CN116395733A - CuAlO with adjustable optical property 2 Preparation method of powder material - Google Patents
CuAlO with adjustable optical property 2 Preparation method of powder material Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims abstract description 55
- 230000003287 optical effect Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 61
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 239000011812 mixed powder Substances 0.000 claims abstract description 15
- 239000007790 solid phase Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 8
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000003825 pressing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 230000004298 light response Effects 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910018572 CuAlO2 Inorganic materials 0.000 claims description 2
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- 238000005303 weighing Methods 0.000 claims description 2
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- 238000002424 x-ray crystallography Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a CuAlO with adjustable optical property 2 The preparation method of the powder material comprises the steps of grinding cuprous oxide powder and aluminum oxide powder in absolute ethyl alcohol medium to obtain mixed powder A; putting the mixed powder A into a tablet press for pressing to obtain a pressed sheet A; placing the sheet A into a crucible and transferring into an atmosphere furnace, introducing atmosphere into the atmosphere furnace for high-temperature solid-phase sintering reaction, cooling and grinding a sintered product to obtain a powder reaction product B; the powder reaction product B is repeatedly subjected to high-temperature solid-phase sintering, and the color of the reaction product is uniform, so that a powder product C with complete reaction is obtained; centrifugally washing the powder product C with complete reaction, and drying the precipitate to obtain the paigeite type CuAlO with adjustable optical properties 2 A powder material. The method prepares the CuAlO responding to visible light by controlling the high-temperature solid-phase synthesis temperature and the oxygen partial pressure of the atmosphere furnace 2 The powder material has the characteristics of controllable visible light absorption intensity, high purity single phase, good crystallinity and the like.
Description
Technical Field
The invention relates to the technical field of metal oxide material preparation, in particular to a CuAlO with adjustable optical property 2 A method for preparing a powder material.
Background
In certain applications, the core of the functional technology is that the semiconductor material should have a suitable band gap and band edge location. Copper-iron type ABO 2 The compound has the unique advantages of adjustable electrical and optical properties and combination of conductivity and optical transparency, which enables the compound to be used in photocatalysts, microelectronic devices and photovoltaic materialsThe material and transparent conductive oxide have huge application potential in a plurality of photoelectric function fields. In recent years, delafossite type ABO 2 The research result of the compound shows that the compound can be used as an effective photocatalyst for degrading organic pollutants in water.
ABO as paigeite type 2 Cupronite-based transparent conductive oxide film, cuAlO, originally developed in the compound family 2 The time application field has higher requirements on the transparency, the power efficiency and the circuit complexity of the material, and the copper-iron CuAlO is developed 2 Functional materials are a potential facilitating factor. Meanwhile, the unique quasi-two-dimensional layered super crystal structure enables the super crystal to have a proper carrier rapid transmission channel, so that photo-generated electrons or photo-generated holes can be rapidly migrated. However, there is a major problem in that the narrow spectral response range limits its application in the field of optoelectronic functional materials. Thus, the delafossite type CuAlO 2 The potential advantages of the ideal photoelectric functional material are reported in the photoelectric technology field. Currently, only the literature [ Brahimi R, bessekhoud Y, bouguelia A, trari M, journal of Photochemistry and Photobiology A: chemistry,2007,186 (2): 242-7 ] reports the passage of CuAlO 2 /TiO 2 Forming heterogeneous solid is now used in the production of hydrogen by visible light. However, the regulation of the oxygen partial pressure is achieved by simple means (regulation of the oxygen partial pressure) for the delafossite type CuAlO 2 The regulation of the visible light response of the material is not reported in the photoelectric technology field.
In the prior art, a manner of effectively realizing visible light response mainly depends on forming a heterojunction with a narrow bandgap material. However, the formation of heterojunction is guaranteed by the presence of the delafossite type CuAlO 2 The realization of wide spectral response has the technical problems that the oxidation-reduction capability and the quantum conversion efficiency are not negatively affected, and the phase change, uncontrollability or poor heterojunction interface contact are easy to occur when the visible light response wide band gap powder material is prepared.
