CN101973759B - Preparation method of noble metal doped In2O3/SnO3 porous-channel structured gas-sensitive material - Google Patents
Preparation method of noble metal doped In2O3/SnO3 porous-channel structured gas-sensitive material Download PDFInfo
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- CN101973759B CN101973759B CN2010102741734A CN201010274173A CN101973759B CN 101973759 B CN101973759 B CN 101973759B CN 2010102741734 A CN2010102741734 A CN 2010102741734A CN 201010274173 A CN201010274173 A CN 201010274173A CN 101973759 B CN101973759 B CN 101973759B
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- sintering
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000000463 material Substances 0.000 title abstract description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title abstract 5
- 239000007789 gas Substances 0.000 claims abstract description 39
- 238000005245 sintering Methods 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 239000007790 solid phase Substances 0.000 claims abstract description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 24
- 235000015895 biscuits Nutrition 0.000 claims description 10
- 239000010970 precious metal Substances 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 8
- 238000004080 punching Methods 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 4
- 229910052697 platinum Inorganic materials 0.000 abstract 2
- 238000004321 preservation Methods 0.000 abstract 2
- 229910000831 Steel Inorganic materials 0.000 abstract 1
- 239000010959 steel Substances 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 description 10
- 150000004706 metal oxides Chemical class 0.000 description 10
- 206010070834 Sensitisation Diseases 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 238000012856 packing Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011540 sensing material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
Abstract
The invention relates to a preparation method of a noble metal doped porous-channel structured In2O3/SnO3 gas-sensitive material, which comprises the following steps of: pressing market In2O3 and SnO2 in the ratio of 4:1 or 7:3 or 3:2 together with noble metal Pt or Pd or Ag powder into a blank in a steel mold; and then, loading the blank into an oxygen atmosphere sintering furnace for solid phase sintering to finally obtain the noble metal doped porous-channel structured In2O3/SnO3 gas-sensitive material. The addition quantity of the noble metal Pt or Pd or Ag powder accounts for 0.05% of the total quantity of In2O3 and SnO2; with respect to the oxygen atmosphere sintering condition for the in-situ sintering growth, the heating rate is 50-500 DEG C/h; a heat preservation process is divided into two stages, the temperature range of the first stage is 600-700 DEG C, and the temperature range of the second stage is 1250-1450 DEG C; the time of heat preservation is 1-5h; and the oxygen flow is 3-8 L/min. The method can increase gas sensitivity by increasing the specific surface area through the porous-channel structure and increases the selectivity of the gas-sensitive material through the nanometer noble metal. The invention has the advantages of low cost, clean production and the like and is easy to control, and the raw materials are simple to prepare.
Description
Technical field
The present invention relates to the stupalith synthesis technical field, specifically is the In of dopen Nano noble metal
2O
3/ SnO
2The preparation method of porous road structure gas sensitive.
Background technology
Along with science and technology development, to the detection of inflammable gas and poisonous gas, monitoring, warning require increasingly highly, this just has higher requirement to detecting the gas sensitive that relies on; Therefore, sensitivity, selectivity and the long-time stability of raising gas sensitive and reduction working temperature, shortening response recovery time etc. become the important directions of gas sensitive development.
The researcher generally believes that the method for improving the gas sensitive combination property mainly contains doped metal ion (comprising noble metal or REE) or metal oxide, increase gas sensitive specific surface area, strengthens the research of gas sensing mechanism etc. at present.
Structural metal, porous road oxide gas-sensing material utilizes the porous structure specific surface area big just; Mesoporous (several nanometers to tens nanometer) structure is strong to the adsorbability of gas; Increased that this material microstructure characteristic of Activity of Chemical Reaction point proposes, the gas sensitization property of the metal oxide gas sensitive of this structure is much better than the common metal oxide composite.Though porous road micromechanism has played vital role to improving gas sensitive gas sensitization property; But with a kind of metal oxide under specific temperature conditions not only to a kind of gas sensitization; Maybe be all responsive to several kinds of gases; Cause people to the difficulty that gaseous species detects, need the selectivity of gas sensitive further be improved, to realize prepared sensor gas sensitization only in use being detected; The realization of this target only depends on very difficulty of a kind of metal oxide materials, and therefore, the gas sensitive research worker has proposed to adopt composite metal oxide to improve the selectivity of gas sensitive.Just be based on the susceptibility of cellular structure metals oxide to gas; And on composite metal oxide the basis that the selectivity and the susceptibility of gas is all increased; Exploitation pore passage structure composite metal oxide gas-sensing material, significant to the gas sensitive effect that improves the metal oxide gas sensitive.
Summary of the invention
The objective of the invention is to combine the susceptibility of porous road structure and nano-noble metal and characteristics optionally, a kind of In that adopts the in-situ sintering growth method to come the synthesis of nano precious metal doping is provided
2O
3/ SnO
2The method of porous road structure gas sensitive.
