CN103241767A - Microemulsion-solvothermal technique of orthorhombic InOOH - Google Patents
Microemulsion-solvothermal technique of orthorhombic InOOH Download PDFInfo
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- CN103241767A CN103241767A CN2012104157811A CN201210415781A CN103241767A CN 103241767 A CN103241767 A CN 103241767A CN 2012104157811 A CN2012104157811 A CN 2012104157811A CN 201210415781 A CN201210415781 A CN 201210415781A CN 103241767 A CN103241767 A CN 103241767A
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- inooh
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- 238000000034 method Methods 0.000 title abstract description 7
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 40
- 150000002471 indium Chemical class 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000001105 regulatory effect Effects 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 18
- 239000010935 stainless steel Substances 0.000 claims abstract description 18
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 67
- 239000002904 solvent Substances 0.000 claims description 43
- 239000008267 milk Substances 0.000 claims description 36
- 210000004080 milk Anatomy 0.000 claims description 36
- 235000013336 milk Nutrition 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 31
- 239000013543 active substance Substances 0.000 claims description 30
- 238000013019 agitation Methods 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000005119 centrifugation Methods 0.000 claims description 17
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 17
- 238000005516 engineering process Methods 0.000 claims description 16
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 6
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 5
- 239000000839 emulsion Substances 0.000 abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000003760 magnetic stirring Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 12
- 238000000634 powder X-ray diffraction Methods 0.000 description 10
- 229920002994 synthetic fiber Polymers 0.000 description 8
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 6
- 239000004141 Sodium laurylsulphate Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 5
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000018199 S phase Effects 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001449 indium ion Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- NQBRDZOHGALQCB-UHFFFAOYSA-N oxoindium Chemical compound [O].[In] NQBRDZOHGALQCB-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
The invention discloses a microemulsion-solvothermal technique of orthorhombic InOOH, which comprises the following steps: (1) preparation of microemulsion: a. sequentially adding microemulsion, mixture of n-hexane, n-pentanol or n-butanol, and surfactant into a beaker in a volume ratio of (18-22):(4-6):(8-12) under magnetic stirring conditions; b. adding 1-2ml of indium salt solution into the beaker, dropwisely adding 1.5-3ml of organic amine or inorganic alkali solution, continuing stirring for 12-18 minutes, and regulating the pH value to 8-11 to obtain an emulsion; and (2) preparation of orthorhombic InOOH by solvothermal technique: a. transferring the emulsion to a polytetrafluoroethylene vessel, closing the polytetrafluoroethylene vessel in a stainless steel high-pressure reaction kettle, heating to 180-220 DEG C to react for 18-20 hours, and cooling to room temperature; b. centrifuging the product, washing, drying the precipitate, and grinding to obtain the orthorhombic InOOH. The technique enhances the yield on the premise of lowering the optimum reaction temperature; and the prepared orthorhombic InOOH has excellent gas sensitivity.
Description
Technical field
The invention belongs to the preparation field of iris InOOH, relate in particular to the method for a kind of micro emulsion-solvent thermal prepared iris InOOH.
Background technology
Indium sesquioxide is a kind of special broad stopband oxide semiconductor, has less resistance and advantages of high catalytic activity, has had in solar cell, flat-panel monitor, optical device and fields such as opto-electronic device and gas sensor widely to use.The structure of cubic phase oxygen indium can be imagined as incomplete oxonium ion close-packed structure, and indium ion constitutes face-centered cubic lattice, and the position, tetrahedral interstice in sublattice has 3/4 for oxonium ion occupies, and 1/4 is empty, and major defect is oxygen room and gap indium ion.And under high pressure, the structure of Indium sesquioxide changes mutually from six sides cube in opposite directions, and six side's phase oxidation indiums belong to
Spacer comprises 6 In2O3 molecules in its structure cell, lattice constant a=0.549 nm, c=0.1452 nm.The presoma as the hexagonal structure Indium sesquioxide of iris InOOH, has one dimension Nano structure, have characteristics such as specific surface area is big, good stability, bibliographical information six side's phase oxidation indiums needed to prepare under High Temperature High Pressure in the past, at 1000 ℃, under 65 kbar, Atou etc. have prepared six side's phase oxidation indiums under 15-25 GPa as Prewitt etc., energy consumption is than higher and relatively harsher to the requirement of equipment, and facility investment is bigger.
