CN106215942B - 一种掺杂了过渡金属或稀土金属的盘状氧化锌的可控合成方法 - Google Patents
一种掺杂了过渡金属或稀土金属的盘状氧化锌的可控合成方法 Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 200
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 99
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 13
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 12
- 238000001308 synthesis method Methods 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 18
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004246 zinc acetate Substances 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
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- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000008033 biological extinction Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
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- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 235000014692 zinc oxide Nutrition 0.000 description 86
- 229960001296 zinc oxide Drugs 0.000 description 76
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 11
- 229910052684 Cerium Inorganic materials 0.000 description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 238000005253 cladding Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000005291 magnetic effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229960004011 methenamine Drugs 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- HRXZUGNDGULQSA-UHFFFAOYSA-N acetic acid;cerium Chemical compound [Ce].CC(O)=O.CC(O)=O.CC(O)=O HRXZUGNDGULQSA-UHFFFAOYSA-N 0.000 description 1
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/39—Photocatalytic properties
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
本发明公开了一种掺杂了过渡金属或稀土金属的盘状氧化锌的可控合成方法。该方法包括如下步骤:在温度为85℃~95℃下,以醋酸锌和六亚甲基四胺为原料,加入不同的金属盐,合成不同金属掺杂的盘状氧化锌。所述金属掺杂的盘状氧化锌的粒径在0.5~6.5um,厚度在0.2~3.75um可控调变。最后的溶液中,掺杂的金属与醋酸锌的摩尔浓度比为0.5%~4.3%。该发明方法实现了金属掺杂的同时调控盘状氧化锌的尺寸、厚薄,从而调节氧化锌的禁带宽度、吸光性质、发光性质以及氧空位的种类和数量。此外,该发明方法具有造价低廉,反应条件温和,颗粒均一,能耗小,工艺简单,可控性好,可大面积合成且无污染,纯度高,物相分布均匀的优点,能够进行工业化生产。
Description
技术领域
本发明属于金属掺杂半导体微米材料制备领域,具体涉及一种过渡金属或稀土金属掺杂的微米盘状氧化锌的可控制备方法。
背景技术
氧化锌材料是一种重要的II-VI族直接带隙半导体材料,在室温下,它的禁带宽度为3.37ev,激子束缚能达60meV,具有较高的稳定性。由于它对可见光的高透过率,能用作透明导电涂层;具有光电效应,能用于紫外激光器件和太阳能电池等;具有热电和压电等效应,可以用作热敏和压敏器件。作为一种多功能材料,其多种特性使它在很多方面都有应用的潜力,例如在煤气脱硫、合成气制甲醇等传统的热催化、光催化、光电器件、气敏传感器、橡胶改性等领域研究应用广泛。此外,氧化锌的原材料在地球上含量丰富,价格相对低廉,更为重要的是它是一种对环境友好的材料,不会产生污染等问题,因而逐渐成为研究人员研究的热点。
文献报道Co掺杂时,氧化锌薄膜表现出对乙醛蒸气的良好的传感响应,这可以应用于乙醛蒸气的选择性检测(Shalini,S.,&Balamurugan,D.(2016).Ambient temperatureoperated acetaldehyde vapour detection of spray deposited cobalt doped zincoxide thin film.Journal Of Colloid And Interface Science,466,352-359.doi:10.1016/j.jcis.2015.12.044);碱土金属离子镁掺杂会使氧化锌的带隙宽增加,在 500–600nm范围内,还会使其吸光率与反射率下降,因为镁的2p能级被激发了 (Si,X.,Liu,Y.,Lei,W.,Xu,J.,Du,W.,Lin,J.,...Zheng,L.(2016).First-principles investigation onthe optoelectronic performance of Mg doped and Mg-Al co-doped ZnO.Materials&Design,93,128-132.doi:10.1016/j.matdes.2015.12.033);Na掺杂使Zn产生局部磁矩,能够有效地稳定ZnO薄膜中由于阳离子缺陷引起的室温铁磁性,这可以成为制备氧化锌高温磁性半导体的方法(Ghosh, GobindaGopalKhan,ShikhaVarma et al.Influence of FilmThickness and Oxygen Partial Pressure on Cation-Defect-Induced IntrinsicFerromagnetic Behavior in Luminescent p-Type Na-Doped ZnO Thin Films[J].ACSapplied materials&;interfaces,2013,5(7):2455-2461.);Al掺杂会使ZnO的电导率提高几个数量级,可作为一种典型的透明导电氧化物(TCO)材料(华南理工大学.一种高电导率铝掺杂氧化锌纳米粉体的制备方法:中国,CN201310461981.5[P].2014-1-8.);Mn等材料掺杂的ZnO,具有磁性(自旋),以及半导体性能,可作为稀磁半导体材料,在信息技术领域有广泛应用(Varshney,D.,&Dwivedi,S.(2016).Structure, morphology,optical andmagnetic response of ZnO,Mn3O4and doped Zn0.5Mn0.5O nanoparticles as-synthesized using a chemical co-precipitation method.Semiconductor ScienceAnd Technology,31(3).doi:10.1088/0268-1242/31/3/035017);铈掺杂的氧化锌具有较高的气体灵敏度(Renganathan,B.,Sastikumar,D.,Gobi,G.,Yogamalar, N.R.,&Bose,A.C.(2011).Gas sensing properties of a clad modified fiber optic sensor withCe,Li and Al doped nanocrystalline zinc oxides.Sensors And Actuators B-Chemical,156(1),263-270.doi:10.1016/j.snb.2011.04.031)。ZnO中掺入铜元素将导致无辐射跃迁的增强,所以铜掺杂降低了ZnO薄膜的发光效率,具有明显的发光猝灭效应(何静芳,郑树凯,周鹏力,史茹倩,闫小兵.Cu-Co共掺杂ZnO光电性质的第一性原理计算[J].物理学报,2014,(04):251-257.);因此,过渡金属及稀土金属掺杂可有效调变氧化锌的磁学与光学性质。
氧化锌晶体具有极性表面,这种极性面具有相对较高的表面能,因此在氧化锌的不同晶面上存在着这种晶面生长速度的差异,导致最终形成不同的氧化锌晶体形貌,而不同形貌的纳米氧化锌暴露在外的极性面与非极性面的比例并不相同,会极大地影响氧化锌的特性和应用。盘状氧化锌是通过抑制氧化锌的极性表面的生长而形成的,这样可以使其极性表面的面积尽量大。这样的特性对于一些反应的催化效率会有显著的优势,比如:负载铜锌催化剂的盘状氧化锌可以作为合成甲醇的催化剂,催化活性结果表明,此类催化剂在二氧化碳催化氢化合成甲醇的有机催化反应中,甲醇选择性达到70%以上(赵晓晓,高志华,郝树宏,黄伟.不同形貌纳米氧化锌的制备及其对有机催化反应活性的影响研究进展[J].化工进展,2014,(S1):210-215.)。因此,提出发展过渡金属及稀土金属掺杂盘状氧化锌的可控合成方法。
然而到目前为止,盘状氧化锌的掺杂方法主要是后掺杂法,即先制备盘状氧化锌然后再进行金属掺杂,该方法不仅耗时耗力,也给合成过程增加了难度。同时,由于氧化锌是两性物质,在后掺杂过程中盘状氧化锌的形貌难以保持。
有鉴于此,我们采用在水热合成盘状氧化锌的过程中直接掺入不同的金属,并对其尺寸厚薄进行控制,同时实现了对其禁带宽度、吸光性质、发光性质以及氧空位的种类和数量等性质的调变。
发明内容
本发明的目的在于提供一种低成本、无污染、不需高温、以及大规模制备掺杂了过渡金属或稀土金属的盘状氧化锌的水热可控合成方法。为了实现本发明的目的,采用如下的技术方案:
在温度为85℃~95℃下,以醋酸锌和六亚甲基四胺为基础原料,分别加入不同种类及浓度的金属盐,水热合成不同金属掺杂的盘状氧化锌。
一种掺杂了过渡金属或稀土金属的盘状氧化锌的可控合成方法,该方法包括如下步骤:
1)配置前驱体溶液:用去离子水溶解醋酸锌与金属掺杂前驱体,并加入六亚甲基四胺,搅拌溶解,混合均匀,得到混合溶液;
2)水热合成:将步骤1)配制好的混合溶液置于反应釜或者密闭的烧杯中,并放入水热合成烘箱,反应结束后,取出反应容器,进行骤冷至室温;
3)离心干燥:倒出反应后的上层液体且留下附着在反应釜或烧杯底部的白色沉淀物,用去离子水和乙醇依次对沉淀物进行离心洗涤,最后在温度为55~75℃的烘箱中烘干,即得到金属掺杂的盘状氧化锌。
进一步地,步骤1)中最终得到的溶液中,所述醋酸锌浓度为0.23~0.76mol/L,六亚甲基四胺浓度为0.04~0.76mol/1。
进一步地,步骤1)中最终得到的溶液中,掺杂的金属离子与醋酸锌的摩尔浓度比为0.5%~4.3%。
进一步地,步骤1)中最终得到的溶液中,所述醋酸锌与六亚甲基四胺的摩尔浓度比例为1:1~12:1。
进一步地,所述金属掺杂前驱体为包括钴、铜、镧及铈在内的过渡金属或稀土金属的醋酸盐或硝酸盐中的至少一种。
进一步地,步骤2)中所述水热合成烘箱设置的反应温度为85℃~95℃,反应时间为5h~17h。
进一步地,所述金属掺杂的盘状氧化锌的粒径在0.5~6.5um,厚度在 0.2~3.75um可控调变;升高水热合成的温度,盘状氧化锌的厚度会增大;掺杂不同金属盐及增加掺杂量,盘状氧化锌的粒径或厚度会降低;但是过高的掺杂量会破坏盘状氧化锌的结构。
与现有技术相比,本发明具有以下优点:
(1)本发明实现了在合成氧化锌的同时掺杂不同含量、不同种类的金属,解决了微米级氧化锌在应用中成本高以及不可控性制备等问题。
(2)本发明方法只采用了两种化学试剂,没有添加任何活性剂或者有机物,不需高温,成本低且合成的微米氧化锌纯度较高。
(3)本发明制备的氧化锌催化剂由片状六边形组成,实现了金属掺杂的同时调控盘状氧化锌的尺寸、厚薄,暴露较高比例极性面,在甲醇合成等热催化、光催化、光电器件、气敏传感器、化学传感器、以及光存储等方面有着巨大的应用前景。
附图说明
图1a为实施例1无金属掺杂的盘状氧化锌扫描电镜照片;
图1b为实施例1铜掺杂的盘状氧化锌扫描电镜照片;
图2a为实施例2无金属掺杂的盘状氧化锌的扫描电镜照片;
图2b为实施例2镧掺杂的盘状氧化锌的扫描电镜照片;
图2c为实施例2铈掺杂的盘状氧化锌的扫描电镜照片;
图3a为实施例3无金属掺杂的盘状氧化锌的扫描电镜照片;
图3b为实施例3钴掺杂的盘状氧化锌的扫描电镜照片;
图3c为实施例3镧掺杂的盘状氧化锌的扫描电镜照片;
图3d为实施例3铈掺杂的盘状氧化锌的扫描电镜照片;
图4a为实施例4无金属掺杂的盘状氧化锌的扫描电镜照片;
图4b为实施例4镧掺杂的盘状氧化锌的扫描电镜照片;
图5a为实施例5无金属掺杂的盘状氧化锌的扫描电镜照片;
图5b为实施例5铜掺杂的盘状氧化锌的扫描电镜照片;
图6a为实施例6无金属掺杂的盘状氧化锌的扫描电镜照片;
图6b为实施例6钴掺杂的盘状氧化锌的扫描电镜照片;
图6c为实施例6铈掺杂的盘状氧化锌的扫描电镜照片;
具体实施方式
下面具体实施例只是进一步说明本发明是如何实现的,而不限制本发明的范围。
实施例1
1)配置前驱体溶液:用70ml去离子水溶解6.3g醋酸锌与0.05g醋酸铜粉末,并加入0.4g的六亚甲基四胺,搅拌溶解,混合均匀得到混合溶液;
2)水热合成:将步骤1)配制好的混合溶液置于反应釜中,放入温度为85℃的干燥烘箱且加热17小时后,取出反应釜,并进行骤冷至室温;
3)离心干燥:倒出反应后的上层液体,留下附着在反应釜底部的白色沉淀物,将所得沉淀物用去离子水洗涤离心三次,用酒精洗涤离心一次,最后60℃烘干,即得到金属铜掺杂的盘状氧化锌。
无金属掺杂的盘状氧化锌与所得金属铜掺杂的盘状氧化锌的扫描电镜照片分别如图1a、图1b所示。
实施例2
1)配置前驱体溶液:用70ml去离子水溶解3g醋酸锌与0.1g硝酸镧(或0.12g 醋酸铈),加入1.2g六亚甲基四胺,搅拌溶解,混合均匀得到混合溶液;
2)水热合成:将步骤1)配制好的混合溶液置于反应釜中,放入温度为95℃的干燥烘箱且加热5小时后,取出反应釜,并进行骤冷至室温;
3)离心干燥:倒出反应后的上层液体,留下附着在反应釜底部的白色沉淀物,将沉淀物用去离子水洗涤离心三次,用酒精洗涤离心一次,最后55℃烘干,即得金属镧掺杂的盘状氧化锌(或金属铈掺杂的盘状氧化锌)。
无金属掺杂的盘状氧化锌与所得金属镧掺杂的盘状氧化锌、金属铈掺杂的盘状氧化锌的扫描电镜照片分别如图2a、图2b、图2c所示。
实施例3
1)配置前驱体溶液:用70ml去离子水分别溶解4.2g醋酸锌与0.07g的硝酸钴(或0.1g硝酸镧,或0.08g醋酸铈),加入1.6g六亚甲基四胺,搅拌溶解,混合均匀得到混合溶液;
2)水热合成:将步骤1)配制好的混合溶液置于反应釜中,放入温度为95℃的干燥烘箱且加热5小时后,取出反应釜,进行骤冷至室温;
3)离心干燥:倒出反应后的上层液体,留下附着在反应釜底部的白色沉淀物,将所得沉淀物用去离子水洗涤离心三次,用酒精洗涤离心一次,最后60℃烘干,即得金属钴掺杂的盘状氧化锌(或金属镧掺杂的盘状氧化锌,或金属铈掺杂的盘状氧化锌)。
无金属掺杂的盘状氧化锌与所得金属钴掺杂的盘状氧化锌、金属镧掺杂的盘状氧化锌、金属铈掺杂的盘状氧化锌的扫描电镜照片分别如图3a、图3b、图3c、图3d所示。
