CN107649161B - A kind of codope Rutile Type TiO2The preparation method of nanometer rods - Google Patents
A kind of codope Rutile Type TiO2The preparation method of nanometer rods Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- 239000012153 distilled water Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 11
- 238000011160 research Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910011208 Ti—N Inorganic materials 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000000187 Abnormal Reflex Diseases 0.000 description 1
- 240000008100 Brassica rapa Species 0.000 description 1
- 235000011292 Brassica rapa Nutrition 0.000 description 1
- 206010021089 Hyporeflexia Diseases 0.000 description 1
- 229910009819 Ti3C2 Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
A kind of codope Rutile Type TiO2The preparation method of nanometer rods, belongs to TiO2The technical field of nanometer polymerization body, it using titanium carbide as raw material, distributes it in water, ethylenediamine is then added, disperse 20-30min, feed liquid after dispersion is added in reaction kettle, at Yu Wendu 170-190 DEG C, reacts 5-6h, it takes out, 20 DEG C are cooled to, through centrifugation, washing, drying, obtains codope Rutile Type TiO2Nanometer rods.Preparation method of the present invention is simple, realizes the Rutile Type TiO of one-step synthesis doping C, N element2Nanometer rods.
Description
Technical field
The invention belongs to TiO2The technical field of nanometer polymerization body is related to Rutile Type TiO2The doping of nanometer rods, specifically relates to
And a kind of codope Rutile Type TiO2The preparation method of nanometer rods.Preparation method of the present invention realizes one-step synthesis doping C, N
The Rutile Type TiO of element2Nanometer rods.
Background technique
As the economic spring tide of reforming and opening up to the outside world swept over the country after 30 or 40 years, environment and energy problem seriously constrain it is current I
State's economy grows continuously and fast.Materialogy in recent years research shows that: TiO2As a kind of wide band gap semiconducter, in photochemistry and
There are many advantages in photocell field, are the best preferred materials for solving above-mentioned two hang-up.
Titanium dioxide (TiO2) semiconductor functional material, due to its low cost, non-toxic, high surface and high stability
The advantages that, be widely used in photocatalysis, solar battery, electrochromic effect device, moisture sensor device, antibacterial device and
The fields such as spintronics devices.But since its forbidden bandwidth is 3.2eV, it is caused to be only capable of directly absorbing less than 388nm wavelength
Sunlight, visible light cannot be effectively absorbed, to limit TiO2Application in practical photocatalysis and photoelectric conversion.
Summary of the invention
The present invention is to solve the above problems, provide a kind of codope Rutile Type TiO2The preparation method of nanometer rods, has
Effect reduces TiO2Energy band band gap, has widened TiO2Light absorption range.
The present invention be realize its purpose the technical solution adopted is that:
A kind of codope Rutile Type TiO2The preparation method of nanometer rods distributes it in water using titanium carbide as raw material,
Then ethylenediamine is added, disperses 20-30min, the feed liquid after dispersion is added in reaction kettle, at Yu Wendu 160-180 DEG C, instead
5-6h is answered, is taken out, is cooled to 20 DEG C, through centrifugation, washing, drying, obtains codope Rutile Type TiO2Nanometer rods.
The mass volume ratio of titanium carbide and ethylenediamine is (0.06g-0.30g): (4mL-8mL).
Water used in water is distributed to as distilled water, the mass volume ratio of titanium carbide and distilled water is (0.06g-
0.30g): (16mL-20mL).
When washing, first with 2% dilute hydrochloric acid pickling 2 times, then washed 3 times with dehydrated alcohol, finally with distillation washing 3 times.
It when dry, is dried using thermostatic drying chamber, drying temperature is 60-80 DEG C, drying time 10-12h.
Dispersion uses ultrasonic disperse, and control ultrasonic disperse frequency is 40-60Hz.
The reaction kettle uses hydrothermal reaction kettle, and the volume of reaction kettle is 6-13 times of ethylenediamine volume used.
The beneficial effects of the present invention are:
Preparation method one-step synthesis of the present invention adulterates the Rutile Type TiO of C, N element2Nanometer rods, the doping of C, N element
Effectively reduce TiO2Energy band band gap, the formation of nanorod structure can more effectively realize that table (boundary) surface charge separates, increase light
Raw charge life decomposes the toxic pollutant in water or air so as to convert by a series of optical-electronics-chemical energy,
Or it is converted into electric energy using solar energy, while also having the effect of improving stream transport factor.
