CN108212190A - A kind of Ag bases three-dimensional sea urchin shape E-g-C3N4/ TiO2 composite materials and preparation method thereof - Google Patents
A kind of Ag bases three-dimensional sea urchin shape E-g-C3N4/ TiO2 composite materials and preparation method thereof Download PDFInfo
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- CN108212190A CN108212190A CN201711478097.7A CN201711478097A CN108212190A CN 108212190 A CN108212190 A CN 108212190A CN 201711478097 A CN201711478097 A CN 201711478097A CN 108212190 A CN108212190 A CN 108212190A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 241000257465 Echinoidea Species 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 16
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000001509 sodium citrate Substances 0.000 claims abstract description 13
- 150000004683 dihydrates Chemical class 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004005 microsphere Substances 0.000 claims abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000013467 fragmentation Methods 0.000 claims description 16
- 238000006062 fragmentation reaction Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- 239000002245 particle Substances 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000000356 contaminant Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000008267 milk Substances 0.000 description 7
- 235000013336 milk Nutrition 0.000 description 7
- 210000004080 milk Anatomy 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000013345 egg yolk Nutrition 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- -1 oxo transition metal Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 239000002023 wood 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/51—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Abstract
The present invention provides a kind of Ag bases three-dimensional sea urchin shape E g C3N4/TiO2Composite material and preparation method thereof.The present invention calcines to obtain three nitrogen of graphite-phase carbon, four (g C by temperature programming using thiocarbamide first3N4), it handles to obtain thin layer g C by ultrasonic cell disruption instrument3N4, then three-dimensional sea urchin TiO prepared by solvent thermal reaction2, thin layer g C3N4, silver nitrate and Sodium Citrate, usp, Dihydrate Powder obtain the Ag base three-dimensional sea urchin shape E g C of surface modification through hydro-thermal reaction3N4/TiO2Composite material.Ag bases three-dimensional sea urchin shape E g C provided by the invention3N4/TiO2For microsphere diameter at 1.5~3.0 μm, photoelectric properties are excellent, and light degradation rate is higher, can be applied to the multiple fields such as degradation of contaminant, production hydrogen, and preparation process provided by the invention is simple, of low cost, have preferable actual application value.
Description
Technical field
The present invention relates to nano-functional material technical field, more particularly to a kind of Ag bases three-dimensional sea urchin shape E-g-C3N4/TiO2
Composite material and preparation method thereof.
Background technology
As energy crisis and environmental problem are of increasing concern, how sustainable development to be kept to have become global human
Common recognition.In currently the approach of energy crisis is solved, it is a kind of side of more mainstream to be converted into bioenergy using biomass
Formula.But for most countries, in face of numerous domestic population, it is impossible to by valuable cereal resource conversion be biology
Fuel.Meanwhile environmental degradation also threatens the health and lives of the mankind, wherein chemical contamination is the current dirt for being badly in need of solving
One of dye.In numerous chemical pollutant processing approach, common mode has：Physical absorption enrichment, chemical/electrochemical oxidation
Landfill etc. is concentrated in reduction.Although these methods can solve current pollutant, secondary pollution and energy wave can be caused
Take, application can not be continued from the perspective of sustainable development.
Become the mainstream of human society and a large amount of achievements of scientific research accumulation, oxo transition metal along with sustainable development
Compound is constantly studied as a kind of excellent photoelectric conversion semi-conducting material.TiO2Because chemical stability height, Thermodynamically stable,
Nontoxic, the advantages that photoelectric property is excellent, attracts attention, and becomes research hotspot.
In numerous TiO2In pattern, relative to one-dimensional, two-dimentional nano wire, nano particle, three-dimensional sea urchin structure Ti O2It is micro-
Ball shows preferable electricity conversion.At present, it has been carried out largely for the inorganic semiconductor material of sea urchin structure both at home and abroad
Research.Either ball-nuclear structure, the multiple material composition sea urchin structure microspheres of egg yolk structure or hollow-core construction, single structure
A kind of material composition sea urchin structure microspheres, solve energy crisis and the problems such as environmental pollution in, since TOF and light are utilized
Efficiency is low, and remaining unchanged apart from practical application needs very big improvement.