The present invention mainly is through to nano-noble metal doping In
2O
3/ SnO
2The dynamics of complex phase metal oxide growth in situ is controlled in the regulation and control of gas sensitive sintering temperature and sintering atmosphere, thereby regulates and control the quantity of pore passage structure and coordination defective thereof, to obtain In
2O
3And SnO
2The porous road structure In that component ratio is different
2O
3/ SnO
2Gas sensitive.
The present invention realizes through following scheme:
At first with commercially available In
2O
3, SnO
2In punching block, be pressed into biscuit in the ratio of 4: 1 or 7: 3 or 3: 2 and precious metals pt or Pd or Ag nano powder, biscuit packed into carry out solid-phase sintering in the oxygen atmosphere sintering stove then, finally obtain nano-noble metal doping porous road structure In
2O
3/ SnO
2Gas sensitive, the addition of precious metals pt or Pd or Ag powder accounts for In
2O
3And SnO
20.05% of total amount.
Raw material: commercially available In
2O
3, SnO
2With precious metals pt or Pd or Ag powder, powder size is between 50-500nm, and purity reaches 99.995%.
Punching block compacting: pressing pressure: 60-90Mpa; Dwell time: 2-5min.
In-situ sintering growth of oxygen atmosphere sintering condition:
1) oxygen that uses requires purity to be higher than 99.999%, and dew point is lower than-72 ℃;
2) sintering condition: heating rate is controlled at 50-500 ℃/h; Insulation is divided into two sections, and first section temperature range is controlled at 600-700 ℃, and second section temperature range is controlled at 1250-1450 ℃; Temperature retention time was controlled at 1-5 hour; Oxygen flow is controlled at 3-8L/min.
The present invention obtains at pass regular micron and submicron order pore passage structure In through the regulation and control to sintering temperature
2O
3/ SnO
2Even growing nano noble metal granule on the gas sensitive; Increase specific surface area to improve gas sensing property through porous road structure on the one hand; Improve the selectivity of gas sensitive on the other hand through nano-noble metal, finally obtain the porous road structure gas sensitive highly sensitive, that selectivity is strong.The method that the present invention adopted has raw material and prepares simple, advantages such as cost is low, easy to control, production cleaning.
Embodiment
Embodiment 1:
With commercially available In
2O
3, SnO
2Powder and Ag powder (In
2O
3And SnO
2Total amount 0.05%), powder size is between 50-500nm, purity reaches 99.995%, (In in the punching block of packing into
2O
3: SnO
2=4: 1), be 90MPa according to pressing pressure, the condition of pressurize 3min is pressed into biscuit; Then biscuit is put into homemade sintering furnace and carry out the in-situ sintering growth, concrete sintering process is: be raised to 600 ℃ with 500 ℃/h heating rate, behind the insulation 1h; Be warmed up to 1300 ℃, insulation 5h cools off with stove at last; Oxygen flow keeps 8L/min in temperature-rise period, and oxygen requires purity to be higher than 99.999%, and dew point is lower than-72 ℃.
Embodiment 2:
With commercially available In
2O
3, SnO
2Powder and Pt powder (In
2O
3And SnO
2Total amount 0.05%), powder size is between 50-500nm, purity reaches 99.995%, (In in the punching block of packing into
2O
3: SnO
2=7: 3), be 65MPa according to pressing pressure, the condition of pressurize 2min is pressed into biscuit; Then biscuit is put into homemade sintering furnace and carry out the in-situ sintering growth, concrete sintering process is: be raised to 700 ℃ with 300 ℃/h heating rate, behind the insulation 2h; Be warmed up to 1450 ℃, insulation 2h preferably cools off with stove; Oxygen flow keeps 5L/min in temperature-rise period, and oxygen requires purity to be higher than 99.999%, and dew point is lower than-72 ℃.
Embodiment 3:
With commercially available In
2O
3, SnO
2Powder and Pd powder (In
2O
3And SnO
2Total amount 0.05%), powder size is between 50-500nm, purity reaches 99.995%, (In in the punching block of packing into
2O
3: SnO
2=3: 2), be 80MPa according to pressing pressure, the condition of pressurize 5min is pressed into biscuit; Then biscuit is put into homemade sintering furnace and carry out the in-situ sintering growth, concrete sintering process is: be raised to 650 ℃ with 80 ℃/h heating rate, behind the insulation 1h; Be warmed up to 1250 ℃, insulation 3h preferably cools off with stove; Oxygen flow keeps 3L/min in temperature-rise period, and oxygen requires purity to be higher than 99.999%, and dew point is lower than-72 ℃.
