CN108295832A - A kind of porous ZnO composite hollow sphere catalyst and preparation method thereof - Google Patents
A kind of porous ZnO composite hollow sphere catalyst and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 63
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 15
- 239000004246 zinc acetate Substances 0.000 claims description 15
- 239000000084 colloidal system Substances 0.000 claims description 13
- 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 description 12
- 239000008103 glucose Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 219
- 239000011787 zinc oxide Substances 0.000 description 117
- 239000000523 sample Substances 0.000 description 20
- 239000003575 carbonaceous material Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 19
- 230000001699 photocatalysis Effects 0.000 description 16
- 238000001354 calcination Methods 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 13
- 238000007146 photocatalysis Methods 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000031700 light absorption Effects 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- -1 ZnO compound Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
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- 230000002349 favourable effect Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- 230000000630 rising effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
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- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005247 gettering Methods 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B01J35/40—
-
- B01J35/51—
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/159—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with reducing agents other than hydrogen or hydrogen-containing gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a kind of porous ZnO composite hollow sphere catalyst, including hollow carbon ball and the ZnO particle that is coated in the carbon ball.In porous ZnO composite hollow sphere catalyst of the present invention, the mass fraction that the carbon ball accounts for the porous ZnO composite hollow sphere catalyst is 56.4% 78.2%.In porous ZnO composite hollow sphere catalyst of the present invention, the diameter dimension of composite hollow ball is 100 600 nanometers in the porous ZnO composite hollow sphere catalyst.The present invention also provides a kind of preparation methods of porous ZnO composite hollow sphere catalyst, include the following steps：S1, synthetic colloidal substance carbon ball；S2 synthesizes porous ZnO composite hollow sphere catalyst.
Description
Technical field
The present invention relates to environmental protection and energy field of functional materials, particularly, are related to a kind of porous ZnO composite hollow ball catalysis
Agent and preparation method thereof.
Background technology
As environmental problem is on the rise in global range, traditional fossil energy it is depleted, environment is controlled
New alternative energy source is repaired and sought to reason becomes the focus of whole world extensive concern.Since the material of nano-scale is in optics, electricity
It learns, magnetics and catalysis etc. have extremely special property, trans-utilization of the Nano semiconductor photocatalysis technology to solar energy
As one of the grand strategy solved these problems.In the oxide semiconductor photochemical catalyst of numerous research and development, due to
TiO2High with the catalytic activity of ZnO, at low cost, stability is high and environmental-friendly, they are considered in Photocatalyzed Hydrogen Production, CO2Also
Former and contaminant degradation etc. is excellent photochemical catalyst.And wherein, zinc oxide (ZnO) can very easily construct ideal
Nanostructure, be influence light-catalyzed reaction activity one of key factor.
Nano-ZnO is direct band gap (3.32eV) semiconductor, and photoelectron combines energy (60meV) high, in solar cell, changes
Sensing is learned, the fields such as piezoelectricity and photoelectric device suffer from a large amount of application.Some characteristics of nano material are all rather depending on it
Extrinsic characteristic, such as appearance structure, crystallite dimension and specific surface area etc..Thus, many outstanding research work are by receiving
Rice appearance of ZnO structure regulates and controls to promote the activity of light-catalyzed reaction, such as nanometer rods, and nano-array, nanoparticle and nanometer are empty
Bulbus cordis etc..Remaining equal reports pass through glucose/ZnCl2After mixed solution hydro-thermal one kettle way ZnO hollow balls have been synthesized through calcining.Experiment
The specific surface area of the semiconductor hollow ball of synthesis as mole proportion of glucose rises and increases, urge by the sample light of best performance
The efficiency for changing rhodamine B degradation (RhB) is higher than commercial catalysts P25.Lee etc. also report a kind of one-step method polyoxometallate
(H3PW12O40) assist non-template electrochemical method synthesize ZnO hollow balls.Hollow ball structure can be effectively increased photocatalysis
The specific surface area and active site of agent, and absorption and utilization to light are increased by scattering of the incident light in hollow-core construction.