Therefore, a kind of high electricity conversion, wide light abstraction width, the photocatalysis for inhibiting electron-hole pair compound are designed
Composite material becomes material people extremely urgent ground problem.
Invention content
In view of this, it is an object of the present invention to provide a kind of Ag bases three-dimensional sea urchin shape E-g-C3N4/TiO2Composite wood
The preparation method of material.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of Ag bases three-dimensional sea urchin shape E-g-C3N4/TiO2The preparation method of composite material, it is characterised in that：The preparation
Method is as follows：
Step 1：Use thiocarbamide that g-C is prepared by temperature programming for raw material3N4；
Step 2：By the g-C in step 13N4Deionized water is dissolved in after milling, fragmentation processing is carried out, then takes upper strata
Milk yellow suspension is placed in evaporating dish；
Step 3：By liquid freezing drying obtained by step 2, thin layer E-g-C is obtained3N4；
Step 4：Take the thin layer E-g-C in step 33N4Water ultrasonic disperse is dissolved in, obtains A liquid；
Step 5：Three-dimensional sea urchin shape TiO is prepared by solvent thermal reaction2, deionized water dispersion is dissolved in, is obtained
B liquid；
Step 6：A liquid, the B liquid that step 4 and step 5 are respectively obtained mix, and silver nitrate and lemon are added in stirring
Mixed liquor is obtained Ag base three-dimensional sea urchin shapes E-g-C by sour sodium after hydro-thermal reaction, drying3N4/TiO2Composite material.
Using above-mentioned technical proposal, beneficial effects of the present invention are as follows：
It is handled by supersonic cell instrument, the g-C quickly removed3N4Thin layer, then pass through simple one step hydro thermal method system
It is standby to obtain Ag base three-dimensional sea urchin shapes E-g-C3N4/TiO2Composite material, easy to operate, function admirable are suitble to industrial production and reality
Using.
Preferably, the g-C3N4:TiO2:H2The mass ratio of O is 2.5wt%~10wt%:1:10.
Using above-mentioned preferred embodiment, advantage is：
Thin layer g-C3N4It is that a kind of electron transport ability is fast, prepares easy two-dimensional material, performance and graphene thin layer phase
Seemingly, but excessive g-C3N4Cladding can also influence the catalytic performance of composite material, and g-C is found through experiment3N4:TiO2:H2The matter of O
Amount is than being 2.5wt%~10wt%:1:10 composite material catalytic effect is best.
Preferably, the hydro-thermal reaction preparation method of the step 6 is specific as follows：
(1) under agitation, B liquid is added dropwise to A liquid, then according to Ag:The atomic molar ratio of Ti is 1%~7%:
1 ratio adds in silver nitrate and Sodium Citrate, usp, Dihydrate Powder, and wherein Sodium Citrate, usp, Dihydrate Powder keeps 1 with added silver nitrate quality:1；
(2) by the above-mentioned Ag base three-dimensional sea urchin shapes E-g-C for obtaining the step (1)3N4/TiO2Composite material precursor
Solution reacts in a heated condition, obtains Ag base three-dimensional sea urchin shapes E-g-C3N4/TiO2Composite material.
Preferably, the heating condition in the step (2) is：Heating temperature is 120~180 DEG C, heating time for 15~
21h。
Using above-mentioned preferred embodiment, beneficial effects of the present invention are as follows：
Reaction temperature and reaction time are to silver nano-grain size and g-C3N4Cladding have a direct impact, the reaction time is long
The bad dispersibility of Ag nano particles, g-C are easily caused with temperature height3N4/ by partial corrosion, it is 120 to obtain heating temperature by experiment
~180 DEG C, heating time is conducive to Ag base three-dimensional sea urchin shapes E-g-C for 15~21h3N4/TiO2The generation of composite material.
Preferably, the fragmentation processing in the step 2 uses ultrasonic cell disruptor of the general power for 650W, with
20% efficiency carries out the fragmentation processing of 10~20min.
Using above-mentioned preferred embodiment, beneficial effects of the present invention are as follows：
Ordinary ultrasonic instrument needs, which take a long time, just reaches peeling effect, while the degree removed is in uneven thickness, thin
Layer size difference is larger.In order to realize g-C3N4Block-like quick stripping, we select ultrasonic cell disruptor to be removed.
