CN106866181B - 一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法 - Google Patents
一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法 Download PDFInfo
- Publication number
- CN106866181B CN106866181B CN201710095842.3A CN201710095842A CN106866181B CN 106866181 B CN106866181 B CN 106866181B CN 201710095842 A CN201710095842 A CN 201710095842A CN 106866181 B CN106866181 B CN 106866181B
- Authority
- CN
- China
- Prior art keywords
- ceramic tube
- iron oxide
- hydrothermal reaction
- nanoneedle
- sea urchin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 42
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 22
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 96
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 16
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 16
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 20
- 229910001887 tin oxide Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 239000010931 gold Substances 0.000 claims description 11
- 239000011206 ternary composite Substances 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 238000005240 physical vapour deposition Methods 0.000 claims description 2
- 238000004549 pulsed laser deposition Methods 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 239000013078 crystal Substances 0.000 description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 239000002086 nanomaterial Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 229960002089 ferrous chloride Drugs 0.000 description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 241000257465 Echinoidea Species 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5036—Ferrites
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
- C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
本发明涉及一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法，属于纳米传感器的制备技术领域。本发明的方法，包括以下步骤：（1）将陶瓷管置于氯化铁和硫酸钠的混合溶液中，进行水热反应；（2）水热反应完成后，将陶瓷管在马弗炉中进行退火处理。本发明制备出海胆状Fe2O3纳米针的关键在于水热反应温度和水热反应时间的控制。首次公开了在氧化铝陶瓷管上原位生长海胆状氧化铁纳米针的方法。本发明的方法，无需事先制备出涂覆法所需粉末，无需手工涂覆；而是在氧化铝陶瓷管上直接生长出海胆状氧化铁纳米针。海胆状氧化铁纳米针的制备过程也是气敏陶瓷管的制备过程；步骤简单、耗时短；简化了传统气敏陶瓷管的制备工艺，省时省力，节约成本。
Description
技术领域
