CN113582218A - Oxygen-deficient gray zinc oxide and preparation method and application thereof - Google Patents
Oxygen-deficient gray zinc oxide and preparation method and application thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 309
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 161
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000001301 oxygen Substances 0.000 title claims abstract description 99
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 99
- 230000002950 deficient Effects 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 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 28
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000012265 solid product Substances 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000746 purification Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 9
- 239000011941 photocatalyst Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000006722 reduction reaction Methods 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 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
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 235000014692 zinc oxide Nutrition 0.000 description 91
- 239000000243 solution Substances 0.000 description 40
- 230000007547 defect Effects 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 14
- 239000002105 nanoparticle Substances 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004435 EPR spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
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- 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
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 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
- 238000007146 photocatalysis Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 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
- 206010021143 Hypoxia Diseases 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
- 238000003917 TEM image Methods 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
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- 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
- 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
- 231100000956 nontoxicity Toxicity 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
- 230000009257 reactivity Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B01J35/23—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses an oxygen-deficient 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, and washing and drying the obtained solid product to obtain the oxygen-deficient gray zinc oxide. The preparation method has simple process and wide universality and is suitable for mass production. The prepared oxygen-deficient zinc oxide is gray, has enhanced light absorption capacity and light response range, and can be used as a gas purification photocatalyst.
Description
Technical Field
The invention belongs to the field of material engineering, and relates to oxygen-deficient gray zinc oxide and a preparation method and application thereof.
Background
Zinc oxide (ZnO) is a common metal oxide semiconductor, belonging to the n-type semiconductor, and has an energy band gap value of 3.37 eV. It is a white solid at normal temperature and is an amphoteric oxide. The zinc oxide has the characteristics of no toxicity, no harm, low price, high chemical stability, easy preparation, low dielectric constant, low optical coupling rate and the like, and is an excellent semiconductor material in a photocatalytic process. The preparation of zinc oxide reported at present is mainly conventional white zinc oxide. For example, CN1887720A discloses a method for preparing nano zinc oxide powder, which comprises dissolving zinc salt in absolute ethanol solution, adding a certain amount of cetyl trimethyl ammonium bromide surfactant, stirring vigorously, and adding a strong alkali solution into the zinc salt solution dropwise to obtain a white turbid solution. After the reaction is completed, the nano zinc oxide powder is obtained by washing and drying. The nano zinc oxide obtained by the method has uniform appearance, but the preparation process is complicated, and then cetyl trimethyl ammonium bromide is often used as a surfactant, so that pollution is easily caused. CN 101643235A discloses a rapid and simple preparation method of white nano zinc oxide particles, which comprises the steps of firstly preparing zinc chloride and sodium hydroxide aqueous solution, then mixing the zinc chloride and the sodium hydroxide aqueous solution with oleic acid and absolute alcohol to form a solution, carrying out chemical reaction and grain growth at the state of 20 ℃, carrying out centrifugal separation, washing and vacuum drying, and finally obtaining the white granular nano zinc oxide. The preparation method is rapid 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 conventional white ZnO as the photocatalyst has the limitations that (1) the forbidden band width is large, and no visible light response exists, so that the utilization rate of the conventional white ZnO to sunlight is low; (2) the photo-generated electrons and holes are easy to recombine, and the quantum efficiency is low. And the gray zinc oxide material is not reported at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an oxygen-deficient gray zinc oxide and a preparation method and application thereof. The preparation method has the advantages of simple process, wide universality, low energy consumption and cost and suitability 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 forbidden band width, and can solve the problem of narrow visible light absorption range of white zinc oxide, thereby being used as a visible light catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of oxygen-deficient 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-deficient 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 0.4-1 mol/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 comprises: 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-deficient gray zinc oxide prepared by the preparation method.
Preferably, the oxygen-deficient zinc oxide is gray, and an amorphous disordered layer with the thickness of 2-5 nm is arranged on the surface.