It is broken for a long time to make the thin layer g-C that stripping obtains3N4Excessively fragmentation, by experiment obtain with 20% efficiency carry out 10~
The fragmentation treatment effect of 20min is best.
It is another object of the present invention to provide the Ag base three-dimensional sea urchin shapes E-g-C that a kind of surface is modified3N4/TiO2It is multiple
Condensation material.
To achieve these goals, technical scheme is as follows：
A kind of Ag bases three-dimensional sea urchin shape E-g-C3N4/TiO2Composite material, including sea urchin shape TiO2Matrix and it is deposited on institute
State sea urchin shape TiO2The Ag nano particles of matrix surface and thin layer E-g-C3N4。
Preferably, Ag bases three-dimensional sea urchin shape E-g-C3N4/TiO2Composite material microsphere diameter is 1.5~3.0 μm.
By using above-mentioned technical proposal, beneficial effects of the present invention are as follows：
Ag bases three-dimensional sea urchin shape E-g-C provided by the invention3N4/TiO2Composite material is with three-dimensional sea urchin shape TiO2For matrix,
g-C3N4Surface modification, increase polluter by adsorbance, while improve light absorption region and promote electron-hole
Separation；The presence of Ag nano particles further increases photoelectric conversion efficiency.This composite material can be applied to degradation of contaminant, production
The multiple fields such as hydrogen, sensitization solar battery.
The present invention is with thin layer g-C3N4, three-dimensional sea urchin shape TiO2, silver nitrate, sodium citrate be raw material, prepared using hydro-thermal method
Go out Ag base three-dimensional sea urchin shapes E-g-C3N4/TiO2Composite material, easy to operate, function admirable are suitble to industrial production and reality should
With.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention, for those of ordinary skill in the art, without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is untreated g-C in present example two3N4SEM electron microscopes；
Fig. 2 is through ultrasonic cell-break treated g-C in present example two3N4TEM electron microscopes；
Fig. 3 is Ag base three-dimensional sea urchin shapes E-g-C in present example two3N4/TiO2The TEM electron microscopes of composite material；
Fig. 4 is pure g-C in present example two3N4With Ag base three-dimensional sea urchin shapes E-g-C3N4/TiO2The XRD of composite material
Figure；
Fig. 5 is Ag base three-dimensional sea urchin shapes E-g-C in example two3N4/TiO2The XPS figures of Ag in composite material.
Specific embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without making creative work
Embodiment shall fall within the protection scope of the present invention.
The invention discloses a kind of Ag bases three-dimensional sea urchin shape E-g-C3N4/TiO2The preparation method of composite material, preparation method
It is as follows：
Step 1：Use thiocarbamide that g-C is prepared by temperature programming for raw material3N4；
Step 2：By the g-C in step 13N4Deionized water is dissolved in after milling, fragmentation processing is carried out, then takes upper strata
Milk yellow suspension is placed in evaporating dish；
Step 3：By liquid freezing drying obtained by step 2, thin layer E-g-C is obtained3N4；
Step 4：Take the thin layer E-g-C in step 33N4Water ultrasonic disperse is dissolved in, obtains A liquid；
Step 5：Three-dimensional sea urchin shape TiO is prepared by solvent thermal reaction2, deionized water dispersion is dissolved in, is obtained
B liquid；
Step 6：A liquid, the B liquid that step 4 and step 5 are respectively obtained mix, and silver nitrate and lemon are added in stirring
Mixed liquor is obtained Ag base three-dimensional sea urchin shapes E-g-C by sour sodium after hydro-thermal reaction, drying3N4/TiO2Composite material.
In order to further realize technical scheme of the present invention, the g-C3N4:TiO2:H2The mass ratio of O for 2.5wt%~
10wt%:1:10.
In order to further realize technical scheme of the present invention, the hydro-thermal reaction preparation method of the step 6 is specific as follows：
(1) under agitation, B liquid is added dropwise to A liquid, then according to Ag:The atomic molar ratio of Ti is 1%~7%:
1 ratio adds in silver nitrate and Sodium Citrate, usp, Dihydrate Powder, and wherein Sodium Citrate, usp, Dihydrate Powder keeps 1 with added silver nitrate quality:1；
(2) by the above-mentioned Ag base three-dimensional sea urchin shapes E-g-C for obtaining the step (1)3N4/TiO2Composite material precursor
Solution reacts in a heated condition, obtains Ag base three-dimensional sea urchin shapes E-g-C3N4/TiO2Composite material.
In order to further realize technical scheme of the present invention, the heating condition in the step (2) is：Heating temperature is
120~180 DEG C, heating time is 15~21h.
In order to further realize technical scheme of the present invention, the fragmentation processing in the step 2 use general power for
The ultrasonic cell disruptor of 650W, the fragmentation that 10~20min is carried out with 20% efficiency are handled.
In order to further realize technical scheme of the present invention, Ag nano particles and thin layer g-C3N4It is deposited on sea urchin shape TiO2
The surface of matrix.
In order to further realize technical scheme of the present invention, Ag base three-dimensional sea urchin shapes E-g-C3N4/TiO2Composite material microballoon
A diameter of 1.5~3.0 μm.
In the following, statement will be further analyzed to technical scheme of the present invention in conjunction with specific embodiments.
Embodiment 1：
(1) thin layer g-C3N4Preparation：
Precise 15g thiocarbamides move into the sealing of 50mL ceramic crucibles, are placed on burner hearth center, set instrument parameter, make liter
Warm rate is calcined 3 hours for 10 DEG C/min and at 550 DEG C, is milled, is taken the g-C that 0.5g is ground3N4Powder is in the thin mouth of 300mL
In vial, a certain amount of deionized water is added in, and with 20% effect in the ultrasonic cell disruptor for being 650W in general power
Rate carries out the fragmentation processing of 10min, and upper strata milk yellow suspension is then taken then to do gained liquid freezing in evaporating dish
It is dry, obtain E-g-C3N4。
(2) Ag bases three-dimensional sea urchin shape E-g-C3N4/TiO2The preparation of composite material：
Prepare A liquid：Step (1) is taken to prepare E-g-C3N40.05g is dissolved in the deionized water of 10ml, ultrasonic 25min
5min is stirred with 800r/min again after (40000Hz)；Prepare B liquid：Weigh three-dimensional sea urchin TiOs of the 0.2g by solvent hot preparation2
It is dissolved in the deionized water of 10mL, stirs 15min (700r/min) ultrasound 15min (40000Hz) afterwards；Under agitation,
The A drops of 3.3mL add in B liquid；Then add in 29.7mg silver nitrates and 29.7mg Sodium Citrate, usp, Dihydrate Powders；Stirring is to dissolving, by this
Reaction solution is transferred to autoclave, and at 180 DEG C, heating time is 21 hours；Treat reaction kettle cooled to room temperature, use is anhydrous
Ethyl alcohol and deionized water washing are for several times, dry, obtain Ag base three-dimensional sea urchin shapes E-g-C3N4/TiO2Composite material.
Embodiment 2：
(1) thin layer g-C3N4Preparation：
Precise 15g thiocarbamides move into the sealing of 50mL ceramic crucibles, are placed on burner hearth center, set instrument parameter, make liter
Warm rate is calcined 3 hours for 10 DEG C/min and at 550 DEG C, is milled, is taken the g-C that 0.5g is ground3N4Powder is in the thin mouth of 300mL
In vial, a certain amount of deionized water is added in, and with 20% effect in the ultrasonic cell disruptor for being 650W in general power
Rate carries out the fragmentation processing of 15min, and upper strata milk yellow suspension is then taken then to do gained liquid freezing in evaporating dish
It is dry, obtain E-g-C3N4。
(2) Ag bases three-dimensional sea urchin shape E-g-C3N4/TiO2The preparation of composite material：
Prepare A liquid：Step (1) is taken to prepare E-g-C3N40.05g is dissolved in the deionized water of 10ml, ultrasonic 25min
5min is stirred with 800r/min again after (40000Hz)；Prepare B liquid：Weigh three-dimensional sea urchin TiOs of the 0.2g by solvent hot preparation2
It is dissolved in the deionized water of 10ml, stirs 15min (700r/min) ultrasound 15min (40000Hz) afterwards；Under agitation,
The A drops of 3.3mL add in B liquid；Then add in 12.7mg silver nitrates and 12.7mg Sodium Citrate, usp, Dihydrate Powders；Stirring is to dissolving, by this
Reaction solution is transferred to autoclave, and at 150 DEG C, heating time is 18 hours；Treat reaction kettle cooled to room temperature, use is anhydrous
Ethyl alcohol and deionized water washing are for several times, dry, obtain Ag base three-dimensional sea urchin shapes E-g-C3N4/TiO2Composite material.
