CN103789834B - Micrometer/nanometer level gallic acid zinc crystal, Its Preparation Method And Use - Google Patents
Micrometer/nanometer level gallic acid zinc crystal, Its Preparation Method And Use Download PDFInfo
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- CN103789834B CN103789834B CN201210418182.5A CN201210418182A CN103789834B CN 103789834 B CN103789834 B CN 103789834B CN 201210418182 A CN201210418182 A CN 201210418182A CN 103789834 B CN103789834 B CN 103789834B
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- gallic acid
- acid zinc
- crystal
- zinc
- gallium
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 title claims abstract description 404
- 239000011701 zinc Substances 0.000 title claims abstract description 226
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 222
- 229940074391 gallic acid Drugs 0.000 title claims abstract description 202
- 235000004515 gallic acid Nutrition 0.000 title claims abstract description 202
- 239000013078 crystal Substances 0.000 title claims abstract description 200
- 238000002360 preparation method Methods 0.000 title description 10
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 229910001868 water Inorganic materials 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 28
- 150000002258 gallium Chemical class 0.000 claims description 24
- 150000003751 zinc Chemical class 0.000 claims description 24
- 229910052733 gallium Inorganic materials 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 19
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical group [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 8
- 201000006747 infectious mononucleosis Diseases 0.000 claims description 8
- -1 monos amine Chemical class 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 5
- 229940044658 gallium nitrate Drugs 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000373 gallium sulfate Inorganic materials 0.000 claims description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 3
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 238000007146 photocatalysis Methods 0.000 abstract description 13
- 238000006722 reduction reaction Methods 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000002135 nanosheet Substances 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 description 28
- 239000002159 nanocrystal Substances 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 14
- 239000001569 carbon dioxide Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 229910007486 ZnGa2O4 Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 9
- 150000004985 diamines Chemical class 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 4
- 238000003775 Density Functional Theory Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102100021164 Vasodilator-stimulated phosphoprotein Human genes 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000000205 computational method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002171 ethylene diamines Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- 108010054220 vasodilator-stimulated phosphoprotein Proteins 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000170916 Paeonia officinalis Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
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- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Abstract
There is provided herein a kind of micrometer/nanometer level gallic acid zinc crystal, including sheet gallic acid zinc crystal, cubic block gallic acid zinc crystal or octahedra gallic acid zinc crystal, the wherein gallic acid zinc crystal of cubic block exposes with { 100 } face；Octahedra gallic acid zinc crystal exposes with { 111 } face.The nano-sheet crystals that the application provides can be self-assembled into flower-shaped spheroid.The method for synthesizing above-mentioned gallic acid zinc crystal is also provided herein.The gallic acid zinc crystal is light-catalyzed reaction, effective for such as photocatalysis CO2In reduction reaction.
Description
The present invention relates to micrometer/nanometer level gallic acid zinc crystal, including sheet gallic acid zinc crystal, cubic block gallic acid zinc crystal or
Octahedra gallic acid zinc crystal, wherein cubic block gallic acid zinc crystal expose with { 100 } face；Octahedra gallic acid zinc crystal has
{ 111 } face exposes.Especially, sheet gallic acid zinc crystal exposes with { 110 } face.The invention further relates to prepare the micrometer/nanometer
The method of level gallic acid zinc crystal, and the purposes of the micrometer/nanometer level gallic acid zinc crystal in photocatalysis.
Background technology
In recent years, gallic acid zinc (ZnGa2O4) received much concern as a kind of important photochemical catalyst.Verified, gallic acid zinc exists
Organic pollutant degradation, water decomposition and photocatalysis CO2There is good effect in terms of reduction.
It has been found that inorganic micrometer/nanometer（Micron and/or nanometer）The physicochemical characteristics of crystal not only can be because of its composition
And be generally fine-tuned, and it is closely related with its size, shape and crystal exposure (facet).Thus, people in past 10 years
It is directed to controlling the research of the shape and exposure of inorganic micrometer/nanometer crystal extensively.Simultaneously as new capability and hierarchy
It is relevant with substantial amounts of avtive spot, so the three-dimensional hierarchical structure based on nano unit is considered to be the structure of more attractability.
On the other hand, because the atomic arrangement on different crystal faces is different with coordination, thus the crystal face difference of catalyst exposure is by direct shadow
Ring its light-catalyzed reaction activity, or even process.Theoretical and experimental study shows the noble metal nano crystal with high miller index surface
Generally only have the crystal of low index crystal plane to show higher catalytic activity than those.
Although photocatalytic activity depends significantly on the geometric configuration of micrometer/nanometer gallic acid zinc catalyst, due to preparing
Difficulty, so far nobody obtained the gallic acid zinc crystal exposed dependent on shape and crystal face.
In order to overcome problem of the prior art, photocatalytic activity is improved, the applicant has synthesized novel nano gallic acid zinc crystalline substance
Body.This new gallic acid zinc crystal can effectively improve gallic acid zinc in photocatalysis degradation organic contaminant, water decomposition and photocatalysis
Efficiency in carbon dioxide reduction.
The content of the invention
The invention provides a kind of micrometer/nanometer level gallic acid zinc crystal, including nano-sheet crystals, have { 100 } face sudden and violent
The cubic block nanocrystal of dew, or the octahedra nanocrystal with the exposure of { 111 } face.The sheet gallic acid zinc nanocrystals have
{ 110 } face exposes.Also, in the nano-sheet crystals (crystalline wafer), preferably the thickness of crystalline wafer is less than or equal to 10nm, is less than
Equal to 8nm, preferably smaller than equal to 6nm.The sheet gallic acid zinc nanocrystals are preferred（From）Assembling exists in the form of flower-shaped spheroid,
Particularly monodispersed flower-shaped spheroid.When forming monodispersed flower-shaped spheroid, the diameter of the sheet gallic acid zinc nanocrystals ball
Generally less than 8 μm.It is preferred that the flower-shaped spheroid is with hierarchy, monodispersed flower-shaped spheroid gallic acid zinc crystal.
For the cubic block nanocrystal exposed with { 100 } face, the cubic block nanocrystal（It is single）The length of side be less than etc.
In 120nm, preferably smaller than equal to 100nm.
Octahedra nanocrystal with the exposure of { 111 } face, the octahedra nanocrystal（It is single）The length of side is less than or equal to 2
μm, preferably smaller than equal to 500nm, more preferably less than or equal to 250nm.
Typically for above-mentioned micrometer/nanometer level gallic acid zinc crystal, have more than 80%, preferably more than 90%, further preferably 95%
More than, more preferably more than 99% exposure, preferably sheet gallic acid zinc crystal have more than 80%, preferably more than 90%, further preferably
More than 95%, more preferably more than 99% { 110 } face exposure.
Specifically, according to this paper one side, there is provided herein a kind of gallic acid zinc crystal of micrometer/nanometer level, including piece
{ 100 } face of shape gallic acid zinc crystal, cubic block gallic acid zinc crystal or octahedra gallic acid zinc crystal, wherein cubic block gallic acid zinc crystal
Exposure；{ 111 } face exposure of octahedra gallic acid zinc crystal；{ 110 } face exposure of wherein described sheet gallic acid zinc crystal.
According to this paper one side, in the micrometer/nanometer gallic acid zinc crystal of offer, above-mentioned crystal face exposure reaches 80%
More than, preferably more than 90%, further preferably more than 95%, more preferably more than 99%, or almost 100%.
According to this paper one side, the crystalline wafer of sheet gallic acid zinc crystal is square, regular hexagon or approximate shapes.
The length and width of the crystalline wafer of the sheet gallic acid zinc crystal is respectively smaller than 8 μm, preferably smaller than 6 μm, more preferably less than 4 μm.And
And the thickness of the crystalline wafer of sheet gallic acid zinc crystal is less than 10nm, preferably smaller than 8nm, more preferably less than 6nm.The sheet gallic acid
Zinc crystal can self assembly exist in the form of flower-shaped spheroid.The diameter of the flower-shaped spheroid be less than 10 μm, preferably 8 μm, more preferably 6
μm。
According to this paper one side, there is provided cubic block gallic acid zinc crystal, the length of side of the cubic block gallic acid zinc crystal are small
In equal to 120nm, preferably smaller than equal to 100nm.
According to this paper one side, there is provided octahedra gallic acid zinc crystal, the length of side of the octahedra gallic acid zinc crystal are small
In equal to 2 μm, preferably smaller than equal to 500nm, more preferably less than or equal to 250nm.
Present invention also offers the method for preparing nanoscale gallic acid zinc crystal, including
Gallium salt and zinc salt are added in solvent, wherein the solvent be selected from C1-C18 organic monos amine or diamine, water or
Its mixture；
By the liquid mixture in 150-240 DEG C of solvent thermal reaction；
Reacted liquid mixture is cooled down to separate out crystal.
According to this paper one side, there is provided a kind of method for preparing micrometer/nanometer level gallic acid zinc crystal, including
Gallium salt and zinc salt are added in solvent, wherein the solvent is selected from C1-C18 organic monos amine or diamine, water
Or its mixture；
By the liquid mixture in 150-240 DEG C of solvent thermal reaction；
Reacted liquid mixture is cooled down to separate out crystal.
According to this paper another aspect, the gallium salt used in preparation method is selected from gallium nitrate, gallium chloride, gallium sulfate and oxygen
Change gallium.Zinc salt is selected from zinc nitrate, zinc acetate, zinc sulfate and zinc oxide.The gallium salt：In zinc salt [gallium]：[zinc] (i.e. gallium element：Zinc
Element) mol ratio be less than 4:1, preferably smaller than equal to 3:1, more preferably 2:1, and [gallium]：[zinc] is more than 1:1.
According to this paper another aspect, the solvent used in preparation method, organic mono amine or diamine are selected from：C2-
C6 diamines, C1-C18 monoamines.Specifically, the solvent is selected from water, ethylenediamine, diamines, C12- amine, C14- amine, C16- amine
With oleyl amine, water or their mixture.It is preferred that the solvent is ethylenediamine, oleyl amine, water or their mixture.
Present invention also offers the purposes of above-mentioned micrometer/nanometer level gallic acid zinc crystal.These micrometer/nanometer level gallic acid zinc are brilliant
Body is suitable for use as organic pollutant degradation, water decomposition and photocatalysis CO2Photochemical catalyst in terms of reduction.
Brief description of the drawings
Fig. 1：The FE-SEM figures of three kinds of samples of gallic acid zinc of preparation；(a1)、(a2) the gallic acid zinc hierarchy based on nanometer sheet
Flower-shaped spheroid (micro-flowers), (b1) and (b2) octahedra gallic acid zinc crystal；(c1) and (c2) it is cubic block gallic acid zinc crystal；And
(a3)、(b3) and (c3) be these three structures gallic acid zinc structural representation
Fig. 2：The different amplification of the flower-shaped spheroid of the micron order with hierarchy of sheet gallic acid zinc Crystallization
FE-SEM photos
Fig. 3：The XRD spectra of the gallic acid zinc crystal of three kinds of patterns：(a) it is based on the micron of sheet gallic acid zinc crystal (nanometer sheet)
The level flower-shaped spheroid of gallic acid zinc（Micron bouquet）；(b) cubic block gallic acid zinc crystal grain；(c) octahedra gallic acid zinc crystal grain；
(d) gallic acid zinc standard card (JCPDS 38-1240)
Fig. 4：(a) scheme with (b) for the TEM of the flower-shaped spheroid of micron order gallic acid zinc of nanometer sheet assembling；(c) ultra-thin gallic acid zinc is received
The TEM figures of rice piece, illustration are the enlarged drawing in black circular frame region；(d) the high-resolution transmission photo of gallic acid zinc nanometer sheet, illustration
For its SEAD style, crystal zone axis is
Fig. 5：Percentage based on sheet gallic acid zinc crystal total surface area estimation { 110 } crystal face
Fig. 6：The XPS collection of illustrative plates of the flower-shaped spheroid of gallic acid zinc micron order
Fig. 7：The uv-visible absorption spectra of the flower-shaped spheroid of gallic acid zinc micron order
Fig. 8：The FE-SEM photos of product prepared by different solvents；(a) pure water；(b)VEN/VWaterFor 1:4；(c)VEN/VWaterFor
1:1；(d) pure EN
Fig. 9：The XRD spectra of product prepared by different solvents；(a) pure water；(b)VEN/VWaterFor 1:4；(c)VEN/VWaterFor 1:1；
(d) pure EN
Figure 10：The amount of the gallic acid zinc catalyst photocatalytic reduction of carbon oxide production methane of three kinds of different crystal morphologies and when
Between relation：(a) cubic block gallic acid zinc crystal；(b) octahedra gallic acid zinc crystal；(c) micron based on sheet gallic acid zinc crystal
Bouquet
Figure 11：The structural representation of micrometer/nanometer gallic acid zinc crystal different faces：(a)(100)；(b)(111)；(c)(110)
Figure 12：(a) the total state density figure of gallic acid zinc, (b), (c) and (d) are respectively the total state density figure of Zn, Ga and O atom
Figure 13：Gallic acid zinc (110) CO absorption2With the structural representation after H（Two side views）
Embodiment
The invention provides a kind of micrometer/nanometer level gallic acid zinc crystal, including sheet gallic acid zinc crystal, there is { 100 } face
Exposed cubic block gallic acid zinc crystal, and the octahedra gallic acid zinc crystal with the exposure of { 111 } face.Sheet gallic acid zinc crystal, bag
The gallic acid zinc micro-flowers based on nanometer sheet are included, there is the exposure of { 110 } face.In the micrometer/nanometer level gallic acid zinc crystal, crystal face it is sudden and violent
Dew is more than or equal to 80%, is preferably greater than or equal to 90%, is more preferably greater than equal to 99%, such as larger than equal to 95%, even as high as 100%.
" face exposure " or " exposure " refer to the visible surface of gallic acid zinc crystal herein.{ 100 } face, { 111 } face of gallic acid zinc crystal
{ 110 } face is identified by the recognition methods of the high resoluting information such as electronic diffraction.
Referring to Fig. 1, the micron-sized gallic acid zinc based on sheet gallic acid zinc crystal obtained by this paper is given in the figure
The FE-SEM figures of flower-shaped spheroid, cubic block gallic acid zinc crystal and octahedra gallic acid zinc crystal different amplification.
Structure such as Fig. 1 (a of sheet gallic acid zinc crystal1)、(a2) and (a3) shown in.{ 110 } face of sheet gallic acid zinc crystal is sudden and violent
Dew.It is preferred that in the crystal face that sheet gallic acid zinc crystal is exposed, { 110 } face accounts for more than 80%, preferably more than 90%, further preferably
More than 95%, more preferably more than 99%, i.e., { 110 } face crystal face expose as more than 80%, preferably more than 90%, further preferably more than 95%, more
It is preferred that more than 99%.Herein, term " crystal face exposure " refers to related crystal face and all crystal face gross areas being exposed
Ratio.
In the sheet gallic acid zinc crystal, flat crystal（Also known as crystalline wafer）For the flaky crystal of Nano grade, with micron
The form of bouquet is present.The thickness of crystalline wafer is generally less than 10nm, preferably smaller than 8nm, more preferably less than 6nm.Sheet gallic acid zinc
The length and width of the crystalline wafer of crystal is, for example, less than 10 μm, preferably smaller than 8 μm, more preferably less than 5 μm, it is however generally that, more than 2
μm.In a preferred embodiment, the length and width of crystalline wafer is respectively 3-5 μm.Sheet gallic acid zinc crystal typically in
Square, regular hexagon or with its approximate shape, see, for example, Fig. 4 (b).
The FE-SEM photos of different amplification sheet gallic acid zinc crystal according to given by Fig. 4, lattice fringe understand, had
Sequence, the sheet gallic acid zinc crystal for thus showing this paper is mono-crystalline structures.In a preferred embodiment, referring to Fig. 4 (d),
Interplanar distance d is 0.48nm, (111) crystal face of corresponding Emission in Cubic gallic acid zinc.Also, the SAED figure diffraction spots in Fig. 4 (d) are clear
Clear, queueing discipline further demonstrates that the mono-crystalline structures that sheet gallic acid zinc crystal is well-crystallized.Ability is utilized to the diffraction spot
Technical indicator known to domain, it is known that sheet gallic acid zinc crystal alongDirection grows.Based on the above results, sheet is shown
Two main exposure crystal faces up and down of gallic acid zinc crystal are { 110 } face.
The sheet gallic acid zinc crystal can（From）Assembling exists in the form of flower-shaped spheroid.The flower-shaped spheroid of gallic acid zinc, it is similar
In the shape of peony, by ultra-thin, the two-dimensional nano piece that individual length and widths up to a hundred are several micron levels（Sheet gallic acid zinc
Crystal）Form it is spherical, referred to herein as gallic acid zinc micron bouquet.It is preferred that the flower-shaped spheroid of gallic acid zinc is monodispersed, tool
There is hierarchy.When forming monodispersed flower-shaped spheroid, the diameter of the flower-shaped spheroid of the sheet gallic acid zinc Crystallization is general
Less than 10 μm, preferably smaller than 8 μm, more preferably less than 6 μm, see, for example, Fig. 1 and Fig. 2.
Herein, term "（From）Assembling " refers to that sheet gallic acid zinc crystal need not be helped by means of outside, is being formed
After sheet gallic acid zinc crystal, flower-shaped spheroid can be spontaneously formed；Term " single dispersing " refers to formed sheet gallic acid zinc
The uniform particle diameter of crystal or the flower-shaped sphere structure of formation；Term " hierarchy " refers to that includes a top other and clump category level
Other hierarchical structure.
The nano-sheet crystals are after flower-shaped spheroid is assembled into, preferably each crystalline wafer（Flower piece）It is individually present.Assembling
During the flower-shaped spheroid of gallic acid zinc, the quantity of crystalline wafer in flower-shaped spheroid, as needed, voluntarily adjust.The gallium formed
The sour flower-shaped spheroid of zinc, respective independence, stably exist.
Be assembled into before the flower-shaped spheroid of gallic acid zinc, among or afterwards, the thickness of each crystalline wafer is constant, be generally less than etc.
In 10nm, preferably smaller than equal to 8nm, more preferably less than or equal to 6nm.Wherein, each " crystalline wafer or nanometer sheet " refers to assembling
Before into the flower-shaped spheroid of gallic acid zinc, among or afterwards, gallic acid zinc crystal in the form of sheets.In a preferred embodiment, group
Thickness into the crystalline wafer of the flower-shaped spheroid of gallic acid zinc is generally less than 10nm, preferably smaller than 8nm, more preferably less than 6nm.
The sheet gallic acid zinc nanocrystals（Hereinafter, when referring to sheet gallic acid zinc nanocrystals, including micron-sized gallium
The sour flower-shaped spheroid of zinc）Each crystalline wafer be respectively provided with { 110 } face exposure.It is higher than it is preferred that the sheet gallic acid zinc nanocrystals have
80%th, 90%, more preferably higher than 95% is preferably above, even more preferably greater than 99% { 110 } face exposure.
Applicants have unexpectedly found that the sheet gallic acid zinc crystal, flower-shaped spheroid is formed by assembling（" nanometer bouquet "）, institute
Obtained structural integrity, stability is high.Because the sheet gallic acid zinc crystal has high { 110 } face exposure, light is effectively increased
Catalytic activity, and can be by controlling the exposure of crystal plane, crystal plane, and adjust, control the photocatalytic activity of photochemical catalyst.
Theory is not limited to, applicant thinks raising and { 110 } face of photocatalysis effect, particularly { 110 } exposure
Inherent catalytic performance has much relations, because positive ion density is high on { 110 } face, is advantageous to CO2Absorption, the low CO of work content2Easily
Activation, so as to enhance its CO2Reduce photocatalysis performance.In addition, gallic acid zinc crystal, such as the flower-shaped spheroid of gallic acid zinc, it is unique
Three-dimensional (3D), hierarchy also enhance its photocatalysis performance, and three-dimensional (3D) structure causes catalyst to have larger ratio surface
Product, and the superthin structure of nanometer sheet is also beneficial to carrier and light-catalyzed reaction is quickly participated in from internal migration to surface.
Gallic acid zinc cubic block crystal structure such as Fig. 1 (c1)、(c2)、(c3) shown in.In general, provided by the present invention should
Cubic block gallic acid zinc crystal is the gallic acid zinc crystal of cubic form that is monodispersed, separate, being mutually stabilized.
The gallic acid zinc cubic block nanocrystal（It is single）The length of side is generally less than and is equal to 150nm, more preferably small preferably smaller than equal to 120nm
In equal to 100nm.
The gallic acid zinc cubic block crystal exposes with { 100 } face.It is preferred that the gallic acid zinc cubic block crystal have more than 80%,
It is preferred that more than 90%, more preferably more than 95%, even more preferably from more than 99% { 100 } face expose.It is preferred that the gallic acid zinc cubic block is brilliant
Body almost 100% { 100 } face exposure.
Structure such as Fig. 1 (b of gallic acid zinc octahedron nanocrystal1), Fig. 1 (b2) and Fig. 1 (b3) shown in.The one of the present invention
In individual embodiment, it is be combined with each other in the gallic acid zinc crystal of octahedral crystal form, forms club shaped structure.In general, the gallium
Sour zinc octahedral crystal（It is single）The length of side is more excellent preferably smaller than equal to 1 μm, more preferably less than or equal to 500nm less than or equal to 2 μm
Choosing is less than or equal to 250nm, even more preferably less than 200nm, most preferably about 150nm or smaller.The gallic acid zinc octahedral crystal
Exposure is { 111 } face.
For cubic symmetry crystal, { 100 } type low index surface typically has minimum surface energy, the surface of high miller index surface
Can be higher.In order to minimize plane of crystal energy, crystal in growth course along high miller index surface direction the speed of growth far faster than
Along low index crystal plane direction, high miller index surface is caused to tend to disappear.Theory is not limited to, sheet gallic acid zinc described herein is brilliant
Body and octahedra gallic acid zinc crystal are due to solvent molecule（Such as ethylenediamine）Ligand solvent molecular template mechanism, adjust { 100 }
Face ratio { 110 } face and { 111 } face speed of growth are fast, brilliant so as to be easier to obtain sheet gallic acid zinc crystal and octahedra gallic acid zinc
Body.
Present invention also offers the method for preparing micrometer/nanometer level gallic acid zinc crystal, including
Gallium salt and zinc salt are added in solvent, wherein the solvent be selected from C1-C18 organic monos amine or diamine, water or
Its mixture；
By the liquid mixture in 150-240 DEG C of solvent thermal reaction；
Reacted liquid mixture is cooled down to separate out crystal.
The gallium salt and zinc salt used in the preparation method is generally soluble-salt, particularly water soluble salt.Above-mentioned gallium
Salt and zinc salt include the oxide of gallium or zinc.For example, gallium salt be selected from gallium nitrate, gallium chloride, gallium sulfate and gallium oxide and they
Hydrate；Zinc salt is selected from zinc nitrate, zinc acetate, zinc sulfate, zinc oxide and their hydrate.
