CN110436515A - A kind of mesoporous SnO of black rich in Lacking oxygen2Nanometer sheet and preparation method thereof - Google Patents
A kind of mesoporous SnO of black rich in Lacking oxygen2Nanometer sheet and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001301 oxygen Substances 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 25
- 229910052786 argon Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 14
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 11
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000003708 ampul Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2006/17—Pore diameter distribution
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Abstract
The present invention relates to a kind of mesoporous SnO of the black rich in Lacking oxygen2Nanometer sheet and preparation method thereof specifically comprises the following steps: that (1) prepares SnS using chemical vapor deposition process2Nanometer sheet precursor；(2) by SnS2Nanometer sheet precursor is placed in atmosphere furnace, and calcining obtains the mesoporous SnO of ordinary white in an oxidizing atmosphere2Nanometer sheet；(3) by the mesoporous SnO of white2Nanometer sheet is placed in atmosphere furnace, is annealed in argon gas and hydrogen mixed gas atmosphere to obtain the mesoporous SnO of black for being rich in Lacking oxygen2Nanometer sheet.The invention has the advantages that its preparation process is simple, at low cost, pollution-free, the sample finally obtained is the nanometer sheet with meso-hole structure, and large specific surface area, electric property are excellent, and has obvious absorption to visible light.Gained sample of the invention can be widely used for the fields such as air-sensitive, catalysis, solar battery, lithium ion battery.
Description
Technical field
The present invention relates to novel inorganic field of nano material preparation, refer in particular to a kind of mesoporous SnO of the black rich in Lacking oxygen2It receives
Rice piece and preparation method thereof.
Background technique
SnO2It is a kind of semiconductor of broad stopband, physicochemical properties are stablized, and have good optical, electricity and structure special
Property, therefore broad application prospect is all had in fields such as air-sensitive, catalysis, solar battery, lithium ion batteries.However, due to
Intrinsic SnO2Greater band gap (3.5~4.0eV), it is difficult to absorb visible light, cause it right in photocatalysis and solar battery
Solar energy use less efficient.In addition, its poor electric conductivity makes its application performance in terms of air-sensitive and lithium ion battery
It is bad.Therefore, regulate and control SnO2Band structure, improve its electrical and optical properties help to be promoted its applications in various fields with
Development prospect.Research has shown that, Lacking oxygen defect is introduced in oxide semiconductor, can generate lack related new with Lacking oxygen
Energy level or shallow donor's energy level are fallen into, so as to adjust its band structure, reaches and widens its optical response range, improves photoproduction current-carrying
The purpose (G.Wang et al., Nano Today, 2017,13,23.) of sub- separative efficiency and electric conductivity.In addition, the knot of material
Structure and pattern are also an important factor for influencing its performance.SnO reported in the literature in relation to being rich in Lacking oxygen defect2It is all nanometer
Grain is stacked between sample, electrical and optical properties it is poor (W.J.Dong et al., Adv.Mater., 2017,29,
1700136；Y.J.Yang et al.,Appl.Surf.Sci.,2017,420,399.).In order to overcome SnO2Nano-powder material
The shortcomings that material, realizes the SnO for being rich in Lacking oxygen2The preparation of nanometer sheet can establish important base for its basic research and practical application
Plinth.Therefore, it is necessary to develop a kind of SnO rich in Lacking oxygen defect2Nanometer sheet and preparation method thereof.
Summary of the invention
The purpose of the present invention is to provide a kind of mesoporous SnO of the black rich in Lacking oxygen2Nanometer sheet and preparation method thereof, this
Invention advantage is that its preparation process is simple, at low cost, pollution-free, and the sample finally obtained is the nanometer with meso-hole structure
Piece, large specific surface area, electric property are excellent, and have obvious absorption to visible light.Gained sample of the invention can be used extensively
In fields such as air-sensitive, catalysis, solar battery, lithium ion batteries.
Technical scheme is as follows:
A kind of mesoporous SnO of black rich in Lacking oxygen2Nanometer sheet and preparation method thereof, the specific steps are as follows:
Step 1: SnS is prepared using chemical vapor deposition process on substrate2Nanometer sheet precursor；
Step 2: by SnS2Nanometer sheet precursor is placed in calcining in atmosphere furnace and obtains the mesoporous SnO of ordinary white2Nanometer
Piece；
Step 3: by the mesoporous SnO of ordinary white2Nanometer sheet is placed in reducing atmosphere furnace, in certain proportion argon gas and hydrogen
It is annealed in mixed atmosphere to obtain the mesoporous SnO of black for being rich in Lacking oxygen2Nanometer sheet.
