CN106745279B - 一种碳修饰锰锌氧纳米材料及其制备方法和应用 - Google Patents
一种碳修饰锰锌氧纳米材料及其制备方法和应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000001301 oxygen Substances 0.000 title claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000004048 modification Effects 0.000 title claims description 17
- 238000012986 modification Methods 0.000 title claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000007789 gas Substances 0.000 claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 20
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 18
- 239000011701 zinc Substances 0.000 claims abstract description 18
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229960004011 methenamine Drugs 0.000 claims abstract description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 10
- 239000008103 glucose Substances 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 9
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 9
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 9
- 150000002696 manganese Chemical class 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 206010013786 Dry skin Diseases 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims description 3
- WEUCTTBUEWINIJ-UHFFFAOYSA-N acetic acid;zinc;dihydrate Chemical compound O.O.[Zn].CC(O)=O WEUCTTBUEWINIJ-UHFFFAOYSA-N 0.000 claims description 3
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 3
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 claims 1
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
- 241000549556 Nanos Species 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000005611 electricity Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 239000003403 water pollutant Substances 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000004044 response Effects 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 241001614291 Anoplistes Species 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- Immunology (AREA)
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Abstract
本发明公开了一种碳修饰锰锌氧纳米材料及其制备方法和应用,锌盐和锰盐与乙二醇混合,氮气氛围中将溶液加热,将乌洛托品溶于乙二醇中,将所得溶液慢慢滴入制得的溶液中,在氮气氛围中反应,温度降至室温,离心洗涤干燥;干燥好的粉末与葡萄糖和抗坏血酸混合,研磨在惰性气体氛围下焙烧,待温度自然降至室温,即可得到纳米Mn1‑xZnxO@C粉末。该方法通过在ZnO纳米材料中引入锰元素,调控其缺陷及电学性质,通过碳元素修饰,进一步提升半导体材料的电学性质及光学性能。本发明所使用的原料便宜易得,成本低,减少了环境污染。同时,本发明制备的Mn1‑xZnxO@C纳米复合材料在气敏传感器、光催化降解染料、吸附水中污染物、锂电等领域有广阔的应用前景。
Description
技术领域
本发明涉及复合纳米材料制备技术,具体是指实现金属氧化物复合材料碳修饰的方法,一种碳修饰锰锌氧纳米材料及其制备方法和应用。
背景技术
金属氧化物如ZnO、SnO2、WO3等及其复合材料由于具有性能优异、环境友善、资源丰富、价格低廉等优点,在气体传感器、水处理、光催化、锂电池等领域应用广泛。其中以ZnO为基底的气敏元件稳定性强,且适合对多种气体的检测,其性质不仅可以通过材料的结构、形貌、晶型来控制,还可通过掺杂进行部分取代进行调整,这种方案在近年来引起了科学工作者的极大兴趣和高度重视。其中,含有变价元素的Mn、Fe等是典型的潜在气敏材料掺杂元素,通过变价元素掺杂提升气敏材料的性质在气敏传感器领域应用前景非常广。通过对材料进行碳(C)修饰,可进一步改善其电学性能,可加快气体的吸附及反应特性,提升材料的气敏性能,大大提高材料的反应活性和响应时间,因此可以提高气敏材料的灵敏度、响应时间和选择性。
但是目前制备Zn1-xMnxO纳米材料的方法主要有气相生长(Applied PhysicsLetters, 2003, 83:4020-4022)、金属有机物化学气相沉积(Journal of AppliedPhysics,2005,97:10D327 - 10D327-3)等,极少有化学法制备Zn1-xMnxO纳米材料的报道,本发明提供一种简单的制备Zn1-xMnxO纳米材料,通过在惰性气体氛围中反应和高温焙烧,实现Zn1-xMnxO纳米材料的碳修饰,使得材料的电学性能大大提高。
发明内容
为克服现有技术的不足,本发明提供一种碳修饰锰锌氧纳米材料及其制备方法和应用。
一种碳修饰锰锌氧纳米材料的制备方法,其特征在于, 所述碳修饰锰锌氧为Mn1- xZnxO@C,包括如下步骤:
(1)将锌盐和锰盐与乙二醇混合,阳离子浓度为0.03~0.3M,置于反应容器中,在氮气氛围中将溶液加热至110~140℃;
(2)将乌洛托品溶于乙二醇中,按乌洛托品与阳离子比例为(2~3):1配料,乌洛托品的浓度为0.06~0.9M;阳离子为锌盐和锰盐;
(3)将步骤(2)所得溶液慢慢滴入步骤(1)制得的溶液中,在氮气氛围中反应4~6小时;
(4)待温度降至室温,将溶液离心,将产物用去离子水和无水乙醇各离心洗涤4~6次,真空干燥箱中60~90℃干燥;
(5)将步骤(4)干燥好的粉末与葡萄糖和抗坏血酸混合,干燥好的粉末、葡萄糖和抗坏血酸质量含量分别为85~88%、10~15%、1.5~3%,研磨30 min后在惰性气体氛围下350~450 ℃焙烧2~3小时,550~650℃焙烧4~6小时,待温度自然降至室温,即可得到纳米Mn1- xZnxO@C粉末。
步骤(1)中所说的锌盐为六水合硝酸锌、氯化锌、二水合乙酸锌、七水合硫酸锌中的至少一种;步骤(1)中所述锰盐为一水合硫酸亚锰、四水合氯化亚锰、四水合乙酸亚锰中的至少一种;锌盐和锰盐的摩尔比为100:(0.1~1)。
步骤(5)中所说的葡萄糖用等质量的蔗糖代替;所说的抗坏血酸用等质量的柠檬酸、酒石酸、苹果酸代替;所说的惰性气体为高纯氮或氩气。
步骤(5)中所说的焙烧时升温速度为2~6℃/min。
一种碳修饰锰锌氧纳米材料,其特征在于,根据上述任一所述方法制备得到。
一种碳修饰锰锌氧纳米材料在乙醇气体检测的应用。
本发明的目的是提供一种简单可行的制备性能优异气敏材料的方法,反应和焙烧过程均在惰性气体氛围环境中进行,可保证产物保持不被氧化,同时有机物碳化实现碳元素修饰,可极大提升金属氧化物的气敏性能,该方法制备工艺简单,使金属氧化物体系材料在气敏传感器领域具有更加广阔的应用前景。
该方法通过在ZnO纳米材料中引入锰元素,调控其缺陷及电学性质,通过碳元素修饰,进一步提升半导体材料的电学性质及光学性能。本发明所使用的原料便宜易得,成本低,减少了环境污染。同时,本发明制备的Mn1-xZnxO@C纳米复合材料在气敏传感器、光催化降解染料、吸附水中污染物、锂电等领域有广阔的应用前景。
附图说明
图1为本发明实施例1样品的Mn1-xZnxO@C纳米材料的SEM图;
图2为本发明的Mn1-xZnxO@C纳米材料对10 ppm无水乙醇的气敏响应曲线。
具体实施方式
实施例1:
称取3 mmol的六水合硝酸锌和0.03mmol的一水合硫酸亚锰,与100 mL的乙二醇混合,置于反应容器中,在氮气氛围中将溶液加热至120 ℃,得到溶液A;取6 mmol的乌洛托品溶于100mL的乙二醇中,将乌洛托品的乙二醇溶液慢慢滴入溶液A中,在氮气氛围中反应4小时;待温度降至室温,将溶液离心,将产物用去离子水和无水乙醇离心洗涤6次,真空干燥箱中90 ℃干燥,得到粉末B;称取0.15 g的粉末B和0.0238 g的葡萄糖和0.0026 g的抗坏血酸混合,研磨30 min后,在惰性气体氛围下450 ℃焙烧2小时,550 ℃焙烧6小时,升温速度均为5 ℃/min,待温度自然降至室温,即可得到纳米Mn1-xZnxO@C粉末。
本实施例制得的粉体分散涂于六脚陶瓷管气敏测试元件上,采用WS-30A 型气敏元件测试系统测试不同浓度下对乙醇气体的响应,对10ppm的乙醇气体灵敏度达到为52.1。
实施例2:
称取10mmol的氯化锌和0.05mmol的四水合氯化亚蒙,与100 mL的乙二醇混合,置于反应容器中,在氮气氛围中将溶液加热至130 ℃,得到溶液A;取30 mmol的乌洛托品溶于100mL的乙二醇中,将乌洛托品的乙二醇溶液慢慢滴入溶液A中,在氮气氛围中反应5小时;待温度降至室温,将溶液离心,将产物用去离子水和无水乙醇离心洗涤6次,真空干燥箱中90 ℃干燥,得到粉末B;称取0.2 g的粉末B和0.0227 g的葡萄糖和0.0045 g的抗坏血酸混合,研磨30 min后,在惰性气体氛围下350 ℃焙烧3小时,650 ℃焙烧4小时,升温速度均为2℃/min,待温度自然降至室温,即可得到纳米Mn1-xZnxO@C粉末。
本实施例制得的粉体分散涂于六脚陶瓷管气敏测试元件上,采用WS-30A 型气敏元件测试系统测试不同浓度下对乙醇气体的响应,对10ppm的乙醇气体灵敏度达到为59.7。
实施例3:
称取3 mmol的二水合乙酸锌和0.003mmol的四水合乙酸亚锰,与10 mL的乙二醇混合,置于反应容器中,在氮气氛围中将溶液加热至140 ℃,得到溶液A;取9 mmol的乌洛托品溶于90 mL的乙二醇中,将乌洛托品的乙二醇溶液慢慢滴入溶液A中,在氮气氛围中反应4小时;待温度降至室温,将溶液离心,将产物用去离子水和无水乙醇离心洗涤4次,真空干燥箱中70 ℃干燥,得到粉末B;称取0.2 g的粉末B和0.0227 g的葡萄糖和0.0045 g的抗坏血酸混合,研磨30 min后,在惰性气体氛围下400 ℃焙烧2.5小时,600 ℃焙烧5小时,升温速度均为6 ℃/min,待温度自然降至室温,即可得到纳米Mn1-xZnxO@C粉末。
本实施例制得的粉体分散涂于六脚陶瓷管气敏测试元件上,采用WS-30A 型气敏元件测试系统测试不同浓度下对乙醇气体的响应,对10ppm的乙醇气体灵敏度达到为47.5。
Claims (6)
1. 一种碳修饰锰锌氧纳米材料的制备方法,其特征在于, 所述碳修饰锰锌氧为Mn1- xZnxO@C,包括如下步骤:
(1)将锌盐和锰盐与乙二醇混合,阳离子浓度为0.03~0.3M,置于反应容器中,在氮气氛围中将溶液加热至110~140℃;
(2)将乌洛托品溶于乙二醇中,按乌洛托品与阳离子比例为(2~3):1配料,乌洛托品的浓度为0.06~0.9M;阳离子为锌盐和锰盐;
(3)将步骤(2)所得溶液慢慢滴入步骤(1)制得的溶液中,在氮气氛围中反应4~6小时;
(4)待温度降至室温,将溶液离心,将产物用去离子水和无水乙醇各离心洗涤4~6次,真空干燥箱中60~90℃干燥;
(5)将步骤(4)干燥好的粉末与葡萄糖和抗坏血酸混合,干燥好的粉末、葡萄糖和抗坏血酸质量含量分别为85~88%、10~15%、1.5~3%,研磨30 min后在惰性气体氛围下350~450 ℃焙烧2~3小时,550~650℃焙烧4~6小时,待温度自然降至室温,即可得到纳米Mn1-xZnxO@C粉末。
2.根据权利要求1所述一种碳修饰锰锌氧纳米材料的制备方法,其特征在于,步骤(1)中所说的锌盐为六水合硝酸锌、氯化锌、二水合乙酸锌、七水合硫酸锌中的至少一种;步骤(1)中所述锰盐为一水合硫酸亚锰、四水合氯化亚锰、四水合乙酸亚锰中的至少一种;锌盐和锰盐的摩尔比为100:(0.1~1)。
3.根据权利要求1所述一种碳修饰锰锌氧纳米材料的制备方法,其特征在于,步骤(5)中所说的葡萄糖用等质量的蔗糖代替;所说的抗坏血酸用等质量的柠檬酸、酒石酸、苹果酸代替;所说的惰性气体为高纯氮或氩气。
4.根据权利要求1所述一种碳修饰锰锌氧纳米材料的制备方法,其特征在于,步骤(5)中所说的焙烧时升温速度为2~6℃/min。
5.一种碳修饰锰锌氧纳米材料,其特征在于,根据权利要求1-4任一所述方法制备得到。
6.根据权利要求5所述碳修饰锰锌氧纳米材料在乙醇气体检测的应用。
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