CN105381813B - A kind of doped carbon, the preparation method of the niobium pentoxide nano piece of nitrogen and its application as photochemical catalyst - Google Patents
A kind of doped carbon, the preparation method of the niobium pentoxide nano piece of nitrogen and its application as photochemical catalyst Download PDFInfo
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- CN105381813B CN105381813B CN201510900783.3A CN201510900783A CN105381813B CN 105381813 B CN105381813 B CN 105381813B CN 201510900783 A CN201510900783 A CN 201510900783A CN 105381813 B CN105381813 B CN 105381813B
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Abstract
The invention discloses a kind of doped carbon, the preparation method of the niobium pentoxide nano piece of nitrogen and its application as photochemical catalyst, the preparation method includes：At room temperature, soluble niobium salt is weighed, absolute ethyl alcohol is added, the ethanol solution of niobium salt is formed, organic ammonium hydroxides solution is added dropwise into solution, white opacity is formed during beginning, continues dropwise addition organic ammonium hydroxides solution to white opacity and disappears, form clear transparent solutions；Resulting solution is transferred in hydrothermal reaction kettle again, loadings are 50%~70% that kettle is accumulated, hydrothermal temperature is 100~280 DEG C, and reactor is down into room temperature naturally after reaction, is washed, and dries, obtains white powder；By gained white powder under nitrogen protection, calcine 2~12 hours at 400~1200 DEG C, you can obtain a kind of doped carbon, the niobium pentoxide nano piece of nitrogen.Present invention also offers synthesized doped carbon, nitrogen niobium pentoxide nano piece as photocatalyst applications in photocatalysis benzyl alcohol oxidation be benzaldehyde.
Description
Technical field
Nano material of the present invention and catalytic field, more particularly to a kind of doped carbon, the system of the niobium pentoxide nano piece of nitrogen
Preparation Method and its application as photochemical catalyst.
Background technology
Two-dimension nano materials such as graphene, molybdenum disulfide (MoS2) nano thin-film, TiO2Nano thin-film, ZnO nanometer sheets etc.
Due to the catalytic reaction activity site enriched with big specific surface area and layer structure material edge, and it is widely used in light
The photocatalysis fields such as catalytic degradation dyestuff, photocatalysis conversion of methane, photolysis water hydrogen and photocatalysis synthesis of organic substance.Half
In conductor catalyst, Nb2O5Although belonging to broad stopband oxide（3.2~4.0 eV）, but Nb2O5With acid and alkali-resistance, fast light
The advantages of corrosion, in photosensitive dye battery, photocatalytic synthesis into receiving researcher in terms of, photocatalysis degradation organic contaminant
Attention.
Existing nano-powder in patent（CN 101700910, a kind of preparation side of spherical nanoscale niobium pentaoxide powder
Method）, nano-hollow ball（A kind of methods for preparing niobium pentoxide hollow nanosphere of the B of CN 101746826）And nano wire（CN
A kind of methods of acetate solvate hot preparation pentoxide nanowire by use of 103253708 B）Report, but niobium pentoxide nano
Piece report is also fewer.In general, niobium pentoxide nano piece is synthesized using the method for chemical stripping, such as CN
101570402 B.The base metal niobate of stratiform is first formed at high temperature, concentrated acid ion exchange is then used, further again with four
The cationic chemical such as butyl ammonium intercalation is peeled off, so as to form nanometer sheet.This method and step is more, and combined coefficient is low.Another
Method is exactly bottom-up mode（Mode i.e. from top to bottom）, protective agent is added, so as to form nanometer sheet.Patent CN
Reported in 104852015 A, in soluble niobium salt（Acetic acid niobium, fluorination niobium, niobium chloride, iodate niobium and bromination niobium）Add water and
In the mixed solution of ethylenediamine, hydro-thermal method forms niobium pentoxide nano piece.It is molten that Keizo Nakagawa report ethanol niobium
Solution adds ammoniacal liquor and keeps pH=12.8, then this suspension is transferred in hydrothermal reaction kettle in triethanolamine, anti-at 160 DEG C
Answer 24 hours, mono-layer oxidized niobium nanometer sheet can be obtained.
This patent, using the hydroxide of organic ammonium as precipitating reagent and template, has synthesized 2~10 using columbium pentachloride as niobium source
There are organoammonium ions in layer nano lamellar thing, interlayer.Calcined under conditions of high temperature isolation air, obtained a kind of ultra-thin dopant
Carbon, the niobium pentoxide nano piece of nitrogen and its it is used as light-catalysed application.
The content of the invention
In summary, in order to achieve the above object.The invention provides a kind of doped carbon, the niobium pentoxide nano piece of nitrogen
Preparation method and its application as photochemical catalyst.