Further, chemical vapor deposition described in step 1 carries out in tube furnace, and raw material is four chlorination of sulphur powder and five water
Glass putty, mass ratio 2/1, growth substrates are Fluorin doped tin dioxide transparent conductive glass (FTO) or carbon paper (CP).
Further, preparation SnS described in step 12The growth temperature of nanometer sheet precursor is 450-500 DEG C, when growth
Between be 5-20min, growth substrates be placed in stannic chloride pentahydrate powder downstream away from its 5~15cm at.When furnace temperature is down to room temperature, taking-up sample
Product obtain yellow SnS2Nanometer sheet presoma.
Further, SnS in step 22Calcination temperature of the nanometer sheet precursor in oxidizing atmosphere furnace is 450-600 DEG C,
Heating rate is 2-5 DEG C/min, soaking time 60-180min.When furnace temperature is down to room temperature, taking-up sample obtains ordinary white
Mesoporous SnO2Nanometer sheet.
Further, the flow of argon gas and hydrogen is respectively 40-80sccm and 10- in mixed atmosphere described in step 3
20sccm, heating rate are 5-10 DEG C/min, and soaking time 30-90min, annealing temperature is 400-500 DEG C.When furnace temperature is down to
Room temperature takes out sample, final to obtain the mesoporous SnO of black for being rich in Lacking oxygen2Nanometer sheet, pore size 10-50nm.
As described above, the present invention is rich in the mesoporous SnO of black of Lacking oxygen2The advantage of nanometer sheet and preparation method thereof is:
1, with SnS2Nanometer sheet is presoma, and calcining obtains the SnO of porous structure2Nanometer sheet, the nanometer sheet maintain SnS2
The vertical arrangement and sheet-like morphology of presoma；
2, the present invention can finally obtain the mesoporous SnO of black2Nanometer sheet, large specific surface area, electric property are excellent, to purple
Outside-visible light has obvious absorption；
3, it is high that size uniformity, good dispersion, crystallinity can be prepared on electro-conductive glass (FTO) and carbon paper (CP) substrate
SnS2Presoma obtains the mesoporous SnO of black of corresponding appearance structure by calcining and making annealing treatment2Nanometer sheet；
4, preparation process of the present invention is simple, reproducible, is the mesoporous SnO of black2Nano material in air-sensitive, urge
The extensive use and basic research in the fields such as change, solar battery, lithium ion battery provide reliable preparation means.
Detailed description of the invention
Fig. 1 is the SnS obtained on FTO substrate according to embodiment 12The SnO of nanometer sheet, white2Nanometer sheet and black are mesoporous
SnO2Nanometer sheet optical contrast photo.
Fig. 2 is the SnS prepared according to embodiment 22The SnO of nanometer sheet, white2Nanometer sheet and the mesoporous SnO of black2Nanometer sheet
Electron scanning micrograph (SEM).
Fig. 3 is the white SnO that the present invention obtains2Nanometer sheet and the mesoporous SnO of black2The X-ray diffraction pattern of nanometer sheet
(XRD)。
Fig. 4 is the white SnO prepared according to embodiment 12Nanometer sheet and the mesoporous SnO of black2(a) ultraviolet-visible of nanometer sheet
Optical absorption spectra and (b) accordingly hold in the palm gram curve graph.
Fig. 5 is the SnS prepared according to embodiment 22The SnO of nanometer sheet, white2Nanometer sheet and the mesoporous SnO of black2Nanometer sheet
(a) nitrogen suction-desorption curve and (b) pore size distribution curve.
Fig. 6 is the white SnO prepared according to embodiment 12Nanometer sheet and the mesoporous SnO of black2The electron spin resonance of nanometer sheet
(ESR) map.
Fig. 7 is the SnS prepared according to embodiment 12The SnO of nanometer sheet, white2Nanometer sheet and the mesoporous SnO of black2Nanometer sheet
Electric conductivity: (a) current -voltage curve of the corresponding semilog form of current -voltage curve and (b).