In order to preferably verify that the present invention prepares product, the thin layer g-C that applicant will be prepared in embodiment 23N4And Ag
Base three-dimensional sea urchin shape E-g-C3N4/TiO2Composite material is observed under Electronic Speculum, obtains microstructure as shown in Figs. 1-3.By
The blocky g-C of cell Ultrasonic Cell Disruptor processing3N4/ peeling effect is apparent, and thickness of thin layer is in 10nm, relatively general ultrasonication
Time is short, stripping sheet is big.
Simultaneously as can be seen that composite material is prepared with more complete sea urchin shape in the present embodiment, high-sequential, tightly
It is close uniform, 1.5~3.0 μm of microsphere diameter.The large specific surface area of three-dimensional sea urchin shape micro nano structure, is conducive to adsorption of chemical species
Absorption；The g-C of lamelliform simultaneously3N4/ increase further increases the specific surface area of composite material, increases adsorbance, so as to improve
Photoelectrocatalysis efficiency.
Such as Fig. 4, shown in Fig. 5, the Ag base three-dimensional sea urchin shapes E-g-C that is prepared in embodiment 23N4/TiO2The progress of composite material
XRD characterization.
In 2 θ=27.3 °, 36.3 °, 41 °, 54.5 °, 63 ° and 69 ° go out characteristic diffraction peak, correspond to rutile TiO respectively2
(PDF#21-1276) (110), (101), (111), (211), (002) and (301) crystal face；Simultaneously 2 θ=38.5 °,
There is the characteristic peak of Ag at 44.4 °, 64.5 ° and 77.5 °, but due to g-C3N4Main diffraction peak (27.4 °) and TiO2
(110) diffraction peak approaches, and can not observe in the composite.g-C3N4With Ag modification sea urchin shapes TiO2, the hetero-junctions of formation
Accelerate the transfer of composite material surface electronics and widened the absorption region of light, further improve the photoelectricity effect of composite material
Rate.
To the Ag base three-dimensional sea urchin shapes E-g-C being prepared in embodiment 23N4/TiO2Composite material carries out XPS spectrum figure point
Analysis, it can be seen that occur the 3d of Ag at 367.6eV5/2There is the 3d of Ag at 373.6eV in characteristic peak3/2Characteristic peak,
And two is peak-to-peak away from for 6eV, shows that Ag is present in composite material in the form of simple substance.The modification of nanometer Ag is improved by SPR effects
The separation and transmission of absorption and carrier to visible ray, further improve photoelectrocatalysis efficiency.
Embodiment 3：
(1) thin layer g-C3N4Preparation：
Precise 15g thiocarbamides move into the sealing of 50mL ceramic crucibles, are placed on burner hearth center, set instrument parameter, make liter
Warm rate is calcined 3 hours for 10 DEG C/min and at 550 DEG C, is milled, is taken the g-C that 0.5g is ground3N4Powder is in the thin mouth of 300mL
In vial, a certain amount of deionized water is added in, and with 20% effect in the ultrasonic cell disruptor for being 650W in general power
Rate carries out the fragmentation processing of 15min, and upper strata milk yellow suspension is then taken then to do gained liquid freezing in evaporating dish
It is dry, obtain E-g-C3N4。
(2) Ag bases three-dimensional sea urchin shape E-g-C3N4/TiO2The preparation of composite material：
Prepare A liquid：Step (1) is taken to prepare E-g-C3N40.05g is dissolved in the deionized water of 10ml, ultrasonic 25min
5min is stirred with 800r/min again after (40000Hz)；Prepare B liquid：Weigh three-dimensional sea urchin TiOs of the 0.2g by solvent hot preparation2
It is dissolved in the deionized water of 10ml, stirs 15min (700r/min) ultrasound 15min (40000Hz) afterwards；Under agitation,
The A drops of 2.0mL add in B liquid；Then add in 4.3mg silver nitrates and 4.3mg Sodium Citrate, usp, Dihydrate Powders；Stirring is to dissolving, by this instead
Liquid is answered to be transferred to autoclave, at 150 DEG C, heating time is 21 hours；Reaction kettle cooled to room temperature is treated, with anhydrous second
Alcohol and deionized water washing are for several times, dry, obtain Ag base three-dimensional sea urchin shapes E-g-C3N4/TiO2Composite material.
