CN113582218B - Oxygen defect type gray zinc oxide and preparation method and application thereof - Google Patents
Oxygen defect type gray zinc oxide and preparation method and application thereof Download PDFInfo
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- CN113582218B CN113582218B CN202110872615.3A CN202110872615A CN113582218B CN 113582218 B CN113582218 B CN 113582218B CN 202110872615 A CN202110872615 A CN 202110872615A CN 113582218 B CN113582218 B CN 113582218B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 291
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 151
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000001301 oxygen Substances 0.000 title claims abstract description 95
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 95
- 230000007547 defect Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 claims abstract description 34
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012265 solid product Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 9
- 239000011941 photocatalyst Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 230000002950 deficient Effects 0.000 claims description 29
- 238000006722 reduction reaction Methods 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 25
- 230000031700 light absorption Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 230000004298 light response Effects 0.000 abstract description 2
- 235000014692 zinc oxide Nutrition 0.000 description 86
- 239000000243 solution Substances 0.000 description 38
- 230000001699 photocatalysis Effects 0.000 description 14
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000002791 soaking Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001362 electron spin resonance spectrum Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
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- 230000000593 degrading effect Effects 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- C01G9/02—Oxides; Hydroxides
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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Abstract
The invention discloses oxygen defect type gray zinc oxide and a preparation method and application thereof, belonging to the field of material engineering. The preparation method comprises the steps of dissolving lithium and naphthalene in a solvent to obtain a lithium naphthalene solution, adding white zinc oxide into the obtained lithium naphthalene solution for reaction, collecting a solid product after the reaction is finished, washing the obtained solid product, and drying to obtain the oxygen defect type gray zinc oxide. The preparation method has simple process and wide universality, and is suitable for mass production. The prepared oxygen defect type zinc oxide is gray, has enhanced light absorption capacity and light response range, and can be used as a gas purifying photocatalyst.
Description
Technical Field
The invention belongs to the field of material engineering, and relates to oxygen defect type gray zinc oxide and a preparation method and application thereof.
Background
Zinc oxide (ZnO) is a common metal oxide semiconductor, belonging to n-type semiconductors, with an energy bandgap value of 3.37eV. The product is white solid at normal temperature, and is an amphoteric oxide. Zinc oxide has the characteristics of innocuity, low price, high chemical stability, easy preparation, low dielectric constant, low optical coupling rate and the like, and is an excellent semiconductor material in the photocatalysis process. The preparation of zinc oxide reported so far is mainly conventional white zinc oxide. For example, CN1887720a discloses a method for preparing nano zinc oxide powder, which comprises the steps of firstly dissolving zinc salt in absolute ethanol solution, then adding a certain amount of cetyltrimethylammonium bromide surfactant, vigorously stirring, and adding strong alkali solution dropwise into the zinc salt solution to obtain white turbid liquid. After the reaction is completed, the nano zinc oxide powder is obtained by washing and drying. The nanometer zinc oxide obtained by the method has uniform appearance, but the preparation process is complex, and secondly, the hexadecyl trimethyl ammonium bromide is often used as a surfactant, so that pollution is easy to generate. CN101643235 a discloses a fast and simple preparation method of white nano zinc oxide particles, firstly preparing zinc chloride and sodium hydroxide aqueous solution, then mixing with oleic acid and absolute alcohol to obtain solution, making chemical reaction and grain growth at 20 deg.c, centrifugal separation, washing and vacuum drying so as to obtain the invented white granular nano zinc oxide. The preparation method is quick and convenient, but the prepared nano zinc oxide product is unstable, the storage environment is strict, and the requirements on humidity, temperature and pH value are extremely high.