Specific embodiment
Embodiment 1
Step 1: firstly, 200mg sulphur powder and 100mg stannic chloride pentahydrate powder are contained in independent aluminum oxide boat,
Be respectively placed in the quartz ampoule of atmosphere furnace, and by FTO substrate be placed in stannic chloride pentahydrate powder downstream away from its 9cm at；Secondly, with
Flow is that 1200sccm argon gas continues 10min and empties quartzy inner air tube, be subsequently passed flow be respectively 45sccm with
The argon gas and hydrogen of 15sccm is as current-carrying gas；Finally, with the heating rate of 10 DEG C/min respectively by sulphur powder and five water tetrachloros
Change warm area locating for glass putty and rises to 250 DEG C and 450 DEG C；Room temperature is down to the rate of temperature fall of 10 DEG C/min after heat preservation 5min, is obtained light
Yellow SnS2Nanometer sheet presoma.
Step 2: by the SnS of preparation2Nanometer sheet presoma is placed in atmosphere furnace, in air with the heating speed of 2 DEG C/min
Furnace temperature is risen to 500 DEG C by rate, and keeps 120min so that faint yellow SnS at such a temperature2Nanometer sheet is converted into ordinary white SnO2
Nanometer sheet.
Step 3: by the white SnO of acquisition2Nanometer sheet is placed in atmosphere furnace, and reducing atmosphere is the mixing of hydrogen/argon gas
Atmosphere (flow 10/60sccm) sets 450 DEG C for warm area holding temperature locating for sample with the heating rate of 10 DEG C/min,
Rate of temperature fall is likewise provided as 10 DEG C/min, anneals 60min to obtain the mesoporous SnO of black for being rich in Lacking oxygen2Nanometer sheet.
Embodiment 2
Step 1: firstly, 200mg sulphur powder and 100mg stannic chloride pentahydrate powder are contained in independent aluminum oxide boat,
Be respectively placed in the quartz ampoule of atmosphere furnace, and by carbon paper CP substrate be placed in stannic chloride pentahydrate powder downstream away from its 9cm at；Its
It is secondary, be that 1200sccm argon gas continues 10min and empties quartzy inner air tube with flow, be subsequently passed flow be respectively 45sccm and
The argon gas and hydrogen of 15sccm is as current-carrying gas；Finally, with the heating rate of 10 DEG C/min respectively by sulphur powder and five water tetrachloros
Change warm area locating for glass putty and rises to 250 DEG C and 450 DEG C；Room temperature is down to the rate of temperature fall of 10 DEG C/min after heat preservation 5min, is obtained light
Yellow SnS2Nanometer sheet presoma.
Step 2: by the SnS of preparation2Nanometer sheet presoma is placed in atmosphere furnace, in air with the heating speed of 2 DEG C/min
Furnace temperature is risen to 500 DEG C by rate, and keeps 120min so that faint yellow SnS at such a temperature2Nanometer sheet is converted into ordinary white SnO2
Nanometer sheet.
Step 3: by the white SnO of acquisition2Nanometer sheet is placed in atmosphere furnace, and reducing atmosphere is the mixing of hydrogen/argon gas
Atmosphere (flow 10/60sccm) sets 450 DEG C for warm area holding temperature locating for sample with the heating rate of 10 DEG C/min,
Rate of temperature fall is likewise provided as 10 DEG C/min, anneals 60min to obtain the mesoporous SnO of black for being rich in Lacking oxygen2Nanometer sheet.
Embodiment 3
Step 1: firstly, 100mg sulphur powder and 50mg stannic chloride pentahydrate powder are contained in independent aluminum oxide boat,
Be respectively placed in the quartz ampoule of atmosphere furnace, and by FTO or CP substrate be placed in stannic chloride pentahydrate powder downstream away from its 11cm at；Its
It is secondary, be that 1200sccm argon gas continues 10min and empties quartzy inner air tube with flow, be subsequently passed flow be respectively 45sccm and
The argon gas and hydrogen of 15sccm is as current-carrying gas；Finally, with the heating rate of 10 DEG C/min respectively by sulphur powder and five water tetrachloros
Change warm area locating for glass putty and rises to 250 DEG C and 480 DEG C；Room temperature is down to the rate of temperature fall of 10 DEG C/min after heat preservation 5min, is obtained light
Yellow SnS2Nanometer sheet presoma.
Step 2: by the SnS of preparation2Nanometer sheet presoma is placed in atmosphere furnace, with the liter of 3 DEG C/min in air atmosphere
Furnace temperature is risen to 550 DEG C by warm rate, and keeps 90nin so that faint yellow SnS at such a temperature2Nanometer sheet is converted into ordinary white
SnO2Nanometer sheet.
Step 3: by the white SnO of acquisition2Nanometer sheet is placed in atmosphere furnace, in hydrogen/argon gas mixed atmosphere (flow
To heat the sample to 400 DEG C in 10/60sccm) with the heating rate of 5 DEG C/min, rate of temperature fall be likewise provided as 10 DEG C/
Min anneals 90min to obtain the mesoporous SnO of black for being rich in Lacking oxygen2Nanometer sheet.
Embodiment 4
Step 1: firstly, 300mg sulphur powder and 150mg stannic chloride pentahydrate powder are contained in independent aluminum oxide boat,
Be respectively placed in the quartz ampoule of atmosphere furnace, and by FTO or CP substrate be placed in stannic chloride pentahydrate powder downstream away from its 5cm at；Its
It is secondary, be that 1200sccm argon gas continues 10min and empties quartzy inner air tube with flow, be subsequently passed flow be respectively 45sccm and
The argon gas and hydrogen of 15sccm is as current-carrying gas；Finally, with the heating rate of 10 DEG C/min respectively by sulphur powder and five water tetrachloros
Change warm area locating for glass putty and rises to 250 DEG C and 500 DEG C；Room temperature is down to the rate of temperature fall of 10 DEG C/min after heat preservation 5min, is obtained light
Yellow SnS2Nanometer sheet presoma.
Step 2: by the SnS of preparation2Nanometer sheet presoma is placed in atmosphere furnace, in air with the heating speed of 3 DEG C/min
Furnace temperature is risen to 600 DEG C by rate, and keeps 120nin so that SnS at such a temperature2Nanometer sheet is converted into ordinary white SnO2Nanometer
Piece.
Step 3: by the mesoporous SnO of white of acquisition2Nanometer sheet is placed in atmosphere furnace, in hydrogen/argon gas mixed atmosphere
500 DEG C are heated the sample to the heating rate of 5 DEG C/min in (flow 10/60sccm), rate of temperature fall is likewise provided as 10
DEG C/min, 30min is annealed to obtain the mesoporous SnO of black for being rich in Lacking oxygen2Nanometer sheet.
Fig. 1 is the SnS obtained on FTO substrate according to embodiment 12The SnO of nanometer sheet, white2Nanometer sheet and black are mesoporous
SnO2Nanometer sheet optical contrast photo.It can be seen that being grown on the SnS on transparent FFTO substrate2Sample is in yellow, high-temperature calcination
It is transformed to the SnO of white afterwards2, then after annealing in hydrogen/argon gas mixed atmosphere become black, and black then mainly by
In SnO2Caused by strong absorption of the doped energy-band caused by Lacking oxygen defect existing for inside nanometer sheet to ultraviolet-visible light.
Fig. 2 is the SnS obtained on carbon paper according to embodiment 22The SnO of nanometer sheet, white2Nanometer sheet and black are mesoporous
SnO2Scanning electron microscope (SEM) figure of nanometer sheet.It can be seen that SnS2Relatively smooth (the figure in nanometer sheet presoma surface
A and d), the white SnO obtained after calcining2The surface of nanometer sheet presents obvious coarse porous structure feature (figure b and e),
The black SnO further obtained after annealing2Nanometer sheet surface equally shows coarse and porous structure feature, and with it is original
SnO2Consistent (the figure c and f) of nanometer sheet, shows that it maintains its original pattern knot during subsequent Lacking oxygen introduces
Structure, and this is exactly one of the peculiar advantage of Lacking oxygen design.