Embodiment 4：
(1) thin layer g-C3N4Preparation：
Precise 15g thiocarbamides move into the sealing of 50mL ceramic crucibles, are placed on burner hearth center, set instrument parameter, make liter
Warm rate is calcined 3 hours for 10 DEG C/min and at 550 DEG C, is milled, is taken the g-C that 0.5g is ground3N4Powder is in the thin mouth of 300mL
In vial, a certain amount of deionized water is added in, and with 20% effect in the ultrasonic cell disruptor for being 650W in general power
Rate carries out the fragmentation processing of 20min, and upper strata milk yellow suspension is then taken then to do gained liquid freezing in evaporating dish
It is dry, obtain E-g-C3N4。
(2) Ag bases three-dimensional sea urchin shape E-g-C3N4/TiO2The preparation of composite material：
Prepare A liquid：Step (1) is taken to prepare E-g-C3N40.05g is dissolved in the deionized water of 10ml, ultrasonic 25min
5min is stirred with 800r/min again after (40000Hz)；Prepare B liquid：Weigh three-dimensional sea urchin TiOs of the 0.2g by solvent hot preparation2
It is dissolved in the deionized water of 10ml, stirs 15min (700r/min) ultrasound 15min (40000Hz) afterwards；Under agitation,
The A drops of 2.0mL add in B liquid；Then add in 12.7mg silver nitrates and 12.7mg Sodium Citrate, usp, Dihydrate Powders；Stirring is to dissolving, by this
Reaction solution is transferred to autoclave, and at 120 DEG C, heating time is 21 hours；Treat reaction kettle cooled to room temperature, use is anhydrous
Ethyl alcohol and deionized water washing are for several times, dry, obtain Ag base three-dimensional sea urchin shapes E-g-C3N4/TiO2Composite material.
Embodiment 5：
(1) thin layer g-C3N4Preparation：
Precise 15g thiocarbamides move into the sealing of 50mL ceramic crucibles, are placed on burner hearth center, set instrument parameter, make liter
Warm rate is calcined 3 hours for 10 DEG C/min and at 550 DEG C, is milled, is taken the g-C that 0.5g is ground3N4Powder is in the thin mouth of 300mL
In vial, a certain amount of deionized water is added in, and with 20% effect in the ultrasonic cell disruptor for being 650W in general power
Rate carries out the fragmentation processing of 15min, and upper strata milk yellow suspension is then taken then to do gained liquid freezing in evaporating dish
It is dry, obtain E-g-C3N4。
(2) Ag bases three-dimensional sea urchin shape E-g-C3N4/TiO2The preparation of composite material：
Prepare A liquid：Step (1) is taken to prepare E-g-C3N40.05g is dissolved in the deionized water of 10ml, ultrasonic 25min
5min is stirred with 800r/min again after (40000Hz)；Prepare B liquid：Weigh three-dimensional sea urchin TiOs of the 0.2g by solvent hot preparation2
It is dissolved in the deionized water of 10ml, stirs 15min (700r/min) ultrasound 15min (40000Hz) afterwards；Under agitation,
The A drops of 2.0mL add in B liquid；Then add in 21.3mg silver nitrates and 21.3mg Sodium Citrate, usp, Dihydrate Powders；Stirring is to dissolving, by this
Reaction solution is transferred to autoclave, and at 150 DEG C, heating time is 18 hours；Treat reaction kettle cooled to room temperature, use is anhydrous
Ethyl alcohol and deionized water washing are for several times, dry, obtain Ag base three-dimensional sea urchin shapes E-g-C3N4/TiO2Composite material.