Summary of the invention
The objective of the invention is to overcome above-mentioned deficiency provides the micro emulsion of a kind of iris InOOH-solvent thermal technology, when having reduced optimal reaction temperature, has improved productive rate, and the air-sensitive performance of the iris InOOH that makes is very good.
Purpose of the present invention is achieved through the following technical solutions:
The micro emulsion of a kind of iris InOOH-solvent thermal technology may further comprise the steps:
(1). preparation of microemulsion
A. microemulsion is 18-22:4-6:8-12 with the volume ratio by normal hexane, Pentyl alcohol or propyl carbinol and tensio-active agent, adds in the beaker successively under the magnetic agitation condition; B. get 1-2ml indium salts solution then and add in the beaker, drip 1.5-3ml organic amine or inorganic alkali lye again, continue to stir 12-18 minute minute, regulating the pH value is 8-11, gets milk sap;
(2). the solvent thermal prepared of iris type InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 180 ℃-220 ℃ reacting by heating 18-20 hour, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make iris type InOOH.
The micro emulsion of above-mentioned iris InOOH-solvent thermal technology, described tensio-active agent is that anion surfactant is 18 carbon-suitable-9-olefin(e) acid, and the tensio-active agent that contrast is used comprises: any in triton x-100 (octyl phenyl Soxylat A 25-7) Sodium dodecylbenzene sulfonate or the sodium lauryl sulphate.
The micro emulsion of above-mentioned prismatic crystal InOOH-solvent thermal technology, alkali lye is the aqueous solution of organic amine or mineral alkali, mass percentage concentration is 10-15%, and described organic ammonium is any in amino dodecane, hexanediamine or the triethylamine, and mineral alkali is sodium hydroxide or potassium hydroxide solution.
The micro emulsion of above-mentioned iris InOOH-solvent thermal technology, the volumetric molar concentration of described indium salts solution are 0.5-1.0mol/l.
The centrifuge washing solutions employed is dehydrated alcohol and distilled water in the micro emulsion of above-mentioned iris InOOH-solvent thermal technology, described step (1), washs 3-4 time respectively.
The micro emulsion of above-mentioned iris InOOH-solvent thermal technology,
(1). preparation of microemulsion
A. microemulsion is 18-22:4-6:8-12 with the volume ratio by mixing and the tensio-active agent of normal hexane, Pentyl alcohol or propyl carbinol, adds in the beaker successively under the magnetic agitation condition; B. get 1-2ml indium salts solution then and add in the beaker, drip 1.5-3ml organic amine or inorganic alkali lye again, continue to stir 15 minutes, regulating the pH value is 8-11, gets milk sap.
The micro emulsion of above-mentioned iris InOOH-solvent thermal technology when having reduced optimal reaction temperature, has improved productive rate, and the air-sensitive performance of the iris InOOH that makes is very good.
Description of drawings
Fig. 1 triton x-100 is as the synthetic material XRD figure spectrum of tensio-active agent.
Fig. 2 triton x-100 is as the synthetic material TEM photo of tensio-active agent.
Fig. 3 (2) Sodium dodecylbenzene sulfonate is as the synthetic material XRD figure spectrum of tensio-active agent.
Fig. 4 Sodium dodecylbenzene sulfonate is as the synthetic material TEM photo of tensio-active agent.
Fig. 5 (3) sodium lauryl sulphate is as the synthetic material XRD figure spectrum of tensio-active agent.
Fig. 6 sodium lauryl sulphate is as the synthetic material TEM photo of tensio-active agent.