In view of the above, there is a need to develop a delafossite type CuAlO with controllable optical properties 2 Method for preparing powder material to solve the above-mentioned problemsProblems.
Disclosure of Invention
The main purpose of the invention is to provide a CuAlO with adjustable optical property 2 The preparation method of the powder material aims at realizing the aim of preparing the paigeite type CuAlO 2 And (3) adjusting the visible light response of the material.
In order to achieve the above purpose, the present invention provides the following technical solutions:
CuAlO with adjustable optical property 2 The preparation method of the powder material comprises the following steps:
(1) Weighing cuprous oxide powder and aluminum oxide powder, and grinding the cuprous oxide powder and the aluminum oxide powder to be fully and uniformly mixed in the presence of absolute ethyl alcohol medium to obtain mixed powder A;
(2) The mixed powder A in the step (1) is put into a tablet press for pressing, and after the tablet pressing is finished, a pressed tablet A is obtained;
(3) Placing the sheet A in the step (2) into a crucible and transferring the crucible into an atmosphere furnace, introducing inert gas and oxidizing gas into the atmosphere furnace for high-temperature solid-phase sintering reaction, cooling and grinding a sintering product after the reaction is finished to obtain a powder reaction product B;
(4) Repeating the step (3) on the powder reaction product B in the step (3) until the color of the high-temperature solid-phase sintering reaction product is uniform, and obtaining a powder product C with complete reaction;
(5) Adding the washing liquid into the powder product C with complete reaction in the step (4) for centrifugal washing to obtain a precipitate, namely the delafossite type CuAlO with adjustable optical properties 2 A powder material.
Preferably, the molar ratio of the cuprous oxide powder to the aluminum oxide powder in the step (1) is 1:1, and the purity of the cuprous oxide powder and the aluminum oxide powder is more than or equal to 97 percent.
Preferably, the tabletting in the step (1) is carried out in a tabletting machine, the pressure of the tabletting machine is 5-10MPa, and the tabletting time is 5-10min.
Preferably, the inert gas in the step (3) is one of argon and nitrogen; the oxidizing gas is high-purity oxygen; the ratio of the inert gas to the oxidizing gas is (100-60): 0-40.
The oxygen partial pressures mentioned below are: the ratio of the inert gas to the oxidizing gas, for example, 90% for argon and 10% for oxygen, is 10% for oxygen partial pressure.
Preferably, the crucible in step (3) is an alumina crucible; the high-temperature solid-phase sintering reaction temperature is 1050-1200 ℃, and the reaction time is 12-36 hours.
Preferably, the number of repetitions in step (4) is 2-4.
Preferably, the washing liquid in the step (5) is deionized water, 10% acid solution and absolute ethanol; the centrifugal washing is to alternately wash for 4-6 times by using deionized water, 10% acid solution and absolute ethyl alcohol; the acidic solution is one of sulfuric acid, nitric acid and hydrochloric acid.
Preferably, the drying temperature in step (5) is 50-80 ℃ and the drying time is 10-15 hours.
Preferably, in the step (5), the absorption range and the intensity of the visible light response intensity of the delafossite type CuAlO2 powder material with adjustable optical properties are regulated and controlled by the temperature in the atmosphere furnace, the ratio of the inert gas to the oxidizing gas; the CuAlO 2 The strongest absorption peak intensity of the powder material in the visible light region is regulated and controlled within 0.1-1.0a.u.
The invention has the beneficial effects that:
1. the invention can obtain a series of visible light response intensity controllable cuAlO by regulating and controlling the atmosphere and annealing conditions of the high-temperature solid-phase sintering reaction and utilizing the high temperature under the atmosphere with different oxygen partial pressures (the ratio of inert gas to oxidizing gas) 2 The powder material solves the problems that the visible light response wide band gap powder material prepared in the prior art is easy to generate phase change, uncontrollable or poor in heterojunction interface contact.
2. The method prepares the delafossite type CuAlO responding to visible light by controlling the high-temperature solid-phase synthesis temperature and the oxygen partial pressure of the atmosphere furnace 2 The powder material has the characteristics of controllable visible light absorption intensity, high purity single phase, good crystallinity and the like.