The limitation of the conventional white ZnO as a photocatalyst is that (1) the forbidden bandwidth is large, no visible light response exists, and the utilization rate of sunlight is low; (2) The photo-generated electrons and holes are easy to be combined, and the quantum efficiency is low. And has not been reported for gray zinc oxide materials.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide oxygen defect type gray zinc oxide and a preparation method and application thereof. The preparation method disclosed by the invention is simple in process, wide in universality, low in energy consumption and low in cost, is suitable for mass production, and the oxygen-deficient zinc oxide prepared by the method is gray, has rich oxygen vacancies, high purity, uniform and stable particle size distribution of the material, and small in forbidden bandwidth, and can solve the problem of narrow visible light absorption range of white zinc oxide, so that the zinc oxide can be used as a visible light catalyst.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of oxygen defect type gray zinc oxide, which comprises the steps of dissolving lithium and naphthalene in a solvent to obtain a lithium naphthalene solution, adding white zinc oxide into the obtained lithium naphthalene solution for reduction reaction, collecting a solid product after the reaction is finished, washing the obtained solid product, and drying to obtain the oxygen defect type zinc oxide.
Preferably, the molar ratio of lithium to naphthalene is (0.5-8): 1.
preferably, the solvent is tetrahydrofuran.
Preferably, the concentration of the lithium naphthalene solution is 0.4 to 1mol/L.
Preferably, the reduction reaction time of the white zinc oxide and the lithium naphthalene solution is 1-30 min, and the reduction reaction temperature is 10-30 ℃.
Preferably, the drying process includes: vacuum drying at 50-80 deg.c.
Preferably, the feeding ratio of the white zinc oxide to the lithium naphthalene solution is 0.2-1 g: 0.5-5 mL.
The invention discloses an oxygen defect type gray zinc oxide prepared by the preparation method.
Preferably, the oxygen-deficient zinc oxide is gray, and has an amorphous disordered layer with a thickness of 2-5 nm on the surface.
The invention discloses an oxygen defect type gray zinc oxide prepared by the preparation method or an application of the oxygen defect type gray zinc oxide as a gas purifying photocatalyst.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of gray zinc oxide with oxygen defect, which uses lithium naphthalene solution to react with conventional zinc oxide to prepare the gray zinc oxide with oxygen defect, and forms an amorphous defect layer on the surface of zinc oxide particles, thereby reducing the energy band gap of zinc oxide and the Zeta potential of the surface, and improving the light absorption range and photocatalysis performance of zinc oxide materials. Meanwhile, the operation process is simplified, the preparation cost and the energy consumption investment are reduced, and the method is suitable for industrial large-scale production.
The invention also discloses the gray zinc oxide with oxygen defect prepared by the preparation method, and the invention is used for improving the photocatalytic activity of ZnO, and the ZnO is structurally designed by energy band engineering, so that the forbidden band width of ZnO particles containing oxygen vacancies is reduced, the separation of photo-generated carriers is promoted, and the catalytic performance of the ZnO particles is obviously improved; znO can be modified by defect engineering. Compared with the existing white zinc oxide, the gray oxygen-defect zinc oxide prepared by the invention contains rich oxygen vacancies, the oxygen vacancy defects cause the ZnO band gap to be narrowed, the conduction band is bent downwards, the potential barrier overcome in the photocatalysis reaction is relatively smaller, and the light absorption capacity is enhanced. Meanwhile, oxygen vacancies can effectively expand the visible light absorption of ZnO, the photoresponse range is enhanced, a proper amount of oxygen vacancies can increase the charge separation efficiency, the interface resistance is reduced, and the rapid separation of photo-generated electrons and holes is facilitated.
Furthermore, the surface of the prepared oxygen defect type gray zinc oxide particles is provided with an amorphous disordered layer, and simultaneously, impurity energy levels are formed under a conduction band due to the existence of oxygen vacancies, so that the effective shuttling of photo-generated carriers is facilitated, and e is promoted - /h + Thereby improving the visible light activity of the material and being applicable to the field of gas purification.
The invention also discloses application of the oxygen defect type gray zinc oxide as a gas purifying photocatalyst. Related tests show that the energy band gap of the material is 3.0+/-0.1 eV, the surface Zeta potential is-10+/-2 mV, and the material is rich in oxygen vacancies and expands the absorption range of visible light compared with white zinc oxide. The photocatalytic performance shows that the gray zinc oxide nano material with the oxygen-containing defect has excellent catalytic degradation capability on nitric oxide which is a gas pollutant under visible light. Compared with a white titanium dioxide material, the gray zinc oxide nano material rich in oxygen vacancy defects has obviously improved degradation efficiency in the degradation process. Therefore, the oxygen-deficient zinc oxide has the characteristic of enhanced photocatalytic activity, and can be applied as a gas purifying photocatalyst.
Drawings
FIG. 1 is an optical photograph of oxygen deficient gray zinc oxide and white zinc oxide according to the present invention; wherein, (a) is conventional white zinc oxide before reaction and (b) is oxygen-deficient gray zinc oxide prepared in example 1;
FIG. 2 is a transmission electron micrograph of the oxygen deficient gray zinc oxide prepared in example 1;
FIG. 3 is an XRD spectrum of oxygen deficient gray zinc oxide and white zinc dioxide nanoparticles according to examples 1-3 of the present invention; wherein, (a) is an XRD total spectrum, and (b) is an XRD local amplification diagram;
FIG. 4 is a Raman spectrum of the oxygen deficient gray zinc oxide and white zinc dioxide nanoparticles of examples 1-3 of the present invention;
FIG. 5 is a graph showing the UV-visible absorption spectra of the oxygen deficient gray zinc oxide and white zinc dioxide nanoparticles of examples 1-3 of the present invention;
FIG. 6 is an electron paramagnetic resonance spectrum of the oxygen deficient gray zinc oxide and white zinc dioxide nanoparticles according to example 1 of the present invention;
FIG. 7 is a schematic Zeta potential diagram of oxygen deficient gray zinc oxide and white zinc dioxide nanoparticles according to examples 1-3 of the present invention;
FIG. 8 is a schematic energy band structure of the oxygen deficient gray zinc oxide and white zinc dioxide nanoparticles of examples 1-3 of the present invention;
FIG. 9 is a graph showing the comparison of NO purification curves of the oxygen deficient gray zinc oxide and white zinc dioxide nanoparticles of examples 1-3 of the present invention under visible light.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention discloses a preparation method of oxygen defect type gray zinc oxide, which comprises the following steps:
(1) Preparing a lithium naphthalene solution: and weighing lithium metal and organic naphthalene, and dissolving the lithium metal and the organic naphthalene in a tetrahydrofuran solution to form a lithium naphthalene solution.
(2) Grey zinc oxide was prepared: dissolving white ZnO (named as W-ZnO) in a lithium naphthalene solution, soaking for a period of time to perform a reduction reaction, collecting a solid product after the reduction reaction is finished, fully washing the obtained solid product with deionized water, and vacuum drying the obtained solid product to obtain gray ZnO powder, namely the oxygen defect type gray zinc oxide.
Further, the molar ratio of lithium to naphthalene required in the step (1) is (0.5 to 8): 1. preferably, the molar ratio of lithium to naphthalene is 1:1.
Further, the concentration of the lithium naphthalene solution required in the step (1) is 0.4-1 mol/L. Preferably, the concentration of the lithium naphthalene solution is 0.8mol/L.
Further, in the step (2), the feeding ratio of the white zinc oxide to the lithium naphthalene solution is 0.2-1 g: 0.5-5 mL.
Further, the time for soaking the lithium naphthalene solution in the step (2) is that the reduction reaction time of the white zinc oxide and the lithium naphthalene solution is 1-30 min. Preferably, the time for soaking the lithium naphthalene solution is 10 minutes. In the preparation process, the reaction of the white zinc oxide and the lithium naphthalene solution is a reduction reaction, and the reduction reaction can be carried out at normal temperature (10-30 ℃).
Further, the vacuum drying temperature in the step (2) is 50-80 ℃. Preferably, the vacuum drying temperature is 80 ℃. In the preparation process, the application range of the drying temperature is wide, and the gray zinc dioxide nano material rich in oxygen vacancy defects can be obtained by simply soaking, so that the process is simple and easy to operate, and the preparation method is suitable for mass rapid preparation at normal temperature.
The oxygen defect type zinc oxide prepared by the preparation method is gray, the energy band gap is 3.0+/-0.1 eV, the surface Zeta potential is-10+/-2 mV, the surface of the zinc oxide is provided with an amorphous disordered layer with the thickness of 2-5 nm, the zinc oxide is rich in oxygen vacancies, the energy band gap is narrowed, the electron paramagnetic resonance peak intensity is increased, the photocatalytic performance shows that the NO degradation rate can reach 54.3% at most, and the zinc oxide can be used as a photocatalyst in the field of gas purification. Therefore, the oxygen-deficient gray zinc oxide of the present invention can be used as a photocatalyst in the field of gas purification.
