CN104888833B - A kind of Ta3N5/ C composite fibre photochemical catalysts and preparation method thereof - Google Patents
A kind of Ta3N5/ C composite fibre photochemical catalysts and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of catalyst preparation comprising metal, and in particular to a kind of Ta3N5/ C composite fibre photochemical catalysts and preparation method thereof, this method prepares Ta using method of electrostatic spinning combination hydro-thermal method, calcining3N5/ C composite fibre photochemical catalysts.Ta prepared by the present invention3N5/ C composite fibre photochemical catalysts, C films uniformly wrap up Ta3N5Being combined for nanofiber, the good hetero-junctions of formation, the light induced electron effectively suppressed and hole, improves Ta3N5Photocatalytic activity and stability, while having the characteristic easily reclaimed, be a kind of excellent catalysis material, there is significant application value in the field such as environment and the energy；The preparation method of the present invention is simple, and equipment and other costs are relatively inexpensive, and experimental condition is controllable, is conducive to large-scale production to prepare.
Description
Technical field
The invention belongs to the field of catalyst preparation comprising metal, and in particular to a kind of Ta3N5/C composite fibres photocatalysis
Agent and preparation method thereof.
Background technology
Photocatalysis technology is a kind of green technology for having important application prospect in fields such as environment, the energy.At present, promote
The core of photocatalysis technology development is to research and develop visible-light photocatalyst that is efficient, stably, easily reclaiming.Ta3N5It is a kind of narrow
The semiconductor (2.1eV) of band gap, it is possible to use wavelength reaches 600nm sunshine, is mainly used in wastewater treatment, air cleaning
And the field such as Photocatalyzed Hydrogen Production, cause the extensive concern of scientific worker.At present, researcher has developed a nanometer chi
Very little Ta3N5(nano particle, flower-shaped supramolecular structure, hollow ball etc.) photochemical catalyst, but the Ta of nano-scale3N5Face two
Big key problem, first, being Ta3N5Energy gap is 2.1eV, belongs to low-gap semiconductor material, light induced electron and hole-recombination
Probability is higher, causes the quantum yield of material low, seriously constrains its photocatalytic activity.Second, due to nano-sized catalyst
It is not easily recycled, have impact on its recycling etc., or even cause secondary pollution.The reality that these factors seriously hinder catalyst should
With.Therefore, how Ta is improved3N5Photocatalysis efficiency and recuperability turn into current environment photocatalysis field research important class
One of topic.
Li etc. is developed using electrostatic spinning technique and easily reclaimed and the high Ta of catalytic activity3N5- Pt hetero-junctions fibers
(S.J.Li, et.al, Scientific report 2014,4,3978), however, precious metals pt relative cost is higher.In addition,
Carbon material can effectively improve the photocatalytic activity and stability of semiconductor with semiconductors coupling.A kind of Chinese patent application " stone
Black alkene/Ta3N5The preparation method of composite photo-catalyst " (application number：201410312816.8, publication No.：CN 104043471A)
In disclosed preparation method, Ta3N5 nanofibers are obtained based on method of electrostatic spinning, then prepare by graphite by the hot method of flux
The Ta of alkene parcel3N5Chopped fiber composite photo-catalyst.However, in this method, by Ta3N5Compound, the one side graphene with graphene
Cost is of a relatively high, on the other hand, realizes that the uniformly compound technology of preparing operation of the two is relative complex.Importantly, the party
In method, the Ta of obtained graphene parcel3N5In composite catalyst, Ta3N5Fiber with graphene preparation process fracture become compared with
Short fiber (length is only 0.5-1 μm).
Based on considerations above, in the research practice of photocatalysis field, need badly it is a kind of using method of electrostatic spinning and hydro-thermal method and
The preparation method being combined is calcined, the Ta that developing low-cost, catalytic activity are high, property is stable, easily reclaim is prepared3N5/ C is combined
Fiber photocatalyst.