Fig. 7 (4) 18 carbon-suitable-9-olefin(e) acids are as the synthetic material XRD figure spectrum of tensio-active agent.
Fig. 8 18 carbon-suitable-9-olefin(e) acid is as the synthetic material TEM photo of tensio-active agent.
Fig. 9 (5) 18 carbon-suitable-9-olefin(e) acids are tensio-active agent, the XRD figure spectrum of amino dodecane solvent system.
Figure 10 18 carbon-suitable-9-olefin(e) acid is tensio-active agent, the XRD figure spectrum of hexanediamine solvent system.
Figure 11 18 carbon-suitable-9-olefin(e) acid is tensio-active agent, the XRD figure spectrum of triethylamine solvent system.
Figure 12 (6) 18 carbon-suitable-9-olefin(e) acids are tensio-active agent, the TEM photo of amino dodecane solvent system.
Figure 13 18 carbon-suitable-9-olefin(e) acid is tensio-active agent, the TEM photo of hexanediamine solvent system.
Figure 14 18 carbon-suitable-9-olefin(e) acid is tensio-active agent, the TEM photo of triethylamine solvent system.
The XPS of XPS spectrum (a) O1s of Figure 15 (7) iris type InOOH resolves spectrum.
The XPS of XPS spectrum (b) In3d of Figure 16 iris type InOOH resolves spectrum.
The XPS of the XPS spectrum (c) of Figure 17 iris type InOOH resolves spectrum.
Figure 18 iris type InOOH makes the heater-type gas sensor to the resistance sensitivity of gas.
Figure 19 material is to the sensitivity curve of different concns hydrogen sulfide.
Embodiment
Embodiment 1:
(1). preparation of microemulsion
A. microemulsion is by 18ml normal hexane, 4ml Pentyl alcohol, 18 carbon-suitable-9-olefin(e) acid adds in the beaker under the magnetic agitation condition successively to add 8ml, b. getting 2ml0.5mol/l indium salts solution then adds in the beaker, drip the 3.0ml mass percent concentration again and be 15% sodium hydroxide solution, continue to stir 15 minutes, regulating the pH value is 8, gets milk sap;
(2). the solvent thermal prepared of iris type InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 180 ℃ of reacting by heating 20 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make one-dimentional structure iris type InOOH.
Embodiment 2:
(1). preparation of microemulsion
A. microemulsion is by 20ml normal hexane, 5ml Pentyl alcohol, 18 carbon-suitable-9-olefin(e) acid adds in the beaker under the magnetic agitation condition successively to add 9ml, b. getting 1.5ml0.8mol/l indium salts solution then adds in the beaker, drip the 2.5ml mass percent concentration again and be 17% sodium hydroxide solution, continue to stir 15 minutes, regulating the pH value is 9, gets milk sap;
(2). the solvent thermal prepared of iris type InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 190 ℃ of reacting by heating 19 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make one-dimentional structure iris type InOOH.
Embodiment 3:
(1). preparation of microemulsion
A. microemulsion is by 22ml normal hexane, 6ml Pentyl alcohol, 18 carbon-suitable-9-olefin(e) acid adds in the beaker under the magnetic agitation condition successively to add 12ml, b. getting 1.2ml 0.7mol/l indium salts solution then adds in the beaker, drip the 2.0ml mass percent concentration again and be 19% sodium hydroxide solution, continue to stir 15 minutes, regulating the pH value is 10, gets milk sap;
(2). the solvent thermal prepared of iris type InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 200 ℃ of reacting by heating 18 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make one-dimentional structure iris type InOOH.
Embodiment 4:
(1). preparation of microemulsion
A. microemulsion is by 20ml normal hexane, 5ml Pentyl alcohol, 18 carbon-suitable-9-olefin(e) acid adds in the beaker under the magnetic agitation condition successively to add 10ml, b. getting 1ml 1.0mol/l indium salts solution then adds in the beaker, drip the 1.5ml mass percent concentration again and be 20% sodium hydroxide solution, continue to stir 15 minutes, regulating the pH value is 11, gets milk sap;
(2). the solvent thermal prepared of iris type InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 220 ℃ of reacting by heating 18 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make one-dimentional structure iris type InOOH.