The invention is described in further detail below in connection with specific examples:
example 1
55.53mg of metallic lithium and 1025.36mg of organic naphthalene (molar ratio 1:1) are weighed and dissolved in 10mL of tetrahydrofuran to form a lithium naphthalene solution of 0.8 mol/L; dissolving 0.2g of white ZnO in 1mL of lithium naphthalene solution, soaking at 20 ℃ for reduction reaction for 10min, collecting a solid product after the reaction is finished, fully washing the obtained solid product by deionized water, and vacuum drying the obtained solid product at 60 ℃ to obtain gray ZnO powder, namely oxygen defect type gray zinc oxide, which is named ZnO-0.8.
The oxygen-deficient zinc oxide prepared in this example is gray, and has an amorphous disordered layer with a thickness of 4-5 nm on the surface.
Example 2
124.92mg of metallic lithium and 6152.16mg of organic naphthalene (molar ratio 3:1) are weighed and dissolved in 10mL of tetrahydrofuran solution to form a lithium naphthalene solution of 0.6 mol/L; dissolving 0.5g of white ZnO in 3mL of lithium naphthalene solution, soaking at 10 ℃ for reduction reaction for 15min, collecting a solid product after the reaction is finished, fully washing the obtained solid product by deionized water, and vacuum drying the obtained solid product at 70 ℃ to obtain gray ZnO powder, namely oxygen defect type gray zinc oxide, which is named ZnO-0.6.
The oxygen-deficient zinc oxide prepared in this example is gray, and has an amorphous disordered layer with a thickness of 3-4 nm on the surface.
Example 3
555.20mg of metallic lithium and 1281.70mg of organic naphthalene (molar ratio 8:1) are weighed and dissolved in 10mL of tetrahydrofuran solution to form 1mol/L of lithium naphthalene solution; 1g of white ZnO is dissolved in 5mL of lithium naphthalene solution, soaked at 30 ℃ for reduction reaction for 30min, solid products are collected after the reaction is finished, the obtained solid products are fully washed by deionized water, and the obtained solid products are dried in vacuum at 80 ℃ to obtain gray ZnO powder, namely the oxygen defect type gray zinc oxide which is named as ZnO-1.
The oxygen-deficient zinc oxide prepared in this example is gray, and has an amorphous disordered layer with a thickness of 4-5 nm on the surface.
Example 4
13.88mg of metallic lithium and 512.68mg of organic naphthalene (molar ratio 0.5:1) are weighed and dissolved in 10mL of tetrahydrofuran solution to form 0.4mol/L of lithium naphthalene solution; dissolving 0.8g of white ZnO in 0.5mL of lithium naphthalene solution, soaking at 15 ℃ for reduction reaction for 1min, collecting a solid product after the reaction is finished, fully washing the obtained solid product by deionized water, and vacuum drying the obtained solid product at 50 ℃ to obtain gray ZnO powder, namely oxygen defect type gray zinc oxide, which is named ZnO-0.4.
The oxygen-deficient zinc oxide prepared in this example is gray, and has an amorphous disordered layer with a thickness of 2-3 nm on the surface.
The invention is described in further detail below with reference to the attached drawing figures:
the left graph (a) in fig. 1 is the purchased white zinc dioxide nano-particles, the right graph (b) is the oxygen defect type gray zinc oxide prepared in example 1, namely the gray zinc dioxide nano-particles rich in oxygen defects, and the comparison shows that the finally prepared oxygen defect type zinc oxide nano-particles are gray.
As shown in fig. 2, a disordered layer of 2 to 3nm was observed in HRTEM of gray ZnO (i.e., oxygen deficient gray zinc oxide) on the surface of the material due to the presence of oxygen vacancies on the surface of the material. Since ZnO is immersed in the lithium naphthalene solution, lithium "robs" oxygen atoms in the ZnO material, resulting in the formation of an amorphous disordered layer on the material surface. The image showed clear lattice fringes, with a lattice spacing of 0.281nm corresponding to the (100) crystal plane of wurtzite ZnO and a lattice spacing of 0.247nm corresponding to the (101) crystal plane of wurtzite ZnO.
As shown in FIG. 3 (a), the diffraction characteristic peaks at 2 theta of 31.9 °,34.6 °,36.4 °,47.6 °,56.8 °,63.0 °,68.1 ° and 69.2 ° correspond to (100), (002), (101), (102), (110), (103), (112) and (201) crystal planes (JCPDS: NO. 36-1451), respectively. As shown in FIG. 3 (b), the XRD patterns of the different zinc oxide materials were shown, and it was found that ZnO obtained in a 0.6mol/L solution, the diffraction peak of which was shifted to a small angle from 36.45℃to 36.42℃and showed an increase in the interplanar spacing. When ZnO was obtained in a 0.8mol/L solution, the diffraction angle was continuously decreased from 36.42℃to 36.38 ℃indicating that the interplanar spacing was continuously increased. These phenomena occur due to the formation of oxygen vacancies. When ZnO was obtained in a 1.0mol/L solution, the diffraction angle was increased (from 36.38 ℃to 36.41 ℃) as compared with that of the product at 0.8mol/L, which indicated that the content of oxygen vacancies was decreased while a new phase was generated, which was cubic-phase ZnO (JCPLS: no. 21-1486).
As shown in FIG. 4, the prepared gray oxygen-deficient ZnO has 5 Raman vibration peaks, each at 203cm -1 、331cm -1 ，382cm -1 ，437cm -1 And 582cm -1 . Wherein 582cm -1 Corresponding to E 1 (longitudinal optical) mode, 382cm -1 Corresponding to A 1 (transverse optical) mode, 437cm -1 Corresponding to E 2 (high) mode, 203cm -1 And 331cm -1 Is derived from E 2 (low)-E 2 (high) vibration. E of ZnO-0.6 and ZnO-0.8 2 The (high) mode was weaker than that of pure ZnO and the peak intensity was lower, and the peak position was shifted from 437cm -1 (ZnO) moved to 435cm -1 (ZnO-0.6) and 433cm -1 (ZnO-0.8); from 331cm -1 (ZnO) moved to 330cm -1 (ZnO-0.6) and 328cm -1 (ZnO-0.8) indicates that oxygen atoms in the crystal lattice are missing. E of ZnO 1 The mode (582 cm-1) was associated with vacancy defects and the E1 mode intensities of ZnO-0.6 and ZnO-0.8 were enhanced compared to ZnO, indicating an increased oxygen vacancy content in the material. ZnO-1.0 is a mixed crystal structure, so that non-harmonic phonon-phonon interaction is caused, and lattice disorder is caused.
As shown in fig. 5, the uv-vis absorption spectrum shows that the light absorption range of gray ZnO treated with the lithium naphthalene solution (i.e., oxygen-deficient gray zinc oxide) is red shifted and the light absorption intensity is increased compared to white ZnO, which is attributed to the formation of oxygen vacancies. Oxygen vacancies can cause disordered layers to appear on the surface of the material during formation. The oxygen vacancies and disordered layer can be regarded as capture sites, preventing recombination of photogenerated carriers, thereby promoting electron transfer and enhancing photocatalytic reactivity.
As shown in fig. 6, the electron paramagnetic resonance spectrum (EPR) shows that both white ZnO and gray ZnO (i.e., oxygen deficient gray zinc oxide) show a Shan Tiaoluo lorentz wire with a g-value of about 2.002; the EPR spectrum formant intensity of gray ZnO (namely the oxygen defect type gray zinc oxide) is higher than that of white ZnO, which shows that the gray ZnO is rich in oxygen vacancy defects.
As shown in FIG. 7, the zeta potential pattern shows that the zeta potential of the W-ZnO, znO-0.6, znO-0.8 and ZnO-1.0 samples was 20.3mV, -9.1mV, -10.3mV and-9.6 mV, respectively. Experiments prove that the surface of the material contains a large number of dangling bonds and carries more hydroxyl groups due to the existence of oxygen vacancies. The more hydroxyl groups on the surface, the more negative the zeta potential, and the higher the photocatalytic activity. Among them, the ZnO-0.8 sample has the largest negative zeta potential, which is beneficial to adsorb more pollutant molecules and enhance the photocatalytic performance.
FIG. 8 is a diagram of the band structure of different materials, with the conduction band of ZnO-0.8 having a forward shift of about 0.1eV compared to the sample W-ZnO. Indicating that the conduction band of ZnO-0.8 with oxygen defects is bent downwards, the potential barrier overcome in the photocatalytic reaction is relatively small. ZnO-0.8 with surface oxygen vacancies has higher photocatalytic performance, and the oxygen vacancy concentration of the material surface is increased in a proper range, so that the reactivity of the photocatalyst can be enhanced.
FIG. 9 shows the NO degradation curves of W-ZnO, znO-0.6, znO-0.8 and ZnO-1.0 under ultraviolet irradiation, and the degradation rate of W-ZnO without surface oxygen defect under ultraviolet irradiation is only 4.4%. After oxygen vacancies are introduced into the material, the photocatalytic activity of the material is enhanced, the NO degradation rate of ZnO-0.6 is 11.2%, and the NO degradation rate of ZnO-0.8 is 54.3%. When the concentration of the lithium naphthalene solution reaches 1.0mol/L, a new phase is generated in the product obtained after the precursor is treated, so that the catalytic activity is reduced, and the NO degradation rate of ZnO-1.0 is 14.5%. The NO degrading efficiency of the oxygen-enriched defective ZnO-0.8 sample is about 12 times of that of the W-ZnO without surface oxygen defects, and the purification effect of ZnO on NO is remarkably improved by introducing oxygen vacancies. Compared with white ZnO, the material with surface oxygen vacancies has higher photocatalytic efficiency, and the oxygen vacancies play a role in capturing electrons, so that the recombination of photo-generated electrons and holes can be inhibited; and the oxygen vacancy concentration on the surface of the material is increased in a moderate range, so that the photocatalytic activity of the sample can be enhanced.
In summary, the invention relates to the field of new materials, and discloses an oxygen defect type gray zinc oxide, a preparation method and application thereof. The oxygen defect type zinc oxide prepared by the method is gray, has an amorphous disordered layer on the surface, is rich in oxygen vacancies, has a narrow forbidden bandwidth, has high electron paramagnetic resonance peak intensity, has more reactive sites, and can be applied to the fields of catalysis and energy.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (6)
1. The preparation method of the oxygen defect type gray zinc oxide is characterized in that lithium and naphthalene are dissolved in a solvent to obtain a lithium naphthalene solution, white zinc oxide is added into the obtained lithium naphthalene solution to perform a reduction reaction, a solid product is collected after the reaction is finished, and the obtained solid product is washed and dried to obtain the oxygen defect type gray zinc oxide;
the molar ratio of lithium to naphthalene is (0.5-8): 1, a step of; the reduction reaction time of the white zinc oxide and the lithium naphthalene solution is 1-30 min, and the reduction reaction temperature is 10-30 ℃;
washing the solid product by deionized water;
the concentration of the lithium naphthalene solution is 0.4-1 mol/L;
the feeding ratio of the white zinc oxide to the lithium naphthalene solution is 0.2-1 g: 0.5-5 mL;
the Zeta potential of the surface of the oxygen defect type gray zinc oxide is-10+/-2 mV.
2. The method for preparing gray zinc oxide having oxygen defects according to claim 1, wherein the solvent is tetrahydrofuran.
3. The method for preparing oxygen-deficient gray zinc oxide according to claim 1, wherein the drying process comprises: vacuum drying at 50-80 deg.c.
4. An oxygen-deficient gray zinc oxide produced by the production process according to any one of claims 1 to 3.
5. The oxygen-deficient gray zinc oxide according to claim 4, wherein the surface of the oxygen-deficient gray zinc oxide has an amorphous disordered layer of 2 to 5 nm.
6. Use of an oxygen-deficient grey zinc oxide produced by the method according to any one of claims 1 to 3 or an oxygen-deficient grey zinc oxide according to any one of claims 4 to 5 as a gas purifying photocatalyst.
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