The content of the invention
The present invention provides a kind of Ta3N5/ C composite fibre photochemical catalysts and preparation method thereof；This method uses method of electrostatic spinning
Ta is prepared with reference to hydro-thermal method, calcining3N5/ C composite fibre photochemical catalysts.
The purpose of the present invention is achieved through the following technical solutions：
A kind of Ta3N5The preparation method of/C composite fibre photochemical catalysts, comprises the steps：
Ta3N5Spinning solution preparation process：Soluble tantalum salt is added in Polymer Solution, 2~12h is stirred,
Obtain the Ta3N5Spinning solution；
Ta2O5Fiber preparation process：By the Ta3N5Spinning solution carries out electrostatic spinning processing, obtains composite fibre；Again will
The composite fibre carries out calcination processing, obtains the Ta2O5Fiber；
Ta3N5Nanofiber preparation process：By the Ta2O5Fiber carries out nitrogen treatment, obtains Ta3N5Nanofiber；
Hydro-thermal reaction mixed system preparation process：By the Ta3N5Nanofiber is added in carbon source solution, is stirred
Processing, obtains the hydro-thermal reaction mixed system；
Hydro-thermal reaction and subsequent processing steps：The hydro-thermal reaction mixed system is subjected to hydro-thermal reaction, hydro-thermal is obtained anti-
Answer product；The hydro-thermal reaction product is subjected to centrifugal treating, washing process, drying and processing, product after being dried.
Calcining step：Product after the drying is subjected to calcination processing, Ta is obtained3N5/ C composite fibre photochemical catalysts.
In the preferred embodiment of method made above, the Ta3N5In spinning solution preparation process, the Polymer Solution
In be mixed by polyvinylpyrrolidone, absolute ethyl alcohol, DMF and acetic acid, the polyvinylpyrrolidine
Ketone, absolute ethyl alcohol, the volume ratio of N,N-dimethylformamide and acetic acid are (3~4)： 1：1, preferably 3：1：1；
The Ta3N5In spinning solution, the mass percent concentration of the PVP is 5~10wt%；The soluble tantalum salt
Mass percent concentration is 5~15wt%, preferably 10wt%；
It is further preferred that the molecular weight of the polyvinylpyrrolidone is 1300000.
In the preferred embodiment of method made above, the Ta3N5In spinning solution preparation process, the soluble tantalum salt
For the one or more in butanol tantalum, ethanol tantalum, tantalic chloride, isopropanol tantalum, sulfuric acid tantalum.
In the preferred embodiment of method made above, the Ta2O5In fiber preparation process, in the calcination processing, temperature
Spend for 500~800 DEG C, the time is 2~15h.
In the preferred embodiment of method made above, the Ta3N5In nanofiber preparation process, the nitrogen treatment
Temperature be 750~900 DEG C, the time be 4~15h；The nitrogen treatment is carried out in ammonia atmosphere.
In the preferred embodiment of method made above, in the hydro-thermal reaction mixed system preparation process, the hydro-thermal
The Ta in reaction mixture3N5The content of nanofiber is 1~25g/L；The concentration of the carbon source solution be 0.05~
0.5mol/L；
Preferably, the carbon source is one or both of glucose and xylose.
In the preferred embodiment of method made above, in the hydro-thermal reaction and subsequent processing steps, the hydro-thermal is anti-
It should be carried out in the reactor of polytetrafluoroethylene (PTFE) material, compactedness of the hydro-thermal reaction mixed system in the reactor is
60-90%, preferably 80%.
In the preferred embodiment of method made above, in the hydro-thermal reaction and subsequent processing steps, the hydro-thermal is anti-
The temperature answered is 160~200 DEG C, and the time is 8~24h.
In the preferred embodiment of method made above, in the calcination processing step, temperature is 500~900 DEG C, is risen
Warm speed is 1~5 DEG C/min, and the time is 1~10h, is carried out under nitrogen or argon.