Embodiment 5:
(1). preparation of microemulsion
A. microemulsion is by 19ml normal hexane, 5ml Pentyl alcohol, 18 carbon-suitable-9-olefin(e) acid adds in the beaker under the magnetic agitation condition successively to add 8ml, b. getting 2ml0.5mol/l indium salts solution then adds in the beaker, drip the 3.0ml mass percent concentration again and be 15% sodium hydroxide solution, continue to stir 12 minutes, regulating the pH value is 8, gets milk sap;
(2). the solvent thermal prepared of iris type InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 180 ℃ of reacting by heating 20 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make one-dimentional structure iris type InOOH.
Embodiment 6:
(1). preparation of microemulsion
A. microemulsion is by 20ml normal hexane, 6ml Pentyl alcohol, 18 carbon-suitable-9-olefin(e) acid adds in the beaker under the magnetic agitation condition successively to add 8ml, b. getting 1.5ml0.8mol/l indium salts solution then adds in the beaker, drip the 2.5ml mass percent concentration again and be 17% sodium hydroxide solution, continue to stir 14 minutes, regulating the pH value is 9, gets milk sap;
(2). the solvent thermal prepared of iris type InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 190 ℃ of reacting by heating 19 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make one-dimentional structure iris type InOOH.
Embodiment 7:
(1). preparation of microemulsion
A. microemulsion is by 22ml normal hexane, 4ml Pentyl alcohol, 18 carbon-suitable-9-olefin(e) acid adds in the beaker under the magnetic agitation condition successively to add 12ml, b. getting 1.2ml 0.7mol/l indium salts solution then adds in the beaker, drip the 2.0ml mass percent concentration again and be 19% sodium hydroxide solution, continue to stir 17 minutes, regulating the pH value is 10, gets milk sap;
(2). the solvent thermal prepared of iris type InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 200 ℃ of reacting by heating 18 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make one-dimentional structure iris type InOOH.
Embodiment 8:
(1). preparation of microemulsion
A. microemulsion is by 20ml normal hexane, 5ml Pentyl alcohol, 18 carbon-suitable-9-olefin(e) acid adds in the beaker under the magnetic agitation condition successively to add 10ml, b. getting 1ml 1.0mol/l indium salts solution then adds in the beaker, drip the 1.5ml mass percent concentration again and be 20% sodium hydroxide solution, continue to stir 18 minutes, regulating the pH value is 11, gets milk sap;
(2). the solvent thermal prepared of iris type InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 220 ℃ of reacting by heating 18 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make one-dimentional structure iris type InOOH.
Embodiment 9:
(1). preparation of microemulsion
A. microemulsion is by 19ml normal hexane, 4ml propyl carbinol, 18 carbon-suitable-9-olefin(e) acid adds in the beaker under the magnetic agitation condition successively to add 8ml, b. getting 2ml0.5mol/l indium salts solution then adds in the beaker, drip the 3.0ml mass percent concentration again and be 15% sodium hydroxide solution, continue to stir 12 minutes, regulating the pH value is 8, gets milk sap;
(2). the solvent thermal prepared of iris type InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 180 ℃ of reacting by heating 20 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make one-dimentional structure iris type InOOH.
Embodiment 10:
(1). preparation of microemulsion
A. microemulsion is by 20ml normal hexane, 5ml propyl carbinol, 18 carbon-suitable-9-olefin(e) acid adds in the beaker under the magnetic agitation condition successively to add 8ml, b. getting 1.5ml0.8mol/l indium salts solution then adds in the beaker, drip the 2.5ml mass percent concentration again and be 17% sodium hydroxide solution, continue to stir 14 minutes, regulating the pH value is 9, gets milk sap;
(2). the solvent thermal prepared of iris type InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 190 ℃ of reacting by heating 19 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make one-dimentional structure iris type InOOH.