本发明涉及一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法，属于纳米传感器的制备技术领域。
背景技术
随着人类科技和工业社会的发展，各种易燃、有毒有害气体的应用越来越广泛。由于我们人类自身感知范围的局限性，对这些有毒有害气体的种类及浓度定量没有判断能力。因此，如何对这些气体作出快速而准确地检测变得尤为重要。
Fe2O3材料是一种n型半导体材料，它的禁带宽度较窄（Eg=2.2 eV），并且具有良好的稳定性，因此可以作为气敏材料。当前，人们已经掌握了采用不同物理、化学方法制备出不同形貌的Fe2O3纳米材料，例如：粒状、棒状、环状、针状、核壳状、空心球状、雪花状、海胆状、螺旋状等。而氧化铁材料的气敏机理为表面电阻型，与气体的响应过程主要是发生在材料的表面。即所制备的氧化铁材料的比表面积越大，其气敏性能越出色。与传统的氧化铁平面薄膜材料相比较，具有良好一维形貌的Fe2O3纳米针材料无疑具有更大的比表面积，所以在气敏传感器领域更加具有应用价值。
目前，以氧化铝陶瓷管为衬底的气敏元件的制备方法包括以下几种：粉末涂覆法和籽晶层辅助生长法；其中较为先进的方法是：首先在氧化铝陶瓷管的表面形成籽晶层，然后在籽晶层的辅助下在籽晶层表面生长纳米材料。但是这种先形成籽晶层再生长纳米材料的方法仍然存在以下有待改进的地方：1）籽晶层溶液的配制需要较繁琐的步骤，且一般还需静置12 h以上；2）籽晶层覆盖到氧化铝陶瓷管表面上后，还需在空气中自然晾干12 h以上。
发明内容
本发明的目的在于提供一种直接生长于陶瓷管的海胆状氧化铁纳米针的新的制备方法。
技术方案
一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法，包括以下步骤：
（1）将陶瓷管置于氯化铁和硫酸钠的混合溶液中，进行水热反应；所述氯化铁和硫酸钠的混合溶液，氯化铁和硫酸钠的浓度均为0.05mol/L；水热反应温度为140℃，水热反应时间为6-8h；
（2）水热反应完成后，将陶瓷管在马弗炉中进行退火处理；退火条件为：以3-4℃/min的速率升温至600-700℃，保温1.5-2.5h，然后自然冷却至室温。
本发明的方法：
首先，与“先在氧化铝陶瓷管的表面形成籽晶层，然后再在籽晶层表面生长纳米材料”的现有方法相比，本发明是直接在氧化铝陶瓷管表面上生长出氧化铁纳米针，并不需要“在氧化铝陶瓷管的表面形成籽晶层”的步骤；更加简单。
其次，本发明实现在陶瓷管上原位生长Fe2O3纳米针的关键之处在于，采用0.05mol/L的硫酸钠溶液和0.05 mol/L的氯化铁溶液作为反应原料，及水热反应条件的控制。本发明通过实验研究发现，采用相同浓度的氯化亚铁或硝酸铁溶液代替氯化铁溶液，均无法获得本发明的“纳米针”形貌。由此可见，虽然氯化铁、氯化亚铁和硝酸铁均为常见铁源，而且在水热反应中通常可以相互替换，但是，在本发明中却超出了预期、产生了完全不同的技术效果。而采用本发明水热条件以外的温度、时间条件，或者无法获得本发明的“纳米针”形貌，或者会导致电极丝发生脱落。例如，当水热温度为155℃时，电极丝发生脱落；而在通常情况下，155℃的温度不会导致电极丝脱落。因此，低于155℃的温度条件同样在本发明中超出本领域技术人员的预期、产生防止电极丝脱落的技术效果。
再次，本发明制备出海胆状Fe2O3纳米针的关键在于水热反应温度和水热反应时间的控制；虽然在“水热反应温度为125-155℃，不包含155℃，水热反应时间为6-18h”的条件下，均能制备出Fe2O3纳米针；但是，只有在“水热反应温度为140℃，水热反应时间为6-8h”的条件下才能获得海胆状Fe2O3纳米针；水热反应温度过高或过低、反应时间过长，均无法获得海胆状Fe2O3纳米针。
上述方法，为了在氧化铝陶瓷管上获得生长形貌良好的氧化铁，优选的，陶瓷管在使用之前用丙酮、乙醇分别超声30 min。
本发明还提供了一种采用上述方法制备的表面生长有海胆状Fe2O3纳米针的氧化铝陶瓷管。其中，氧化铝陶瓷管的尺寸，可以根据具体生产需要进行确定；例如，长度为4mm，内径1 mm，外径1.4 mm。
本发明还提供了一种氧化铁/氧化锡纳米针异质结陶瓷管，是利用脉冲激光沉积技术，在上述氧化铝陶瓷管的海胆状Fe2O3纳米针表面沉积n型半导体材料氧化锡而成。
本发明还提供了一种三元复合陶瓷管，是利用脉冲激光沉积技术和物理气相沉积技术，在上述的氧化锡/氧化铁纳米针异质结陶瓷管的异质结表面溅射金颗粒而成。
本发明还提供了一种采用上述陶瓷管制备的气敏传感器。该气敏传感器可应用于有机气体的检测，包括乙醇、异丙醇、丙酮、笨、对二甲苯、三乙胺等有机气体。该气敏传感器，其氧化铝陶瓷管两端集成金电极，金电极之间相距2 mm，金电极上集成四根铂导线。
有益效果
首次公开了在氧化铝陶瓷管上原位生长海胆状氧化铁纳米针的方法。本发明的方法，无需事先制备出涂覆法所需粉末，无需手工涂覆；而是在氧化铝陶瓷管上直接生长出海胆状氧化铁纳米针。海胆状氧化铁纳米针的制备过程也是气敏陶瓷管的制备过程；步骤简单、耗时短；简化了传统气敏陶瓷管的制备工艺，省时省力，节约成本。
