CN105435767A - Preparation method of photocatalyst adopting one-dimensional CNF (carbon nanofiber)/TiO2 core-shell structure - Google Patents
Preparation method of photocatalyst adopting one-dimensional CNF (carbon nanofiber)/TiO2 core-shell structure Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 15
- 239000011941 photocatalyst Substances 0.000 title abstract description 9
- 239000011258 core-shell material Substances 0.000 title abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000010306 acid treatment Methods 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 238000001523 electrospinning Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 41
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 27
- 238000009987 spinning Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 8
- 235000018417 cysteine Nutrition 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 8
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 238000010041 electrostatic spinning Methods 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 150000004965 peroxy acids Chemical class 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000009776 industrial production Methods 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 19
- 229920000049 Carbon (fiber) Polymers 0.000 description 11
- 239000004917 carbon fiber Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 238000005286 illumination Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method 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
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/39—
-
- B01J35/397—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
Abstract
The invention discloses a preparation method of a photocatalyst adopting a one-dimensional CNF (carbon nanofiber)/TiO2 core-shell structure. The preparation method comprises the following steps: firstly, CNFs are prepared with an electrospinning method and then subjected to acid treatment; then the CNF/TiO2 core-shell structure is synthesized with a hydrothermal method; finally, cleaning treatment is performed, a product obtained from the CNF/TiO2 core-shell structure synthesized with the hydrothermal method is cleaned sufficiently with deionized water and dried in a drying oven, and the photocatalyst adopting the one-dimensional CNF/TiO2 core-shell structure is prepared. According to the preparation method, the photocatalyst adopting the one-dimensional CNF/TiO2 core-shell structure is prepared with the electrospinning method and the hydrothermal method, the operation is simple, the repeatability is reliable, the photocatalytic activity of the photocatalyst is higher, and the method is applicable to industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of material, particularly relate to a kind of one dimension carbon nano-fiber TiO
2the preparation method of photochemical catalyst of nucleocapsid structure.
Background technology
Along with industrialized development and population increase rapidly, the mankind are day by day serious to the dependence of fossil fuel.But the storage capacity of fossil fuel is very limited and non-renewable, and discharge a large amount of CO in the process of combustion of fossil fuel
2cause greenhouse effects.Photocatalitic Technique of Semiconductor utilizes solar energy by CO
2photo catalytic reduction becomes reproducible hydrocarbon fuel (methane, methyl alcohol etc.), be considered to solve energy crisis and environmental pollution by one of effect approach.Since the people such as Inoue report semi-conducting material photo catalytic reduction CO in aqueous
2research since, various semi-conducting material, as TiO
2, ZnO, ZnGa
2o
4, WO
3deng, be widely studied.In these semiconductors, TiO
2due to inexpensive, nontoxic, long-term stability, is considered to one of promising photochemical catalyst of most.But TiO
2photochemical catalyst holds to reunite in preparation process to be made it have less specific area and causes its photo-generated carrier charge recombination rate higher, in addition due to TiO
2have larger band gap can only absorbing wavelength at the sunshine of ultra-violet (UV) band, cause TiO
2the photocatalysis efficiency of photochemical catalyst is usually lower.Given this, a large amount of research work is attempted by strengthening TiO
2light absorpting ability and reduce TiO
2the recombination rate of photo-generated carrier improves its photocatalytic activity.
Summary of the invention
In order to solve the deficiencies in the prior art, the object of the present invention is to provide a kind of one dimension carbon nano-fiber TiO of simple and easy to do, low cost
2the preparation method of photochemical catalyst of nucleocapsid structure.
For achieving the above object, the technology used in the present invention means are: one dimension carbon nano-fiber TiO
2the preparation method of photochemical catalyst of nucleocapsid structure, first utilize electrospinning process to prepare carbon nano-fiber, then to carbon nano-fiber acid treatment, recycling water heat transfer carbon nano-fiber TiO
2nucleocapsid structure, finally carries out cleaning treatment, will utilize water heat transfer carbon nano-fiber TiO
2after in nucleocapsid structure, gained reactant deionized water is fully cleaned, dry oven dry in an oven, i.e. obtained one dimension carbon nano-fiber TiO
2the photochemical catalyst of nucleocapsid structure.
Further, in described baking oven, dry temperature of drying is 60 ~ 80 DEG C, and the time is 6 ~ 8h.
Further, described electrospinning process is prepared carbon nano-fiber and is referred to: the DFM solution of preparation PAN is as spinning solution, utilize dull and stereotyped as receiving pole, the mode of vertical reception is adopted to carry out electrostatic spinning, obtain flexible PAN precursor, then by Muffle furnace low temperature pre-oxidation and the process of tube furnace high temperature cabonization, carbon nano-fiber is obtained.
Further, the mass ratio of described spinning solution is the DFM solution of the PAN of 10wt%, must heat while stirring in preparation process, and heating-up temperature is 60 ~ 80 DEG C, heat time 2 ~ 3h.
Further, in described electrostatic spinning process, wherein high tension voltage is set as 14 ~ 18kV, the internal diameter of spray silk syringe needle is 0.4 ~ 0.8mm, dash receiver distance spinning syringe needle distance is 12 ~ 17cm, the discharging speed of spinning solution is 0.4 ~ 0.8mL/h, and the relative air humidity of spinning cavity controls to be 30% ~ 40%; At 24 ~ 28 DEG C, continuous spinning 9 ~ 11h obtains the PAN precursor of white, by PAN precursor in Muffle furnace 250 ~ 350
ounder C, 2 ~ 3h is stablized in pre-oxidation, and the heating rate of Muffle furnace is 2
oc/min, finally puts into tube furnace by fiber after pre-oxidation and at N
2protection lower 750 ~ 850
oc carbonization 2 ~ 3h, the heating rate of tube furnace is set as 5
oc/min, obtains carbon nano-fiber after carbonization.
Further, described carbon nano-fiber acid treatment refers to: the carbon nano-fiber prepared by electrospinning process is added in acid solution, and acid treatment is carried out in heating, then uses the acid of washed with de-ionized water carbon nano-fiber remained on surface, and dries in an oven.
Further, described acid is 4M salpeter solution, and in oil bath pan, 80 ~ 100 DEG C add hot reflux 6 ~ 8h and carry out acid treatment, and then use washed with de-ionized water carbon nano-fiber surface to pH=7, deionized water centrifuge washing is used in cleaning.
Further, describedly water heat transfer carbon nano-fiber TiO is utilized
2nucleocapsid structure refers to: by carbon nano-fiber after peracid treatment, and ultrasonic disperse, in deionized water, then adds cysteine, titanium sulfate, urea, continues ultrasonic disperse, is finally transferred in hydrothermal reaction kettle by mixed solution and carry out hydro-thermal reaction.
Further, described interpolation cysteine: titanium sulfate: the mol ratio of urea is 2:1:4.
Further, in described hydrothermal reaction kettle, hydrothermal temperature is set as that between 160 ~ 200 DEG C, the reaction time is set as 10 ~ 14h.
The invention has the beneficial effects as follows: utilize electrospinning process and hydrothermal method to prepare the photochemical catalyst of the nucleocapsid structure of one dimension carbon nano-fiber TiO2, simple to operate, repeatability is reliable, and the photocatalytic activity of photochemical catalyst is higher, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further elaborated.
Carbon fiber stereoscan photograph after the acid treatment of Fig. 1 prepared by the embodiment of the present invention 1;
The one dimension carbon nano-fiber TiO of Fig. 2 prepared by the embodiment of the present invention 1
2the stereoscan photograph of photochemical catalyst of nucleocapsid structure;
The one dimension carbon nano-fiber TiO of Fig. 3 prepared by the embodiment of the present invention 1
2the transmission electron microscope photo of photochemical catalyst of nucleocapsid structure and high-resolution-ration transmission electric-lens photo;
The TiO of Fig. 4 prepared by comparative example 1 of the present invention
2the stereoscan photograph of microsphere photocatalyst;
The UV-Vis DRS absorption spectrum comparison diagram of the finished product of Fig. 5 prepared by the embodiment of the present invention 1 and comparative example 1;
The carbon nano-fiber TiO of Fig. 6 prepared by the embodiment of the present invention 1
2nucleocapsid structure photochemical catalyst illumination before and illumination 1h after the original collection of illustrative plates of chromatogram;
The carbon nano-fiber TiO of Fig. 7 prepared by the embodiment of the present invention 1
2the photochemical catalyst of nucleocapsid structure and the TiO prepared by comparative example 1
2the photocatalysis CO of microsphere photocatalyst
2reducing activity comparison diagram.
Detailed description of the invention
embodiment 1
One dimension carbon nano-fiber TiO
2preparation method's step of photochemical catalyst of nucleocapsid structure as follows:
A) utilize electrospinning process carbon nano-fiber: 1gPAN to be added in 10mLDMF solution and at 80 DEG C of temperature strong agitation 2h, preparation spinning original solution, utilize dull and stereotyped as receiving pole, spinning high tension voltage is set as 15kV, the internal diameter of spinning syringe needle is 0.6mm, and the distance of spray silk syringe needle and dash receiver is 15cm, and the feeding speed of spinning solution is 0.5mL/h, the relative air humidity of spinning cavity controls to be 30%, spins the PAN precursor that 10h obtains white at 26 DEG C continuously.Then PAN fiber in Muffle furnace at 300 DEG C pre-oxidation stablize 2h, the heating rate of Muffle furnace is 2 DEG C/min, finally brown fibre after pre-oxidation is put into tube furnace and at N
2protect lower 800 DEG C of carbonization 2h, the heating rate of tube furnace is set as 5 DEG C/min, obtains carbon nano-fiber after carbonization;
B) carbon nano-fiber acid treatment: evenly spread to by the carbon nano-fiber of step a) gained in 4M salpeter solution, then in oil bath pan 80
oc adds hot reflux 6h and carries out acid treatment, then uses the nitric acid of washed with de-ionized water carbon nano-fiber remained on surface, and by pH detection paper until it is in neutral, finally by acid-treated carbon nano-fiber 80
odry oven dry 6h in C baking oven;
C) hydrothermal method synthesize nano carbon fiber TiO is utilized
2nucleocapsid structure: the acid-treated 20mg carbon nano-fiber of step b) gained is distributed in 30mL deionized water, make the carbon nano-fiber of acidifying dispersed with ripple ultrasonic echography dispersion 30min again, then 1mmol titanium sulfate, 2mmol cysteine, 4mmol urea continuation ultrasonic disperse 10min is added, then transferred in 50mL hydrothermal reaction kettle by mixed solution and carry out hydro-thermal reaction, hydrothermal temperature is set as 180
oc, the reaction time is set as 12h;
D) cleaning treatment: step c) gained reactant is spent deionized water 6 times, the impurity that fully cleaning is residual, then by it at baking oven 80
oin C, dry oven dry 6h, namely obtains one dimension carbon nano-fiber TiO
2the photochemical catalyst of nucleocapsid structure.
Carbon fiber diameter as shown in Figure 1 after acid treatment is relatively more even, about about 300nm, and the surperficial smoother of carbon fiber; One deck TiO is grown at the surface uniform of carbon fiber after Fig. 2 shows hydro-thermal
2crystal grain, defines one dimension carbon nano-fiber TiO
2nucleocapsid structure, and carbon fiber is by TiO
2what crystal grain was coated is not very tight, and can see the space exposing carbon fiber, this prevents TiO to a great extent
2the reunion of crystal grain, adds its specific area, is very beneficial for the carrying out of light-catalyzed reaction.Can be found by Fig. 3 coated by some little crystal grain at the edge of carbon fiber clearly, and pass through the lattice fringe of the transmission electron microscope that high-resolution amplifies in illustration, can judge that these crystal grain belong to anatase TiO
2.By the TiO not adding carbon fiber as shown in Figure 4
2crystal grain is assembled closely and is defined TiO
2microballoon, causes its specific area lower, is unfavorable for the carrying out of light-catalyzed reaction.Fig. 5 can find that, compared to comparative example 1, embodiment 1 compares obvious enhancing in the absorption of visible region, thus improves the utilization rate of photochemical catalyst to sunshine.
embodiment 2
One dimension carbon nano-fiber TiO
2preparation method's step of photochemical catalyst of nucleocapsid structure as follows:
A) electrospinning process carbon nano-fiber is utilized: to be added to by 1gPAN in 10mLDMF solution and 80
ostrong agitation 2h at C temperature, preparation spinning original solution, utilize dull and stereotyped as receiving pole, spinning high tension voltage is set as 16kV, the internal diameter of spinning syringe needle is 0.5mm, and the distance of spray silk syringe needle and dash receiver is 16cm, and the feeding speed of spinning solution is 0.6mL/h, the relative air humidity of spinning cavity controls to be 35%, 28
othe PAN precursor that 9h obtains white is spun continuously under C.Then PAN fiber in Muffle furnace 260
ounder C, 2.5h is stablized in pre-oxidation, and the heating rate of Muffle furnace is 2
oc/min, finally puts into tube furnace by brown fibre after pre-oxidation and at N
2protection lower 800
oc carbonization 2h, the heating rate of tube furnace is set as 5
oc/min, obtains carbon nano-fiber after carbonization;
B) carbon nano-fiber acid treatment: evenly spread to by the carbon nano-fiber of step a) gained in 4M salpeter solution, then in oil bath pan 60
oc adds hot reflux 8h and carries out acid treatment, then uses the nitric acid of washed with de-ionized water carbon nano-fiber remained on surface, and by pH detection paper until it is in neutral, finally by acid-treated carbon nano-fiber 80
odry oven dry 6h in C baking oven;
C) hydrothermal method synthesize nano carbon fiber TiO is utilized
2nucleocapsid structure: the acid-treated 10mg carbon nano-fiber of step b) gained is distributed in 30mL deionized water, make the carbon nano-fiber of acidifying dispersed with ripple ultrasonic echography dispersion 30min again, then 1mmol titanium sulfate, 2mmol cysteine, 4mmol urea continuation ultrasonic disperse 10min is added, then transferred in 50mL hydrothermal reaction kettle by mixed solution and carry out hydro-thermal reaction, hydrothermal temperature is set as 160
oc, the reaction time is set as 14h;
D) cleaning treatment: step c) gained reactant is spent deionized water 6 times, the impurity that fully cleaning is residual, then by it at baking oven 80
oin C, dry oven dry 6h, namely obtains one dimension carbon nano-fiber TiO
2the photochemical catalyst of nucleocapsid structure.
embodiment 3
One dimension carbon nano-fiber TiO
2preparation method's step of photochemical catalyst of nucleocapsid structure as follows:
A) electrospinning process carbon nano-fiber is utilized: to be added to by 1gPAN in 10mLDMF solution and 60
ostrong agitation 3h at C temperature, preparation spinning original solution, utilize dull and stereotyped as receiving pole, spinning high tension voltage is set as 18kV, the internal diameter of spinning syringe needle is 0.6mm, and the distance of spray silk syringe needle and dash receiver is 15cm, and the feeding speed of spinning solution is 0.5mL/h, the relative air humidity of spinning cavity controls to be 40%, 24
othe PAN precursor that 11h obtains white is spun continuously under C.Then PAN fiber in Muffle furnace 300
ounder C, 2h is stablized in pre-oxidation, and the heating rate of Muffle furnace is 2
oc/min, finally puts into tube furnace by brown fibre after pre-oxidation and at N
2protection lower 750
oc carbonization 2.5h, the heating rate of tube furnace is set as 5
oc/min, obtains carbon nano-fiber after carbonization;
B) carbon nano-fiber acid treatment: evenly spread to by the carbon nano-fiber of step a) gained in 4M salpeter solution, then in oil bath pan 80
oc adds hot reflux 6h and carries out acid treatment, then uses the nitric acid of washed with de-ionized water carbon nano-fiber remained on surface, and by pH detection paper until it is in neutral, finally by acid-treated carbon nano-fiber 60
odry oven dry 8h in C baking oven;
C) hydrothermal method synthesize nano carbon fiber TiO is utilized
2nucleocapsid structure: the acid-treated 5mg carbon nano-fiber of step b) gained is distributed in 30mL deionized water, make the carbon nano-fiber of acidifying dispersed with ripple ultrasonic echography dispersion 30min again, then 1mmol titanium sulfate, 2mmol cysteine, 4mmol urea continuation ultrasonic disperse 10min is added, then transferred in 50mL hydrothermal reaction kettle by mixed solution and carry out hydro-thermal reaction, hydrothermal temperature is set as 200
oc, the reaction time is set as 10h;
D) cleaning treatment: step c) gained reactant is spent deionized water 6 times, the impurity that fully cleaning is residual, then by it at baking oven 80
oin C, dry oven dry 6h, namely obtains one dimension carbon nano-fiber TiO
2the photochemical catalyst of nucleocapsid structure.
comparative example 1
TiO
2preparation method's step of microsphere photocatalyst is as follows:
A) hydrothermal method is utilized to synthesize TiO
2: 1mmol titanium sulfate, 2mmol cysteine, 4mmol urea are distributed in 30mL deionized water, make it dispersed with ripple ultrasonic echography dispersion 10min again, then transferred in 50mL hydrothermal reaction kettle by mixed solution and carry out hydro-thermal reaction, hydrothermal temperature is set as 180
oc, the reaction time is set as 12h;
B) cleaning treatment: step a) gained reactant is spent deionized water 6 times, the impurity that fully cleaning is residual, then by it at baking oven 80
oin C, dry oven dry 6h, namely obtains spherical TiO
2photochemical catalyst.
comparative example 2
Photocatalysis CO
2reduction test
For investigating catalyst at room temperature photocatalysis CO prepared by the embodiment of the present invention
2the performance of reduction, embodiment 1 and the product prepared by comparative example 1 are made catalyst by the present inventor, and concrete implementation step is as follows:
A) get the catalyst ultrasonic disperse of equal in quality in 10mL deionized water, ultrasonic disperse is transferred to after 10 minutes in 200mL heat resistant glass reactor, then reaction vessel is placed in baking oven in 80
oat C temperature, heating evaporation falls water and makes it can form a smooth film at reactor bottom;
B) 120mgNaHCO is added by step a) gained reactor
3, then pass into N wherein
230min seals after driving the air in reactor away, guarantees that reactor is in anaerobic state, then in reactor, injects 0.25mL4MHCl solution with syringe, makes itself and NaHCO
3reaction produces CO
2and H
2o gas;
C) step b) gained reactor is placed in distance light source 22cm place to irradiate, UV, visible light light source is provided by the xenon lamp of 300W, from reactor, 1mL gas is extracted every 1h, be injected into the gas chromatograph (GC-2014C being equipped with flame ionic detector (FID), Shimadzu) in, analyze the constituent concentration of mist, product gas selects different calibrating gas to carry out demarcation calibration, and the characteristic retention time of gas with various is determined.
Carbon nano-fiber TiO prepared by the embodiment of the present invention 1
2the photochemical catalyst of nucleocapsid structure before illumination and after illumination 1h the original collection of illustrative plates of chromatogram as shown in Figure 6, by the calibration of normal mixture body, the known highest peak 2.68 minutes positions is principal product CH
4, and time strong peak (2.86min) on side is accessory substance CH
3oH, other small peak corresponds to other hydrocarbon.The photocatalysis CO of embodiment 1 and the catalyst prepared by comparative example 1
2reduction efficiency as shown in Figure 7, at this to its topmost product CH
4study, before illumination, do not occur any peak, show that above-mentioned product is all that light-catalyzed reaction produces.One dimension carbon nano-fiber TiO as shown in Figure 7 prepared by embodiment 1
2the photochemical catalyst of nucleocapsid structure than Powdered TiO
2catalyst has higher photocatalytic activity.
The carbon nano-fiber of one-dimentional structure has higher electron mobility and extremely strong separation of charge ability under normal circumstances, unique performance makes it have on the basis of the breakthrough application of photocatalysis field, one-dimensional carbon nano material can absorb most sunshine, or a kind of fabulous light absorbent.Carbon nanomaterial and the TiO of one dimension is prepared by electrospinning process and hydro-thermal method
2core-shell photocatalyst, give full play to the fabulous electric conductivity of material with carbon element and light absorptive, improve the absorbing ability of photochemical catalyst to a great extent and promote the separative efficiency of its photo-generated carrier, thus improving its photocatalytic activity.This preparation method can solve TiO simultaneously
2the low problem of the low and quantum efficiency of extinction efficiency, there is very large actual application value.
The explanation of disclosed embodiment of this invention just to technical scheme of the present invention, can not as the restriction to content of the present invention, and the simple change of those skilled in the art on basis of the present invention, still in protection scope of the present invention.
Claims (10)
1. one dimension carbon nano-fiber TiO
2the preparation method of photochemical catalyst of nucleocapsid structure, first utilize electrospinning process to prepare carbon nano-fiber, then to carbon nano-fiber acid treatment, recycling water heat transfer carbon nano-fiber TiO
2nucleocapsid structure, finally carries out cleaning treatment, will utilize water heat transfer carbon nano-fiber TiO
2after in nucleocapsid structure, gained reactant deionized water is fully cleaned, dry oven dry in an oven, i.e. obtained one dimension carbon nano-fiber TiO
2the photochemical catalyst of nucleocapsid structure.