However, since high temperature is unfavorable for Zn2+Absorption in carbon ball template, one pot of hydro-thermal method low output, size are uneven.And ZnO
It is sensitive to pH, electrochemistry H2O2Oxidizing process can make ZnO hollow ball structures unstable.
Invention content
In order to solve the problems in the existing technology the present invention, provides a kind of porous ZnO composite hollow sphere catalyst,
Including hollow carbon ball and the ZnO particle being coated in the carbon ball.
In porous ZnO composite hollow sphere catalyst of the present invention, the carbon ball accounts for the porous ZnO composite hollow ball
The mass fraction of catalyst is 56.4%-78.2%.
It is multiple in the porous ZnO composite hollow sphere catalyst in porous ZnO composite hollow sphere catalyst of the present invention
The diameter dimension for closing hollow ball is 100-600 nanometers.
The present invention also provides a kind of preparation methods of porous ZnO composite hollow sphere catalyst, include the following steps：
S1, synthetic colloidal substance carbon ball；
S2 synthesizes porous ZnO composite hollow sphere catalyst.
In the preparation method of porous ZnO composite hollow sphere catalyst of the present invention, step S1 specifically includes as follows
Step：
Glucose is dissolved in pure water by S11, stirs to clarify solution, and the glucose that a concentration of 0.1g/ml is made is molten
Liquid；
The glucose solution prepared is transferred in reaction kettle hydro-thermal 8 hours under 180 degree by S12；
The product obtained in step S12 is washed with deionized water and ethyl alcohol, and dried by S13.
In the preparation method of porous ZnO composite hollow sphere catalyst of the present invention, step S2 specifically includes as follows
Step：
Zinc acetate is dissolved in pure water by S21, stirs to being completely dissolved, the zinc acetate solution of 5mg/ml is made；
The colloid carbon ball prepared in step S1 is added in zinc acetate solution, and seals ultrasonic disperse 10 and divides by S22
Then clock stirs 6 hours；
S23, by the mixed solution obtained in S22 still aging 10 hours obtained C/ZnO composite materials at room temperature；
The C/ZnO composite materials are placed in crucible and are capped by S24, are calcined 1 hour under 400-500 degrees Celsius.
In the preparation method of porous ZnO composite hollow sphere catalyst of the present invention, step S22 is specially：Take 60
The colloid carbon ball prepared in 0.3 gram of step S1 is added in the zinc acetate solution prepared in the step S21 of milliliter, and seals super
Sound disperses 10 minutes, then stirs 6 hours.
In one embodiment of the preparation method of porous ZnO composite hollow sphere catalyst of the present invention, step S24
It is capped specifically, the C/ZnO composite materials are placed in crucible, is calcined 1 hour under 400 degrees Celsius.
In another embodiment of the preparation method of porous ZnO composite hollow sphere catalyst of the present invention, step
S24 is capped specifically, the C/ZnO composite materials are placed in crucible, is calcined 1 hour under 450 degrees Celsius.
Advantageous effect：The present invention has synthesized porous ZnO based on the preparation of carbon ball template using simple ionic adsorption principle and has answered
Hollow ball catalyst is closed, and by adjusting the content of carbonaceous material in calcination temperature systematicness control hollow ball.Experimental result is sent out
It is existing, when carbon content is about 56.4%, photo catalytic reduction CO2 activity highests.The introducing of carbon material significantly improves composite photocatalyst
The visible absorption and CO2 of agent are adsorbed, and will produce local heat effect, are conducive to charge transmission.It is of the present invention porous
ZnO composite hollow sphere catalysts have preparation method simple, the high advantageous effect of photocatalysis effect.
Description of the drawings
Fig. 1 is the structure and its Catalysis Principles figure of the porous ZnO composite hollow sphere catalyst described in the embodiment of the present invention；
Fig. 2 a-2f are that product is swept in porous ZnO composite hollow ball catalyst preparation process described in the embodiment of the present invention
Electron microscope is retouched, wherein Fig. 2 a are the scanning electron microscope (SEM) photograph of colloid carbon ball, and Fig. 2 b are the scanning electron microscope (SEM) photograph of C/ZnO composite materials, Fig. 2 c
For the scanning electron microscope (SEM) photograph of the porous ZnO composite hollow sphere catalyst prepared in first embodiment of the invention, Fig. 2 d are the present invention the
The scanning electron microscope (SEM) photograph of the porous ZnO composite hollow sphere catalyst prepared in two embodiments, Fig. 2 e are in third embodiment of the invention
The scanning electron microscope (SEM) photograph of the porous ZnO composite hollow sphere catalyst of preparation, Fig. 2 f are the business ZnO scanning electricity directly bought from market
Mirror figure.
Fig. 3 is the thermogravimetric analysis figure of the porous ZnO composite hollow sphere catalyst prepared in different embodiments in the present invention；
Fig. 4 is the formation mechenism figure of C/ZnO composite materials of the present invention；
Fig. 5 is that the UV, visible light of the porous ZnO composite hollow sphere catalyst prepared in different embodiments in the present invention is unrestrained anti-
Penetrate spectrogram；
Fig. 6 is the CO of the porous ZnO composite hollow sphere catalyst prepared in different embodiments in the present invention2Adsorption isotherm
Figure；
Fig. 7 a are the porous ZnO composite hollow sphere catalyst prepared in second embodiment of the invention and business ZnO urge
Change result gas chromatogram, Fig. 7 b be the porous ZnO composite hollow sphere catalyst prepared in different embodiments of the invention and
The photocatalysis yield comparison diagram of business ZnO；
Fig. 8 is the electrochemical impedance spectroscopy of the porous ZnO composite hollow sphere catalyst prepared in different embodiments of the invention.
Specific implementation mode
Present invention is further described in detail with specific implementation mode below in conjunction with the accompanying drawings.
In order to solve the problems in the existing technology the present invention, provides a kind of porous ZnO composite hollow sphere catalyst,
As shown in Figure 1, the ZnO composite hollows sphere catalyst includes hollow carbon ball and the ZnO particle being coated in the carbon ball.
When using ZnO composite hollow balls catalyst of the present invention, CO2Molecular Adsorption and ZnO hollow ball tables
Face, while a large amount of CO2Since the pi-conjugated effects of π-are adsorbed on hollow ball inside carbon core.When illumination, it is empty that ZnO generates a large amount of electronics
Cave pair.Since carbon fermi level is less than ZnO conduction band positions, accelerate in electron-transport to carbon material and by local heat effect, promotes
The separation of photo-generate electron-hole.On carbon material there is corresponding reducing power electronics to have caused CO2With the photo-reduction of hydrone
Reaction.Hole can aoxidize H in ZnO valence band2O generates O2And H+Ion.CO simultaneously2Same H+Reduction reaction occurs with electronics to generate
CH3OH。
The quasi-Fermi level difference of carbon material and semiconductor ZnO are that light induced electron moves power (from ZnO to carbon).And
And a large amount of electronics are transferred to the electron amount reduced on carbon core in ZnO lattices from ZnO, so as to effectively inhibit electronics empty
Cave generation is compound, while the surfaces ZnO being made to have more multi-hole to aoxidize hydrone.Therefore, in this process, photocatalysis
CO2The efficiency of reduction full response is obviously improved.
Porous ZnO composite hollow ball method for preparing catalyst of the present invention includes the following steps：
S1, synthetic colloidal substance carbon ball.
Specifically, glucose is taken to be dissolved in pure water, the Portugal of a concentration of 0.1g/ml is made in stirring and dissolving to clear solution
Grape sugar juice；Then the glucose solution prepared is transferred to 180 degrees Celsius of hydro-thermal 8h in reaction kettle；Then it will prepare
Product deionized water and ethyl alcohol centrifuge washing, and dry, obtain colloid carbon ball；
S2 synthesizes porous ZnO composite hollow sphere catalyst.
Specifically, zinc acetate is dissolved in pure water, 10min is to completing to dissolve for stirring, and the zinc acetate that 5mg/ml is made is molten
Liquid is added the colloid carbon ball prepared in S1, and seals ultrasonic disperse 10min, then stirs 6h；Then by the mixing after stirring 6h
C/ZnO composite materials are made in still aging 10h to solution at room temperature, and the C/ZnO composite materials are placed in crucible and are capped,
Calcining 1h is carried out under 400-500 degrees Celsius, and porous ZnO composite hollow sphere catalyst is made.
Embodiment one
In the present embodiment, in step S2, the zinc acetate solution of 60ml is taken, and the colloid prepared in 0.3g steps S1 is added
Carbon ball, and ultrasonic disperse 10min is sealed, then stir 6h；Then the mixed solution after stirring 6h is still aging at room temperature
C/ZnO composite materials are made in 10h, and the C/ZnO composite materials are placed in crucible and are capped, are calcined under 400 degrees Celsius
Porous ZnO composite hollow sphere catalyst is made in 1h.
Embodiment two
In the present embodiment, in step S2, the zinc acetate solution of 60ml is taken, and the colloid prepared in 0.3g steps S1 is added
Carbon ball, and ultrasonic disperse 10min is sealed, then stir 6h；Then the mixed solution after stirring 6h is still aging at room temperature
C/ZnO composite materials are made in 10h, and the C/ZnO composite materials are placed in crucible and are capped, are calcined under 450 degrees Celsius
Porous ZnO composite hollow sphere catalyst is made in 1h.
Embodiment three
In the present embodiment, in step S2, the zinc acetate solution of 60ml is taken, and the colloid prepared in 0.3g steps S1 is added
Carbon ball, and ultrasonic disperse 10min is sealed, then stir 6h；Then the mixed solution after stirring 6h is still aging at room temperature
C/ZnO composite materials are made in 10h, and the C/ZnO composite materials are placed in crucible and are capped, are calcined under 500 degrees Celsius
Porous ZnO composite hollow sphere catalyst is made in 1h.
Experimental data
In order to verify the properity and principle of the porous ZnO composite hollow sphere catalyst prepared in the present invention, below will
Carry out experimental test and verification.The porous ZnO composite hollow sphere catalyst prepared in embodiment one is marked as T400, embodiment
The porous ZnO composite hollow sphere catalyst prepared in two is marked as T450, the porous ZnO composite hollow prepared in embodiment three
Sphere catalyst is marked as T500.The colloid carbon ball prepared in step S1 is marked as Csp.It introduces and is directly bought from market simultaneously
Business ZnO compare, be labeled as c-ZnO.
(1) sample crystal phase structure and microscopic appearance
As shown in Fig. 2 a-2f, Fig. 2 a-2f be in different embodiments the porous ZnO composite hollow sphere catalyst for preparing and
The field emission scanning electron microscope figure of the product of different phase in preparation process.Wherein, Fig. 2 a are the colloid carbon ball prepared in step S1
Scanning electron microscope (SEM) photograph, from Fig. 2 a as can be seen that synthesis carbon ball template be diameter about 800nm uniform-spherical, all spheres
It is uniform in size, no significant difference.
Fig. 2 b are the scanning electron microscope (SEM) photograph of the composite materials of C/ZnO before calcination prepared in step S2, when carbon ball is added to acetic acid
In zinc solution, there is fraction of single-size sense in carbon ball surface after agitated ripening, illustrates Zn2+Ionic adsorption is in carbon ball
Surface hydrolysis reaction generates hydroxide and some zinc system objects.
Fig. 2 c are the scanning electron microscope (SEM) photograph of the porous ZnO composite hollow sphere catalyst prepared in first embodiment afterwards, and Fig. 2 d are
The scanning electron microscope (SEM) photograph of the porous ZnO composite hollow sphere catalyst prepared in second embodiment, Fig. 2 e are to be prepared in 3rd embodiment
Porous ZnO composite hollow sphere catalyst scanning electron microscope (SEM) photograph.With the rising of calcination temperature, composite hollow ball diameter dimension is not
It is disconnected to decline, drop to 100nm from 600nm.And it can be found that calcination temperature is higher, the crystallite dimension of zinc oxide increases.Work as calcining
It when temperature rise is to 500 degree, is completely disappeared by the carbon core inside the heat preservation of 1h, this is also with the broad peak of carbon in XRD spectrum
Weaken to disappear and mutually prove, while hollow ball structure becomes the porosity and looseness surface topography of typical particle composition.And second is real
It applies the porous ZnO composite hollow ball catalyst structure prepared in example to stablize, the surface of coarse particle packing is very beneficial for sky
The light absorption of bulbus cordis increases specific surface area and the surface-active site of composite material.Fig. 2 f are the quotient directly bought from market
Industry ZnO scanning electron microscope (SEM) photographs.
(2) thermogravimetric analysis (TGA)
As shown in figure 3, Fig. 3 shows the thermogravimetric analysis figure of different embodiments, to analyze the porous ZnO compound air of preparation
The content of carbon in bulbus cordis catalyst.From figure 3, it can be seen that the porous ZnO composite hollow ball catalysis prepared in 3rd embodiment
Agent T500 and business c-ZnO is substantially without apparent weightless.And the porous ZnO compound air prepared in first embodiment and second embodiment
Bulbus cordis catalyst occurs weightless for the first time, mainly a small amount of gas molecule of material surface absorption in 100-400 DEG C of range, water and
The decomposition of a part of agraphitic carbon.Illustrate that the introducing of carbon material improves the adsorption capacity of material simultaneously.Temperature further on
It rises, T450 and T400 occur obviously weightless due to the continuous decomposition of internal carbon core between 400-580 DEG C.Pass through meter
The percent weight loss for calculating sample, can obtain the carbon material percentage composition of all samples：T500 and c-ZnO is about 0%, and
T400 is most, has reached 78.2%, is recorded together into the following table 1 with other data.
Table 1
(3) Analysis on Mechanism
Fig. 4 shows the formation mechenism of C/ZnO composite materials in step S2.Glucose itself has a large amount of hydroxyl etc. oxygen-containing
Group, forms the carbon core that internal layer is aromatisation after high temperature hydrothermal carbonization, and outer layer is the colloid carbon ball of a large amount of hydrophilic radicals.Hydroxyl
Base is a kind of polar group, can be easy to ionize out the aobvious faintly acids of H+ when being connected to aromatisation carbon core, own face is negatively charged.
The test result of Zeta electric potential shows, the surface of carbon ball due to-The effect of the groups such as OH carries a large amount of negative electrical charge.Thus work as
When carbon ball is blended in zinc acetate solution, a large amount of Zn2+Cation can be adsorbed in carbon ball surface due to electrostatic adsorption.Another party
Face, zinc acetate can interact with carbon ball surface group occurs hydrolysis, generates Zn (OH)2With some zinc system objects.
(4) UV-vis DRS spectrum (DRS)
The light absorption of material influences clearly the catalytic efficiency of photochemical catalyst.Being illustrated in figure 5 the ultraviolet of sample can
See diffusing reflection spectrum.From figure 5 it can be seen that show from near-infrared wavelength to ultra-violet (UV) band (800-300nm) complete for carbon ball sample
The high-selenium corn of wave band, this is because carbon material has " black body effect ", its energy gap is substantially zeroed, can absorb all waves
The light of section.In photocatalysis CO2It is found in reactivity test process, after illumination 1h, the entire temperature for making heat resistant glass reaction by oneself
The bottom temp that degree is especially paved with composite catalyst obviously rises.This phenomenon, which demonstrates carbonaceous material such as graphene etc., to be had
The characteristics of zero forbidden band, can absorb the full spectral band of the sun and cause " local heat effect " substantially, can increase photochemical catalyst week
Enclose temperature.Thus light induced electron can obtain more energy, and rate travel is accelerated to be effectively facilitated electron hole separation.