3. The preparation process provided by the invention has the advantages of simple method, easily controlled parameters, environment protection, high yield, rapidness, low cost and the like, and can be widely used for the delafossite type CuAl O 2 And (3) preparing the novel photoelectric functional material.
Drawings
FIG. 1 shows the preparation of a controlled optical property of delafossite type CuAlO according to example 1 of the present invention 2 (0％O 2 ) Powder X-ray crystal diffraction pattern of the sample;
FIG. 2 shows the preparation of a controlled optical property of delafossite type CuAlO according to example 1 of the present invention 2 (0％O 2 ) An ultraviolet-visible diffuse reflectance absorption spectrum of the sample;
FIG. 3 shows the preparation of a controlled optical property of delafossite type CuAlO according to example 2 of the present invention 2 (10％O 2 ) Powder X-ray crystal diffraction pattern of the sample;
FIG. 4 shows the preparation of a controlled optical property of delafossite type CuAlO according to example 2 of the present invention 2 (10％O 2 ) An ultraviolet-visible diffuse reflectance absorption spectrum of the sample;
FIG. 5 shows the preparation of a controlled optical property of delafossite type CuAlO according to example 3 of the present invention 2 (20％O 2 ) Powder X-ray crystal diffraction pattern of the sample;
FIG. 6 shows the preparation of a controlled optical property of delafossite type CuAlO according to example 3 of the present invention 2 (20％O 2 ) An ultraviolet-visible diffuse reflectance absorption spectrum of the sample;
FIG. 7 shows the preparation of a controlled optical property of delafossite type CuAlO according to example 4 of the present invention 2 (30％O 2 ) Powder X-ray crystal diffraction pattern of the sample;
FIG. 8 shows the preparation of a controlled optical property of delafossite type CuAlO according to example 4 of the present invention 2 (30％O 2 ) An ultraviolet-visible diffuse reflectance absorption spectrum of the sample;
FIG. 9 shows the preparation of a controlled optical property of delafossite type CuAlO according to example 5 of the present invention 2 (40％O 2 ) Powder X-ray crystal diffraction pattern of the sample;
FIG. 10 shows the preparation of a delafossite type with controllable optical properties according to example 5 of the present inventionCuAlO 2 (40％O 2 ) An ultraviolet-visible diffuse reflectance absorption spectrum of the sample;
FIG. 11 shows the preparation of visible light responsive delafossite type CuAlO according to examples 1-5 of the present invention 2 Photocurrent density versus time curve of the sample;
FIG. 12 shows the preparation of visible light responsive delafossite type CuAlO according to examples 1, 2, 3, 4 and 5 of the present invention 2 Photocatalytic degradation curve of sample degrading tetracycline hydrochloride under visible light;
FIG. 13 shows the preparation of visible light responsive delafossite type CuAlO according to examples 1, 2, 3, 4 and 5 of the present invention 2 A photocatalytic degradation rate curve of the sample for degrading tetracycline hydrochloride in a full spectrum;
FIG. 14 shows the preparation of visible light responsive delafossite type CuAlO according to example 1 of the present invention 2 Sample pictures;
FIG. 15 shows the preparation of visible light responsive delafossite type CuAlO according to example 2 of the present invention 2 Sample pictures;
FIG. 16 shows preparation of visible light responsive delafossite type CuAlO according to example 3 of the present invention 2 Sample pictures;
FIG. 17 shows preparation of visible light responsive delafossite type CuAlO according to example 4 of the present invention 2 Sample pictures;
FIG. 18 shows preparation of visible light responsive delafossite type CuAlO according to example 5 of the present invention 2 Sample pictures;
FIG. 19 shows the preparation of a controlled optical property of delafossite type CuAlO according to example 1 of the present invention 2 (0％O 2 ) A transmission spectrum of the sample;
FIG. 20 shows the preparation of a controlled optical property of delafossite type CuAlO according to example 2 of the present invention 2 (10％O 2 ) A transmission spectrum of the sample;