2. one dimension carbon nano-fiber TiO according to claim 1
2the preparation method of photochemical catalyst of nucleocapsid structure, it is characterized in that: in described baking oven, dry temperature of drying is 60 ~ 80 DEG C, and the time is 6 ~ 8h.
3. one dimension carbon nano-fiber TiO according to claim 1
2the preparation method of photochemical catalyst of nucleocapsid structure, it is characterized in that: described electrospinning process is prepared carbon nano-fiber and referred to: the DFM solution of preparation PAN is as spinning solution, utilize dull and stereotyped as receiving pole, the mode of vertical reception is adopted to carry out electrostatic spinning, obtain flexible PAN precursor, then by Muffle furnace low temperature pre-oxidation and the process of tube furnace high temperature cabonization, carbon nano-fiber is obtained.
4. one dimension carbon nano-fiber TiO according to claim 3
2the preparation method of photochemical catalyst of nucleocapsid structure, it is characterized in that: the mass ratio of described spinning solution is the DFM solution of the PAN of 10wt%, must heat while stirring in preparation process, and heating-up temperature is 60 ~ 80 DEG C, heat time 2 ~ 3h.
5. one dimension carbon nano-fiber TiO according to claim 4
2the preparation method of photochemical catalyst of nucleocapsid structure, it is characterized in that: in described electrostatic spinning process, wherein high tension voltage is set as 14 ~ 18kV, the internal diameter of spray silk syringe needle is 0.4 ~ 0.8mm, dash receiver distance spinning syringe needle distance is 12 ~ 17cm, the discharging speed of spinning solution is 0.4 ~ 0.8mL/h, and the relative air humidity of spinning cavity controls to be 30% ~ 40%; At 24 ~ 28 DEG C, continuous spinning 9 ~ 11h obtains the PAN precursor of white, by PAN precursor in Muffle furnace 250 ~ 350
ounder C, 2 ~ 3h is stablized in pre-oxidation, and the heating rate of Muffle furnace is 2
oc/min, finally puts into tube furnace by fiber after pre-oxidation and at N
2protection lower 750 ~ 850
oc carbonization 2 ~ 3h, the heating rate of tube furnace is set as 5
oc/min, obtains carbon nano-fiber after carbonization.
6. one dimension carbon nano-fiber TiO according to claim 1
2the preparation method of photochemical catalyst of nucleocapsid structure, it is characterized in that: described carbon nano-fiber acid treatment refers to: the carbon nano-fiber prepared by electrospinning process is added in acid solution, acid treatment is carried out in heating, then use the acid of washed with de-ionized water carbon nano-fiber remained on surface, and dry in an oven.
7. one dimension carbon nano-fiber TiO according to claim 6
2the preparation method of photochemical catalyst of nucleocapsid structure, it is characterized in that: described acid is 4M salpeter solution, in oil bath pan, 80 ~ 100 DEG C add hot reflux 6 ~ 8h and carry out acid treatment, and then use washed with de-ionized water carbon nano-fiber surface to pH=7, deionized water centrifuge washing is used in cleaning.
8. one dimension carbon nano-fiber TiO according to claim 1
2the preparation method of photochemical catalyst of nucleocapsid structure, it is characterized in that: describedly utilize water heat transfer carbon nano-fiber TiO
2nucleocapsid structure refers to: by carbon nano-fiber after peracid treatment, and ultrasonic disperse, in deionized water, then adds cysteine, titanium sulfate, urea, continues ultrasonic disperse, is finally transferred in hydrothermal reaction kettle by mixed solution and carry out hydro-thermal reaction.
9. one dimension carbon nano-fiber TiO according to claim 8
2the preparation method of photochemical catalyst of nucleocapsid structure, it is characterized in that: described interpolation cysteine: titanium sulfate: the mol ratio of urea is 2:1:4.
10. one dimension carbon nano-fiber TiO according to claim 8
2the preparation method of photochemical catalyst of nucleocapsid structure, it is characterized in that: in described hydrothermal reaction kettle, hydrothermal temperature is set as that between 160 ~ 200 DEG C, the reaction time is set as 10 ~ 14h.
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