The preparation method of a kind of doped carbon, the niobium pentoxide nano piece of nitrogen, comprises the following steps：
Step one：At room temperature, the soluble niobium salt of 0.1~10 mass parts is weighed, the anhydrous of 10~70 parts by volume is added
Ethanol, forms settled solution standby；
Step 2：In the settled solution prepared to step one, 25% organic ammonium hydroxides solution is added dropwise, speed is added dropwise in control
Degree, forms white opacity during beginning, continue to be added dropwise organic ammonium hydroxides solution to white opacity disappearance, form clear solution standby
With；
Step 3：Clear solution obtained by step 2 is transferred in hydrothermal reaction kettle, loadings be kettle accumulate 50%~
70%, hydrothermal temperature is 100~280 DEG C, and the reaction time is 8~96 hours, and reactor is down into room temperature naturally after reaction,
Washing, dries, obtains white powder；
Step 4：White powder obtained by step 3 is calcined 2~12 hours at nitrogen atmosphere, 400~1200 DEG C, you can
Obtain a kind of doped carbon, the niobium pentoxide nano piece of nitrogen.
Further, the soluble niobium salt in described step one is：The hydrogen fluoride of ammonium niobium oxalate or columbium pentachloride or niobic acid
Lysate.
Further, the organic ammonium hydroxides in described step two are：TMAH or tetraethyl ammonium hydroxide
Or TBAH.
A kind of doped carbon, nitrogen niobium pentoxide nano piece as photochemical catalyst application.
Beneficial effect：
Doped carbon, nitrogen niobium pentoxide nano piece synthesized by the present invention have preferable pattern, and nanometer sheet thickness is 0.3
~10 nanometers, size is 100~1000 nm, and product specific surface area is big, with multistage microstructural；This method has simply, instead
Answer temperature low, reproducible, the low advantage of cost.Doped carbon, nitrogen niobium pentoxide nano piece synthesized by the present invention can be made
For solid acid catalyst, it can also be applied in photosensitive dye battery, lithium ion battery.Mixed the invention further relates to synthesized
Miscellaneous carbon, nitrogen niobium pentoxide nano piece are as photocatalyst applications in the organic synthesis that photocatalysis benzyl alcohol oxidation is benzaldehyde
In.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of the niobium pentoxide nano piece prepared by the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of the niobium pentoxide nano piece prepared by the present invention.
Fig. 3 is the transmission electron microscope picture of the niobium pentoxide nano piece prepared by the present invention.
Fig. 4 is the atomic force microscopy diagram of the niobium pentoxide nano piece prepared by the present invention.
Fig. 5 is the infrared spectrogram of the niobium pentoxide nano piece prepared by the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated：
Embodiment 1
The preparation method of a kind of doped carbon, the niobium pentoxide nano piece of nitrogen, comprises the following steps：
At room temperature（10-40℃）, 3.24g columbium pentachlorides are dissolved in 40ml absolute ethyl alcohols, ultrasonic 10 minutes, form clarification
Transparent solution, then will be added dropwise the tetramethyl ammonium hydroxide solution that 25ml concentration is 25%, control drop into ethanol solution
Rate of acceleration is 0.27 ml/min, stirs 30 minutes, obtains a settled solution.By the solution be transferred to 100ml have polytetrafluoro
In the reactor of ethene liner, 240 DEG C of hydro-thermal reactions 24 hours are cooled to after room temperature, filtered with filter paper, with 2000~3000 millis
The distillation water washing risen, is then washed with absolute ethyl alcohol.Much filtrate is dried 8 hours at 100 DEG C, niobium pentaoxide is obtained and receives
Rice piece.The niobium pentoxide nano piece of gained is calcined 2 hours at nitrogen atmosphere, 500 DEG C in Muffle furnace, it is possible to mixed
The niobium pentoxide nano piece of miscellaneous carbon, nitrogen.
Fig. 1 is the X-ray diffractogram of the niobium pentoxide nano piece prepared by the present invention, and niobium pentoxide nano piece spreads out
Penetrate peak and number the stratiform niobium oxide for being #91098 corresponding to ICSD.And in N2After the calcining 2 hours of 500 DEG C of atmosphere, doped carbon, nitrogen
The diffraction maximum of niobium pentoxide nano piece corresponds to monocline niobium pentaoxides of the JCPDS marked as 27-1311.
Fig. 2 is the scanning electron microscope (SEM) photograph of the niobium pentoxide nano piece prepared by the present invention.It can be seen that synthesized
Nanometer sheet constitute flower-shaped, the impurity without other patterns.