Claims (1)
1. the In of a doped precious metal
2O
3/ SnO
2The preparation method of porous road structure gas sensitive is characterized in that: with commercially available In
2O
3, SnO
2In punching block, be pressed into biscuit in the ratio of 4: 1 or 7: 3 or 3: 2 and precious metals pt or Pd or Ag powder, biscuit packed into carry out solid-phase sintering in the oxygen atmosphere sintering stove then, finally obtain nano-noble metal doping porous road structure In
2O
3/ SnO
2Gas sensitive, the addition of precious metals pt or Pd or Ag powder accounts for In
2O
3And SnO
20.05% of total amount; In-situ sintering growth of oxygen atmosphere sintering condition: heating rate 50-500 ℃/h; Insulation is divided into two sections, and first section temperature range 600-700 ℃, second section temperature range 1250-1450 ℃; Temperature retention time 1-5 hour; Oxygen flow 3-8L/min; Punching block pressing pressure: 60-90MPa; Dwell time: 2-5min; Oxygen requires purity to be higher than 99.999%, and dew point is lower than-72 ℃; Commercially available In
2O
3, SnO
2With precious metals pt or Pd or Ag powder, powder size is between 50-500nm, and purity reaches 99.995%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102741734A CN101973759B (en) | 2010-09-07 | 2010-09-07 | Preparation method of noble metal doped In2O3/SnO3 porous-channel structured gas-sensitive material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102741734A CN101973759B (en) | 2010-09-07 | 2010-09-07 | Preparation method of noble metal doped In2O3/SnO3 porous-channel structured gas-sensitive material |
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| Publication Number | Publication Date |
|---|---|
| CN101973759A CN101973759A (en) | 2011-02-16 |
| CN101973759B true CN101973759B (en) | 2012-11-28 |
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|---|---|---|---|
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104569081A (en) * | 2015-02-04 | 2015-04-29 | 吉林大学 | Ethanol gas sensor based on In2O3 microflower/SnO2 nanoparticle composite material and preparation method of sensor |
| CN104677950B (en) * | 2015-02-15 | 2018-03-06 | 南京益得冠电子科技有限公司 | Formaldehyde sensitive material and semiconductor formaldehyde sensor for semiconductor formaldehyde sensor |
| CN105523781B (en) * | 2015-12-04 | 2017-12-22 | 中国科学院合肥物质科学研究院 | It is modified with indium oxide film material of alumina-coated palladium nano-particles and its production and use |
| CN107352577B (en) * | 2017-06-28 | 2020-06-02 | 齐鲁工业大学 | Micro-nano net structure In2O3/SnO2Composite material and growing method thereof |
| CN107632115A (en) * | 2017-08-31 | 2018-01-26 | 武汉工程大学 | It is a kind of based on specific morphology, the MEMS gas sensings chip of size classification structured metal oxide and its manufacture method |
| CN108046829B (en) * | 2017-12-20 | 2020-06-16 | 东北大学 | Nonmetal mineral porous substrate and preparation method and application thereof |
| CN108918632B (en) * | 2018-06-29 | 2020-05-29 | 中国科学院合肥物质科学研究院 | Preparation method and application of palladium nanoparticle modified indium oxide nanosheet composite material |
Citations (4)
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|---|---|---|---|---|
| CN1167835A (en) * | 1997-03-17 | 1997-12-17 | 江阴市宏发合金材料厂 | Wire for silver-tin oxide or indium oxide electric contact and producing method thereof |
| CN1234591A (en) * | 1999-05-10 | 1999-11-10 | 昆明理工大学 | Synthesis method for preparing silver-tin dioxide electric contact materials |
| CN101170137A (en) * | 2007-11-21 | 2008-04-30 | 清华大学 | Medium hole carbon pole of dye sensitized solar battery and its making method |
| CN101219908A (en) * | 2007-09-21 | 2008-07-16 | 南京大学 | Multi-component metal oxide semiconductor mesoporous material and synthesizing method thereof |
-
2010
- 2010-09-07 CN CN2010102741734A patent/CN101973759B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167835A (en) * | 1997-03-17 | 1997-12-17 | 江阴市宏发合金材料厂 | Wire for silver-tin oxide or indium oxide electric contact and producing method thereof |
| CN1234591A (en) * | 1999-05-10 | 1999-11-10 | 昆明理工大学 | Synthesis method for preparing silver-tin dioxide electric contact materials |
| CN101219908A (en) * | 2007-09-21 | 2008-07-16 | 南京大学 | Multi-component metal oxide semiconductor mesoporous material and synthesizing method thereof |
| CN101170137A (en) * | 2007-11-21 | 2008-04-30 | 清华大学 | Medium hole carbon pole of dye sensitized solar battery and its making method |
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| CN101973759A (en) | 2011-02-16 |
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