The invention discloses an oxygen-deficient gray zinc oxide prepared by the preparation method or application of the oxygen-deficient gray zinc oxide as a gas purification photocatalyst.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of oxygen-deficient gray zinc oxide, which comprises the steps of reacting lithium naphthalene solution with conventional zinc oxide to obtain gray oxygen-deficient zinc oxide, forming an amorphous defect layer on the surface of zinc oxide particles, reducing the energy band gap width and surface Zeta potential of zinc oxide, and improving the light absorption range and photocatalytic 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 an oxygen defect type gray zinc oxide prepared by the preparation method, and in order to improve the photocatalytic activity of ZnO, the ZnO is structurally designed by energy band engineering, so that the forbidden bandwidth of ZnO particles containing oxygen vacancies is reduced, the separation of photon-generated carriers is promoted, and the catalytic performance of the ZnO is obviously improved; ZnO can be modified through defect engineering. The oxygen-deficient zinc oxide prepared by the invention is gray, compared with the existing white zinc oxide, the gray oxygen-deficient zinc oxide contains abundant oxygen vacancies, the oxygen vacancy defects cause the band gap of a ZnO energy band to be narrowed, the conduction band is bent downwards, the potential barrier overcome in the photocatalytic reaction is relatively small, and the light absorption capacity is enhanced. Meanwhile, the oxygen vacancy can effectively expand the visible light absorption of ZnO, the photoresponse range is enhanced, the separation efficiency of charges can be increased by a proper amount of oxygen vacancy, the interface resistance is reduced, and the rapid separation of photo-generated electrons and holes is facilitated.
Furthermore, the particle surface of the oxygen-deficient gray zinc oxide prepared by the invention has an amorphous disordered layer, and meanwhile, the existence of oxygen vacancies can form an impurity energy level under a conduction band, which is beneficial to effective shuttling of photon-generated carriers and promotion of e-/h+Thereby improving the visible light activity of the material and being used in the field of gas purification.
The invention also discloses application of the oxygen-deficient gray zinc oxide as a gas purification photocatalyst. Relevant tests show that the material has the energy band gap width of 3.0 +/-0.1 eV, the surface Zeta potential of-10 +/-2 mV, and is rich in oxygen vacancies, so that the material enlarges the absorption range of visible light compared with white zinc oxide. The photocatalytic performance shows that the zinc oxide nano material with the gray oxygen-containing defects has excellent catalytic degradation capability on gas pollutants nitric oxide under visible light. Compared with a white titanium dioxide material, the degradation efficiency of the gray zinc oxide nano material rich in oxygen vacancy defects in the degradation process is obviously improved. Therefore, the oxygen-deficient zinc oxide has the characteristic of enhanced photocatalytic activity and can be applied as a gas purification photocatalyst.
Drawings
FIG. 1 is an optical photograph of an oxygen deficient gray zinc oxide and white zinc oxide according to the present invention; wherein, (a) is conventional white zinc oxide before reaction, (b) is the 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 oxide nanoparticles according to examples 1-3 of the present invention; wherein, (a) is an XRD general spectrum, and (b) is an XRD local enlarged view;
FIG. 4 is a Raman spectrum of oxygen deficient gray zinc oxide and white zinc oxide nanoparticles according to examples 1-3 of the present invention;
FIG. 5 is a graph of the UV-VIS absorption spectra of oxygen deficient gray zinc oxide and white zinc dioxide nanoparticles of examples 1-3 of the present invention;
FIG. 6 is the electron paramagnetic resonance spectrum of the oxygen deficient gray zinc oxide and white zinc oxide nanoparticles of example 1 of the present invention;
FIG. 7 is a Zeta potential diagram of oxygen deficient gray zinc oxide and white zinc oxide nanoparticles of examples 1-3 of the present invention;
FIG. 8 is a schematic diagram of the band structures of oxygen deficient gray zinc oxide and white zinc oxide nanoparticles according to examples 1-3 of the present invention;
fig. 9 is a graph comparing the NO purification curves of 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 to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or 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-deficient gray zinc oxide, which comprises the following steps:
(1) preparation of lithium naphthalene solution: weighing metal lithium and organic naphthalene, and dissolving the metal lithium and the organic naphthalene in a tetrahydrofuran solution to form a lithium naphthalene solution.
(2) Preparation of gray zinc oxide: dissolving white ZnO (named as W-ZnO) in a lithium naphthalene solution, soaking for a period of time for reduction reaction, collecting a solid product after the reduction reaction is finished, fully washing the obtained solid product with deionized water, and drying the solid product in vacuum to obtain gray ZnO powder, namely the oxygen deficiency type gray zinc oxide.
Further, the molar ratio of lithium to naphthalene required in the step (1) is (0.5-8): 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. The concentration of the lithium naphthalene solution is preferably 0.8 mol/L.
Further, the feeding ratio of the white zinc oxide to the lithium naphthalene solution in the step (2) is 0.2-1 g: 0.5-5 mL.
Further, the time for soaking the lithium naphthalene solution in the step (2), namely the reduction reaction time of the white zinc oxide and the lithium naphthalene solution, is 1-30 min. The time for soaking the lithium naphthalene solution is preferably 10 min. 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 ℃. The preferred vacuum drying temperature is 80 ℃. In the preparation process, the application range of the drying temperature is wide, the gray zinc dioxide nano material rich in oxygen vacancy defects can be obtained only by simple soaking, the process is simple and easy to operate, and therefore the preparation method is suitable for large-scale rapid preparation at normal temperature.
The oxygen-deficient zinc oxide prepared by the preparation method is gray, the energy band gap width 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 gap width 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 to be applied to the field of gas purification. Therefore, the oxygen-deficient gray zinc oxide can be used as a photocatalyst and applied to the field of gas purification.
The present invention is described in further detail below with reference to specific examples:
example 1
55.53mg of metallic lithium and 1025.36mg of organic naphthalene (molar ratio is 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 with deionized water, and drying in vacuum at 60 ℃ to obtain gray ZnO powder, namely the oxygen-deficient gray zinc oxide, which is named as ZnO-0.8.
The oxygen-deficient zinc oxide prepared by the embodiment is gray, and an amorphous disordered layer with the thickness of 4-5 nm is arranged on the surface.
Example 2
124.92mg of metal lithium and 6152.16mg of organic naphthalene (the molar ratio is 3:1) are weighed and dissolved in 10mL of tetrahydrofuran solution to form 0.6mol/L lithium naphthalene solution; 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 with deionized water, and drying the solid product in vacuum at 70 ℃ to obtain gray ZnO powder, namely the oxygen-deficient gray zinc oxide, which is named as ZnO-0.6.
The oxygen-deficient zinc oxide prepared by the embodiment is gray, and an amorphous disordered layer with the thickness of 3-4 nm is arranged on the surface.
Example 3
555.20mg of metal lithium and 1281.70mg of organic naphthalene (the molar ratio is 8:1) are weighed and dissolved in 10mL of tetrahydrofuran solution to form 1mol/L lithium naphthalene solution; dissolving 1g of white ZnO in 5mL of lithium naphthalene solution, soaking at 30 ℃ for reduction reaction for 30min, collecting a solid product after the reaction is finished, fully washing the obtained solid product with deionized water, and drying the solid product in vacuum at 80 ℃ to obtain gray ZnO powder, namely the oxygen-deficient gray zinc oxide, which is named as ZnO-1.
The oxygen-deficient zinc oxide prepared by the embodiment is gray, and an amorphous disordered layer with the thickness of 4-5 nm is arranged on the surface.
Example 4
Weighing 13.88mg of metal lithium and 512.68mg of organic naphthalene (the molar ratio is 0.5:1) and dissolving the metal lithium and the organic naphthalene in 10mL of tetrahydrofuran solution to form 0.4mol/L 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 with deionized water, and drying the solid product in vacuum at 50 ℃ to obtain gray ZnO powder, namely the oxygen-deficient gray zinc oxide, which is named as ZnO-0.4.
The oxygen-deficient zinc oxide prepared by the embodiment is gray, and an amorphous disordered layer with the thickness of 2-3 nm is arranged on the surface.
The invention is described in further detail below with reference to the accompanying drawings:
in fig. 1, the left picture (a) is the purchased white zinc dioxide nanoparticles, and the right picture (b) is the oxygen-deficient gray zinc oxide prepared in example 1, i.e. the gray zinc dioxide nanoparticles rich in oxygen defects, and the comparison shows that the finally prepared oxygen-deficient zinc oxide nanoparticles are gray.
As shown in FIG. 2, the presence of a disordered layer of 2-3 nm on the surface of the material was observed in HRTEM of gray ZnO (i.e., oxygen deficient gray zinc oxide), which is attributed to the presence of oxygen vacancies on the surface of the material. Because ZnO is immersed in the lithium naphthalene solution, lithium can "rob" the ZnO material for oxygen atoms, resulting in the formation of an amorphous disordered layer on the surface of the material. The image showed clear lattice streaks with a lattice spacing of 0.281nm corresponding to the (100) crystal plane of wurtzite-type ZnO and a lattice spacing of 0.247nm corresponding to the (101) crystal plane of wurtzite-type ZnO.
As shown in FIG. 3(a), the prepared ZnO has diffraction characteristic peaks at 31.9 °, 34.6 °, 36.4 °, 47.6 °, 56.8 °, 63.0 °, 68.1 ° and 69.2 ° at 2 θ corresponding to crystal planes (JCPDS: NO.36-1451) of (100), (002), (101), (102), (110), (103), (112) and (201), respectively. XRD enlargements of different zinc oxide materials As shown in FIG. 3(b), we found that the diffraction peak of ZnO obtained in 0.6mol/L solution is shifted to a small angle from 36.45 DEG to 36.42 DEG, indicating an increase in interplanar spacing. When ZnO was obtained in a solution of 0.8mol/L, the diffraction angle continued to decrease from 36.42 ° to 36.38 °, indicating that the interplanar spacing continued to increase. 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 ℃ C.) compared to the product at 0.8mol/L, indicating that the content of oxygen vacancies was reduced and a new phase was formed, which was cubic phase ZnO (JCPDS: 21-1486).
As shown in FIG. 4, the Raman spectrum of the gray oxygen-deficient ZnO has 5 Raman vibration peaks at 203cm-1、331cm-1，382cm-1，437cm-1And 582cm-1. Wherein, 582cm-1Is corresponding to E1(longitudinal optical) mode,382cm-1corresponds to A1(transverse optical) mode, 437cm-1Is corresponding to E2(high) mode, 203cm-1And 331cm-1Is derived from E2(low)-E2(high) vibrating. E of ZnO-0.6 and ZnO-0.82The (high) mode is reduced in peak intensity and shifted from 437cm, compared with pure ZnO-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), indicating that the oxygen atom in the crystal lattice is missing. E of ZnO1The mode (582cm-1) is associated with vacancy defects, and the E1 mode strengths for ZnO-0.6 and ZnO-0.8 are enhanced compared to ZnO, indicating an increased oxygen vacancy content in the material. ZnO-1.0 has a mixed crystal structure, and thus causes non-harmonic phonon-phonon interaction and lattice disorder.
As shown in fig. 5, the uv-vis absorption spectrum shows that the light absorption range of the gray ZnO treated with the lithium naphthalene solution (i.e., the oxygen deficient gray zinc oxide) is red-shifted and the light absorption intensity is increased, compared to the white ZnO, due to the formation of oxygen vacancies. Oxygen vacancies can lead to a disordered layer on the surface of the material during formation. Oxygen vacancies and disordered layers can be considered as trapping sites, preventing recombination of photogenerated carriers, thereby facilitating electron transfer and increasing photocatalytic reactivity.
As shown in fig. 6, Electron Paramagnetic Resonance (EPR) shows that both white ZnO and gray ZnO (i.e., gray zinc oxide that is oxygen deficient) show a single lorentz line with a g value of about 2.002; the EPR spectrogram formant intensity of the gray ZnO (namely the oxygen defect type gray zinc oxide) is higher than that of the white ZnO, which indicates that the gray ZnO is rich in oxygen vacancy defects.
As shown in FIG. 7, the zeta potential diagram shows zeta potentials of samples in which W-ZnO, ZnO-0.6, ZnO-0.8 and ZnO-1.0 had zeta potentials of 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, the higher the photocatalytic activity. Among them, the ZnO-0.8 sample has the largest negative zeta potential, which is beneficial to adsorbing more pollutant molecules and enhancing the photocatalytic performance.
FIG. 8 is a diagram showing the energy band structure of different materials, and the conduction band of ZnO-0.8 has a forward shift of about 0.1eV compared with that of the sample W-ZnO. The ZnO-0.8 conduction band with oxygen defect is bent downwards, and the potential barrier overcome in the photocatalysis reaction is relatively small. ZnO-0.8 with surface oxygen vacancy has higher photocatalytic performance, and the reaction activity of the photocatalyst can be enhanced by increasing the oxygen vacancy concentration on the surface of the material within a proper range.
FIG. 9 shows the NO degradation curves of W-ZnO, ZnO-0.6, ZnO-0.8 and ZnO-1.0 under UV irradiation, and the degradation rate of W-ZnO without surface oxygen defect under UV 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 percent, and the NO degradation rate of ZnO-0.8 is 54.3 percent. When the concentration of the lithium naphthalene solution reaches 1.0mol/L, a product obtained after the precursor is treated has new phase generation, so that the catalytic activity is reduced, and the NO degradation rate of ZnO-1.0 is 14.5%. The efficiency of degrading NO of the oxygen-rich defective ZnO-0.8 sample is about 12 times of that of W-ZnO without surface oxygen defect, and the introduction of oxygen vacancy obviously improves the purification effect of ZnO on NO. Compared with white ZnO, the material with surface oxygen vacancy has higher photocatalysis efficiency, and the oxygen vacancy plays a role in capturing electrons and can inhibit the recombination of photo-generated electrons and holes; and the concentration of oxygen vacancies on the surface of the material is increased within a proper range, so that the photocatalytic activity of the sample can be enhanced.
In conclusion, the invention relates to the field of new materials, and discloses oxygen-deficient gray zinc oxide and a preparation method and application thereof. The oxygen-deficient zinc oxide prepared by the method is gray, has an amorphous disordered layer on the surface, is rich in oxygen vacancies, has a narrowed forbidden band width and high electron paramagnetic resonance peak strength, has more reaction active sites, and can be applied to the fields of catalysis and energy.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of oxygen-deficient gray zinc oxide is characterized by 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-deficient gray zinc oxide.
2. The method for preparing the oxygen-deficient gray zinc oxide according to claim 1, wherein the molar ratio of lithium to naphthalene is (0.5-8): 1.
3. the method for preparing the oxygen-deficient gray zinc oxide according to claim 1, wherein the solvent is tetrahydrofuran.
4. The method for preparing oxygen-deficient gray zinc oxide according to claim 1, wherein the concentration of the lithium naphthalene solution is 0.4-1 mol/L.
5. The method for preparing oxygen-deficient gray zinc oxide according to claim 1, wherein the reduction reaction time of white zinc oxide and lithium naphthalene solution is 1-30 min, and the reduction reaction temperature is 10-30 ℃.
6. The method for preparing the oxygen-deficient gray zinc oxide according to claim 1, wherein the drying treatment comprises: vacuum drying at 50-80 deg.C.
7. The method for preparing oxygen-deficient gray zinc oxide according to claim 1, wherein the feeding ratio of white zinc oxide to lithium naphthalene solution is 0.2-1 g: 0.5-5 mL.
8. An oxygen-deficient gray zinc oxide prepared by the preparation method of any one of claims 1 to 7.
9. The oxygen-deficient gray zinc oxide according to claim 8, wherein the surface of the oxygen-deficient gray zinc oxide has an amorphous disordered layer of 2-5 nm.
10. Use of an oxygen-deficient gray zinc oxide prepared by the preparation method of any one of claims 1 to 7 or an oxygen-deficient gray zinc oxide of any one of claims 8 to 9 as a photocatalyst for gas purification.
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