本发明所制备的原位生长于氧化铝陶瓷管的海胆状氧化铁纳米针形貌可控、纳米针结晶良好、分布均匀，纳米针长度约为100 nm，彼此相互连接形成网络。
本发明的氧化铁/氧化锡纳米针异质结传感器，能改善氧化铁纳米针的气敏性能；对三乙胺表现出较好的选择性，且对三乙胺的响应有所提高。
附图说明
图1为实施例1制备的原位生长于氧化铝陶瓷管的氧化铁纳米针的X射线衍射图谱；
图2为实施例1制备的原位生长于氧化铝陶瓷管的氧化铁纳米针的场发射扫描电镜图及EDS能量色散谱图；
图3为实施例1制备的气敏传感器的气敏性能图谱；
图4为实施例2的原位生长于氧化铝陶瓷管的氧化铁/氧化锡异质结扫描电镜图片；
图5为实施例2制备的原位生长于氧化铝陶瓷管的氧化铁/氧化锡/金三元复合纳米结构的扫描电镜图片；
图6为本发明制备的氧化铁/氧化锡异质结气敏传感器及氧化铁/氧化锡/金三元复合气敏传感器的气敏性能图；
图7为对比例1制备的原位生长于氧化铝陶瓷管的纳米氧化铁的场发射扫描电镜图片；
图8为对比例2制备的原位生长于氧化铝陶瓷管的纳米氧化铁的场发射扫描电镜图片。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述。
实施例 1
将氧化铝陶瓷管用丙酮、乙醇、去离子水分别超声30 min清洗干净，并烘干备用。将清洗干净的陶瓷管置入装有氯化铁和硫酸钠的混合溶液（混合溶液中，氯化铁和硫酸钠的浓度均为0.05 mol/L）高压反应釜中，于140℃下水热生长6 h，将生长过后的陶瓷管在马弗炉中进行以3℃ /min的速率升温至600℃并保温2 h退火处理，然后自然冷却至室温；即得原位生长于氧化铝陶瓷管的海胆状氧化铁纳米针。该氧化铁纳米针的X射线衍射图谱如图1所示；从图1可以看出，氧化铁纳米针结晶良好，无其它杂质存在。该氧化铁纳米针的扫描电镜如图2所示；从图2 可以看出，Fe2O3纳米针尺寸均一，纳米针结晶良好，呈海胆状。将表面生长有Fe2O3纳米针的氧化铝陶瓷管焊接成气敏传感器测试其气敏性能，如图3所示；从图3中可以看出，在最佳工作温度下，纯相Fe2O3纳米针对三乙胺的灵敏度可以达到27，且对三乙胺表现出较好的选择性。
实施例2
利用脉冲激光沉积技术在实施例1所制备的原位生长有氧化铁纳米针的陶瓷管的针状结构纳米氧化铁表面沉积n型半导体材料氧化锡，得氧化铁/氧化锡异质结陶瓷管；扫描电镜如图4。从图4可以看出氧化铁/氧化锡异质结的Fe2O3纳米针结构仍为海胆状，在其上明显存在SnO2颗粒。结合真空离子镀金镀碳仪在上述制备的氧化铁/氧化锡异质结陶瓷管的异质结表面溅射Au纳米颗粒，构筑氧化铁/氧化锡/Au三元复合气敏材料，其扫描电镜如图5所示。从图5可以看出Fe2O3纳米针结构仍为海胆状。分别将氧化铁/氧化锡异质结陶瓷管、氧化铁/氧化锡/Au三元复合陶瓷管焊接成气敏传感器测试其气敏性能，如图6所示。从图6中可以看出，氧化铁/氧化锡气敏元件及氧化铁/氧化锡/金三元复合气敏元件的的气敏性能逐次提升，三元复合气敏元件对三乙胺响应值达到38，且都对三乙胺表现出最好的选择性。
实施例3-6
采用实施例1的方法步骤，采用下表中的参数，其他参数同实施例1；
表中，参数A：水热生长温度；
参数B：水热生长时间；
实施例3、4、5所制备的原位生长于氧化铝陶瓷管的纳米氧化铁的场发射扫描电镜图片如图7所示；
实施例6所制备的原位生长于氧化铝陶瓷管的纳米氧化铁的电极丝发生脱落。
对比例1
将氧化铝陶瓷管用丙酮、乙醇、去离子水分别超声30 min清洗干净，并烘干备用。将清洗干净的陶瓷管置入装有氯化亚铁和硫酸钠的混合溶液（混合溶液中，氯化亚铁和硫酸钠的浓度均为0.05 mol/L）高压反应釜中，于140℃下水热生长12 h，然后将生长过后的陶瓷管在马弗炉中进行以3℃ /min的速率升温至600℃保温2 h的退火处理，然后自然冷却至室温；即得到原位生长于氧化铝陶瓷管的纳米氧化铁。该纳米氧化铁的扫描电镜如图7所示；从图7 可以看出，以氯化亚铁为铁源制备的样品，表面没有特定的纳米材料形貌，更没有海胆状纳米针结构。
对比例2
将氧化铝陶瓷管用丙酮、乙醇、去离子水分别超声30 min清洗干净，并烘干备用。将清洗干净的陶瓷管置入装有硝酸铁和硫酸钠的混合溶液（混合溶液中，硝酸铁和硫酸钠的浓度均为0.05 mol/L）高压反应釜中，于140℃下水热生长12 h，然后将生长过后的陶瓷管在马弗炉中进行以3℃/min的速率升温至600℃保温2 h的退火处理，然后自然冷却至室温；即得到原位生长于氧化铝陶瓷管的纳米氧化铁。该纳米氧化铁的扫描电镜如图8所示；从图8可以看出陶瓷管上生长着一层厚厚的类似纺锤体纳米结构，但这些纺锤体结构在衬底上堆积倒伏，分布不均，且取向杂乱。
对比例3
将玻璃基片用丙酮、乙醇、去离子水分别超声30 min清洗干净，并烘干备用。将清洗干净的玻璃基片置入装有氯化铁和硫酸钠的混合溶液（混合溶液中，氯化铁和硫酸钠的浓度均为0.05 mol/L）高压反应釜中，于140℃下水热生长12 h，然后将生长过后的玻璃基片在马弗炉中进行以3℃ /min的速率升温至600℃保温2 h的退火处理，然后自然冷却至室温。发现在玻璃基片上，很难生长出氧化铁纳米针结构。