Existing C, N adulterate TiO2Although the absorption to visible light a degree of can be widened, due to light corruption
Erosion and charge compound influence again, are unable to maintain that visible light catalysis activity, this is the bottleneck faced at present, and the present invention
It solves the problems, such as.The incorporation of nitrogen can make TiO2Band-gap energy between lattice reduces, but can equally Lacking oxygen be brought to increase, and makes
Increase at electrons and holes recombination rate, to cause electron-hole recombination rate high, the present invention by long-term some analyses and
Research, finally found that reason is C, N codope to TiO2Effect, C, N codope TiO of various concentration, form etc.2It influences big
It is not identical, further research in, these be all by preparation method caused by.The present invention is raw material by using titanium carbide,
React with ethylenediamine and realizes C, N codope, nearby band density increases for top of valence band and conduction band bottom in the doping system of acquisition, from
And the transition probability of electronics is increased, increase absorption efficiency.The control of titanium carbide and ethylenediamine ratio, so that N doping is formed
Inside band gap state sufficiently close to TiO2Conduction band and generate electronics coupled, so that it is compound to reduce electron-hole.Titanium carbide is first
Dispersion, then the control of addition ethylenediamine redisperse and jitter time is the codope Rutile Type TiO in order to make to obtain2Nanometer
The partial size of stick is small and particle diameter distribution is uniform, and nanoparticle good dispersion is acted on by dimensional quantum, improves photocatalytic activity.
The control of 160-180 DEG C of reaction temperature, reaction time 5-6h can make the codope Rutile Type TiO obtained2Nanometer rods are can
The hyporeflexia in light-exposed area extends optical response range, thus further so that the light quantity subnumber for participating in light-catalyzed reaction be made to increase
Improve the response to visible light.
N of the present invention doping exists in the form of calking rather than displacement format, N existing for calking form formed Ti-N and
The collective effect of Ti-O, in conjunction with can also will be above 396eV, but will be lower than N-O bond energy at 400eV；It is at 286.53eV
C-O key shows that Ti-C key fragments into for Ti-O-C key.C, N doping hinders crystal growth, refines crystal, promotes ratio
The increase of surface area can generate more Lacking oxygens, and the electric conductivity for being conducive to nanometer rods improves.
N element replaces the oxygen atom in titanium dioxide lattice, forms Ti-N, and the forbidden bandwidth between Ti-N lattice reduces,
The photocatalytic activity of titanium dioxide under visible light can be improved；Carbon atom forms Ti-O-C-structure in conjunction with oxygen atom, changes
Oxygen atom outermost electron, reduces TiO2Forbidden bandwidth, electric conductivity enhancing.
Chlorohydric acid pickling is used before calcination, to maintaining calcination product thermal stability to have positive influence, promotes Anatase content
Increase, is conducive to the raising of product photocatalytic activity；Reusability distilled water and ethyl alcohol rinse, to remove the ion on surface.
Gained codope Rutile Type TiO of the invention2Nanorod length is about 0.4 μm, width 10nm.
Detailed description of the invention
Fig. 1 is codope Rutile Type TiO of the present invention2Nanometer rods XPS figure.
Fig. 2 is codope TiO2Photocatalysis Decomposition aquatic products hydrogen curve of the nanometer rods under ultraviolet lighting.
Fig. 3 is codope TiO2Photocatalysis Decomposition aquatic products hydrogen curve of the nanometer rods under ultraviolet-visible illumination.
Fig. 4 is codope Rutile Type TiO of the present invention2Nanometer rods TEM figure.
Specific embodiment
Preparation method of the present invention is easy to operate, and reaction process is mildly stablized, easily controllable, realizes one-step synthesis C, N member
Plain codope Rutile Type TiO2Nanometer rods.The present invention is further illustrated combined with specific embodiments below.
One, specific embodiment
Embodiment 1
The titanium carbide of 0.06g is weighed, the ethylenediamine of 4mL is added into 16mL distilled water in ultrasonic disperse, after dispersing 30min
Be fitted into 50mL hydrothermal reaction kettle, 180 DEG C of set temperature, the time be 6 hours, take out later, naturally cool to 20 DEG C, pour into from
It is centrifuged in heart pipe, using 2% dilute hydrochloric acid pickling 2 times, is respectively washed 3 times using dehydrated alcohol and distilled water afterwards, it is dry in constant temperature
Dry in dry case, temperature 70 C, time 12h obtains product.It naturally cools to 20 DEG C and carries out subsequent operation, the control of temperature again
The synergistic effect that C, N codope can be enhanced with the type of cooling makes C, N doping enter the lattice of titanium oxide, is titanium oxide to can
Light-exposed response enhancing, further increases catalytic degradation ability.
Embodiment 2
The titanium carbide of 0.12g is weighed, the ethylenediamine of 5mL is added into 17mL distilled water in ultrasonic disperse, after dispersing 30min
Be fitted into 50mL hydrothermal reaction kettle, 180 DEG C of set temperature, the time be 6 hours, take out later, naturally cool to 20 DEG C, pour into from
It is centrifuged in heart pipe, using 2% dilute hydrochloric acid pickling 2 times, is respectively washed 3 times using dehydrated alcohol and distilled water afterwards, it is dry in constant temperature
Dry in dry case, temperature 70 C, time 12h obtains product.
Embodiment 3
The titanium carbide of 0.18g is weighed, the ethylenediamine of 6mL is added into 18mL distilled water in ultrasonic disperse, after dispersing 30min
Be fitted into 50mL hydrothermal reaction kettle, 180 DEG C of set temperature, the time be 6 hours, take out later, naturally cool to 20 DEG C, pour into from
It is centrifuged in heart pipe, using 2% dilute hydrochloric acid pickling 2 times, is respectively washed 3 times using dehydrated alcohol and distilled water afterwards, it is dry in constant temperature
Dry in dry case, temperature 70 C, time 12h obtains product.
Embodiment 4
The titanium carbide of 0.24g is weighed, the ethylenediamine of 7mL is added into 19mL distilled water in ultrasonic disperse, after dispersing 30min
Be fitted into 50mL hydrothermal reaction kettle, 180 DEG C of set temperature, the time be 6 hours, take out later, naturally cool to 20 DEG C, pour into from
It is centrifuged in heart pipe, using 2% dilute hydrochloric acid pickling 2 times, is respectively washed 3 times using dehydrated alcohol and distilled water afterwards, it is dry in constant temperature
Dry in dry case, temperature 70 C, time 12h obtains product.
Embodiment 5
The titanium carbide of 0.30g is weighed, the ethylenediamine of 8mL is added into 20mL distilled water in ultrasonic disperse, after dispersing 30min
Be fitted into 50mL hydrothermal reaction kettle, 180 DEG C of set temperature, the time be 6 hours, take out later, naturally cool to 20 DEG C, pour into from
It is centrifuged in heart pipe, using 2% dilute hydrochloric acid pickling 2 times, is respectively washed 3 times using dehydrated alcohol and distilled water afterwards, it is dry in constant temperature
Dry in dry case, temperature 70 C, time 12h obtains product.
Embodiment 6
The titanium carbide of 0.10g is weighed, the ethylenediamine of 4mL is added into 16mL distilled water in ultrasonic disperse, after dispersing 20min
Be fitted into 50mL hydrothermal reaction kettle, 170 DEG C of set temperature, the time be 5 hours, take out later, naturally cool to 20 DEG C, pour into from
It is centrifuged in heart pipe, using 2% dilute hydrochloric acid pickling 2 times, is respectively washed 3 times using dehydrated alcohol and distilled water afterwards, it is dry in constant temperature
Dry in dry case, temperature 60 C, time 10h obtains product.
Embodiment 7
The titanium carbide of 0.15g is weighed, the ethylenediamine of 6mL is added into 18mL distilled water in ultrasonic disperse, after dispersing 25min
It is fitted into 50mL hydrothermal reaction kettle, 160 DEG C of set temperature, the time is 5.5 hours, takes out later, naturally cools to 20 DEG C, pour into
It is centrifuged in centrifuge tube, using 2% dilute hydrochloric acid pickling 2 times, is respectively washed 3 times using dehydrated alcohol and distilled water afterwards, in constant temperature
Dry in drying box, 65 DEG C of temperature, time 11h obtains product.
Embodiment 8
The titanium carbide of 0.27g is weighed, the ethylenediamine of 5mL is added into 17mL distilled water in ultrasonic disperse, after dispersing 23min
It is fitted into 50mL hydrothermal reaction kettle, 175 DEG C of set temperature, the time is 5.7 hours, takes out later, naturally cools to 20 DEG C, pour into
It is centrifuged in centrifuge tube, using 2% dilute hydrochloric acid pickling 2 times, is respectively washed 3 times using dehydrated alcohol and distilled water afterwards, in constant temperature
Dry in drying box, 75 DEG C of temperature, time 10.5h obtains product.
Embodiment 9
The titanium carbide of 0.25g is weighed, the ethylenediamine of 7mL is added into 19mL distilled water in ultrasonic disperse, after dispersing 27min
It is fitted into 50mL hydrothermal reaction kettle, 165 DEG C of set temperature, the time is 5.3 hours, takes out later, naturally cools to 20 DEG C, pour into
It is centrifuged in centrifuge tube, using 2% dilute hydrochloric acid pickling 2 times, is respectively washed 3 times using dehydrated alcohol and distilled water afterwards, in constant temperature
Dry in drying box, 80 DEG C of temperature, time 11.5h obtains product.
Ultraviolet reflection spectral data are as follows:
Obtain band gap magnitude by Kubelka-Munk equation calculation: 3.24eV (P25), 3.17 (T1), 3.04 (T2),
2.89eV (T3), 2.79eV (T4), 2.71eV (T5), so, the change that band gap narrows has occurred in the doping of C, N element.
Analyze to obtain from Fig. 1, several elements such as C, Ti, N, O 285.1,530.4,399.8, the letter of the position 528.3eV
Number surface exists.
Two, research and analysis
1, the ratio control of titanium carbide and ethylenediamine of the present invention, obtained codope Rutile Type TiO2C, N in nanometer rods
Ratio, distribution are excellent, increase the electric conductivity and wetability of nanocomposite.Using the electrode of this material as working electrode,
Platinum plate electrode is to electrode, and silver-colored silver chlorate is reference electrode, under the KOH electrolyte of 6mol/L, using CHI660E electrochemistry work
Make station and carry out electrochemical property test, such as Linear Circulation volt-ampere curve, constant current charge-discharge, AC impedance, there is high specific volume
Amount, good rate capability and cyclical stability.
2, Photocatalyzed Hydrogen Production activity research
The experiment carries out in quartz reaction bottle, weighs 0.1g codope Rutile Type TiO of the present invention2Nanometer rods are put into
In 360mL quartz bottle, the Na of 200mL 0.1mol/L is added2S (98.0%, AR, Shanghai Ling Feng chemical reagent Co., Ltd) and
The Na of 0.04mol/L2SO3The mixed solution of (97.0%, AR, Brassica rapa L analyse Chemical Industry Science Co., Ltd), tests used light source
The respectively ultraviolet lamp of 8W (253.7nm, luminous intensity 0.75mW/cm2) and the xenon lamp of 500W (ultraviolet-visible light, Beijing are freely opened up
Science and Technology Ltd., luminous intensity 120mW/cm2).Before reaction, then the first ultrasound 15min of sample leads to N2It is sealed after purging 30min
Closure system, which is placed under light source, starts light-catalyzed reaction, under magnetic stirring 2 h of continuous illumination, the H that light-catalyzed reaction generates2It will
It is enclosed in the space in quartz reaction bottle on liquid level, every 20min acquires a gaseous sample from quartz reaction bottle and carries out H2
The quantitative analysis (GC7900 type gas chromatograph, Shanghai Techcomp Instrument Ltd.) of content, detector TCD, chromatography
Column is 5A molecular sieve, N2It does carrier gas luminous intensity and passes through light power meter (ORIEL company) and UV-A type ultraviolet radiation meter UV-A type
Ultraviolet radiation meter UV-254 (TaiWan, China Turner company) is measured.
It can be seen that codope Rutile Type TiO of the present invention by Fig. 2 and Fig. 32The catalysis of nanometer rods in the UV lamp produces
Hydrogen activity highest, 120min is up to 91.3 μm of ol, 45.65 μm of ol/h of hydrogen-producing speed；Hydrogen activity is produced in the catalysis of ultraviolet-visible light
It is 120min up to 12.4 μm of ol, 6.2 μm of ol/h of hydrogen-producing speed.