Embodiment 11:
(1). preparation of microemulsion
A. microemulsion is by 22ml normal hexane, 6ml propyl carbinol, 18 carbon-suitable-9-olefin(e) acid adds in the beaker under the magnetic agitation condition successively to add 12ml, b. getting 1.2ml 0.7mol/l indium salts solution then adds in the beaker, drip the 2.0ml mass percent concentration again and be 19% sodium hydroxide solution, continue to stir 15 minutes, regulating the pH value is 10, gets milk sap;
(2). the solvent thermal prepared of iris type InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 200 ℃ of reacting by heating 18 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make one-dimentional structure iris type InOOH.
Embodiment 12:
(1). preparation of microemulsion
A. microemulsion is by 20ml normal hexane, 5ml propyl carbinol, 18 carbon-suitable-9-olefin(e) acid adds in the beaker under the magnetic agitation condition successively to add 10ml, b. getting 1ml 1.0mol/l indium salts solution then adds in the beaker, drip the 1.5ml mass percent concentration again and be 20% sodium hydroxide solution, continue to stir 18 minutes, regulating the pH value is 11, gets milk sap;
(2). the solvent thermal prepared of iris type InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 220 ℃ of reacting by heating 18 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make one-dimentional structure iris type InOOH.
The tensio-active agent contrast experiment
The comparative example 1
(1). preparation of microemulsion
A. microemulsion is by 20ml normal hexane, 5ml Pentyl alcohol, add the 10ml triton x-100, under the magnetic agitation condition, add in the beaker successively, b. getting 2ml0.5mol/l indium salts solution then adds in the beaker, drip the 2.0ml mass percent concentration again and be 20% sodium hydroxide solution, continue to stir 15 minutes, regulating the pH value is 11, gets milk sap;
(2). the solvent thermal prepared of cubic InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 200 ℃ of reacting by heating 20 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make cubic In (OH)
3
Comparative example 2,3
(1). preparation of microemulsion
A. microemulsion is by 20ml normal hexane, 5ml Pentyl alcohol, add 0.200g Sodium dodecylbenzene sulfonate and sodium lauryl sulphate respectively, under the magnetic agitation condition, add in the beaker successively, b. getting 2ml0.5mol/l indium salts solution then adds in the beaker, drip the 2.0ml mass percent concentration again and be 20% sodium hydroxide solution, continue to stir 15 minutes, regulating the pH value is 11, gets milk sap;
(2). the solvent thermal prepared of cubic InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 200 ℃ of reacting by heating 20 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make cubic In (OH)
3
Basic solvent system contrast experiment
Comparative example 4-5
(1). preparation of microemulsion
A. microemulsion is by 20ml normal hexane, 5ml Pentyl alcohol, add the 0.200g sodium lauryl sulphate, under the magnetic agitation condition, add in the beaker successively, b. getting 2ml0.5mol/l indium salts solution then adds in the beaker, add respectively and drip 2ml amino dodecane or hexanediamine or triethylamine, continue to stir 15 minutes, regulating the pH value is 11, gets milk sap;
(2). the solvent thermal prepared of cubic InOOH
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 200 ℃ of reacting by heating 20 hours, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make iris type InOOH.
Below be each composition analysis of the present invention and product analysis:
(1) selection of tensio-active agent
Use no tensio-active agent, as the X-ray powder diffraction (XRD) of triton x-100, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, 18 carbon-suitable-synthetic materialss such as 9-olefin(e) acid as Fig. 1-Fig. 8, as we can see from the figure, the sample that 18 carbon-suitable-the 9-olefin(e) acid makes as tensio-active agent, all diffraction fringes consistent with the standard diagram of iris type InOOH (JCPDS No.17-0549); And the synthetic sample of other tensio-active agents, the In of diffraction fringe and cubic (OH)
3Standard diagram unanimity (JCPDS No.76-1464), see from the TEM photo to be the square shape.Hence one can see that, and 18 carbon-suitable-9-olefin(e) acid is the tensio-active agent of synthetic iris type InOOH.