As can be seen from the above embodiments, it is provided by the invention or three-dimensional extra large according to Ag bases prepared by preparation method of the present invention
Courage shape E-g-C3N4/TiO2The grain size of composite material is 1.5~3.0 μm, and existing high absorption property has again with wide light absorption range can
Inhibit the performances such as electron-hole is compound, can be applied to the multiple fields such as degradation of contaminant, production hydrogen.Preparation work provided by the invention
Skill is simple, of low cost, has preferable actual application value.
The above is only the preferred embodiment of the present invention, not makees limitation in any form to the present invention.It should
It points out, for those skilled in the art, under the premise of not from the principle of the invention, can also make several
Improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
The foregoing description of the disclosed embodiments enables professional and technical personnel in the field to realize or use the present invention.
A variety of modifications of these embodiments will be apparent for those skilled in the art, it is as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.
Claims (7)
1. a kind of Ag bases three-dimensional sea urchin shape E-g-C3N4/TiO2The preparation method of composite material, it is characterised in that：The preparation side
Method is as follows：
Step 1：Use thiocarbamide that g-C is prepared by temperature programming for raw material3N4；
Step 2：By the g-C in step 13N4Deionized water is dissolved in after milling, fragmentation processing is carried out, then takes upper strata yellow fraction
Color suspension is placed in evaporating dish；
Step 3：By liquid freezing drying obtained by step 2, thin layer E-g-C is obtained3N4；
Step 4：Take the thin layer E-g-C in step 33N4Water ultrasonic disperse is dissolved in, obtains A liquid；
Step 5：Three-dimensional sea urchin shape TiO is prepared by solvent thermal reaction2, deionized water dispersion is dissolved in, obtains B liquid；
Step 6：A liquid, the B liquid that step 4 and step 5 are respectively obtained mix, and silver nitrate and citric acid are added in stirring
Mixed liquor is obtained Ag base three-dimensional sea urchin shapes E-g-C by sodium after hydro-thermal reaction, drying3N4/TiO2Composite material.
2. a kind of Ag bases three-dimensional sea urchin shape E-g-C according to claim 13N4/TiO2The preparation method of composite material,
It is characterized in that, the g-C3N4:TiO2:H2The mass ratio of O is 2.5wt%~10wt%:1:10.
3. a kind of Ag bases three-dimensional sea urchin shape E-g-C according to claim 13N4/TiO2The preparation method of composite material,
It is characterized in that, the hydro-thermal reaction preparation method of the step 6 is specific as follows：
(1) under agitation, B liquid is added dropwise to A liquid, then according to Ag:The atomic molar ratio of Ti is 1%~7%:1
Ratio adds in silver nitrate and Sodium Citrate, usp, Dihydrate Powder, and wherein Sodium Citrate, usp, Dihydrate Powder keeps 1 with added silver nitrate quality:1；
(2) by the above-mentioned Ag base three-dimensional sea urchin shapes E-g-C for obtaining the step (1)3N4/TiO2Composite material precursor solution
It reacts in a heated condition, obtains Ag base three-dimensional sea urchin shapes E-g-C3N4/TiO2Composite material.
4. a kind of Ag bases three-dimensional sea urchin shape E-g-C according to claim 33N4/TiO2The preparation method of composite material,
It is characterized in that, the heating condition in the step (2) is：Heating temperature is 120~180 DEG C, and heating time is 15~21h.
5. a kind of Ag bases three-dimensional sea urchin shape E-g-C according to claim 13N4/TiO2The preparation method of composite material,
It is characterized in that, the fragmentation processing in the step 2 uses ultrasonic cell disruptor of the general power for 650W, with 20%
Efficiency carries out the fragmentation processing of 10~20min.
6. a kind of Ag bases three-dimensional sea urchin shape E-g-C3N4/TiO2Composite material, which is characterized in that Ag nanometers in the composite material
Particle and thin layer g-C3N4It is deposited on sea urchin shape TiO2The surface of matrix.
7. a kind of Ag bases three-dimensional sea urchin shape E-g-C according to claim 63N4/TiO2Composite material, which is characterized in that institute
State Ag base three-dimensional sea urchin shapes E-g-C3N4/TiO2Composite material microsphere diameter is 1.5~3.0 μm.
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