CN109847753A - A kind of porous C o@C nano material and its preparation method and application - Google Patents
A kind of porous C o@C nano material and its preparation method and application Download PDFInfo
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- CN109847753A CN109847753A CN201910099773.2A CN201910099773A CN109847753A CN 109847753 A CN109847753 A CN 109847753A CN 201910099773 A CN201910099773 A CN 201910099773A CN 109847753 A CN109847753 A CN 109847753A
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention belongs to material preparation and photocatalysis technology fields, and in particular to a kind of porous C o@C nano material and its preparation method and application.The present invention synthesizes porous C o@C nano material by hard template method, at low cost with preparation process simplicity, is easy to large-scale industrial production.The nano tubular structure mutually grown naturally compared to body, its surface porosity, the transfer of excitation state electronics is greatly facilitated and improves surface and produces hydrogen dynamic behavior, to significantly improve photosensitizer dye-alcohol-aqueous systems Photocatalyzed Hydrogen Production performance, have broad application prospects in terms of developing sustainable green energy resource.
Description
Technical field
The invention belongs to material preparation and photocatalysis technology fields.Specifically related to a kind of porous C o@C nano material and its
Preparation method and the application in Photocatalyzed Hydrogen Production.
Background technique
With petering out for fossil energy, environmental pollution and greenhouse effects increasingly sharpen, and develop new energy (including too
Positive energy, biomass energy and wind energy etc.) worldwide common recognition is had become, also it is put into our country energy development strategy.Utilize photocatalysis skill
The direct conversion from solar energy to Hydrogen Energy is realized in art hydrogen manufacturing, is a kind of desirable route for obtaining new energy.Currently, although many light
Catalysis material itself has good absorbing properties, but the quantum efficiency of its Photocatalyzed Hydrogen Production system is also relatively low, former
Because having: the liberation of hydrogen dynamic behavior of absorber of light itself is poor.In order to solve this problem, noble metal liberation of hydrogen catalyst has been used to
Photocatalyzed Hydrogen Production system has been demonstrated to be very effective method.However, noble metal is not only expensive but also rare, necessarily affected its
Practical large-scale application.Therefore, cheap high catalytic activity liberation of hydrogen catalyst is developed to replace noble metal to be applied to Photocatalyzed Hydrogen Production
System seems most important.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of porous C o@C nano material and its preparation method and application, the material
Expect that synthetic technology is simple, easily operated, good catalytic activity is shown in Photocatalyzed Hydrogen Production, before there is potential application
Scape.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of porous C o@C nano material, comprising the following steps:
(1) a certain amount of cobalt precursor object and carbon matrix precursor are dissolved at 80 DEG C water, stir 2h, SiO is then added2Template, institute
The SiO of addition2The total mass ratio of quality and cobalt precursor object and carbon matrix precursor is 1~8:1, and the continuation heating stirring time is 2 h；With
After be put into liquid nitrogen and cool down, be freeze-dried；Then program is calcined in tube furnace argon atmosphere, the calcination temperature of first stage
It is 500~550 DEG C, calcination time is 1 h, and the calcination temperature of second stage is 700~800 DEG C, and calcination time is 2 h, is obtained
To Co@C and SiO2Mixture；
The cobalt precursor object is CoCl2·6H2O、Co(CH3COO)2·4H2O or Cobalt Phthalocyanine；Carbon matrix precursor is cyanamide, two paracyanogen
Amine or melamine；
(2) by Co@C and SiO2Mixture is immersed in 12~36 h in the ammonium hydrogen fluoride solution of 1~4 M concentration, centrifugation, vacuum
Baking oven drying, obtains Co@C nano material.
The load capacity of Co is 0.7 wt% in the porous C o@C nano material.
Application of the porous C o@C nano material as photochemical catalyst in Photocatalyzed Hydrogen Production: the Photocatalyzed Hydrogen Production is in light
It is carried out in quick dose of dyestuff-alcohol-aqueous systems.
The photosensitizer dye includes: eosin Y, rhodamine B, one of methyl orange or a variety of；The alcohol includes: three second
Hydramine, ethylene glycol, methanol, one of ethyl alcohol or a variety of.
Compared with prior art, the present invention having the advantage that
(1) present invention is prepared for porous C o@C nano material by hard template method, which possesses vesicular texture, for analysis
Hydrogen increases the active site of reaction, promotes the transfer of light induced electron, improves surface and produces hydrogen dynamic behavior, thus significantly
Improve the performance of Photocatalyzed Hydrogen Production system.Result of study shows that the activity of cellular Co@C nano material is apparently higher than body
The nano tubular structure Co@C mutually grown naturally.