Claims (6)
1.一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法，其特征在于，包括以下步骤：
（1）将陶瓷管置于氯化铁和硫酸钠的混合溶液中，进行水热反应；所述氯化铁和硫酸钠的混合溶液，氯化铁和硫酸钠的浓度均为0.05mol/L；水热反应温度为140℃，水热反应时间为6-8h；
（2）水热反应完成后，将陶瓷管在马弗炉中进行退火处理；退火条件为：以3-4℃/min的速率升温至600-700℃，保温1.5-2.5h，然后自然冷却至室温。
2.根据权利要求1所述方法，其特征在于，陶瓷管在使用之前用丙酮、乙醇分别超声30min。
3.一种采用权利要求1或2所述方法制备的表面生长有海胆状Fe2O3纳米针的氧化铝陶瓷管。
4.一种氧化铁/氧化锡纳米针异质结陶瓷管，其特征在于，是利用脉冲激光沉积技术，在权利要求3所述氧化铝陶瓷管的海胆状Fe2O3纳米针表面沉积n型半导体材料氧化锡而成。
5.一种三元复合陶瓷管，其特征在于，是利用脉冲激光沉积技术和物理气相沉积技术，在权利要求4所述的氧化锡/氧化铁纳米针异质结陶瓷管的异质结表面溅射金颗粒而成。
6.一种采用权利要求3、4或5所述陶瓷管制备的气敏传感器。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710095842.3A CN106866181B (zh) | 2017-02-22 | 2017-02-22 | 一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710095842.3A CN106866181B (zh) | 2017-02-22 | 2017-02-22 | 一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106866181A CN106866181A (zh) | 2017-06-20 |
| CN106866181B true CN106866181B (zh) | 2020-01-03 |
Family
ID=59167894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710095842.3A Active CN106866181B (zh) | 2017-02-22 | 2017-02-22 | 一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106866181B (zh) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475116A (zh) * | 2014-11-24 | 2015-04-01 | 中国人民解放军军械工程学院 | 二氧化锡纳米线修饰的三氧化二铁纳米棒阵列的制备方法 |
| CN105869908A (zh) * | 2016-05-25 | 2016-08-17 | 东华大学 | 核壳Co3O4@Fe2O3纳米线阵列的制备方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101466701B1 (ko) * | 2012-03-20 | 2014-11-28 | 고려대학교 산학협력단 | 다양한 나노 구조를 갖는 헤마타이트 산화철의 제조방법 |
-
2017
- 2017-02-22 CN CN201710095842.3A patent/CN106866181B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475116A (zh) * | 2014-11-24 | 2015-04-01 | 中国人民解放军军械工程学院 | 二氧化锡纳米线修饰的三氧化二铁纳米棒阵列的制备方法 |
| CN105869908A (zh) * | 2016-05-25 | 2016-08-17 | 东华大学 | 核壳Co3O4@Fe2O3纳米线阵列的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106866181A (zh) | 2017-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rajput et al. | Influence of sol concentration on CdO nanostructure with gas sensing application | |
| CN109709192B (zh) | 一种基于氧化钨/氧化锡核壳纳米片结构的气敏纳米材料、制备工艺及其应用 | |