(2) selection of basic solvent system
Think tensio-active agent, use amino dodecane, hexanediamine, triethylamine and sodium hydroxide solution as solvent system, the XRD figure of the sample that makes spectrum is seen Fig. 9-Figure 14.From Fig. 9-11 as can be seen, 18 carbon-suitable-9-olefin(e) acid is tensio-active agent, in any alkaline solvent system, all can obtain the InOOH of iris type, simultaneously from Figure 12-14 as can be seen, the InOOH of iris type does not have oriented growth to become one-dimentional structure in the organic basic system, and Fig. 7-the 8th, the InOOH of the one dimension pine needle shape that adding mineral alkali sodium hydroxide obtains.
According to reacting phenomenon, supposition obtains, tensio-active agent 18 carbon-suitable-9-olefin(e) acid and alkaline solution reaction, form the anion surfactant of 18 carbon-suitable-9-olefin(e) acid amine or 18 carbon-suitable-9-olefin(e) acid sodium salt, the alkalescence of system is reduced, make-OOH can stable existence, thus generate the iris type InOOH of one-dimentional structure.The 18 carbon-suitable-9-olefin(e) acid amine or the 18 carbon-suitable-9-olefin(e) acid sodium salt concentration that form directly influence the stability of emulsion system, and system is more stable, more is conducive to the oriented growth of crystal.
(3) composition analysis of iris type InOOH
By x-ray photoelectron spectroscopy (XPS) oblique side InOOH composition is analyzed, be the results are shown in Figure 15-17.The InOOH nanometer rod is mainly elementary composition by In and two kinds of O as can be seen from Figure 15, the result of ultimate analysis shows, the mass ratio of O and In is 13.56:22.55, the atomicity of O and In is than being 13.32:3.09, the InOOH of nonstoichiometry ratio, illustrate among the synthetic iris type InOOH of micro emulsion-solvent-thermal method and may contain moisture, do not detect other impurity.From Figure 16 O1s spectrum as can be known, the bound energy of O appears at 530.06 eV, 531.5eV, 534.9eV respectively, and corresponding respectively is lattice oxygen O among the InOOH
2 -, oxygen physisorption O
2With chemically adsorbing oxygen O
-2From the In3d spectrogram of Figure 17 as can be seen, In3d
3/2(B.E.=452 eV) peak splits and is divided into 450.431 eV and two peak positions of 452.536eV, In3d
5/2The peak of (B.E.=444.3 eV) splits and is divided into 442.813 eV and 444.666 eV, one to the high bonding energy direction, one is moved to low bonded energy direction, variation has taken place in the chemical environment that In is described, with the effect of In atom be two kinds of atoms, H atom and O atom make electron density around the In atom increase respectively and reduce the result that shielding effect strengthens or weakens.
(4) air-sensitive performance test
After the calcining of gained sample, make gas sensor according to traditional heater-type work, under the 5v heater voltage, by static distribution method its air-sensitive performance is tested, obtain it to resistance sensitivity such as Figure 18 of the multiple gases of 50ppm.As can be seen from Figure 18, element has all surpassed 3 to the sensitivity rate of change of indoor common several toxic and harmfuls, can be used for the detection of IAQ (indoor air quality), and is especially higher to the sensitivity of hydrogen sulfide, is expected to develop these hydrogen sulfide gas sensor.
Element is seen Figure 19 to the sensitivity of the hydrogen sulfide of different concns, and as can be seen from the figure, element increases along with the increase of concentration the sensitivity of hydrogen sulfide, but is not linear relationship, by fitting of a curve, meets the boltzmann funtcional relationship.