FIG. 21 shows the preparation of a controlled optical property of delafossite type CuAlO according to example 3 of the present invention 2 (20％O 2 ) A transmission spectrum of the sample;
FIG. 22 shows the preparation of a controlled optical property of delafossite type CuAlO according to example 4 of the present invention 2 (30％O 2 ) A transmission spectrum of the sample;
FIG. 23 shows the optical property control obtained in example 5 of the present inventionCopper iron ore type CuAlO 2 (40％O 2 ) Transmission spectrum of the sample.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
The terms "first," "second," "third," and the like in this application are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "first," "second," and "third" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise. All directional indications (such as up, down, left, right, front, back … …) in the embodiments of the present application are merely used to explain the relative positional relationship, movement, etc. between the components in a particular gesture (as shown in the drawings), and if the particular gesture changes, the directional indication changes accordingly. Furthermore, the terms "comprise" and "have," as well as any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those listed steps or elements but may include other steps or elements not listed or inherent to such process, method, article, or apparatus.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the present application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
Example 1
The embodiment provides a delafossite type CuAlO with controllable optical properties 2 The preparation method of the powder material comprises the following specific steps:
step (1): 5mmol Cu with purity not less than 97% 2 O and 5mmolAl 2 O 3 Putting into a mortar, adding proper amount of absolute ethanol into the mortar for Cu 2 O and Al 2 O 3 Manually grinding the powder, and continuously grinding to obtain uniformly mixed powder A;
step (2): transferring the mixed powder A into a die, then putting the die on a manual hydraulic tablet press to be pressed into tablets at 5MPa/5min+5MPa/5min, and opening the die after pressure relief to obtain the tablet A;
step (3): placing the sheet A into an alumina crucible, transferring the alumina crucible into an atmosphere furnace, then introducing argon (the flow is 100ml/min; the oxygen partial pressure is 0%) into the alumina crucible, heating the alumina crucible to 1200 ℃ and carrying out solid-phase sintering reaction for 36 hours; this step was repeated 3 times to obtain a uniform and homogeneous color reaction product B.
Step (4): the reaction product B is alternately washed by deionized water, dilute nitric acid (the concentration of nitric acid is 65-68%, dilute nitric acid is prepared according to the concentration of nitric acid and water being 1:9) and absolute ethyl alcohol and centrifuged for 6 times, the centrifugal speed is 7000 r/min, the centrifugal speed is 10 minutes each time, and the drying is carried out for 12 hours at 60 ℃ to obtain the delafossite CuAlO 2 A powder material.
The optical property of the prepared delafossite type CuAlO is controllable 2 (oxygen partial pressure: 0%) the X-ray crystal diffraction pattern is shown in fig. 1. As can be seen from FIG. 1, the prepared visible light controllable delafossite type CuAlO 2 (0％O 2 ) Characteristic diffraction peaks of (2) and delafossite type 3R CuAlO 2 The standard characteristic diffraction peaks of (2) completely correspond to each other, which indicates that the sample does not undergo phase change or decomposition in the high-temperature solid-phase synthesis process and still maintains the delafossite CuAlO 2 Is a high-purity single phase of (a).
The optical property of the prepared delafossite type CuAlO is controllable 2 (0％O 2 ) The ultraviolet-visible diffuse reflection absorption spectrum of (c) is shown in figure 2. As can be seen from FIG. 2, the optical properties of the CuAlO are controllable 2 (0％O 2 ) The strongest absorption peak intensity in the visible region was about 0.135a.u., the band gap was according to the formula
The band gap was calculated to be about 3.46 eV. As can be seen from fig. 19, the transmittance of the film prepared therefrom reaches 87.10%.