实施例4
1)配置前驱体溶液:用60ml去离子水溶解8.4g醋酸锌与0.1g硝酸镧,加入6.4g六亚甲基四胺,搅拌溶解,混合均匀得到混合溶液;
2)水热合成:将步骤1)配制好的混合溶液置于反应釜中,放入温度为95℃的干燥烘箱且加热5小时后,取出反应釜,进行骤冷至室温;
3)离心干燥:倒出反应后的上层液体,留下附着在反应釜底部的白色沉淀物,将所得沉淀物用去离子水洗涤离心三次,用酒精洗涤离心一次,最后60℃烘干,即得金属镧掺杂的盘状氧化锌。
无金属掺杂的盘状氧化锌与所得金属镧掺杂的盘状氧化锌的扫描电镜照片分别如图4a、图4b所示。
实施例5
1)配置前驱体溶液:用70ml去离子水分别溶解4.2g醋酸锌与0.2g的醋酸铜,加入1.6g六亚甲基四胺,搅拌溶解,混合均匀得到混合溶液;
2)水热合成:将步骤1)配制好的混合溶液置于反应釜中,放入温度为85℃的干燥烘箱且加热17小时后,取出反应釜,进行骤冷至室温;
3)离心干燥:倒出反应后的上层液体,留下附着在反应釜底部的白色沉淀物,将所得沉淀物用去离子水洗涤离心三次,用酒精洗涤离心一次,最后60℃烘干,即得金属铜掺杂的盘状氧化锌。
无金属掺杂的盘状氧化锌与所得金属铜掺杂的盘状氧化锌的扫描电镜照片分别如图5a、图5b所示。
实施例6
1)配置前驱体溶液:用70ml去离子水分别溶解4.2g醋酸锌与0.07g的硝酸钴(或0.08g醋酸铈),加入1.6g六亚甲基四胺,搅拌溶解,混合均匀得到混合溶液;
2)水热合成:将步骤1)配制好的混合溶液置于反应釜中,放入温度为90℃的干燥烘箱且加热14小时后,取出反应釜,进行骤冷至室温;
3)离心干燥:倒出反应后的上层液体,留下附着在反应釜底部的白色沉淀物,将所得沉淀物用去离子水洗涤离心三次,用酒精洗涤离心一次,最后75℃烘干,即得金属铜掺杂的盘状氧化锌。
无金属掺杂的盘状氧化锌与所得金属钴掺杂的盘状氧化锌、金属铈掺杂的盘状氧化锌的扫描电镜照片分别如图6a、图6b、图6c所示。
实施例1~6的制备条件及得到的产品形貌的如表1所示。
表1 样品制备条件及形貌
由表1可知,得到的金属掺杂的盘状氧化锌的粒径在0.5~6.5um,厚度在 0.2~3.75um可控调变;升高水热合成的温度,金属掺杂的盘状氧化锌的厚度会增大;掺杂不同金属盐及增加掺杂量,盘状氧化锌的粒径或厚度会降低;但是过高的掺杂量会破坏盘状氧化锌的结构。
Claims (3)
1.一种掺杂了过渡金属或稀土金属的盘状氧化锌的可控合成方法,其特征在于,包括如下步骤:
1)配置前驱体溶液:用去离子水溶解醋酸锌与金属掺杂前驱体,并加入六亚甲基四胺,搅拌溶解,混合均匀,得到混合溶液;最终得到的溶液中,所述醋酸锌浓度为0.23~0.76mol/L,六亚甲基四胺浓度为0.04~0.76mol/L,所述醋酸锌与六亚甲基四胺的摩尔浓度比例为1:1~12:1;所述金属掺杂前驱体为包括钴、铜、镧及铈在内的过渡金属或稀土金属的醋酸盐或硝酸盐中的至少一种;
2)水热合成:将步骤1)配制好的混合溶液置于反应釜或者密闭的烧杯中,并放入水热合成烘箱中,反应结束后,取出反应容器,进行骤冷至室温;所述水热合成烘箱设置的反应温度为85℃~95℃,反应时间为5h~17h;
3)离心干燥:倒出反应后的上层液体且留下附着在反应釜或烧杯底部的白色沉淀物,用去离子水和乙醇依次对沉淀物进行离心洗涤,最后在温度为55~75℃的烘箱中烘干,即得到金属掺杂的盘状氧化锌。
2.根据权利要求1所述的一种掺杂了过渡金属或稀土金属的盘状氧化锌的可控合成方法,其特征在于,步骤1)中最终得到的溶液中,掺杂的金属离子与醋酸锌的摩尔浓度比为0.5%~4.3%。
3.根据权利要求1所述的一种掺杂了过渡金属或稀土金属的盘状氧化锌的可控合成方法,其特征在于,所述金属掺杂的盘状氧化锌的粒径在0.5~6.5um,厚度在0.2~3.75um可控调变;升高水热合成的温度,盘状氧化锌的厚度会增大;掺杂不同金属盐及增加掺杂量,盘状氧化锌的粒径或厚度会降低;但是过高的掺杂量会破坏盘状氧化锌的结构。
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