Claims (6)
1. the micro emulsion of an iris InOOH-solvent thermal technology may further comprise the steps:
(1). preparation of microemulsion
A. microemulsion is 18-22:4-6:8-12 with the volume ratio by mixing and the tensio-active agent of normal hexane, Pentyl alcohol or propyl carbinol, adds in the beaker successively under the magnetic agitation condition; B. get 1-2ml indium salts solution then and add in the beaker, drip 1.5-3ml organic amine or inorganic alkali lye again, continue to stir 12-18 minute, regulating the pH value is 8-11, gets milk sap;
Iris type InOOH solvent thermal prepared
A. milk sap is moved to polytetrafluoroethylcontainer container, again the tetrafluoroethylene container is enclosed in the stainless steel autoclave, 180 ℃-220 ℃ reacting by heating 18-20 hour, be cooled to room temperature again,
B. the product centrifugation is come out and wash, the throw out oven dry, grind and make iris type InOOH.
2. the micro emulsion of iris InOOH according to claim 1-solvent thermal technology, it is characterized in that: described tensio-active agent is anion surfactant 18 carbon-suitable-9-olefin(e) acid.
3. the micro emulsion of iris InOOH according to claim 1-solvent thermal technology, it is characterized in that: alkali lye is the aqueous solution of organic amine or mineral alkali, mass percentage concentration is 10-15%, described organic ammonium is any in amino dodecane, hexanediamine or the triethylamine, and mineral alkali is sodium hydroxide or potassium hydroxide solution.
4. according to the micro emulsion-solvent thermal technology of each described iris InOOH among the claim 1-3, it is characterized in that: the volumetric molar concentration of described indium salts solution is 0.5-1.0mol/l, and used naoh concentration is 3-5mol/l.
5. the micro emulsion of iris InOOH according to claim 4-solvent thermal technology is characterized in that: the centrifuge washing solutions employed is dehydrated alcohol and distilled water in the described step (1), washs 3-4 time respectively.
6. the micro emulsion of iris InOOH according to claim 4-solvent thermal technology may further comprise the steps:
(1). preparation of microemulsion
A. microemulsion is 18-22:4-6:8-12 with the volume ratio by mixing and the tensio-active agent of normal hexane, Pentyl alcohol or propyl carbinol, adds in the beaker successively under the magnetic agitation condition; B. get 1-2ml indium salts solution then and add in the beaker, drip 1.5-3ml organic amine or inorganic alkali lye again, continue to stir 15 minutes, regulating the pH value is 8-11, gets milk sap.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104058448A (en) * | 2014-07-18 | 2014-09-24 | 吉林大学 | Method for preparing hydroxyl indium oxide nanowires and indium oxide nano particles |
| CN105016377A (en) * | 2015-07-02 | 2015-11-04 | 长沙学院 | A kind of method for preparing nanometer KInO2 material by microemulsion method |
| CN112744863A (en) * | 2021-02-03 | 2021-05-04 | 浙江爱科新材料有限公司 | Preparation method of high-purity superfine zirconia |
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| CN101182031A (en) * | 2007-11-27 | 2008-05-21 | 山东大学 | A kind of preparation method of indium oxide nanowire ordered aggregate |
| CN101508462A (en) * | 2009-03-11 | 2009-08-19 | 长沙理工大学 | Process for producing flower shaped indium hydroxide powder having high specific surface area |
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| CN101182031A (en) * | 2007-11-27 | 2008-05-21 | 山东大学 | A kind of preparation method of indium oxide nanowire ordered aggregate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104058448A (en) * | 2014-07-18 | 2014-09-24 | 吉林大学 | Method for preparing hydroxyl indium oxide nanowires and indium oxide nano particles |
| CN105016377A (en) * | 2015-07-02 | 2015-11-04 | 长沙学院 | A kind of method for preparing nanometer KInO2 material by microemulsion method |
| CN112744863A (en) * | 2021-02-03 | 2021-05-04 | 浙江爱科新材料有限公司 | Preparation method of high-purity superfine zirconia |
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