Example 2
The embodiment provides a delafossite type CuAlO with controllable optical properties 2 The preparation method of the powder material comprises the following specific steps:
step (1): will have the purity of more than or equal to 97 percent and 5mmol Cu 2 O and 5mmolAl 2 O 3 Putting into a mortar, adding proper amount of absolute ethanol into the mortar for Cu 2 O and Al 2 O 3 Manually grinding the powder, and continuously grinding to obtain uniformly mixed powder A;
step (2): transferring the mixed powder A into a die, then putting the die on a manual hydraulic tablet press to be pressed into tablets at the speed of 5MPa/5min+5MPa/5min, and opening the die after pressure relief to obtain the tablet A;
step (3): sheet A was placed in an alumina crucible and transferred into an atmosphere furnace, followed by introducing a mixed atmosphere of argon and oxygen (flow rate of 90ml/min Ar+10ml/min O 2 Oxygen partial pressure: 10%) heating to 1200 ℃ and carrying out solid-phase sintering reaction for 36 hours; this step was repeated 3 times to obtain a uniform and homogeneous color reaction product B.
Step (4): the reaction product B is alternately washed by deionized water, dilute sulfuric acid (the concentration of the sulfuric acid is 65-68 percent, the dilute sulfuric acid is prepared according to the sulfuric acid: water being 1:9) and absolute ethyl alcohol and centrifuged for 4 times, the centrifugal speed is 7000 r/min, the centrifugal speed is 10 minutes each time, and the drying is carried out for 12 hours at the temperature of 60 ℃ to obtain the delafossite CuAlO 2 A powder material.
The light prepared in this exampleCupronite type CuAlO with controllable chemical property 2 (oxygen partial pressure: 10%) the X-ray crystallography chart is shown in FIG. 3. As can be seen from FIG. 3, the prepared delafossite-type CuAlO with controllable optical properties 2 (10％O 2 ) Characteristic diffraction peaks of (2) and delafossite type 3R CuAlO 2 The standard characteristic diffraction peaks of (2) completely correspond to each other, which indicates that the sample does not undergo phase change or decomposition in the high-temperature solid-phase synthesis process and still maintains the delafossite CuAlO 2 Is a high-purity single phase of (a).
The optical property of the prepared delafossite type CuAlO is controllable 2 (10％O 2 ) The ultraviolet-visible diffuse reflection absorption spectrum of (c) is shown in fig. 4. As can be seen from FIG. 4, the optical properties of the CuAlO are controllable 2 (10％O 2 ) The strongest absorption peak intensity in the visible region was about 0.550a.u., and the band gap was according to the formula
The band gap was calculated to be about 3.34 eV. As can be seen from fig. 20, the transmittance of the film prepared therefrom reaches 30.80%.
Example 3
The embodiment provides a delafossite type CuAlO with controllable optical properties 2 The preparation method of the powder material comprises the following specific steps:
step (1): 5mmol Cu with purity not less than 97% 2 O and 5mmolAl 2 O 3 Putting into a mortar, adding proper amount of absolute ethanol into the mortar for Cu 2 O and Al 2 O 3 Manually grinding the powder, and continuously grinding to obtain uniformly mixed powder A;
step (2): transferring the mixed powder A into a die, then putting the die on a manual hydraulic tablet press to be pressed into tablets at the speed of 5MPa/5min+5MPa/5min, and opening the die after pressure relief to obtain the tablet A;
step (3): sheet A was placed in an alumina crucible and transferred into an atmosphere furnace, followed by introducing a mixed atmosphere of argon and oxygen (flow rate 80ml/min Ar+20ml/min O 2 Oxygen partial pressure: 20%) to 1200 ℃ and carrying out solid phase sintering reaction for 36 hours; repeating the steps for 4 times to obtain the uniform and even color inverseProduct B should be obtained.
Step (4): the reaction product B is alternately washed by deionized water, dilute nitric acid (the concentration of nitric acid is 65-68%, dilute nitric acid is prepared according to the concentration of nitric acid and water being 1:9) and absolute ethyl alcohol and centrifuged for 5 times, the centrifugal speed is 7000 r/min, the centrifugal speed is 10 minutes each time, and the drying is carried out for 12 hours at 60 ℃ to obtain the delafossite CuAlO 2 A powder material.
The prepared delafossite type CuAlO with controllable optical properties prepared in the example 2 (oxygen partial pressure: 20%) the X-ray crystallography chart is shown in FIG. 5. As can be seen from FIG. 5, the prepared delafossite-type CuAlO with controllable optical properties 2 (20％O 2 ) Characteristic diffraction peaks of (2) and delafossite type 3R CuAlO 2 The standard characteristic diffraction peaks of (2) completely correspond to each other, which indicates that the sample does not undergo phase change or decomposition in the high-temperature solid-phase synthesis process and still maintains the delafossite CuAlO 2 Is a high-purity single phase of (a).
The optical property of the prepared delafossite type CuAlO is controllable 2 (20％O 2 ) The ultraviolet-visible diffuse reflection absorption spectrum of (c) is shown in fig. 6. As can be seen from FIG. 6, the visible light response of the delafossite type CuAlO 2 (20％O 2 ) The strongest absorption peak intensity in the visible region was about 0.683a.u., the band gap was according to the formula
The band gap was calculated to be about 3.28 eV. As can be seen from fig. 21, the transmittance of the film prepared therefrom reaches 27.10%.
Example 4
The embodiment provides a delafossite type CuAlO with controllable optical properties 2 The preparation method of the powder material comprises the following specific steps:
step (1): 5mmol Cu with purity not less than 97% 2 O and 5mmolAl 2 O 3 Putting into a mortar, adding proper amount of absolute ethanol into the mortar for Cu 2 O and Al 2 O 3 Manually grinding the powder, and continuously grinding to obtainUniformly mixing powder A;
step (2): transferring the mixed powder A into a die, then putting the die on a manual hydraulic tablet press to be pressed into tablets at 10MPa/10min+10MPa/10min, and opening the die after pressure relief to obtain the tablet A;
step (3): sheet A was placed in an alumina crucible and transferred into an atmosphere furnace, followed by introducing a mixed atmosphere of argon and oxygen (flow rate of 70ml/min Ar+30ml/min O 2 Oxygen partial pressure: 30%) heating to 1100 ℃ and carrying out solid-phase sintering reaction for 12 hours; this step was repeated 2 times to obtain a uniform and homogeneous color reaction product B.
Step (4): the reaction product B is alternately washed by deionized water, dilute hydrochloric acid (the concentration of the hydrochloric acid is 65-68%, the dilute hydrochloric acid is prepared according to the concentration of the hydrochloric acid and the water of 1:9) and absolute ethyl alcohol and centrifuged for 6 times, the centrifugal speed is 7000 r/min, the centrifugal speed is 10 minutes each time, and the drying is carried out for 10 hours at 80 ℃ to obtain the delafossite CuAlO 2 A powder material.
The prepared delafossite type CuAlO with controllable optical properties prepared in the example 2 (30％O 2 ) The X-ray crystal diffraction pattern is shown in fig. 7. As can be seen from FIG. 7, the prepared delafossite-type CuAlO with controllable optical properties 2 (30％O 2 ) Characteristic diffraction peaks of (2) and delafossite type 3R CuAlO 2 The standard characteristic diffraction peaks of (2) completely correspond to each other, which indicates that the sample does not undergo phase change or decomposition in the high-temperature solid-phase synthesis process and still maintains the delafossite CuAlO 2 Is a high-purity single phase of (a).
The optical property of the prepared delafossite type CuAlO is controllable 2 (30％O 2 ) The ultraviolet-visible diffuse reflection absorption spectrum of (c) is shown in fig. 8. As can be seen from FIG. 8, the optical properties of the CuAlO are controllable 2 (30％O 2 ) The strongest absorption peak intensity in the visible region was about 0.937a.u., the band gap was according to the formula
The band gap was calculated to be about 3.10 eV. As can be seen from fig. 22, the transmittance of the film prepared therefrom reaches 26.00%.