Comparative example product is carried out to the test of the same terms Photocatalyzed Hydrogen Production activity research, comparative example: taking Ti3C2 powder
50mg and 50mL aqueous solution of urea are stirred 2h, urea in aqueous solution of urea: the mass ratio of water is 1:1；By resulting solution
Be put into water heating kettle, the hydro-thermal 12h at 160 DEG C, then by after reaction powder deionized water and washes of absolute alcohol for several times,
Drying in 40 DEG C of vacuum drying oven is placed into, C, N doping titanium dioxide nano stick are obtained.
From figures 2 and 3, it will be seen that comparative example codope TiO2The catalysis of nanometer rods in the UV lamp produces hydrogen activity
120min is up to 74.6 μm of ol, 37.3 μm of ol/h of hydrogen-producing speed；Producing hydrogen activity in the catalysis of ultraviolet-visible light is that 120min is reachable
2.4 μm of ol, 1.2 μm of ol/h of hydrogen-producing speed.
Pass through Fig. 2 and Fig. 3, it can be seen that codope Rutile Type TiO of the present invention2The catalysis of nanometer rods in the UV lamp
Hydrogen activity highest is produced, and also higher in the catalysis of ultraviolet-visible light production hydrogen activity, produces hydrogen activity in the catalysis of ultraviolet-visible light
Achieve breakthrough.
Claims (7)
1. a kind of codope Rutile Type TiO2The preparation method of nanometer rods, which is characterized in that using titanium carbide as raw material, by its point
It is scattered in water, ethylenediamine is then added, disperse 20-30min, the feed liquid after dispersion is added in reaction kettle, Yu Wendu 160-
At 180 DEG C, 5-6h is reacted, is taken out, is cooled to 20 DEG C, through centrifugation, washing, drying, obtains codope Rutile Type TiO2Nanometer
Stick.
2. a kind of codope Rutile Type TiO according to claim 12The preparation method of nanometer rods, which is characterized in that carbon
The mass volume ratio for changing titanium and ethylenediamine is (0.06g-0.30g): (4mL-8mL).
3. a kind of codope Rutile Type TiO according to claim 12The preparation method of nanometer rods, which is characterized in that point
Water used in water is scattered to as distilled water, the mass volume ratio of titanium carbide and distilled water is (0.06g-0.30g): (16mL-
20mL)。
4. a kind of codope Rutile Type TiO according to claim 12The preparation method of nanometer rods, which is characterized in that wash
When washing, first with 2% dilute hydrochloric acid pickling 2 times, then washed 3 times with dehydrated alcohol, finally with distillation washing 3 times.
5. a kind of codope Rutile Type TiO according to claim 12The preparation method of nanometer rods, which is characterized in that dry
It when dry, is dried using thermostatic drying chamber, drying temperature is 60-80 DEG C, drying time 10-12h.
6. a kind of codope Rutile Type TiO according to claim 12The preparation method of nanometer rods, which is characterized in that point
It dissipates and uses ultrasonic disperse, control ultrasonic disperse frequency is 40-60Hz.
7. a kind of codope Rutile Type TiO according to claim 12The preparation method of nanometer rods, which is characterized in that institute
Reaction kettle is stated using hydrothermal reaction kettle, the volume of reaction kettle is 6-13 times of ethylenediamine volume used.
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| CN101074113A (en) * | 2007-05-16 | 2007-11-21 | 浙江大学 | Production and use for non-metallic doped nano-TiO |
| CN102527421A (en) * | 2011-11-10 | 2012-07-04 | 重庆工商大学 | C and N dual-doped nano TiO2 photochemical catalyst and preparation method thereof |
| CN106024416A (en) * | 2016-05-31 | 2016-10-12 | 陕西科技大学 | Nitrogen-doped rod-like titanium oxide/two-dimensional laminated titanium carbide nanometer composite electrode material, and preparation method and application therefor |
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| CN102527421A (en) * | 2011-11-10 | 2012-07-04 | 重庆工商大学 | C and N dual-doped nano TiO2 photochemical catalyst and preparation method thereof |
| CN106024416A (en) * | 2016-05-31 | 2016-10-12 | 陕西科技大学 | Nitrogen-doped rod-like titanium oxide/two-dimensional laminated titanium carbide nanometer composite electrode material, and preparation method and application therefor |
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