Other composite samples visible region (800-400nm) light absorption with the rising of calcination temperature and constantly under
Drop, business ZnO is minimum, rule T400>T450>T500>c-ZnO.Illustrate the carbonaceous controlled with calcination temperature in composite sample
Material content directly affects the light absorption of composite photo-catalyst.And the light absorption of the substantially zeroed sample T500 of carbon content is higher than c-
ZnO is mainly due to ZnO hollow ball structures and is conducive to incident light to scatter in sphere so that light absorption is promoted.It is all multiple
The spectral line for closing sample all shows the light absorption threshold value in 400nm or so, this derives from the Intrinsic Gettering of ZnO.However, it is possible to send out
Now the light activated threshold value of all samples containing ZnO has minute differences, mainly since calcination temperature affects grain size, nanometer
Dimensional effect causes the energy gap of ZnO to be changed.It is obviously carried it is demonstrated experimentally that the visible absorption of composite photo-catalyst has
It rises, visible light can be efficiently absorbed by arising primarily at the carbon material inside hollow-core construction, be very beneficial for light-catalyzed reaction
Efficiency.
(5)CO2Adsorb test analysis
CO2Molecular Adsorption is first important step of light-catalyzed reaction in catalyst surface.Fig. 6 shows multiple samples
CO2Adsorption isotherm.Wherein, sample T400, T450 and carbon ball are in low-pressure area (P/P0<0.2) with CO2Air pressure rises quick
Rise, this is mainly derived from micropore and small mesoporous strong adsorption capacity in carbon material.The size rule and specific surface area of adsorbance
It is consistent, also with carbon content positive correlation.Delocalization conjugatedπbond π in carbon core6 6With CO2Middle delocalized pi-bond (π4 3) the pi-conjugated effects of π-
Composite photo-catalyst has been obviously improved to CO2The adsorbance of molecule.Test result shows that the carbon content of T400 and T450 are higher simultaneously
And large specific surface area, show larger CO2Adsorbance.And pure carbon ball (Csp) adsorbance be less than T400 and T450, mainly because
It is ZnO hollow-core constructions to CO2Absorption, while calcination processing also improves the pore structure of carbon core.Abundant pore structure and Gao Bi
Surface area is conducive to adsorb more CO2Molecule.Experimental result explanation：Specific surface area in addition to improving composite material, ZnO are empty
Carbon core in core structure is also very advantageous in the CO for promoting composite material2Adsorbance.Carbonaceous material in hollow ball is obviously improved
CO2Absorption, light-catalyzed reaction is carried out being very favorable.
(6) photocatalysis CO2Reducing property
Photo catalytic reduction CO2It is that the sample that will be prepared is in anaerobic to generate the test of solar energy fuel activity, is full of CO2Gas
In atmosphere, light source is simulated solar irradiation (λ>200nm).It is the chromatography artwork of sample as shown in Figure 7a, light is added in control experiment
Catalyst is added without CO in reactor2After gas and one hour of illumination, it is found that chromatogram does not detect any apparent spectrum
Peak, so as to exclude photocatalysis CO2The carbon of reduzate is derived from except experiment provides CO2Other outer possible carbon sources.And
It can be seen that there is same position, the spectral peak that retention time is about 2.91min in the chromatogram of sample T450 and c-ZnO, it is indicated that
Detect same products methanol (CH3OH).And the peak area of T450 chromatographic peaks is significantly greater than c-ZnO, illustrates that sample T450 light is urged
More CH can be generated by changing reaction3OH.Even more noteworthy, the electron-transport efficiency for introducing the T450 of carbon material is obviously excellent
In business ZnO, lead to the C for having a small amount of2H5The generation of OH, as shown in following reaction equation.
CO2+6H++6e–→CH3OH+H2O (1)
CO2+9H++12e–→C2H5OH+12OH– (2)
Fig. 7 b show composite photo-catalyst and the photocatalysis CO of business ZnO2It is transformed into CH3The yield of OH compares.Photocatalysis
The CH of the optimal T450 of activity3OH yields are about 2 times of c-ZnO.And the sample T400 light-catalyzed reaction efficiency that carbon content is most
Be it is minimum, mainly due in ZnO hollow balls carbon core it is excessive, the larger carbon material of volume largely absorbs incident light, hence it is evident that shadow
The light excitation of semiconductor ZnO is rung.The substantially zeroed T500 catalytic activity of carbon content is also superior to business ZnO, this is because sample
Product T500 is hollow ball structure, and large specific surface area, the active site exposed is more, and light absorption and adsorption capacity are superior to c-ZnO.