Fig. 3 is the transmission electron microscope picture of the niobium pentoxide nano piece prepared by the present invention.As can be seen from the figure it is synthesized
Nanometer sheet it is very thin, electronic diffraction be shown as rule point diffraction, illustrate synthesized by nanometer sheet there are mono-crystalline structures.
Fig. 4 is the atomic force microscopy diagram of the niobium pentoxide nano piece prepared by the present invention.Nanometer as can be seen from Fig.
The thickness of piece is about 2.8 nanometers.
Fig. 5 is the infrared spectrogram of the niobium pentoxide nano piece prepared by the present invention.1488cm in figure-1The absworption peak at place
For the stretching vibration peak of C-N keys in quaternary ammonium salt, show to contain tetramethyl-ammonium radical ion between synthesized nanoscale twins, in N2Atmosphere
During lower roasting, carbon, nitrogen-doping can be entered in niobium oxide.
Embodiment 2
The preparation method of a kind of doped carbon, the niobium pentoxide nano piece of nitrogen, comprises the following steps：
At room temperature（10-40℃）, 3.24g columbium pentachlorides are dissolved in 40 ml absolute ethyl alcohols, ultrasonic 10 minutes, are formed clear
Clear bright solution, then the tetraethyl ammonium hydroxide solution that 30 ml concentration are 25%, control will be added dropwise into ethanol solution
Drop rate processed is 0.27 ml/min, stirs 30 minutes, obtains a settled solution.The solution is transferred to having for 100ml poly-
In the reactor of tetrafluoroethene liner, 220 DEG C of hydro-thermal reactions 24 hours are cooled to after room temperature, filtered with filter paper, with 2000~
3000 milliliters of distillation water washing, is then washed with absolute ethyl alcohol.Much filtrate is dried 8 hours at 100 DEG C, five oxidations are obtained
Two niobium nanometer sheets.The niobium pentoxide nano piece of gained is calcined 2 hours at nitrogen atmosphere, 400 DEG C in Muffle furnace, it is possible to
Obtain doped carbon, the niobium pentoxide nano piece of nitrogen.
Embodiment 3
The preparation method of a kind of doped carbon, the niobium pentoxide nano piece of nitrogen, comprises the following steps：
At room temperature（10-40℃）, 1.5g ammonium niobium oxalates are dissolved in 30 ml absolute ethyl alcohols, ultrasonic 10 minutes, form clarification
Transparent solution, then will be added dropwise the tetramethyl ammonium hydroxide solution that 35ml concentration is 25%, control drop into ethanol solution
Rate of acceleration is 0.27 ml/min, stirs 30 minutes, obtains a settled solution.By the solution be transferred to 100ml have polytetrafluoro
In the reactor of ethene liner, 250 DEG C of hydro-thermal reactions 24 hours are cooled to after room temperature, filtered with filter paper, with 2000~3000 millis
The distillation water washing risen, is then washed with absolute ethyl alcohol.Much filtrate is dried 8 hours at 100 DEG C, niobium pentaoxide is obtained and receives
Rice piece.The niobium pentoxide nano piece of gained is calcined 2 hours at nitrogen atmosphere, 600 DEG C in Muffle furnace, it is possible to mixed
The niobium pentoxide nano piece of miscellaneous carbon, nitrogen.
Embodiment 4
The preparation method of a kind of doped carbon, the niobium pentoxide nano piece of nitrogen, comprises the following steps：
At room temperature（10-40℃）, 1.5g ammonium niobium oxalates are dissolved in 20 ml absolute ethyl alcohols, ultrasonic 10 minutes, form clarification
Transparent solution, then will be added dropwise the TBAH solution that 35ml concentration is 25%, control drop into ethanol solution
Rate of acceleration is 0.27 ml/min, stirs 30 minutes, obtains a settled solution.By the solution be transferred to 100ml have polytetrafluoro
In the reactor of ethene liner, 220 DEG C of hydro-thermal reactions 24 hours are cooled to after room temperature, filtered with filter paper, with 2000~3000 millis
The distillation water washing risen, is then washed with absolute ethyl alcohol.Much filtrate is dried 8 hours at 100 DEG C, niobium pentaoxide is obtained and receives
Rice piece.The niobium pentoxide nano piece of gained is calcined 2 hours at nitrogen atmosphere, 500 DEG C in Muffle furnace, it is possible to mixed
The niobium pentoxide nano piece of miscellaneous carbon, nitrogen.
Embodiment 5
A kind of doped carbon, nitrogen niobium pentoxide nano piece as photochemical catalyst application：
The 10 mmol/L mL of the phenmethylol aqueous solution 10 is taken, the mg of catalyst 50 added after calcining, together with small magneton together
It is put into the jacketed reactor with temperature-adjustable, reactor is placed on electromagnetic mixing apparatus, setting rotating speed is 30 r/
Min, dark treatment half an hour.Oxygen is connected, low temperature thermostat bath is opened, makes the temperature control entirely tested at 25 DEG C.Again mixing
Solution afterwards is transferred to illumination under xenon lamp, light-catalyzed reaction 2~24 hours.Then reactor is removed, sample is extracted with syringe,
With the membrane filtration with 0.2 micron of filter opening.By the phenmethylol in solution after gas chromatograph test reaction of the solution after filtering
With the concentration of benzaldehyde, the conversion ratio of phenmethylol and the selectivity of benzaldehyde are calculated.Such as niobium pentoxide nano piece light in table one
Catalytic phenylmethanol is oxidized to the catalytic activity of benzaldehyde.Table one shows that synthesized niobium oxide nanometer sheet has photochemical catalytic oxidation benzene
After the catalytic activity of methanol, and carbon, N doping, catalytic activity is significantly improved.Under ultraviolet light, the conversion ratio of phenmethylol
For 51.3%.
The niobium pentaoxide nanometer sheet photocatalysis benzyl alcohol oxidation of table one is the catalytic activity of benzaldehyde
Nb2O5- NS is niobium pentoxide nano piece, Nb2O5- NS-C-N is doped carbon, the niobium pentoxide nano piece of nitrogen.
Reaction condition is：Phenmethylol 10 mmol/L, 10 ml, catalyst quality 50 mg, light application time 2h.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (3)
1. the preparation method of the niobium pentoxide nano piece of a kind of doped carbon, nitrogen, it is characterised in that comprise the following steps：
Step one：At room temperature, the soluble niobium salt of 0.1~10 mass parts is weighed, the absolute ethyl alcohol of 10~70 parts by volume is added,
Form settled solution standby；
Step 2：In the settled solution prepared to step one, 25% organic ammonium hydroxides solution is added dropwise, controls rate of addition, opens
White opacity is formed during the beginning, continues to be added dropwise organic ammonium hydroxides solution to white opacity disappearance, forms clear solution standby；
Step 3：Clear solution obtained by step 2 is transferred in hydrothermal reaction kettle, loadings are 50%~70% that kettle is accumulated,
Hydrothermal temperature is 100~280 DEG C, and the reaction time is 8~96 hours, and reactor is down into room temperature naturally after reaction, is washed,
Dry, obtain white powder；
Step 4：White powder obtained by step 3 is calcined 2~12 hours at nitrogen atmosphere, 400~1200 DEG C, you can obtain
A kind of niobium pentoxide nano piece of ultra-thin dopant carbon, nitrogen；
Organic ammonium hydroxides in step 2 are：TMAH or tetraethyl ammonium hydroxide or TBAH.
2. the preparation method of the niobium pentoxide nano piece of a kind of doped carbon according to claim 1, nitrogen, its feature exists
In the soluble niobium salt in described step one is：The hydrogen fluoride lysate of ammonium niobium oxalate or columbium pentachloride or niobic acid.
3. doped carbon prepared by a kind of preparation method as claimed in claim 1, the niobium pentoxide nano piece of nitrogen are used as photochemical catalyst
Application.
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| CN108097250B (en) * | 2017-11-09 | 2019-11-19 | 浙江裕文环保科技有限公司 | Can the infrared shortwave of efficient absorption Thief zone nanometer infrared excitation matchmaker, preparation method, and its application in air cleaning |
| CN109046421B (en) * | 2018-07-24 | 2019-06-28 | 山东科技大学 | It is a kind of to prepare C, N co-doped nano pipe/stick catalysis material method using quaternary ammonium base |
| CN110935482A (en) * | 2019-11-20 | 2020-03-31 | 华南农业大学 | Semiconductor NbNO nanosheet and preparation method and application thereof |
| CN111153437B (en) * | 2019-12-25 | 2022-03-18 | 苏州机数芯微科技有限公司 | Blue niobium pentoxide and preparation method and application thereof |
| CN111470535B (en) * | 2020-04-17 | 2023-03-24 | 扬州大学 | Niobium pentoxide yolk structure nano material with controllable core volume and preparation method thereof |
| CN112337457B (en) * | 2020-11-11 | 2023-02-03 | 郑州轻工业大学 | Mo-doped HNb 3 O 8 Preparation method and application of nanosheet |
| CN112661675B (en) * | 2021-01-07 | 2022-10-21 | 中国科学院青岛生物能源与过程研究所 | Synthetic method of alpha-carbonyl sulfonate and catalyst used by same |
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