(2) the method for the present invention simple process, low in raw material price, reaction condition is mild, and production cost is low, environmentally protective,
It is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is that embodiment 1(is right) and comparative example 1(it is left) the SEM spectrogram of photochemical catalyst for preparing；
Fig. 2 is the XRD spectra of photochemical catalyst prepared by embodiment 1 and comparative example 1；
Fig. 3 is the specific surface area and pore volume distribution data of photochemical catalyst prepared by embodiment 1 and comparative example 1；
Fig. 4 is the Photocatalyzed Hydrogen Production performance of photochemical catalyst prepared by embodiment 1 and comparative example 1.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1 (porous C o@C)
By 1 g CoCl2·6H2In deionized water, 2 h are stirred in 80 DEG C of oil baths, then for O and the dispersion of 2 g cyanamid dimerizations
12 g SiO are added2Template, continuous heating stir 2 h.It is subsequently placed into liquid nitrogen to cool down, be freeze-dried, to sample moisture
It drains.Then program is calcined in tube furnace argon atmosphere, and the calcination temperature of first stage is 500 DEG C, calcination time 1
H, the calcination temperature of second stage are 750 DEG C, and calcination time is 2 h, obtains Co@C and SiO2Mixture.By Co@C and SiO2
Mixture is immersed in 24 h in the ammonium hydrogen fluoride solution of 4 M concentration, centrifugation, and vacuum drying oven drying obtains cellular Co@C
Grain, wherein the load capacity of Co is 0.7 wt%, is labeled as Co@CNS.
Embodiment 2(porous C o@C)
By 1 g CoCl2·6H2In deionized water, 2 h are stirred in 80 DEG C of oil baths, then for O and the dispersion of 2 g cyanamid dimerizations
15 g SiO are added2Template, continuous heating stir 2 h.It is subsequently placed into liquid nitrogen to cool down, be freeze-dried, to sample moisture
It drains.Then program is calcined in tube furnace argon atmosphere, and the calcination temperature of first stage is 550 DEG C, calcination time 1
H, the calcination temperature of second stage are 800 DEG C, and calcination time is 2 h, obtains Co@C and SiO2Mixture.By Co@C and SiO2
Mixture is immersed in 24 h in the ammonium hydrogen fluoride solution of 4 M concentration, centrifugation, and vacuum drying oven drying obtains cellular Co@C
Grain, wherein the load capacity of Co is 0.7 wt%.
Comparative example 1 (body phase Co@C)
By 1 g CoCl2·6H2In deionized water, 4 h are stirred in 80 DEG C of oil baths for O and the dispersion of 2 g cyanamid dimerizations, are added without
Template.It is subsequently placed into liquid nitrogen to cool down, be freeze-dried, to sample moisture pump.Then the program in tube furnace argon atmosphere
Calcining, the calcination temperature of first stage are 500 DEG C, and calcination time is 1 h, and the calcination temperature of second stage is 750 DEG C, are forged
The burning time is 2 h, obtains black tubular body phase Co@C.Co@C is immersed in 24 h in the ammonium hydrogen fluoride solution of 4 M concentration,
Centrifugation, vacuum drying oven drying, obtains black tubular body phase Co@C, and wherein the load capacity of Co is 1.5 wt%, is labeled as Co@CNT.
Application examples
Co@C nano material made from 1 mg embodiment 1 and comparative example 1 and 50 mg eosin Y are added to 100 respectively
It in mL triethanolamine (10 vol%) aqueous solution, is poured into reactor after ultrasonic mixing is uniform, controls magnetic agitation certain
Revolving speed makes reaction system maintain 5 DEG C or so to maintain the suspended state of catalyst in solution by circulating condensing water.?
After being repeated several times the air vacuumized in abstraction reactor and solution, opens light source (300 W xenon lamp) and carry out light-catalyzed reaction, benefit
With the amounts of hydrogen generated in gas Chromatographic Determination system, detector is thermal-conductivity detector, and argon gas is as carrier gas.