The Ta3N5/C composite fibre photochemical catalysts that method and its preferred embodiment made above are obtained, its shape characteristic
For：The surface of the Ta3N5 nanofibers is uniformly wrapped up by one layer of C film, forms Ta3N5/ C nano fibre structure.
Compared with prior art, the present invention has the advantages that：
1st, the Ta prepared by the present invention3N5/ C composite fibre photochemical catalysts, C films uniformly wrap up Ta3N5 nanofibers, are formed
Being combined for good hetero-junctions, the light induced electron effectively suppressed and hole, improves Ta3N5 photocatalytic activity and stability
Can, while having the characteristic easily reclaimed, it is a kind of excellent catalysis material, there is important application in the field such as environment and the energy
Value.
2nd, in preparation method of the invention, Ta is first obtained using method of electrostatic spinning3N5Nanofiber, then passes through hydro-thermal method
Reaction prepares Ta3N5/ C composite fibre photochemical catalysts；The preparation method makes C films uniformly wrap up Ta3N5Nanofiber, the two
It is compound uniform, abundant, beneficial to raising photocatalytic activity.
3rd, in preparation method of the invention, control adds Ta in hydro-thermal reaction mixed system3N5Nanofiber and C sources
Ratio, can control Ta3N5The thickness of/C composite fibre photochemical catalyst C films, controllability is strong.
4th, preparation method of the invention is simple, and equipment and other costs are relatively inexpensive, and experimental condition is controllable, is conducive to scale
It is prepared by metaplasia production.
5th, Ta prepared by the present invention3N5/ C composite fibres maintain the Ta3N5 fibre structures of overlength, a diameter of 150-
300nm, length is 60-100 μm, with higher photocatalytic activity, and property is stable, easily reclaims.
Brief description of the drawings
Fig. 1 is the Ta prepared in the present invention3N5ESEM (SEM) picture of/C composite fibre photochemical catalysts.
Fig. 2 is the Ta prepared in the present invention3N5The TEM pictures of/C composite fibre photochemical catalysts.
Fig. 3 is Ta prepared by the embodiment 1,2,3 under radiation of visible light3N5/ C composite fibres photochemical catalyst is to MB solution
Single photocatalytic degradation curve map.
Fig. 4 is Ta prepared by the embodiment 2 under radiation of visible light3N5/ C composite fibres photochemical catalyst is followed to 4 times of MB solution
Ring photocatalytic degradation curve map.
Embodiment
A kind of Ta3N5The preparation method of/C hetero-junctions fiber photocatalysts, comprises the steps：
Step 1: preparing Ta3N5Spinning solution：Soluble tantalum salt is added in Polymer Solution, it is stirred 2~
12h, obtains Ta3N5Spinning solution.
In the Polymer Solution, contain polyvinylpyrrolidone (PVP), absolute ethyl alcohol, DMF, second
Acid, wherein, the volume ratio of the absolute ethyl alcohol, DMF and acetic acid is (3~4)： 1：1 (exemplarily, also may be used
Think 3.2：1：1,3.5：1：1,3.8：1：Isosorbide-5-Nitrae：1：Arbitrary proportion in 1, preferably 3：1：1)；The molecular weight of the PVP is
1300000；
The Ta3N5In spinning solution, the mass percent concentration of the PVP be 5~10wt% (exemplarily, can be 5wt%,
Arbitrary value or any scope between the two in 6wt%, 8wt%, 10wt% etc.), the mass percent of the soluble tantalum salt is dense
It (can be exemplarily, arbitrary value or to appoint in 5wt%, 8wt%, 10wt%, 12wt%, 15wt% etc. to spend for 5~15wt%
The scope of meaning between the two, preferably 10wt%)；
The soluble tantalum salt is the one or more in butanol tantalum, ethanol tantalum, tantalic chloride, isopropanol tantalum, sulfuric acid tantalum.