| Van Hieu | Comparative study of gas sensor performance of SnO2 nanowires and their hierarchical nanostructures | |
| Drmosh et al. | Engineering the depletion layer of Au-modified ZnO/Ag core-shell films for high-performance acetone gas sensing | |
| KR101659320B1 (ko) | 산화아연/산화중석 나노선을 포함한 가스센서의 제조방법 및 이를 이용한 가스 검출 방법 | |
| Wu et al. | Enhanced response characteristics of p-porous silicon (substrate)/p-TeO2 (nanowires) sensor for NO2 detection | |
| CN107337473B (zh) | 在陶瓷管上原位生长MoO3纳米片的方法及气敏传感器 | |
| WO2010088726A1 (en) | Fabrication of nanoparticles on solid surfaces | |
| CN110261445B (zh) | 一种基于非金属矿物电极衬底表面原位生长纳米In2O3的室温NO2传感器及制备方法 | |
| Labis et al. | Designing zinc oxide nanostructures (nanoworms, nanoflowers, nanowalls, and nanorods) by pulsed laser ablation technique for gas‐sensing application | |
| Gorup et al. | Methods for design and fabrication of nanosensors: the case of ZnO-based nanosensor | |
| CN106929921B (zh) | 一种在陶瓷管上原位生长分级结构二硫化钼纳米花球的方法 | |
| Bai et al. | Synthesis of zinc oxide nanosheet thin films and their improved field emission and photoluminescence properties by annealing processing | |
| US11493493B2 (en) | Method of determining a concentration of hydrogen gas with a hydrogen gas sensor | |
| Zappa et al. | Copper oxide nanowires prepared by thermal oxidation for chemical sensing | |
| KR101889175B1 (ko) | Au, Pt 및 Pd 금속입자로 기능화된 ZnO 나노선의 상온 감응 특성을 이용한 가스센서 및 그 제조 방법 | |
| Akgun et al. | Hydrothermal zinc oxide nanowire growth with different zinc salts | |
| CN106866181B (zh) | 一种在陶瓷管上原位生长海胆状Fe2O3纳米针的方法 | |
| US20090178925A1 (en) | Chemical Sensor Based on Zinc Oxide Nanostructures for Detection of Hydrazine | |
| Kim et al. | ZnO–SnO2 branch–stem nanowires based on a two-step process: Synthesis and sensing capability | |
| KR101151424B1 (ko) | 금속 나노입자를 표면에 형성한 1차원 나노구조물의 제조방법 | |
| CN104761154B (zh) | 一种利用有机大分子材料作催化剂制备ito纳米线的方法 | |
| Qurashi et al. | In2O3 nanostructures and their chemical and biosensor applications | |
| Brahma et al. | Low temperature and rapid deposition of ZnO nanorods on Si (100) substrate with tunable optical emissions | |
| CN106745315B (zh) | 一种在陶瓷管上原位生长Fe2O3纳米针的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |