuse reflection absorption spectrum of (c) is shown in figure 3. As can be seen from FIG. 3, 3R-phase delafossite AgFeO is shown 2 Is located at about 722 nanometers, the band gap of which is defined by the formula α (hν) =a (hν -E g ) n/2 The band gap was calculated to be 1.69eV.
Example 2
This embodiment provides 2H-phase paigeite AgFeO 2 The preparation method of the powder material comprises the following specific steps:
step (1): 4mmol Fe (NO) 3 ) 3 ·9H 2 O was dissolved in 25mL deionized water, 4mmol AgNO 3 Dissolving in 25mL of deionized water to prepare 0.16mol/L silver nitrate solution and ferric nitrate solution, mixing the silver nitrate solution and the ferric nitrate solution according to the proportion of 1:1, continuously stirring to obtain a mixed solution A, and strongly stirring for 1 hour to form a suspension, wherein the stirring speed is 300 revolutions per minute;
step (2): adding 20mL of sodium hydroxide with the concentration of 1.6mol/L into the suspension under strong stirring, and continuing strong stirring for 5 hours, wherein the stirring speed is 300 rpm, so as to obtain a mixed solution B;
step (3): transferring the mixed solution B in the step (2) into a 100mL stainless steel autoclave with polytetrafluoroethylene lining, reacting at 80 ℃ for 12 hours after sealing the autoclave body, naturally cooling the autoclave body to room temperature after the reaction is finished, opening the autoclave body to take out the reaction solution, alternately washing the reaction product by deionized water and absolute ethyl alcohol, centrifuging for 6 times to obtain a reaction product, centrifuging for 10 minutes each time at a rotational speed of 7000 r/min, and drying at 60 ℃ for 12 hours to obtain 2H-phase cupronite AgFeO 2 A powder material.
The specific embodiment prepares 2H-phase copper-iron ore AgFeO 2 The powder X-ray crystal diffraction pattern of (2) is shown in fig. 4. As can be seen from FIG. 4, 2H-phase paigeite AgFeO 2 The characteristic diffraction peak of (2) phase corresponds to the standard PDF card JCPDS#25-0765 completely, which shows that 2H phase copper iron ore AgFeO is successfully prepared 2 . No other diffraction peaks were found, indicating that the samples had high purity and crystallinity.
2H-phase delafossite AgFeO prepared in the embodiment 2 A scanning electron microscope image of (2) is shown in fig. 5. As can be seen from FIG. 5, 2H-phase paigeite AgFeO 2 And are in a small sphere structure and are clustered together, and the grain size distribution is about 30 nanometers.
2H-phase delafossite AgFeO prepared in the embodiment 2 Uv-visible diffusion of (c)The reflection absorption spectrum is shown in fig. 6. As can be seen from FIG. 6, 2H-phase paigeite AgFeO 2 Is located at about 735 nanometers, and has a band gap according to the formula α (hν) =a (hν -E g ) n/2 The band gap was calculated to be 1.67eV.
Example 3
The specific embodiment provides 3R-2H mixed phase delafossite AgFeO 2 The preparation method of the powder material comprises the following specific steps:
step (1): 4mmol Fe (NO) 3 ) 3 ·9H 2 O was dissolved in 25mL deionized water, 4mmolAgNO 3 Dissolving in 25mL of deionized water to prepare 0.16mol/L silver nitrate solution and ferric nitrate solution, mixing the silver nitrate solution and the ferric nitrate solution according to the proportion of 1:1, continuously stirring to obtain a mixed solution, and strongly stirring for 1 hour to form a suspension, wherein the stirring speed is 300 revolutions per minute;
step (2): adding 20mL of sodium hydroxide with the concentration of 1.6mol/L into the suspension under strong stirring, and continuing strong stirring for 5 hours, wherein the stirring speed is 300 rpm, so as to obtain a mixed solution B;
step (3): transferring the mixed solution in the step (2) into a 100mL stainless steel autoclave with polytetrafluoroethylene lining, wherein the filling ratio is 45%, sealing the autoclave body, reacting at 170 ℃ for 12 hours, naturally cooling the autoclave body to room temperature after the reaction is finished, opening the autoclave body to take out the reaction solution, alternately washing the reaction product by deionized water and absolute ethyl alcohol, centrifuging for 6 times to obtain a reaction product, centrifuging for 10 minutes each time at a rotational speed of 7000R/min, and drying at 60 ℃ for 12 hours to obtain 3R-2H mixed-phase delafossite AgFeO 2 A powder material.
The 3R-2H mixed phase delafossite AgFeO prepared by the specific embodiment 2 The powder X-ray crystal diffraction pattern of (2) is shown in fig. 7. As can be seen from FIG. 7, 3R-2H mixed phase delafossite AgFeO 2 The characteristic diffraction peak of (C) corresponds to the standard PDF card of 3R phase and 2H phase, which shows that the 3R-2H mixed phase delafossite AgFeO is successfully prepared 2 。
The 3R-2H mixed phase delafossite AgFeO prepared by the specific embodiment 2 The scanning electron microscope image of (2) is shown in FIG. 8Shown. As can be seen from FIG. 8, the agglomeration of a part of the polyhedral structure and a part of the spherule are respectively corresponding to the 3R phase and the 2H phase, and the successful preparation of the 3R-2H mixed phase delafossite AgFeO is further proved 2 . At the same time, the 2H-phase paigeite AgFeO hydrothermally synthesized at low temperature is proved 2 The transformation of the crystal phase into the 3R-phase cupronickel AgFeO can occur by increasing the reaction temperature 2 。
The 3R-2H mixed phase delafossite AgFeO prepared by the specific embodiment 2 The ultraviolet-visible diffuse reflection absorption spectrum of (2) is shown in fig. 9. As can be seen from FIG. 9, 3R-2H mixed phase delafossite AgFeO 2 Is located at about 720 nanometers, and has a band gap according to the formula α (hν) =a (hν -E g ) n/2 The band gap was calculated to be 1.71eV.
Example 4
The specific embodiment provides the delafossite AgFeO with controllable crystal phase 2 The preparation method of the powder material comprises the following specific steps:
step (1): 4mmol Fe (NO) 3 ) 3 ·9H 2 O was dissolved in 25mL deionized water, 4mmol AgNO 3 Dissolving in 25mL of deionized water to prepare 0.1mol/L silver nitrate solution and ferric nitrate solution, mixing the silver nitrate solution and the ferric nitrate solution according to the proportion of 1:2, continuously stirring to obtain a mixed solution A, and strongly stirring for 3 hours to form a suspension, wherein the stirring speed is 300 revolutions per minute;
step (2): adding 20mL of potassium hydroxide with the concentration of 1.6mol/L into the suspension under strong stirring, and continuing strong stirring for 8 hours at the stirring speed of 300 rpm to obtain a mixed solution B;
step (3): transferring the mixed solution B in the step (2) into a 100mL stainless steel autoclave with polytetrafluoroethylene lining, wherein the filling ratio is 80%, and reacting for 10 hours at 70 ℃ after sealing the autoclave body; after the reaction is finished, naturally cooling the kettle body to room temperature, opening the kettle body to take out a reaction solution, alternately washing and centrifuging the reaction product with deionized water and absolute ethyl alcohol for 3 times to obtain the reaction product, centrifuging the reaction product at a speed of 7000 rpm for 10 minutes each time, and drying the reaction product at 80 ℃ for 10 hours to obtain the delafossite AgFeO with controllable crystalline phase 2 A powder material.