Example 5
The embodiment provides a delafossite type CuAlO with controllable optical properties 2 The preparation method of the powder material comprises the following specific steps:
step (1): the purity is more than or equal to 97 percent and 5mmol of Cu 2 O and 5mmolAl 2 O 3 Putting into a mortar, adding proper amount of absolute ethanol into the mortar for Cu 2 O and Al 2 O 3 Manually grinding the powder, and continuously grinding to obtain uniformly mixed powder A;
step (2): transferring the mixed powder A into a die, then putting the die on a manual hydraulic tablet press to be pressed into tablets at 8MPa/8min and 8MPa/8min, and opening the die after pressure relief to obtain the tablet A;
step (3): sheet A was placed in an alumina crucible and transferred into an atmosphere furnace, followed by introducing a mixed atmosphere of nitrogen and oxygen (flow rate of 60ml/min Ar+40ml/min O 2 ) Heating to 1050 ℃ and carrying out solid-phase sintering reaction for 25 hours; this step was repeated 3 times to obtain a uniform and homogeneous color reaction product B.
Step (4): the reaction product B is alternately washed by deionized water, dilute nitric acid (the concentration of nitric acid is 65-68%, dilute nitric acid is prepared according to the concentration of nitric acid and water being 1:9) and absolute ethyl alcohol and centrifuged for 6 times, the centrifugal speed is 7000 r/min, the centrifugal speed is 10 minutes each time, and the drying is carried out for 15 hours at 50 ℃ to obtain the delafossite CuAlO 2 A powder material.
The prepared delafossite type CuAlO with controllable optical properties prepared in the example 2 (oxygen partial pressure: 40%) the X-ray crystallography chart is shown in FIG. 9. As can be seen from FIG. 9, the prepared delafossite-type CuAlO with controllable optical properties 2 (40％O 2 ) Characteristic diffraction peaks of (2) and delafossite type 3R CuAlO 2 The standard characteristic diffraction peaks of (2) completely correspond to each other, which indicates that the sample does not undergo phase change or decomposition in the high-temperature solid-phase synthesis process and still maintains the delafossite CuAlO 2 Is a high-purity single phase of (a).
The optical property of the prepared delafossite type CuAlO is controllable 2 (40％O 2 ) The ultraviolet-visible diffuse reflection absorption spectrum of (c) is shown in fig. 10. As can be seen from FIG. 10, the optical properties of the delafossite type CuA are controllablelO 2 (40％O 2 ) The strongest absorption peak intensity in the visible region was about 0.9511 a.u., the band gap was according to the formula
The band gap was calculated to be about 2.97 eV. As can be seen from fig. 23, the transmittance of the film prepared therefrom reaches 13.10%.
The optical properties of the prepared delafossite type CuAlO of examples 1-5 were controlled 2 The powder material was tested for photocurrent density versus time curve using an electrochemical workstation, and the results are shown in fig. 11. As can be seen from FIG. 11, the present invention provides a method for controlling oxygen partial pressure to achieve delafossite type CuAlO 2 Preparation method of visible light response of powder material, and preparation method of delafossite CuAlO with different absorption intensities to visible light 2 The powder material can obtain different transient photocurrent responses 40% (8.2 mu A/cm 2 )>30％(2.4μA/cm 2 )>20％(1.7μA/cm 2 )>10％(1.3μA/cm 2 )>0％(0.8μA/cm 2 )。
The optical properties of the prepared delafossite type CuAlO of examples 1, 2, 3, 4 and 5 are controllable 2 The powder material was tested for photocatalytic degradation of tetracycline hydrochloride and the results are shown in fig. 13. As can be seen from FIG. 13, the present invention provides a method for controlling oxygen partial pressure to achieve delafossite type CuAlO 2 Preparation method of visible light response of powder material, and preparation method of delafossite CuAlO with different absorption intensities to visible light 2 The powder material can obtain different degradation rates of CAO-0%, CAO-10%, CAO-20%, CAO-30% and CAO-40%, and the reaction rate constants (k) are respectively 0.51h -1 、0.44h -1 、0.92h -1 、0.52h -1 And 1.01h -1 。
In conclusion, the invention obtains the CuAlO with the strongest absorption peak intensity regulated and controlled within 0.1-1.0a.u. in the visible light region by regulating and controlling the temperature and the oxygen partial pressure in the atmosphere furnace 2 A powder material.
