CN105858730A - Carbon nitride/tungsten oxide composite hollow microsphere and preparation method thereof - Google Patents
Carbon nitride/tungsten oxide composite hollow microsphere and preparation method thereof Download PDFInfo
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- CN105858730A CN105858730A CN201610274264.5A CN201610274264A CN105858730A CN 105858730 A CN105858730 A CN 105858730A CN 201610274264 A CN201610274264 A CN 201610274264A CN 105858730 A CN105858730 A CN 105858730A
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- tungsten oxide
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- carbon nitride
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- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 50
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000004005 microsphere Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- -1 tungsten oxide compound Chemical class 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- 238000005829 trimerization reaction Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 abstract 1
- 239000011805 ball Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 8
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a carbon nitride/tungsten oxide composite hollow microsphere and a preparation method thereof. The microsphere is a hollow spherical shell layer jointly formed by carbon nitride and tungsten oxide. The microsphere is prepared by adopting tungstate and a carbon nitride precursor as raw materials and glucose sintered carbon spheres as structural templates and adopting a hydrothermal method and high-temperature calcination. The carbon nitride/tungsten oxide composite hollow microsphere has the beneficial effects that the microsphere has a hollow inner cavity; the shell is simultaneously formed by carbon nitride and tungsten oxide uniformly in a certain proportion, thus showing good uniformity; the hollow microsphere has larger specific surface area; the hollow inner cavity can provide more electromagnetic wave reflection paths, thus improving the external radiation energy absorption and utilization capabilities of the material.
Description
Technical field
The invention belongs to semiconductor composite technical field, be specifically related to a kind of carbonitride/tungsten oxide composite hollow micro-
Ball and preparation method thereof.
Background technology
Tungsten oxide inorganic semiconductor material has obtained the extensive concern of people because of the physicochemical properties of its uniqueness.Mesh
Before, tungsten oxide quasiconductor has obtained concrete in fields such as photocatalysis, photochromic, air-sensitive, electrochromism and Flied emission
Application.Researcher can prepare the tungsten oxide micro Nano material of multiple different size and pattern by all means, such as nanometer
Sheet, nanometer rods and hollow ball etc..Wherein, hollow ball tungsten oxide receives much concern with the pattern of its uniqueness, and it has higher ratio
Surface area, the advantage such as excellent weight capacity and low-density, this makes tungsten oxide have the most wide application space.As one
Kind of n-type semiconductor, tungsten oxide has certain photocatalytic activity, narrower energy gap can make its by excited by visible light, its
Valence band (VB) uppermost edge and TiO2Close, exceed H2O/O2Oxidation potential, therefore, produced by tungsten oxide bandgap excitation
Photohole can aoxidize a lot of Organic substance.Conduction band current potential yet with tungsten oxide is the lowest, light induced electron be prone to in air
O2Reaction, causes the decline of its photocatalytic activity.In order to improve physics and the chemical property of tungsten oxide further, pass through pattern
Regulation and control, element doping and compound from different semi-conducting materials, become the study hotspot of tungsten oxide material in recent years.
Patent CN102161510A discloses the preparation method of a kind of hollow porous tungsten oxide sphere, and the method is by wolframic acid
Ammonium, ammonium metatungstate are configured to solution, use spray drying device spray drying to prepare ammonium tungstate, ammonium metatungstate or its mixture
Hollow powder body, puts into this powder body heating in electric furnace and prepares hollow POROUS TUNGSTEN ball.But this tungsten oxide ball complicated process of preparation, and need
Want special spray-drying installation.Patent CN102266783A discloses a kind of Fe2O3 doping tungsten trioxide photocatalyst and preparation thereof
Method, with the compound of tungstenic and iron content as precursor, by both are mixed, the process such as grinding, high-temperature calcination, make raw material
It is converted into WO eventually3With the form of ferrum oxide, prepare the Tungstic anhydride. of Fe2O3 doping, but the composite specific surface area of this method be less,
Pattern does not has outstanding feature, and visible light-responded indifferent.
Summary of the invention
It is an object of the invention to provide one carbonitride/tungsten oxide compound hollow microballoon and preparation method thereof, prepared by this microsphere
Technique is simple, controlled, has higher specific surface area and good visible light-responded property, can be applicable to photocatalytic degradation and pollutes
Multiple fields such as thing, photovoltaic cell, solaode.
The technical solution realizing the object of the invention is: a kind of carbonitride/tungsten oxide compound hollow microballoon, described microsphere
It it is the hollow ball shell Rotating fields collectively formed by carbonitride, tungsten oxide.
Wherein, in described microsphere, the content of carbonitride is 5-10wt%.
The preparation method of above-mentioned compound hollow microballoon, employing tungstates and carbon nitride precursor are as raw material, with glucose
Sintering carbon ball is stay in place form, is prepared from by hydro-thermal method and high-temperature calcination, and it concretely comprises the following steps:
The Portugal that step a) adds in 0.02～0.05mol/L tungstates aqueous solution with tungstates mol ratio is 20:1～30:1
Grape sugar and with the carbon nitride precursor that tungstates mol ratio is 2:1～8:1, stir 0.5～1h, obtain uniform mixed solution；
Step b), by hydro-thermal reaction 16～24h at 180-200 DEG C of the mixed solution of gained in step a), naturally cools to room
Temperature, centrifugation, washing, and at 60 ± 10 DEG C, it is vacuum dried 6～12h, obtain carbonitride/tungsten oxide composite carbon ball；
The carbonitride of gained in step b)/tungsten oxide composite carbon ball is calcined 2～5h at 500～550 DEG C by step c), nature
It is cooled to room temperature, obtains carbonitride/tungsten oxide compound hollow microballoon material.
In step a), described tungstates is the one in sodium tungstate, ammonium tungstate, and described carbon nitride precursor is trimerization
One in cyanamide, dicyanodiamine, cyanamide, carbamide.
In step b), heating rate is 2 DEG C/min.
In step c), heating rate is 2～6 DEG C/min.
Compared with prior art, the invention has the beneficial effects as follows:
(1) present invention uses tungstates to be compound in carbon ball surface by hydro-thermal reaction, finally by forging with the presoma of carbonitride
Burning-off de-carbon ball template obtains hollow ball structure, and preparation process is simple, controlled.
(2) carbonitride of the present invention/tungsten oxide compound hollow microballoon has hollow lumen, and shell is simultaneously by carbonitride and oxygen
Changing tungsten uniformly to be constituted with certain proportion, demonstrate good homogeneity, tiny balloon has bigger specific surface area, hollow lumen energy
Enough providing more electromagnetic transmission reflection path, that improves material emittance to external world absorbs ability.
(3) carbonitride and two kinds of quasiconductor uniform contact in shell of tungsten oxide, form typical heterojunction semiconductor knot
Structure, can improve the material response range to light and the separation efficiency of photo-generated carrier, and then can significantly improve the photoelectricity of material
Performance.
Below in conjunction with the accompanying drawings the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of carbonitride/tungsten oxide compound hollow microballoon.
Fig. 2 is that (a is complete, b for the SEM photograph of embodiment 5 gained carbonitride/tungsten oxide compound hollow microballoon different-shape
Breach).
Fig. 3 is the TEM photo (a 40000 under embodiment 5 gained carbonitride/tungsten oxide compound hollow microballoon different multiples
Times, b 10 0000 times).
Fig. 4 is the XRD spectra of embodiment 5 carbonitrides/tungsten oxide compound hollow microballoon.
Fig. 5 is the FTIR spectrogram of embodiment 5 carbonitrides/tungsten oxide compound hollow microballoon.
Detailed description of the invention
The following examples can make those skilled in the art that the present invention is more fully understood.
Embodiment 1
Na by 0.330g (1.0mmol)2WO4·2H2O, 4.504g (25mmol) glucose and the single cyanogen of 0.336g (8mmol)
Amine is dissolved in 50ml deionized water, ultrasonic, and stirring 30min forms homogeneous solution.Above-mentioned middle mixed solution is transferred to rustless steel
In water heating kettle, in Muffle furnace, it is warming up to 200 DEG C with 2 DEG C/min, is incubated 20 hours.After natural cooling, centrifugal, use distilled water
With dehydrated alcohol cyclic washing 3 times, it is vacuum dried at 60 DEG C, obtains WO3-CN composite carbon ball.The composite carbon ball obtained is managed
Formula stove is heated to 500 DEG C with 2 DEG C/min, calcines 2 hours, natural cooling, finally give carbonitride/tungsten oxide and be combined
Tiny balloon.
Embodiment 2
Na by 0.330g (1.0mmol)2WO4·2H2O, 4.504g (25mmol) glucose and 0.252g (2mmol) trimerization
Cyanamide is dissolved in 50ml deionized water, ultrasonic, and stirring 30min forms homogeneous solution.Above-mentioned middle mixed solution is transferred to stainless
In steel water heating kettle, in Muffle furnace, it is warming up to 200 DEG C with 2 DEG C/min, is incubated 20 hours.After natural cooling, centrifugal, with distillation
Water and dehydrated alcohol cyclic washing 5 times, be vacuum dried at 60 DEG C, obtain WO3-CN composite carbon ball.The composite carbon ball obtained is existed
Tube furnace is heated to 500 DEG C with 5 DEG C/min, calcines 2 hours, natural cooling, finally give carbonitride/tungsten oxide multiple
Close tiny balloon.
Embodiment 3
Na by 0.330g (1.0mmol)2WO4·2H2O, 4.504g (25mmol) glucose and 0.481g (8mmol) carbamide
Being dissolved in 50ml deionized water, ultrasonic, stirring 30min forms homogeneous solution.Above-mentioned middle mixed solution is transferred to stainless steel water
In hot still, in Muffle furnace, it is warming up to 200 DEG C with 2 DEG C/min, is incubated 24 hours.After natural cooling, centrifugal, with distilled water and
Dehydrated alcohol cyclic washing 4 times, is vacuum dried at 60 DEG C, obtains WO3-CN composite carbon ball.By the composite carbon ball that obtains in tubular type
Stove is heated to 550 DEG C with 5 DEG C/min, calcines 5 hours, natural cooling, finally give carbonitride/tungsten oxide compound air
Heart microsphere.
Embodiment 4
(NH by 0.380g (0.125mmol)4)10W12O41, 4.504g (25mmol) glucose and 0.481g (8mmol) urine
Element is dissolved in 50ml deionized water, ultrasonic, and stirring 30min forms homogeneous solution.Above-mentioned middle mixed solution is transferred to rustless steel
In water heating kettle, in Muffle furnace, it is warming up to 200 DEG C with 2 DEG C/min, is incubated 18 hours.After natural cooling, centrifugal, use distilled water
With dehydrated alcohol cyclic washing 5 times, it is vacuum dried at 60 DEG C, obtains WO3-CN composite carbon ball.The composite carbon ball obtained is managed
Formula stove is heated to 500 DEG C with 2 DEG C/min, calcines 2 hours, natural cooling, finally give carbonitride/tungsten oxide and be combined
Tiny balloon.
Embodiment 5
Na by 0.330g (1.0mmol)2WO4·2H2O, 4.504g (25mmol) glucose and 0.336g (4mmol) dicyan
Diamidogen is dissolved in 50ml deionized water, ultrasonic, and stirring 30min forms homogeneous solution.Above-mentioned middle mixed solution is transferred to stainless
In steel water heating kettle, in Muffle furnace, it is warming up to 200 DEG C with 2 DEG C/min, is incubated 20 hours.After natural cooling, centrifugal, with distillation
Water and dehydrated alcohol cyclic washing 3 times, be vacuum dried at 60 DEG C, obtain WO3-CN composite carbon ball.The composite carbon ball obtained is existed
Tube furnace is heated to 550 DEG C with 2 DEG C/min, calcines 2 hours, natural cooling, finally give carbonitride/tungsten oxide multiple
Close tiny balloon.
Fig. 2 is the SEM photograph of carbonitride/tungsten oxide compound hollow microballoon, Fig. 2 a can be seen that carbonitride/tungsten oxide is combined
Tiny balloon rough surface, microsphere diameter is 1-3 μm, Fig. 2 b can be seen that microsphere has hollow structure, and shell is by receiving in a large number
Rice grain is constituted, wall thickness about 300nm.Analyzing through EDS, microsphere top layer is made up of tetra-kinds of elements of C, N, O, W, and wherein carbonitride contains
Amount is at about 5wt%.
Fig. 3 is the TEM photo of carbonitride/tungsten oxide compound hollow microballoon, it can be seen that micro-sphere structure is complete, diameter 1-3
μm, and microsphere has obvious hollow-core construction, and wall thickness is about 300nm.
Fig. 4 is the XRD spectra of carbonitride/tungsten oxide compound hollow microballoon, WO in figure3Each diffraction maximum and pure WO3Spread out
Penetrate peak the most completely the same, be g-C at 14.1 ° and 27.4 °3N4Two characteristic diffraction peaks, wherein diffraction maximum is corresponding at 14.1 °
In (100) crystal face, for seven piperazine architectural feature peak in layer, 27.4 ° of correspondence (002) crystal faces, for interlayer stacking characteristic peak, see spectrogram
Going out, at 14.1 °, characteristic peak is more weak little obvious, has less spike to occur at 27.4 °.This XRD spectra show this composite by
WO3And g-C3N4Collectively constitute.
Fig. 5 is the FTIR spectrogram of carbonitride/tungsten oxide compound hollow microballoon, and figure is at 600-800cm-1、1000-1500cm-1With 2800-3400 cm -1Absorption band is occurred in that at three.Wherein at 600-800 cm-1Strong absworption peak be WO3Feature is inhaled
Receive peak and composition g-C3N4The bending vibration characteristic peak of carbon azo-cycle of unit triazine；1000-1500 cm-1's
Weak absorbing band, then be g-C3N4 Carbon azacyclo-on C=N, C-N and the outer C-N stretching vibration absworption peak of ring；And
At 2800-3400 cm-1Absorption band be then probably g-C3N4NH and NH on edge breakage aromatic rings 2Group
Stretching vibration, or the stretching vibration of the hydrone of its Adsorption on Surface.
Claims (8)
1. carbonitride/tungsten oxide compound hollow microballoon, it is characterised in that described microsphere is common by carbonitride, tungsten oxide
The hollow ball shell Rotating fields constituted.
2. carbonitride/tungsten oxide compound hollow microballoon as claimed in claim 1, it is characterised in that nitrogenize in described microsphere
The content of carbon is 5-10wt%.
3. the preparation method of carbonitride/tungsten oxide compound hollow microballoon, it is characterised in that the steps include:
The Portugal that step a) adds in 0.02～0.05mol/L tungstates aqueous solution with tungstates mol ratio is 20:1～30:1
Grape sugar and with the carbon nitride precursor that tungstates mol ratio is 2:1～8:1, stir 0.5～1h, obtain uniform mixed solution；
Step b), by hydro-thermal reaction 16～24h at 180-200 DEG C of the mixed solution of gained in step a), naturally cools to room
Temperature, centrifugation, washing, and at 60 ± 10 DEG C, it is vacuum dried 6～12h, obtain carbonitride/tungsten oxide composite carbon ball；
The carbonitride of gained in step b)/tungsten oxide composite carbon ball is calcined 2～5h at 500～550 DEG C by step c), nature
It is cooled to room temperature, obtains carbonitride/tungsten oxide compound hollow microballoon material.
4. preparation method as claimed in claim 3, it is characterised in that in step a), described tungstates is sodium tungstate, wolframic acid
One in ammonium.
5. preparation method as claimed in claim 3, it is characterised in that in step a), described carbon nitride precursor is trimerization
One in cyanamide, dicyanodiamine, cyanamide, carbamide.
6. preparation method as claimed in claim 3, it is characterised in that in step b), heating rate is 2 DEG C/min.
7. preparation method as claimed in claim 3, it is characterised in that in step c), heating rate is 2～6 DEG C/min.
8. the application of the carbonitride as described in claim 1-7 is arbitrary/tungsten oxide compound hollow microballoon.
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| CN106311217A (en) * | 2016-08-19 | 2017-01-11 | 浙江师范大学 | Preparation method of Activated carbon functionalized tungsten oxide |
| CN106602023A (en) * | 2016-12-26 | 2017-04-26 | 武汉理工大学 | Method for in-situ synthesis of graphite phase carbon nitride-copper oxide composite material |
| CN106975476A (en) * | 2017-04-24 | 2017-07-25 | 陕西科技大学 | A kind of efficient tungstic acid microsphere photocatalyst and preparation method thereof |
| CN107999110A (en) * | 2017-11-14 | 2018-05-08 | 肇庆市华师大光电产业研究院 | A kind of Lacking oxygen tungsten oxide/nitridation carbon composite photocatalyst and its preparation method and application |
| CN108313989A (en) * | 2018-02-11 | 2018-07-24 | 济南大学 | One type lamella shape nitrogenizes the preparation method and products obtained therefrom of carbosphere |
| CN110545652A (en) * | 2019-07-26 | 2019-12-06 | 郑州航空工业管理学院 | Co/CoO-C composite material with porous structure and preparation method and application thereof |
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| CN111068730A (en) * | 2019-11-29 | 2020-04-28 | 东南大学 | Graphite-like hollow microsphere photocatalyst and preparation method and application method thereof |
| CN111408397A (en) * | 2020-03-30 | 2020-07-14 | 浙江工商大学 | Modified carbon nitride and tungsten oxide coupled p-n type heterojunction composite material and preparation method and application thereof |
| CN111889122A (en) * | 2019-05-06 | 2020-11-06 | 天津大学 | Tungsten trioxide/graphite phase carbon nitride composite material and preparation method thereof |
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| CN104772158A (en) * | 2015-03-23 | 2015-07-15 | 上海应用技术学院 | Preparation method of WO3/C3N4 mixed photocatalyst |
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Patent Citations (1)
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| CN104772158A (en) * | 2015-03-23 | 2015-07-15 | 上海应用技术学院 | Preparation method of WO3/C3N4 mixed photocatalyst |
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| CN108313989A (en) * | 2018-02-11 | 2018-07-24 | 济南大学 | One type lamella shape nitrogenizes the preparation method and products obtained therefrom of carbosphere |
| CN108313989B (en) * | 2018-02-11 | 2021-08-10 | 济南大学 | Preparation method of mushroom-like pleated carbon nitride microspheres and obtained product |
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| CN111977689A (en) * | 2020-07-09 | 2020-11-24 | 南阳师范学院 | Niobium pentoxide microsphere with hollow structure and preparation method and application thereof |
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| CN114772646B (en) * | 2022-04-29 | 2023-11-10 | 福州大学 | Preparation method of tungsten oxide nano material and application of tungsten oxide nano material in photocatalytic desulfurization |
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