Step 2: preparing Ta2O5Fiber：The Ta3N5 spinning solutions are subjected to electrostatic spinning processing, condition is：Operating voltage
(direct current) 8~25kV, operating distance (i.e. shower nozzle tip and the distance of receiver) 10~25cm, the fltting speed of spinning solution
(i.e. the fltting speed of propeller) is：0.1~1mL/h, syringe needle internal diameter is 0.6~1.2mm；Composite fibre is made；
The composite fibre is carried out in tube furnace again 500~800 DEG C (exemplarily, can for 500 DEG C, 700 DEG C,
Arbitrary value or any scope between the two, preferably 600 DEG C in 800 DEG C of grades) 2~15h of calcination processing (exemplarily, can be with
For arbitrary value in 2h, 5h, 8h, 10h, 12h, 15h etc. or any scope between the two, preferably 6h), obtain Ta2O5Fiber.
Step 3: preparing Ta3N5 nanofibers：By the Ta2O5Fiber is placed in tube furnace, in 750~900 DEG C of (examples
Property, can be arbitrary value or any scope between the two in 750 DEG C, 850 DEG C, 900 DEG C etc., preferably 800 DEG C), in ammonia
It (can be exemplarily, arbitrary value or any two in 4h, 6h, 10h, 12h, 15h etc. that atmosphere, which encloses 4~15h of progress nitrogen treatment,
Scope between person, preferably 8h), obtain Ta3N5Nanofiber.
Step 4: preparing hydro-thermal reaction mixed system：By the Ta3N5Nanofiber is added in carbon source solution, is stirred place
0.5~10h is managed, hydro-thermal reaction mixed system is obtained.
The concentration of the carbon source solution be 0.05~0.5mol/L (exemplarily, can be 0.05mol/L, 0.1 mol/L,
Arbitrary value or any scope between the two in 0.2mol/L, 0.3mol/L, 0.5mol/L etc., preferably 0.15)；
In the hydro-thermal reaction mixed system, the Ta3N5The content of nanofiber is 1~25g/L (exemplarily, Ke Yiwei
Arbitrary value or any scope between the two, preferably 5g/L in 1g/L, 8g/L, 10g/L, 15g/L, 20g/L, 25g/L etc.)；
The carbon source is one or both of glucose and xylose.
In this step, by controlling carbon source and Ta3N5The ratio that nanofiber is added, can control what is finally obtained
The thickness of the carbon film of Ta3N5/C composite fibre photochemical catalysts, the controllability for product quality is strong.
Step 5: hydro-thermal reaction and subsequent treatment：The material that the hydro-thermal reaction mixed system is transferred into liner is polytetrafluoro
In the reactor of ethene, control compactedness (i.e. the volume of hydro-thermal reaction mixed system and the percentage of reactor cumulative volume) is
60-90% (can be exemplarily, arbitrary value or any scope between the two in 60%, 65%, 70%, 90% etc., preferably
80%), to carry out hydro-thermal reaction：Temperature, which is 160~200 DEG C, (exemplarily, can be 160 DEG C, 170 DEG C, 190 DEG C, 200 DEG C
Arbitrary value or any scope between the two, preferably 180 DEG C in), the time be 8~24h (exemplarily, can be 8h,
Arbitrary value or any scope between the two, preferably 12h in 10h, 16h, 20h, 24h etc.), obtain hydro-thermal reaction product；
The hydro-thermal reaction product is first at room temperature, 5min is centrifuged with 5000rpm；Washing process is carried out again：Use anhydrous second
Alcohol and deionized water are respectively washed 3 times；Then at 40~80 DEG C (exemplarily, can be 40,50,60,70 etc. in arbitrary value or any two
Scope between person, preferably 80) carrying out 5~20h of drying and processing (exemplarily, can be 5h, 8h, 12h, 15h, 18h, 20h
Arbitrary value or any scope between the two, preferably 10h in), product after being dried.