The experimental results showed that：The TC@ZH composite materials of suitable phosphorus content, can either play the absorbing ability of carbon material, conductive capability
And CO2Adsorption site, and can avoid that light shield occurs and influences the photostimulation of semiconductor since carbon is excessive, light is urged
It is highly beneficial to change reaction efficiency.
(7) electrochemical impedance spectroscopy (EIS)
The unique electronic enrichment of carbon material and transmittability enable carbon-based catalysis material material to effectively inhibit light
Raw electron-hole recombinations, promote light-catalyzed reaction efficiency.Electrochemical impedance spectroscopy is used to analyze the charge transfer efficiency of sample.Such as figure
Shown in 8, the electrochemical impedance spectroscopy of sample is shown.The radius curve diameter of carbon containing sample T450 and T400 is significantly less than c-
ZnO and T500 illustrates that the charge transfer impedance of carbon containing composite sample is less than pure ZnO hollow balls and business ZnO, charge transmission effect
Rate obviously rises.And it was found that the impedance of T400 is higher than T450, this is mainly due to hydro-thermal carbon ball sheets as agraphitic carbon, high temperature
The calcination processing of degree improves the crystallinity of carbon material, is more favorable for the transmission of charge.And high-temperature is calcined so that carbon core exists
Disperse more uniform inside hollow-core construction, even closer, the equally advantageous charge for promoting T450 is contacted with ZnO spherical shell inner surfaces
Efficiency of transmission.In addition, experimental result is shown：The charge transfer efficiency of c-ZnO is slightly above sample T500, this is because business ZnO
It is the synthesis of gas phase fire method, crystallinity is more advantageous to the transmission of charge higher than T500 prepared by 500 degree of calcinings, high crystalline.Though
The efficiency of transmission of the photo-generated carrier of right c-ZnO is higher than T500, but the hollow ball structure of T500 provides more absorption and anti-
Active site is answered, and conducive to the scattering of light, so the photocatalysis CO of T5002Reduction efficiency higher.What composite photo-catalyst was promoted
Electric conductivity has a significant actively impact for light-catalyzed reaction, substantially with photocatalysis CO2Reduction activation is consistent.
The present invention has synthesized porous ZnO composite hollow ball based on the preparation of carbon ball template using simple ionic adsorption principle and has urged
Agent, and by adjusting the content of carbonaceous material in calcination temperature systematicness control hollow ball.Experimental result is found, works as carbon content
It is about 56.4%, photo catalytic reduction CO2Active highest.The visible light that the introducing of carbon material significantly improves composite photo-catalyst is inhaled
Receipts and CO2Absorption, and local heat effect is will produce, be conducive to charge transmission.Porous ZnO composite hollow ball of the present invention
Catalyst has preparation method simple, the high advantageous effect of photocatalysis effect.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent substitution, improvement and etc. done should be included within the scope of protection of the invention god.
Claims (9)
1. a kind of porous ZnO composite hollow sphere catalyst, which is characterized in that including hollow carbon ball and be coated in the carbon ball
ZnO particle.
2. porous ZnO composite hollow sphere catalyst as described in claim 1, which is characterized in that the carbon ball accounts for described porous
The mass fraction of ZnO composite hollow sphere catalysts is 56.4%-78.2%.
3. porous ZnO composite hollow sphere catalyst as described in claim 1, which is characterized in that the porous ZnO composite hollow
The diameter dimension of composite hollow ball is 100-600 nanometers in sphere catalyst.
4. a kind of preparation method of porous ZnO composite hollow sphere catalyst, which is characterized in that include the following steps：
S1, synthetic colloidal substance carbon ball；
S2 synthesizes porous ZnO composite hollow sphere catalyst.