Example 5
The specific embodiment provides the delafossite AgFeO with controllable crystal phase 2 The preparation method of the powder material comprises the following specific steps:
step (1): 4mmol Fe (NO) 3 ) 3 ·9H 2 O was dissolved in 25mL deionized water, 4mmol AgNO 3 Dissolving in 25mL of deionized water to prepare 0.3mol/L silver nitrate solution and ferric nitrate solution, mixing the silver nitrate solution and the ferric nitrate solution according to the proportion of 1:2, continuously stirring to obtain a mixed solution A, magnetically stirring for 2 hours to form a suspension, wherein the stirring speed is 300 revolutions per minute;
step (2): adding 20mL of potassium hydroxide and sodium hydroxide with the concentration of 1.6mol/L into the suspension under strong stirring, and continuing magnetic stirring for 4 hours at the stirring speed of 300 rpm to obtain a mixed solution B;
step (3): transferring the mixed solution B in the step (2) into a 100mL stainless steel autoclave with polytetrafluoroethylene lining, wherein the filling ratio is 60%, and reacting for 20 hours at 70 ℃ after sealing the autoclave body; after the reaction is finished, naturally cooling the kettle body to room temperature, opening the kettle body to take out a reaction solution, alternately washing and centrifuging the reaction product with deionized water and absolute ethyl alcohol for 5 times to obtain the reaction product, wherein the centrifugal speed is 7000 rpm, centrifuging for 10 minutes each time, and drying for 15 hours at 50 ℃ to obtain the delafossite AgFeO with controllable crystalline phase 2 A powder material.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (5)
1. Crystal phase controllable delafossite AgFeO 2 The preparation method of the powder material is characterized by comprising the following specific steps:
(1) Weighing silver nitrate and ferric nitrate powder, and respectively dissolving the silver nitrate and the ferric nitrate powder in deionized water to obtain a silver nitrate solution and a ferric nitrate solution; mixing the silver nitrate solution and the ferric nitrate solution, stirring to obtain a mixed solution A, and strongly stirring the mixed solution A to form a suspension;
(2) Adding mineralizer into the suspension in the step (1) under the condition of strong stirring, continuing strong stirring for 4-8 hours, and obtaining a mixed solution B through coprecipitation reaction;
(3) Transferring the mixed solution B in the step (2) into an autoclave, sealing the autoclave body, then putting the autoclave body into an oven, heating to a certain temperature, and performing hydrothermal reaction for a certain time until the hydrothermal reaction is finished, thereby obtaining a reaction solution C;
(4) After the reaction solution C in the step (3) is naturally cooled to room temperature in an autoclave, opening the autoclave body to take out the reaction solution C, centrifuging the reaction solution C, alternately washing the reaction solution C with deionized water and absolute ethyl alcohol for a plurality of times to obtain a powder reaction product, and drying the powder reaction product to obtain the pyrite AgFeO with controllable crystalline phase 2 A powder material;
the concentration of the silver nitrate solution and the ferric nitrate solution in the step (1) is 0.1-0.3mol/L; the molar ratio of the silver nitrate to the ferric nitrate in the mixed solution A is 1:1-2;
the mineralizer in the step (2) is one of sodium hydroxide and potassium hydroxide;
the mineralizer is added in the step (2) in an amount of 10-50% of the volume of the suspension;
the hydrothermal reaction time is 10-20 hours;
the water heatingThe reaction temperature is 80 ℃, 170 ℃ or 190 ℃; when the hydrothermal reaction temperature is 80 ℃, the obtained paigeite AgFeO 2 The powder material is hexagonal 2H phase; when the hydrothermal reaction temperature is 170 ℃, the obtained paigeite AgFeO 2 The powder material is mixed phase 3R-2H of rhombohedral 3R phase and hexagonal 2H phase; when the hydrothermal reaction temperature is 190 ℃, the obtained paigeite AgFeO 2 The powder material is rhombohedral 3R phase;
the crystalline phase controllable delafossite AgFeO in the step (4) 2 The particle size distribution of the powder material is in the range of 30nm to 2 mu m.
2. A crystalline phase controllable delafossite AgFeO according to claim 1 2 The preparation method of the powder material is characterized in that the strong stirring in the step (1) and the step (2) is magnetic stirring, and the rotating speed of the magnetic stirring is 300 revolutions per minute.
3. A crystalline phase controllable delafossite AgFeO according to claim 2 2 The preparation method of the powder material is characterized in that the magnetic stirring time in the step (1) is 1-3 hours.
4. A crystalline phase controllable delafossite AgFeO according to claim 1 2 The preparation method of the powder material is characterized in that the autoclave in the step (3) is a stainless steel autoclave with a polytetrafluoroethylene lining, and the filling ratio of the mixed solution B in the lining is 40-80%.
5. A crystalline phase controllable delafossite AgFeO according to claim 1 2 The preparation method of the powder material is characterized in that deionized water and absolute ethyl alcohol are used for washing alternately for 3-6 times in the step (4); the drying temperature is 50-80 ℃, and the drying time is 10-15 hours.
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