Step 6: calcination processing：Product carries out calcination processing in tube furnace after this is dried：Temperature is 500~900
DEG C (exemplarily, can be in 550 DEG C, 600 DEG C, 700 DEG C, 750 DEG C, 850 DEG C, 900 DEG C etc. arbitrary value or it is any between the two
Scope, preferably 800 DEG C), heating rate be 1~5 DEG C/min (exemplarily, can be 1 DEG C/min, 2 DEG C/min, 4 DEG C/
Arbitrary value or any scope between the two, preferably 3 DEG C/min in min, 5 DEG C/min etc.), the time is that 1~10h is (exemplary
Ground, can be arbitrary value in 1h, 3h, 6h, 8h, 10h etc. or any scope between the two, preferably 5h), and in tube furnace
N2 or argon gas protection are passed through, Ta3N5/C composite fibre photochemical catalysts are obtained.
The Ta obtained according to above-mentioned preparation method3N5/ C composite fibre photochemical catalysts, its shape characteristic is：Ta3N5Nanowire
The surface of dimension is uniformly wrapped up by one layer of C film, forms Ta3N5/ C nano fibre structure；A diameter of 150-300nm, length is 60-
100 μm, maintain the Ta of overlength3N5Fibre structure, with higher photocatalytic activity, property is stable, easily reclaims.
Ta prepared by the present invention3N5/ C composite fibre photochemical catalysts, C films uniformly wrap up Ta3N5Nanofiber, is formed good
Being combined for good hetero-junctions, the light induced electron effectively suppressed and hole, improves Ta3N5Photocatalytic activity and stability, together
When with the characteristic easily reclaimed, be a kind of excellent catalysis material, there is significant application value in the field such as environment and the energy.
The present invention first obtains Ta using method of electrostatic spinning3N5Nanofiber, is then prepared by hydro-thermal method reaction
Ta3N5/ C composite fibre photochemical catalysts；The preparation method makes C films uniformly wrap up Ta3N5Nanofiber, the two is compound uniform, fill
Point, beneficial to raising photocatalytic activity.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments be only used for the present invention without
For limiting the scope of the present invention.Externally it should be understood that after present disclosure has been read, those skilled in the art are to this hair
Bright to make various changes or modifications, these equivalent form of values equally fall within the application appended claims limited range.
Embodiment 1：
(1) Ta is prepared3N5Spinning solution：Ethanol tantalum is added in Polymer Solution, 8h is stirred, obtains Ta3N5Spin
Silk liquid.
In the Polymer Solution, mixed by polyvinylpyrrolidone (PVP), absolute ethyl alcohol, DMF, acetic acid
Conjunction is formed, wherein, the volume ratio of the absolute ethyl alcohol, DMF and acetic acid is 3： 1：1；The molecular weight of the PVP is
1300000；
The Ta3N5In spinning solution, the mass percent concentration of the PVP is 10wt%, the mass percent of the soluble tantalum salt
Concentration is 10wt%.
(2) Ta is prepared2O5Fiber：The Ta3N5 spinning solutions are subjected to electrostatic spinning processing, condition is：Operating voltage (direct current
Electricity) 12kV, operating distance (i.e. the distance of shower nozzle tip and receiver) 20cm, fltting speed (the i.e. propeller of spinning solution
Fltting speed) be：0.5mL/h, syringe needle internal diameter is 0.8mm；Composite fibre is made；
The composite fibre is subjected to 600 DEG C of calcination processing 6h in tube furnace again, Ta is obtained2O5Fiber.
(3) Ta is prepared3N5Nanofiber：By the Ta2O5Fiber is placed in tube furnace, in 800 DEG C, is carried out in ammonia atmosphere
Nitrogen treatment 6h, obtains Ta3N5Nanofiber.
(4) hydro-thermal reaction mixed system is prepared：Weigh the Ta3N5Nanofiber 0.2g, add 40ml concentration be
In 0.05mol/L glucose solutions, 3h is stirred, is well mixed, obtains hydro-thermal reaction mixed system.
(5) hydro-thermal reaction and subsequent treatment：The material that the hydro-thermal reaction mixed system is transferred into liner is polytetrafluoroethylene (PTFE)
Reactor in, control compactedness be 80%, in 180 DEG C carry out hydro-thermal reaction 12h, obtain hydro-thermal reaction product；
The hydro-thermal reaction product is first at room temperature, 5min is centrifuged with 5000rpm；Washing process is carried out again：Use anhydrous second
Alcohol and deionized water are respectively washed 3 times；Then at 80 DEG C of progress drying and processing 10h, product after being dried.(6) calcination processing：This is dried
Product carries out calcination processing in tube furnace after dry：Temperature is 800 DEG C, and heating rate is 3 DEG C/min, and the time is 5h, and tubular type
N is passed through in stove2Protection, obtains Ta3N5/ C composite fibre photochemical catalysts.
The Ta prepared in the present embodiment3N5The diameter of/C composite fibre photochemical catalysts is about 200nm, and length is about 80 μm, carbon
The thickness of film is about 2nm.
The Ta of the present embodiment3N5/ C composite fibres photochemical catalyst is in single degradation of methylene blue (MB) experiment (referring to examination
Test example), degradation efficiency reaches 83.5%.
Embodiment 2：
(1) Ta is prepared3N5Spinning solution：Ethanol tantalum is added in Polymer Solution, 2~12 h is stirred, obtains
Ta3N5Spinning solution.
The Polymer Solution is mixed by polyvinylpyrrolidone (PVP), absolute ethyl alcohol, N,N-dimethylformamide, acetic acid
It is made, wherein, the volume ratio of the absolute ethyl alcohol, DMF and acetic acid is 3：1： 1；The molecular weight of the PVP is
1300000；
The Ta3N5In spinning solution, the mass percent concentration of the PVP is 10wt%, the mass percent of the soluble tantalum salt
Concentration is 10wt%.
(2) Ta is prepared2O5Fiber：By the Ta3N5Spinning solution carries out electrostatic spinning processing, and condition is：Operating voltage (direct current
Electricity) 12kV, operating distance (i.e. the distance of shower nozzle tip and receiver) 20cm, fltting speed (the i.e. propeller of spinning solution
Fltting speed) be：0.5mL/h, syringe needle internal diameter is 0.8 mm；Composite fibre is made；
The composite fibre is subjected to 600 DEG C of calcination processing 6h in tube furnace again, Ta2O5 fibers are obtained.
(3) Ta is prepared3N5Nanofiber：The Ta2O5 fibers are placed in tube furnace, in 800 DEG C, carried out in ammonia atmosphere
Nitrogen treatment 6h, obtains Ta3N5Nanofiber.
(4) hydro-thermal reaction mixed system is prepared：Weigh the Ta3N5Nanofiber 0.2g, add 40ml concentration be
In 0.1mol/L glucose solutions, 3h is stirred, it is well mixed, obtains hydro-thermal reaction mixed system.
(5) hydro-thermal reaction and subsequent treatment：The material that the hydro-thermal reaction mixed system is transferred into liner is polytetrafluoroethylene (PTFE)
Reactor in, control compactedness be 80%, in 180 DEG C carry out hydro-thermal reaction 12h, obtain hydro-thermal reaction product；
The hydro-thermal reaction product is first at room temperature, 5min is centrifuged with 5000rpm；Washing process is carried out again：Use anhydrous second
Alcohol and deionized water are respectively washed 3 times；Then at 80 DEG C of progress drying and processing 10h, product after being dried.
(6) calcination processing：Product carries out calcination processing in tube furnace after this is dried：Temperature is 800 DEG C, heating rate
For 3 DEG C/min, the time is to be passed through N in 5h, and tube furnace2Protection, obtains Ta3N5/ C composite fibre photochemical catalysts.
Fig. 1 is the Ta prepared in the present embodiment3N5ESEM (SEM) figure of/C composite fibre photochemical catalysts, multiplication factor
For 2000 times, it can be seen that the Ta3N5/ C composite fibres maintain good fibroid, and its diameter is about 200nm, and length is about
80μm。
Fig. 2 is the Ta prepared in the present invention3N5The TEM pictures of/C composite fibre photochemical catalysts, it can be seen that Ta3N5 surfaces
One layer of carbon film is wrapped up, and the thickness of carbon film is about 4nm.
The Ta of the present embodiment3N5/ C composite fibres photochemical catalyst is in single degradation of methylene blue (MB) experiment (referring to examination
Test example), degradation efficiency reaches 96%；(referring to test example) in 4 circulation photocatalytic degradation MB experiments, first time degradation efficiency
96% is reached, the 4th degradation efficiency is still up to 89%.
Embodiment 3：
(1) Ta is prepared3N5Spinning solution：Ethanol tantalum is added in Polymer Solution, 8h is stirred, obtains Ta3N5Spin
Silk liquid.
The Polymer Solution is by having polyvinylpyrrolidone (PVP), absolute ethyl alcohol, N,N-dimethylformamide, acetic acid to mix
Conjunction is made, wherein, the volume ratio of the absolute ethyl alcohol, DMF and acetic acid is 3：1： 1；The molecular weight of the PVP is
1300000；
The Ta3N5In spinning solution, the mass percent concentration of the PVP is 10wt%, the mass percent of the soluble tantalum salt
Concentration is 10wt%.
(2) Ta is prepared2O5Fiber：The Ta3N5 spinning solutions are subjected to electrostatic spinning processing, condition is：Operating voltage (direct current
Electricity) 12kV, operating distance (i.e. the distance of shower nozzle tip and receiver) 20cm, fltting speed (the i.e. propeller of spinning solution
Fltting speed) be：0.5mL/h, syringe needle internal diameter is 0.8 mm；Composite fibre is made；
The composite fibre is subjected to 600 DEG C of calcination processing 6h in tube furnace again, Ta is obtained2O5Fiber.
(3) Ta is prepared3N5Nanofiber：By the Ta2O5Fiber is placed in tube furnace, in 800 DEG C, is carried out in ammonia atmosphere
Nitrogen treatment 6h, obtains Ta3N5Nanofiber.
(4) hydro-thermal reaction mixed system is prepared：Weigh the Ta3N5Nanofiber 0.2g, add 40ml concentration be
In 0.15mol/L glucose solutions, 3h is stirred, it is well mixed, obtains hydro-thermal reaction mixed system.
(5) hydro-thermal reaction and subsequent treatment：The material that the hydro-thermal reaction mixed system is transferred into liner is polytetrafluoroethylene (PTFE)
Reactor in, control compactedness be 80%, in 180 DEG C carry out hydro-thermal reaction 12h, obtain hydro-thermal reaction product；
The hydro-thermal reaction product is first at room temperature, 5min is centrifuged with 5000rpm；Washing process is carried out again：Use anhydrous second
Alcohol and deionized water are respectively washed 3 times；Then at 80 DEG C of progress drying and processing 10h, product after being dried.
(6) calcination processing：Product carries out calcination processing in tube furnace after this is dried：Temperature is 900 DEG C, heating rate
For 3 DEG C/min, the time is to be passed through N2 protections in 5h, and tube furnace, obtains Ta3N5/ C composite fibre photochemical catalysts.
The Ta prepared in the present embodiment3N5The diameter of/C composite fibre photochemical catalysts is about 200nm, and length is about 80 μm, carbon
The thickness of film is about 7nm.
The Ta of the present embodiment3N5/ C composite fibres photochemical catalyst is in single degradation of methylene blue (MB) experiment (referring to experiment
Example), degradation efficiency reaches 80.5%.
Test example：
Tests below examines embodiment 1-3 to be difficult to biodegradable methylene blue (MB) dyestuff as target contaminant
Ta3N5The visible light photocatalysis performance of/C composite fibre photochemical catalysts.