It is the scanning electron microscope (SEM) photograph of body phase Co@C on the left of Fig. 1, is clear that in figure that body phase Co@C is with nanometer
The form of pipe exists.It is the scanning electron microscope (SEM) photograph of cellular Co@C on the right side of Fig. 1, granular size is 30 nm or so.Fig. 2 is more
Hole and body phase Co C X ray diffracting spectrum show that the two has the cobalt and carbon of phase allomeric composition.Fig. 3 is porous and body phase
Co@C specific surface area and pore volume distribution data show that the specific surface area of porous C o@C is 257 m2 g-1, and body phase Co@C ratio
Surface area is 75 m2 g-1, porous C o@C specific surface area is more than 3 times of body phase Co@C.Fig. 4 is porous and body phase Co@C sample
Photocatalyzed Hydrogen Production activity figure, 4 circulation in, the production hydrogen activity of porous C o@C is apparently higher than body phase Co@C: the 1 circulation, more
Hole Co@C Photocatalyzed Hydrogen Production performance is more than 3 times of body phase Co@C, as body phase Co@C is damply more brighter than porous C o@C
Aobvious, to the 4th wheel circulation, porous C o C Photocatalyzed Hydrogen Production performance is more than 5 times of body phase Co C.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (4)
1. a kind of preparation method of porous C o@C nano material, it is characterised in that: the following steps are included:
(1) cobalt precursor object and carbon matrix precursor are dissolved at 80 DEG C water, stir 2h, SiO is then added2Template is added
SiO2The total mass ratio of quality and cobalt precursor object and carbon matrix precursor is 1~8:1, and the continuation heating stirring time is 2 h；It is subsequently placed into
Liquid nitrogen cools down, freeze-drying；Then program is calcined in tube furnace argon atmosphere, and the calcination temperature of first stage is 500
~550 DEG C, calcination time is 1 h, and the calcination temperature of second stage is 700~800 DEG C, and calcination time is 2 h, obtains Co@C
With SiO2Mixture；
The cobalt precursor object is CoCl2·6H2O、Co(CH3COO)2·4H2O or Cobalt Phthalocyanine；Carbon matrix precursor is cyanamide, cyanamid dimerization
Or melamine；
(2) by Co@C and SiO2Mixture is immersed in 12~36 h in the ammonium hydrogen fluoride solution of 1~4 M concentration, and centrifugation, vacuum is dried
Case drying, obtains porous C o@C nano material.
2. a kind of preparation method of porous C o@C nano material according to claim 1, it is characterised in that: porous C o@C receives
The load capacity of Co is 0.7 wt % in rice material.
3. the porous C o@C nano material that preparation method as claimed in claim 1 or 2 obtains.
4. application of the porous C o@C nano material according to claim 3 as photochemical catalyst in Photocatalyzed Hydrogen Production,
It is characterized by: the Photocatalyzed Hydrogen Production carries out in photosensitizer dye-alcohol-aqueous systems；The photosensitizer dye includes: daybreak
Red Y, rhodamine B, one of methyl orange or a variety of；The alcohol includes: triethanolamine, ethylene glycol, methanol, one of ethyl alcohol
Or it is a variety of.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686732A (en) * | 2020-06-29 | 2020-09-22 | 福州大学 | Carbon-coated iron-based catalyst, preparation method thereof and application of catalyst in preparation of phenol by benzene hydroxylation |
| CN112331869A (en) * | 2020-11-06 | 2021-02-05 | 五邑大学 | Cobalt-nitrogen double-doped hybrid carbon material and preparation method thereof |
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| CN106587079A (en) * | 2016-12-30 | 2017-04-26 | 湖北工程学院 | One-dimensional SiO2 nano material and preparation method thereof |
| CN106744744A (en) * | 2017-01-20 | 2017-05-31 | 济南大学 | The preparation method and products therefrom of a kind of cellular graphite phase carbon nitride nano material of cobalt doped |
| CN107138172A (en) * | 2017-05-09 | 2017-09-08 | 南昌航空大学 | A kind of preparation method of electrode catalytic materialses and its application in glucose fuel cell |
| CN108421555A (en) * | 2018-02-24 | 2018-08-21 | 江南大学 | A kind of preparation method of cobalt/carboritride hydridization photochemical catalyst |
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2019
- 2019-01-31 CN CN201910099773.2A patent/CN109847753B/en active Active
Patent Citations (5)
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|---|---|---|---|---|
| CN104645989A (en) * | 2015-01-30 | 2015-05-27 | 武汉理工大学 | Heteroatom-doping porous carbon material and preparation method thereof |
| CN106587079A (en) * | 2016-12-30 | 2017-04-26 | 湖北工程学院 | One-dimensional SiO2 nano material and preparation method thereof |
| CN106744744A (en) * | 2017-01-20 | 2017-05-31 | 济南大学 | The preparation method and products therefrom of a kind of cellular graphite phase carbon nitride nano material of cobalt doped |
| CN107138172A (en) * | 2017-05-09 | 2017-09-08 | 南昌航空大学 | A kind of preparation method of electrode catalytic materialses and its application in glucose fuel cell |
| CN108421555A (en) * | 2018-02-24 | 2018-08-21 | 江南大学 | A kind of preparation method of cobalt/carboritride hydridization photochemical catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686732A (en) * | 2020-06-29 | 2020-09-22 | 福州大学 | Carbon-coated iron-based catalyst, preparation method thereof and application of catalyst in preparation of phenol by benzene hydroxylation |
| CN112331869A (en) * | 2020-11-06 | 2021-02-05 | 五邑大学 | Cobalt-nitrogen double-doped hybrid carbon material and preparation method thereof |
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