The kind and the dosage of M, M' element are regulated, the band gap of the delafossite oxide can be accurately regulated and controlled within the range of 0.5-3.2 eV, and the band edge position of the delafossite oxide can be continuously changed along with the kind and the proportion of the element.
The embodiments of the invention have been described in detail above, but they are merely examples, and the invention is not limited to the above-described embodiments. It will be apparent to those skilled in the art that any equivalent modifications or substitutions to this invention are within the scope of the invention, and therefore, all equivalent changes and modifications, improvements, etc. that do not depart from the spirit and scope of the principles of the invention are intended to be covered by this invention.
Claims (9)
1. CuAlO with adjustable optical property 2 The preparation method of the powder material is characterized by comprising the following steps:
(1) Weighing cuprous oxide powder and aluminum oxide powder, and grinding the cuprous oxide powder and the aluminum oxide powder to be fully and uniformly mixed in the presence of absolute ethyl alcohol medium to obtain mixed powder A;
(2) The mixed powder A in the step (1) is put into a tablet press for pressing, and after the tablet pressing is finished, a pressed tablet A is obtained;
(3) Placing the sheet A in the step (2) into a crucible and transferring the crucible into an atmosphere furnace, introducing inert gas and oxidizing gas into the atmosphere furnace for high-temperature solid-phase sintering reaction, cooling and grinding a sintering product after the reaction is finished to obtain a powder reaction product B;
(4) Repeating the step (3) on the powder reaction product B in the step (3) until the color of the high-temperature solid-phase sintering reaction product is uniform, and obtaining a powder product C with complete reaction;
(5) Adding a washing solution into the powder product C with complete reaction in the step (4) for centrifugal washing to obtain a precipitate; drying the precipitate to obtain the optical property-adjustable delafossite CuAlO 2 A powder material.
2. An optically variable CuAlO according to claim 1 2 A process for producing a powdery material, characterized in that the cuprous oxide powder and the aluminum oxide powder in step (1)The molar ratio of the copper oxide powder to the aluminum oxide powder is 1:1, and the purity of the copper oxide powder and the aluminum oxide powder is more than or equal to 97 percent.
3. An optically variable CuAlO according to claim 1 2 The preparation method of the powder material is characterized in that the tabletting in the step (1) is carried out by putting the powder material into a tabletting machine, the pressure of the tabletting machine is 5-10MPa, and the tabletting time is 5-10min.
4. An optically variable CuAlO according to claim 1 2 The preparation method of the powder material is characterized in that the inert gas in the step (3) is one of argon and nitrogen; the oxidizing gas is high-purity oxygen; the ratio of the inert gas to the oxidizing gas is (100-60): 0-40.
5. An optically variable CuAlO according to claim 4 2 The preparation method of the powder material is characterized in that the crucible in the step (3) is an alumina crucible; the high-temperature solid-phase sintering reaction temperature is 1050-1200 ℃, and the reaction time is 12-36 hours.
6. An optically variable CuAlO according to claim 1 2 The preparation method of the powder material is characterized in that the repetition number in the step (4) is 2-4.
7. An optically variable CuAlO according to claim 1 2 The preparation method of the powder material is characterized in that the washing liquid in the step (5) is deionized water, 10% acid solution and absolute ethyl alcohol; the centrifugal washing is to alternately wash for 4-6 times by using deionized water, 10% acid solution and absolute ethyl alcohol; the acidic solution is one of sulfuric acid, nitric acid and hydrochloric acid.
8. An optically variable CuAlO according to claim 7 2 A process for producing a powdery material, characterized by comprising the step (5)The drying temperature is 50-80 ℃, and the drying time is 10-15 hours.
9. An optically variable CuAlO according to claim 1 2 The preparation method of the powder material is characterized in that the absorption range and the intensity of the visible light response intensity of the delafossite type CuAlO2 powder material with adjustable optical property in the step (5) are regulated and controlled by the temperature in an atmosphere furnace, the ratio of inert gas to oxidizing gas; the CuAlO 2 The intensity of the strongest absorption peak of the powder material in the visible light region can be regulated and controlled within 0.1-1.0a.u.
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