Fig. 3 is the SnO of the white prepared according to embodiment 22Nanometer sheet and the mesoporous SnO of black2The X-ray diffraction of nanometer sheet
(XRD) phenogram.It can be seen that the mesoporous SnO of ordinary white2The XRD characteristic peak of sample corresponds to four directions SnO2(JCPDS
No.41-1445), the mesoporous sample of black after annealing maintains the crystal structure, illustrates its crystal knot after introducing Lacking oxygen defect
There is no variations for structure.
Fig. 4 is the SnO of the white prepared according to embodiment 12Nanometer sheet and the mesoporous SnO of black2(a) of nanometer sheet be ultraviolet-and it can
Light-exposed absorption spectra and (b) accordingly hold in the palm gram curve graph.From figure a as can be seen that with ordinary white SnO2Nanometer sheet sample is compared, black
Color SnO2The absorption of ultraviolet-visible light is remarkably reinforced in nanometer sheet sample, to the light in entire 300~800nm wave-length coverage
Stronger absorption is all had, and then has confirmed the fact that there are a large amount of Lacking oxygen defects in black sample from side.In addition, figure
That the linear segment of support gram curve is extrapolated in b is white SnO2With black SnO2The optical energy band of sample.As seen from the figure, white
The bandwidth of tinctorial pattern product is about 3.48eV, and black sample bandwidth is then reduced to 2.96eV.Sample is obviously reduced after annealing
Optical energy band and the light absorpting ability that significantly increases be mainly due to black SnO2What Lacking oxygen present in sample was formed lacks
Fall into energy level.
Fig. 5 is the SnS prepared according to embodiment 22The SnO of nanometer sheet, white2Nanometer sheet and the mesoporous SnO of black2Nanometer sheet
(a) nitrogen suction-desorption curve and (b) pore size distribution curve.As can be seen that the nitrogen adsorption desorption curve of all test samples is equal
It can be attributed to IV- type thermoisopleth, SnS2The specific surface area of sample is about 12.67m2/ g, white SnO2With black SnO2The ratio of sample
Surface area has then respectively reached 41.26m2/ g and 44.87m2/ g is more than as many as the former three times (figure a).With ordinary white
SnO2Sample is compared, black SnO2Specific surface area possessed by sample is bigger.In addition, figure b the results show that each sample aperture
It focuses primarily upon between 10~50nm, shows its meso pore characteristics.Wherein, SnS2The aperture of sample be 29.40nm, and white and
SnO2With black SnO2The average pore size of sample is then respectively 17.28nm and 16.57nm.
Fig. 6 is the SnO of white prepared by the present invention2Nanometer sheet and the mesoporous SnO of black2The electron spin resonance of nanometer sheet
(ESR) map.As can be seen that an apparent signal peak occur at g=2.003 in all samples, and this is just derived from
By SnO2ESR characteristic signal caused by the unpaired electron that Lacking oxygen fetters in sample.It can be sentenced according to ESR signal strength
It is disconnected, black SnO2Oxygen vacancy concentration possessed by sample will be much higher than ordinary white sample.
Fig. 7 is SnS prepared by the present invention2The SnO of nanometer sheet, white2Nanometer sheet and the mesoporous SnO of black2The conduction of nanometer sheet
Property: (a) current -voltage curve of current -voltage curve and (b) corresponding semilog form.As can be seen that as reference
SnS2Slope of the sample in entire test scope is almost nil, illustrates that its electric conductivity is very poor；White SnO2With black SnO2Sample
With the slope significantly increased, show its electric conductivity with higher.And with ordinary white SnO2Sample is compared, and black is mesoporous
SnO2The electric conductivity of sample is significantly better than the former again.
Claims (6)
1. a kind of mesoporous SnO of black rich in Lacking oxygen2Nanometer sheet and preparation method thereof, it is characterised in that this method specifically includes
Following steps:
Step 1: SnS is grown using chemical vapor deposition process on substrate2Nanometer sheet precursor；
Step 2: by SnS2Nanometer sheet precursor is calcined in atmosphere furnace obtains the mesoporous SnO of ordinary white2Nanometer sheet；
Step 3: by the mesoporous SnO of ordinary white2Nanometer sheet is placed in reducing atmosphere furnace, is moved back in argon gas and hydrogen mixed gas atmosphere
Fire is rich in the mesoporous SnO of black of Lacking oxygen to obtain2Nanometer sheet.