5. the preparation method of porous ZnO composite hollow sphere catalyst as claimed in claim 4, which is characterized in that step S1 tools
Body includes the following steps：
Glucose is dissolved in pure water by S11, stirs to clarify solution, and the glucose solution of a concentration of 0.1g/ml is made；
The glucose solution prepared is transferred in reaction kettle hydro-thermal 8 hours under 180 degree by S12；
The product obtained in step S12 is washed with deionized water and ethyl alcohol, and dried by S13.
6. the preparation method of porous ZnO composite hollow sphere catalyst as claimed in claim 5, which is characterized in that step S2 tools
Body includes the following steps：
Zinc acetate is dissolved in pure water by S21, stirs to being completely dissolved, the zinc acetate solution of 5mg/ml is made；
The colloid carbon ball prepared in step S1 is added in zinc acetate solution, and seals ultrasonic disperse 10 minutes by S22, so
It stirs 6 hours afterwards；
S23, by the mixed solution obtained in S22 still aging 10 hours obtained C/ZnO composite materials at room temperature；
The C/ZnO composite materials are placed in crucible and are capped by S24, are calcined 1 hour under 400-500 degrees Celsius.
7. the preparation method of porous ZnO composite hollow sphere catalyst as claimed in claim 6, which is characterized in that
Step S22 is specially：The zinc acetate solution prepared in 60 milliliters of step S21 is taken, is prepared in 0.3 gram of step S1 of addition
The colloid carbon ball, and seal ultrasonic disperse 10 minutes, then stir 6 hours.
8. the preparation method of porous ZnO composite hollow sphere catalyst as claimed in claim 7, which is characterized in that step S24 tools
Body is that the C/ZnO composite materials are placed in crucible and are capped, and is calcined 1 hour under 400 degrees Celsius.
9. the preparation method of porous ZnO composite hollow sphere catalyst as claimed in claim 7, which is characterized in that step S24 tools
Body is that the C/ZnO composite materials are placed in crucible and are capped, and is calcined 1 hour under 450 degrees Celsius.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110993975A (en) * | 2019-10-12 | 2020-04-10 | 中国科学院金属研究所 | Nitrogen-doped porous carbon non-metal catalyst, preparation method thereof and application thereof in redox reaction |
| CN111740095A (en) * | 2020-07-01 | 2020-10-02 | 湖北大学 | Carbon microsphere coated zinc oxide nanosheet material and preparation method and application thereof |
| CN112108178A (en) * | 2019-06-21 | 2020-12-22 | 中国科学院大连化学物理研究所 | Catalyst for preparing aromatic hydrocarbon by directly converting synthesis gas and preparation and application thereof |
| CN112657514A (en) * | 2021-01-13 | 2021-04-16 | 三明学院 | Photocatalyst filled with porous nano ZnS @ ZnO hollow spheres and preparation method thereof |
| CN112973744A (en) * | 2021-02-03 | 2021-06-18 | 华北电力大学 | Novel photoelectric catalyst and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112108178A (en) * | 2019-06-21 | 2020-12-22 | 中国科学院大连化学物理研究所 | Catalyst for preparing aromatic hydrocarbon by directly converting synthesis gas and preparation and application thereof |
| CN110993975A (en) * | 2019-10-12 | 2020-04-10 | 中国科学院金属研究所 | Nitrogen-doped porous carbon non-metal catalyst, preparation method thereof and application thereof in redox reaction |
| CN110993975B (en) * | 2019-10-12 | 2021-06-01 | 中国科学院金属研究所 | Nitrogen-doped porous carbon non-metal catalyst, preparation method thereof and application thereof in redox reaction |
| CN111740095A (en) * | 2020-07-01 | 2020-10-02 | 湖北大学 | Carbon microsphere coated zinc oxide nanosheet material and preparation method and application thereof |
| CN112657514A (en) * | 2021-01-13 | 2021-04-16 | 三明学院 | Photocatalyst filled with porous nano ZnS @ ZnO hollow spheres and preparation method thereof |
| CN112973744A (en) * | 2021-02-03 | 2021-06-18 | 华北电力大学 | Novel photoelectric catalyst and preparation method thereof |
| CN112973744B (en) * | 2021-02-03 | 2022-06-14 | 华北电力大学 | Photoelectric catalyst and preparation method thereof |
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