In general the mixed proportion of gallium salt and zinc salt is higher than the dosage of zinc salt for gallium salt（Mole）.It is preferred that gallium salt and zinc
The mol ratio of salt is (with gallium element and the molar ratio computing of Zn-ef ficiency, i.e. [gallium]：The mol ratio of [zinc]) it is less than or equal to 4:1, preferably
Less than or equal to 3:1, more preferably equal to 2:1, and preferably gallium salt：Zinc salt ([gallium]：[zinc]) mol ratio be more than or equal to 1:1.
Herein, organic amine, water and their mixture are selected from for dissolving the solvent of gallium salt and zinc salt, preferably used
The dual solvent system of C1-C18 organic amines and water.Organic amine for synthesis is C1-C18 organic amines, including monoamine and two
First amine, preferably monoamine are selected from C12-C18 monoamines, such as lauryl amine, tetradecy lamine, cetylamine or octadecylamine, including for example with
The unsaturated amine of one or more double bond, such as oleyl amine；Diamine is preferably selected from C2-C6 diamines, for example, ethylenediamine or
Hexamethylene diamine.
When using the dual solvent system of organic amine and water, the ratio of organic amine and water can be 1:1, it is preferably organic
Amine：Water is 1:4（Volume ratio）Or it is lower, more preferably 1:2（Volume ratio）It is or lower.
When preparing micrometer/nanometer level gallic acid zinc crystal, the mixture of gallium salt and zinc salt is added in solvent, is selected from
In the solvent of organic amine, water and their mixture, it is sufficiently stirred, gallium salt and zinc salt is dissolved in the solvent, obtain liquid
Body mixture.In course of dissolution, as needed, addition sequence can be adjusted, such as gallium salt is first added, then add zinc
Salt；Or they are added simultaneously；Zinc salt can also be first added, adds gallium salt afterwards.
When using mixed solvent, the order for the solvent to be added can also be adjusted, such as can be first by gallium salt and zinc
Salt mixes, and adds in organic amine, is then added to the water, or is conversely first added to the water, and then adds in organic amine solvent.Dissolving
During, temperature can be adjusted to be advantageous to dissolve.
Liquid mixture obtained by being dissolved in after gallium salt and zinc salt are mixed in solvent directly carries out solvent-thermal process reaction,
Temperature is 150-240 DEG C, preferably 160-200 DEG C.After to required temperature, kept for a period of time, such as 10-40 hours, it is excellent
12-30 hours, more preferably 15-24 hours are selected, concentration reaches saturation in liquid mixture to mixture.Keeping temperature when
Between with factors such as material quantities have relation, can adjust as needed.
After solvent thermal reaction step, the liquid mixture cooling after solvent thermal reaction is separated out into crystal.The cooling procedure
It can carry out at room temperature.As needed, the known method that can improve precipitation degree can also be used, such as be subcooled and cool,
The methods of adding crystal seed, improve crystal speed of separating out and eduction rate.
After crystal separates out, the gallic acid zinc obtained by being handled by post-processing approach commonly used in the prior art is brilliant
Body.Post-processing approach includes, but not limited to be collected by centrifugation；Crystal is cleaned, such as is cleaned with water or ethanol；Drying and other steps.Through
Micrometer/nanometer level gallic acid zinc crystal after the processing can use directly as photochemical catalyst.
According to this paper embodiment, there is provided a kind of method for preparing gallic acid zinc nano crystals, including
By gallium nitrate and zinc oxalate（Zn(CH3COO)2）It is dissolved in after mixing in the solution containing ethylenediamine, it is molten forms mixing
Liquid；
The mixed solution is subjected to solvent thermal reaction under the conditions of 180 DEG C -240 DEG C, preferably 24-30 hours form mixing
Thing；
The mixture is cooled to room temperature；
Separate out sheet gallic acid zinc crystal.
According to this paper another embodiment, there is provided a kind of method for preparing gallic acid zinc nano crystals, including
By gallium oxide and zinc oxalate（Zn(CH3COO)2）Added in water, uniform stirring forms solution；
Organic amine, preferably oleyl amine are added in the solution, mixed solution is formed after stirring；
The mixed solution is burnt under the conditions of 180 DEG C -240 DEG C, preferably 18-24 hours, form mixture；
The mixture is cooled down, separates out cubic block gallic acid zinc crystal.
According to this paper further embodiment, there is provided a kind of method for preparing gallic acid zinc crystal, including
By gallium oxide and zinc oxalate（Zn(CH3COO)2）Mixing, such as with mol ratio 1:1 ratio, add in ethylenediamine,
It is sufficiently stirred to form mixed solution；
By the mixed solution under the conditions of 180 DEG C -240 DEG C solvent thermal reaction, preferably 24-30 hours, formed mixture；
The mixture is cooled down, separates out octahedra gallic acid zinc crystal.
The crystal that will be collected into, is post-processed.For example, after collecting crystal, optionally cleaned with deionized water, ethanol,
It is dried to obtain gallic acid zinc crystal after purification.
By preparation method described herein, by solvent-thermal process (solvothermal route) method, obtain
The gallic acid zinc crystal of different crystal forms or pattern, wherein uniform three-dimensional point be self-assembly of by ultra-thin gallic acid zinc nanometer sheet
Level structure has { 110 } face of up to more than 99% exposure.On { 110 } face surface atom arrangement and coordination be different from cube
{ 100 } face of block particle and { 111 } face of octahedra particle, the surface positive ion density is high, is more beneficial for carbon dioxide molecule
Absorption, work content low carbon dioxide easily activates.Also, unique three dimensional micron/nanoscale hierarchy is also beneficial to light and urged
Change the raising of activity.
The micrometer/nanometer level gallic acid zinc crystal being prepared by the method for the present invention, can act as photochemical catalyst, for organic dirt
In the degraded, the cracking of water and the reduction of photocatalysis carbon dioxide that contaminate thing.
The purpose that following examples are merely to illustrate, it is not used in the limitation present invention.In addition, the number range that the application is related to
End points including numerical value is in itself.Typically, when not indicating particularly, based on weight.
Embodiment
Experiment and computational methods
Feature：Following crystalline phases for preparing product are radiated in 40kV and 40mA using CuK α（λ=0.154178nm）Penetrated by X
Line diffraction（XRD）（Ultima III of science, Japan）Determine.In 10 °~80 ° of scanning ranges with 10 °/min scanning
Speed obtains XRD spectrum at room temperature.
The form of powder is by field emission scanning electron microscope（FESEM, FEI NOVA NANOSEM230）Detection.Six
Lanthanum boride filament and the Ultima type IIIs X-ray diffractometer produced with Rigaku company carry out material phase analysis to product, with
Cu K α are radiation source, and wavelength isUsing continuous scan mode, sweep speed is 5 °/min, scanning range be 2 θ=
10°-80°。
The types of TriStar 3000 that specific surface area size is produced by Micromeritics companies of the U.S. are than surface-aperture
Distribution Analyzer is determined, and the adsorption/desorption of nitrogen is completed at a temperature of 77K, and its specific surface area is calculated with BET methods.
ESEM (SEM) photo uses the Tecnai G2F30S-Twin type field emission scanning electron microscopes of Dutch FEI Co.
(FE-SEM) shoot, accelerating potential is arranged to 15kV.
Transmission electron microscope (TEM) photo and the JEM- of the Japanese JEOL companies of high resolution TEM (HR-TEM) photo
3010 type transmission electron microscopes obtain, operating voltage 200kV.
The constituent analysis of sample is using the scientific and technological K-Alpha types x-ray photoelectron power spectrum of the silent winged generation that of match（XPS）Test, with
C1S combines the electron binding energy that energy 284.8eV is reference corrected each element.Ultraviolet-visible reflective spectrum is by Japanese Shimadzu Corporation
The UV-2500PC types ultraviolet-visible spectrophotometer analysis of production is obtained, and absorption light is changed into by Kubelka-Munk methods
Spectrum.
Sample：All chemicals are analysis level, open bag and use, without being further purified.
The preparation of gallic acid zinc crystal
Embodiment 1
Sheet gallic acid zinc crystal：By 0.26g Ga (NO3)3（1mmol）With 0.11gZn (CH3COO)2·2H2O（0.5mmol）
It is added in 15mL solvents, wherein the solvent includes 10mL water and 5mL ethylenediamines（EN）.The mixed solution is stirred 40 minutes,
It is then transferred into the stainless steel cauldron with polytetrafluoroethyllining lining that volume is 25mL.It is molten under 180 °C in electric oven
Agent thermal response 24 hours, then naturally cools to room temperature.Product is by being collected by centrifugation, and with deionized water and alcohol, thoroughly cleaning is more
It is secondary, then 60 DEG C of dryings 12 hours.Finally obtain white gallic acid zinc powder.
The products obtained therefrom of embodiment 1 such as Fig. 2 TEM image shows, it based on thickness is~6nm to obtain size to be 2~4 μm
Sheet gallic acid zinc crystal（Nanometer sheet）Flower-shaped spheroid, the flower-shaped spheroid is by numerous nanometer sheets（Fig. 2）Formed.The light pair of nanometer sheet
Than showing that thickness is relatively thin.Nanometer sheet is shaped as square and/or regular hexagon with~3 μm of average length profile.
The thickness of nanometer sheet from the edge metering of arc nanometer sheet about~6nm, nanometer sheet perpendicular to support film（Fig. 4 c）, show with scanning electron
Micro mirror observation is consistent.
High resolution TEM（HRTEM）Image shows that the lattice fringe interplanar d spacing for measuring large area is
0.48nm（Referring to Fig. 4）, brilliant corresponding to gallic acid zinc cubic block（111）Face.Its SEAD（SAED）In figure（Fig. 4 c are inserted
Figure）Diffraction spot is clear, queueing discipline, nano surface piece be well-crystallized mono-crystalline structures, nanometer sheet alongGive birth in direction
It is long.
According to Fig. 4, it is clear that two main exposure crystal faces up and down of nanometer sheet are { 110 } face.Percentage shared by exposure
Than being calculated according to the area in { 110 } face than the total surface area of upper nanometer sheet.Nanometer sheet { 110 } exposure percentage is up to 99.6%,
Calculating process is referring to Fig. 5.6nm thickness is equivalent to the thickness of 7 unit cells, i.e. 7 × 0.8335nm=5.8345nm.
In order to understand the Forming Mechanism of sheet gallic acid zinc crystal, different reaction conditions have studied.Increase the body of organic amine
Product ratio, can obtain larger sized sheet gallic acid zinc nanocrystals.When increasing the ratio of organic amine and water, such as from 1:4 to 1:2
When, only there is little difference in terms of the length of nanometer sheet and thickness（Referring to Fig. 8）.And when the volume ratio of organic amine and water is 1:
When 1, it will obtain the sheet gallic acid zinc crystal (Fig. 8 (c)) of very small (tiny).It is it is therefore preferable that brilliant preparing sheet gallic acid zinc
During body, using two kinds of solvents, cooperative effect is produced, is more beneficial for producing nano-grade gallic acid zinc crystal.
Embodiment 2
Cubic block crystal：By gallium oxide (Ga2O3)（0.94g）With Zn (CH3COO)2·2H2O（1.11g）It is added to 15mL
H2In O.After resulting solution lightly is stirred into a few minutes, 1mL oleyl amines are added.These mixed solutions are stirred 40 minutes,
It is then transferred into the stainless steel cauldron for the polytetrafluoroethyllining lining that inner volume is 25mL.In electric oven, 180 °C of hydro-thermals are anti-
It should react 24 hours, then naturally cool to room temperature.Product is by being collected by centrifugation, and with deionized water and ethanol, thoroughly cleaning is more
It is secondary, then dried 12 hours at 60 DEG C.Finally obtain white ZnGa2O4Powder, referring to Fig. 1（c1）With（c2）FE-SEM figure.
Embodiment 3
Octahedra gallic acid zinc crystal：By 0.23g Ga2O3（1.25mmol）0.27g Zn (CH3COO)2·2H2O
（1.25mmol）It is added in 15mL solvent, wherein the solvent includes 10mL water and 5mL ethylenediamines（EN）.These mixing are molten
Liquid stirs 40 minutes, is then transferred into the stainless steel cauldron for the polytetrafluoroethyllining lining that volume is 25mL.In electric oven
180 °C of solvent thermal reactions 24 hours, then naturally cool to room temperature.Product is thorough with deionized water and ethanol by being collected by centrifugation
Bottom cleaning is multiple, is then dried 12 hours at 60 DEG C.Finally obtain white ZnGa2O4Powder, referring to Fig. 1 (b1) and (b2).
It is classified ZnGa2O4Crystallite is by binary ethylenediamine（EN）/ aqueous solvent by volume 1:2 using the synthesis of solvent heat route.
In identical dual solvent system, with Ga2O3Obtained for gallium source with edge size~150nm and the exposure of { 111 } face（Fig. 1）'s
Octahedra ZnGa2O4.ZnGa with average edge length~100nm and the exposure of { 100 } face2O4Cubic block nanoparticle is oil
(Fig. 1) that amine and water as solvent synthesize under hydro-thermal process.
X-ray diffraction（XRD）Gallic acid zinc of the diffraction maximum of these three crystal of collection of illustrative plates display gained all with Emission in Cubic
The diffraction maximum of (JCPDS 38-1240, space group Fd3m (227)) corresponds, and lattice constant isα=β=
γ=90 ° (referring to Fig. 3).The ZnO and Ga easily occurred in other preparation methods is not observed in figure2O3Dephasign diffraction maximum is deposited
Illustrating that preparation method described herein can synthesize the required gallic acid zinc crystal of complete pure phase.Referring to Fig. 3, based on piece
The diffraction maximum of the gallic acid zinc micron bouquet of shape gallic acid zinc crystal is wider, and this shows the gallic acid zinc crystal at least in a dimension
With less particle size, this is consistent with the result that FE-SEM is observed.Compared with standard card, in the diffraction maximum (220)
The ratio of crystal face intensity and (111) and (400) crystal face intensity significantly increases, and this illustrates sheet gallic acid zinc crystal along { 110 } face
Preferential growth.Referring to Fig. 6, narrow scan XPS collection of illustrative plates also demonstrates Zn, Ga, O presence.
CO2Photocatalytic conversion
Embodiment 4
It is 4.2cm that the gallic acid zinc crystal photochemical catalyst that 0.1g embodiments 1,2 and 3 obtain is dispersed in into area respectively2
Glass reactor on, using 300W xenon lamp as light source, the volume about 230mL of whole reaction system.Before the reaction, will react
Air in device is fully drawn out, and the pressure of high-purity Ar gas control reative cell is imported, after repetition is processed as several times, by high-purity
It is chamber pressure that carbon dioxide, which is passed through and made the pressure of reaction unit,.0.4mL secondary deionized waters are injected into reaction system
As reducing agent, the absorption of half-light saturation is several as a child to turn on light, during light-catalyzed reaction, at interval of a period of time from reative cell
About 0.5mL gas is taken to be injected into gas chromatograph（GC-14B, Japanese Shimadzu Corporation）Middle analysis product.
The micrometer/nanometer level gallic acid zinc crystal obtained herein can act as sewage disposal, water decomposition hydrogen manufacturing and photocatalysis CO2
The important catalyst of reduction.Figure 10 is the three kinds of gallic acid zinc photochemical catalyst photo catalytic reductions with different faces exposure obtained herein
The amount of carbon dioxide production methane and the graph of a relation of time, wherein Figure 10 (a) are cubic block gallic acid zinc crystal；Figure 10 (b) is eight
Face body gallic acid zinc crystal；Figure 10 (c) is sheet gallic acid zinc crystal or the gallic acid zinc micro-flowers obtained based on sheet gallic acid zinc crystal
Ball.Gallic acid zinc micron bouquet based on the assembling of sheet gallic acid zinc crystal in photocatalytic reduction of carbon oxide, the yield of methane with
The increase of light application time and increase, as a child, it is 8.3 μm of ol to obtain methane content for continuous illumination 12, equivalent to CH4Generation speed
Spend for 0.69 μm of ol/gh.Do not have illumination or without photochemical catalyst in the presence of reduce carbon dioxide, as a result show not
There is the generation of methane, this proves that the generation of methane is obtained under illumination condition by photochemical catalyst reduction carbon dioxide.
The photocatalysis carbon dioxide reduction activity in gallic acid zinc (100), (111) and (110) face uses density functional theory
(DFT) calculated.Structure after the optimization of these three faces is as shown in figure 11.（100）On face, outermost gallium Atomic coordinate number
For 5, the zinc atom that ligancy is 4 in the second layer is also exposed.（111）On face, the atom being exposed mainly is coordinated
The oxygen atom that number is 3 zinc atom and ligancy is 3.It is generally believed that compared with the low face of unsaturated coordination atom number percentage,
With the high face of unsaturated coordination atom percentage generally with higher reactivity, because these unsaturations of surface are matched somebody with somebody
The positive ion density of position is respectively 5.84atoms nm-2、3.37atoms nm-2With 8.26atoms nm-2。
In addition, unique three-dimensional crystalline structure is also beneficial to promote photocatalysis performance.Ultra-thin sheet gallic acid zinc nanocrystalline
Body possesses about ~ 55.5m2/ g high-specific surface area, it is 5.5 times of cubic block and octahedra particle；Nanometer sheet is super in micro-flowers
Thin structure is also beneficial to carrier and light-catalyzed reaction is quickly participated in from internal migration to surface；Three-dimensional hierarchical structure promotes light
Scattering, be advantageous to strengthen the absorption of light.
Computational methods:
Density functional technology herein, uses VASP（Vienna ab initio Simulation Packabe）Material
Expect the PBE functionals of simulation softward.VASP is to utilize pseudo potential and plane wave base figure based on density functional theory, carries out from the beginning two word power
The software kit of credit subdynamics technology.PBE functionals are at present most popular exchange-correlation energies in solid structure calculating
Form.The interaction of ion and electronics is using projection enhancing plane wave（PAW）Method describes.
It is spaced about between k pointsUsed in calculating（1×1）Surface Yuan Bao is used as clean surface, the first cloth
Li Yuan areas be 6 × 6 × 1 gamma dot grid.（110）、（100）、（111）When surface small molecule absorption calculates, use（1
×2）,（2×2）,（2×2）Super bag, corresponding k point values are respectively 4 × 3 × 1,3 × 3 × 1 very 3 × 3 × 1.The receipts of gross energy
Hold back standard 10-4EV, interatomic interaction force convergence areIn whole calculating, plane wave cut-off energy
It is set to 350eV.
If CO2/H2O is adsorbed onto on clean surface, and energy of adsorption is calculated using equation below：
Eads=Eslab(ZnGa2O4)+Emol(CO2/H2O)-Eslab(ZnGa2O4+CO2)
Wherein Eslab（ZnGa2O4+CO2）It is Planar adsorbent CO2Gross energy;Eslab（ZnGa2O4）And Emol（CO2/
H2O）ZnGa is represented respectively2O4The energy of plane and single gas phase carbon dioxide molecule.Work as CO2It is adsorbed onto containing a hydrogen atom
Surface on when, its energy of adsorption is defined as：
Eads=Eslab(ZnGa2O4+H)+Emol(CO2)-Eslab(ZnGa2O4+H+CO2)
The density of states using density functional theory to gallic acid zinc（DOS）Calculated, as a result as shown in figure 12.From figure
As can be seen that the valence band close to fermi level is mainly determined by O 2p and Zn 3d states, and conduction band bottom is then mainly by the spy of gallium and oxygen
State is levied to determine.The band gap magnitude being calculated is about 2.71eV, is coincide with the calculated results of other reports, general band gap magnitude meter
It is all smaller than actual value to calculate result.For（100）、（111）With（110）Three crystal faces, the band gap magnitude of calculating be respectively 2.05eV,
2.45eV and 1.70eV.It is generally acknowledged that the first step of carbon dioxide photo catalytic reduction be oxide surface formed carbon dioxide-
Exciton.The surface that work content represents object loses minimum energy needed for an electronics, so the structure that a work content is small
It is easier to make carbon dioxide activation.For these three crystal faces of gallic acid zinc, the size order of work content is followed successively by (110) (3.7eV)<
(100)(6.5eV)<(111)(6.9eV).So in these three crystal faces, (110) are the high activities of carbon dioxide photo catalytic reduction
Surface.
By above example, applicant demonstrates the synthesis side of micrometer/nanometer level gallic acid zinc crystal in a manner of enumerating
Method and resulting gallic acid zinc crystal, and give the synthetic method for example with solvent heat route.But this area is common
Technical staff should it will be appreciated that：The application content claimed is not limited to above-described embodiment, and the application is required to be protected
The scope of shield is as shown in the application claims.This area can commonly change experiment condition and feature on this basis, and
Obtain technical scheme claimed in the application Claims scope.
Claims (16)
1. a kind of gallic acid zinc crystal of micrometer/nanometer level, including sheet gallic acid zinc crystal, wherein the sheet gallic acid zinc crystal
{ 110 } face exposes.
2. gallic acid zinc crystal according to claim 1, wherein crystal face exposure more than 80%.
3. gallic acid zinc crystal according to claim 2, wherein crystal face exposure more than 90%.
4. gallic acid zinc crystal according to claim 2, wherein crystal face exposure more than 95%.
5. gallic acid zinc crystal according to claim 2, wherein crystal face exposure more than 99%.
6. gallic acid zinc crystal according to claim 1, wherein the thickness of the crystalline wafer of the sheet gallic acid zinc crystal is less than 10nm.
7. gallic acid zinc crystal according to claim 6, wherein the thickness of the crystalline wafer of the sheet gallic acid zinc crystal is less than 8nm.
8. gallic acid zinc crystal according to claim 6, wherein the thickness of the crystalline wafer of the sheet gallic acid zinc crystal is less than 6nm.
9. gallic acid zinc crystal according to claim 1, wherein the sheet gallic acid zinc crystal exists in the form of flower-shaped spheroid.
10. a kind of method for the micrometer/nanometer level gallic acid zinc crystal for preparing any one of claim 1-9, including
Gallium salt and zinc salt are added in solvent and form mixed solution, wherein the solvent is selected from C1-C18 organic monos amine or two
First amine, water or its mixture；
By the mixed solution in 150-240 DEG C of solvent thermal reaction；With
Reacted mixed solution is cooled down to separate out crystal.
11. method according to claim 10, wherein the gallium salt is selected from gallium nitrate, gallium chloride, gallium sulfate and gallium oxide；It is described
Zinc salt is selected from zinc nitrate, zinc acetate, zinc sulfate and zinc oxide.
12. according to the method for claim 10 or 11, wherein the gallium salt：In zinc salt [gallium]：The mol ratio of [zinc] is less than 4:
1, and [gallium]：The mol ratio of [zinc] is more than 1:1.
13. method according to claim 12, wherein the gallium salt：In zinc salt [gallium]：The mol ratio of [zinc] is less than or equal to 3:1.
14. method according to claim 12, wherein the gallium salt：In zinc salt [gallium]：The mol ratio of [zinc] is equal to 2:1.
15. method according to claim 10, including
It is dissolved in after gallium salt is mixed with zinc salt in the solvent comprising ethylenediamine, forms mixed solution；
By the mixed solution under the conditions of 180 DEG C -240 DEG C solvent thermal reaction, formed mixture；
The mixture is cooled to room temperature；With
Separate out sheet gallic acid zinc crystal.
16. method according to claim 15, wherein the mixed solution carries out solvent thermal reaction 24-30 hours.
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