2. the mesoporous SnO of a kind of black rich in Lacking oxygen according to claim 12Nanometer sheet and preparation method thereof, feature
Be: chemical vapor deposition described in step 1 carries out in atmosphere protection stove, and protective atmosphere is the inert gases such as argon gas, raw material
For sulphur powder and stannic chloride pentahydrate powder, mass ratio 2/1, growth substrates are Fluorin doped tin dioxide transparent conductive glass
(FTO) or carbon paper (CP).
3. the mesoporous SnO of a kind of black rich in Lacking oxygen according to claim 12Nanometer sheet and preparation method thereof, feature
It is: preparation SnS described in step 12The growth temperature of nanometer sheet precursor is 450-500 DEG C, growth time 5-
20min, growth substrates are placed in stannic chloride pentahydrate powder downstream, at its 5~15cm.
4. the mesoporous SnO of a kind of black rich in Lacking oxygen according to claim 12Nanometer sheet and preparation method thereof, feature
It is: SnS in step 22Calcination temperature of the nanometer sheet precursor in atmosphere furnace is 450-600 DEG C, and oxidizing atmosphere can be with
It is air or oxygen, heating rate is 2-5 DEG C/min, soaking time 60-180min.
5. the mesoporous SnO of a kind of black rich in Lacking oxygen according to claim 12Nanometer sheet and preparation method thereof, feature
Be: the flow of argon gas and hydrogen is respectively 40-80sccm and 10-20sccm, heating in mixed atmosphere described in step 3
Rate is 5-10 DEG C/min, and soaking time 30-90min, annealing temperature is 400-500 DEG C.
6. the mesoporous SnO of a kind of black rich in Lacking oxygen according to claim 12Nanometer sheet and preparation method thereof, feature
It is: the mesoporous SnO of black2The pore size of nanometer sheet is 10-50nm.
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| CN111362306A (en) * | 2020-03-20 | 2020-07-03 | 湖南特种金属材料有限责任公司 | Preparation method and preparation equipment of spherical porous manganous-manganic oxide |
| CN113024128A (en) * | 2021-03-31 | 2021-06-25 | 桂林理工大学 | Tin disulfide-C3N4Nano-sheet array photo-anode and preparation method thereof |
| CN113461052A (en) * | 2021-07-08 | 2021-10-01 | 中国科学技术大学 | Black oxygen-enriched vacancy bismuth subcarbonate nanosheet and preparation method and application thereof |
| CN114314521A (en) * | 2022-01-21 | 2022-04-12 | 陕西科技大学 | Method for controllable generation of oxygen vacancy in metal oxide |
| CN114477269A (en) * | 2022-01-29 | 2022-05-13 | 扬州大学 | Preparation method and application of oxygen-defect-rich perovskite gas sensitive material |
| CN115676873A (en) * | 2022-10-08 | 2023-02-03 | 电子科技大学长三角研究院(湖州) | Defect-state tin oxide normal-temperature sensing material, preparation method and application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111362306A (en) * | 2020-03-20 | 2020-07-03 | 湖南特种金属材料有限责任公司 | Preparation method and preparation equipment of spherical porous manganous-manganic oxide |
| CN111362306B (en) * | 2020-03-20 | 2022-06-17 | 湖南特种金属材料有限责任公司 | Preparation method and preparation equipment of spherical porous manganous-manganic oxide |
| CN113024128A (en) * | 2021-03-31 | 2021-06-25 | 桂林理工大学 | Tin disulfide-C3N4Nano-sheet array photo-anode and preparation method thereof |
| CN113461052A (en) * | 2021-07-08 | 2021-10-01 | 中国科学技术大学 | Black oxygen-enriched vacancy bismuth subcarbonate nanosheet and preparation method and application thereof |
| CN114314521A (en) * | 2022-01-21 | 2022-04-12 | 陕西科技大学 | Method for controllable generation of oxygen vacancy in metal oxide |
| CN114477269A (en) * | 2022-01-29 | 2022-05-13 | 扬州大学 | Preparation method and application of oxygen-defect-rich perovskite gas sensitive material |
| CN115676873A (en) * | 2022-10-08 | 2023-02-03 | 电子科技大学长三角研究院(湖州) | Defect-state tin oxide normal-temperature sensing material, preparation method and application |
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