Light-catalyzed reaction experiment is carried out in the simple Photoreactor built certainly, is used 300W xenon lamps for light source, is equipped with
400nm optical filter, retention wavelength (λ) is less than 400nm ultraviolet light, it is ensured that wavelength (λ) is more than the photograph of 400nm visible ray
Penetrate, controlled reaction temperature at 21 DEG C or so by external condensation water installations, light-catalyzed reaction solution is poured into 100mL beakers,
Keep constant during magnetic agitation tachyphylaxis.
Experiment one, single photocatalytic degradation MB steps are as follows：
(1) 60mL 10mg L accurately are measured-1Methylene blue (MB) solution in beaker, respectively in different beakers
Add Ta prepared by 20mg embodiment 23N5Ta prepared by nanofiber and embodiment 1-33N5/ C composite fibre photocatalysis
Agent, while setting blank control test, stirs 2 h, catalyst is reached with methylene blue (MB) solution in dark conditions
Adsorption equilibrium, then takes out 2-3mL reaction solutions as first sample (balancing sample).
(2) glass beaker is positioned in photo catalysis reactor again, takes a sample every 10min, pass through high speed centrifugation
(8000r/min, 5min) separates catalyst.Supernatant is taken after centrifugation, is surveyed using ultraviolet-visible absorption spectroscopy instrument (UV-Vis)
Determine the change in concentration of reaction solution (i.e. supernatant) Methylene Blue (MB) dyestuff.
Experiment two, 4 circulation photocatalytic degradation MB steps are as follows：
(1) 60mL 10mg L accurately are measured-1Methylene blue (MB) solution in beaker, add 20 mg embodiment 2
The Ta of preparation3N5/ C composite fibre photochemical catalysts, stir 2h in dark conditions, make catalyst and methylene blue (MB) solution
Reach adsorption equilibrium；
(2) glass beaker is positioned in photo catalysis reactor again, passes through high speed centrifugation (8000r/ after illumination 60min
Min, 5min) catalyst is separated, supernatant is taken after centrifugation, reaction solution is determined using ultraviolet-visible absorption spectroscopy instrument (UV-Vis)
The change in concentration of (i.e. supernatant) Methylene Blue (MB) dyestuff.
(3) catalyst for taking step (2) to be centrifugally separating to obtain, is rinsed 4 times with deionization, is placed in baking oven 60 DEG C and is dried
Dry-cure 10h, is then placed in another equipped with 60mL 10mg L-1Methylene blue (MB) beaker in, according to step (1) carry out
Operation, makes catalyst reach adsorption equilibrium with methylene blue (MB) solution；Glass beaker is positioned in photo catalysis reactor again,
Catalyst is separated by high speed centrifugation (8000 r/min, 5min) after illumination 60min, supernatant is taken after centrifugation, using ultraviolet
Visible absorption spectra instrument
(UV-Vis) change in concentration of reaction solution (i.e. supernatant) Methylene Blue (MB) dyestuff is determined.Step (3) is repeated
3 times.
Experiment one in, Fig. 3 be radiation of visible light under, different catalysts (blank test, embodiment 2 prepare Ta3N5Nanometer
Ta prepared by fiber, embodiment 13N5Ta prepared by/C composite fibre photochemical catalysts sample, embodiment 23N5/ C composite fibre light
Ta prepared by catalyst sample, embodiment 33N5/ C composite fibre photochemical catalysts sample) to the photocatalytic degradation curve of MB solution.
In blank test, illumination reaction 60min, MB solution is not degraded substantially.When with Ta3N5When fiber is photochemical catalyst, instead
Answer after 60min, can only degrade 68.6% MB.When using the sample of embodiment 1 as photochemical catalyst, after reaction 60min, only may be used
With the MB of degraded 83.5%.The sample of embodiment 1 is to MB photocatalytic degradation efficiency apparently higher than the sample of embodiment 3, embodiment 3
After example reaction 60min, can only degrade 80.5% MB.When using the sample of embodiment 2 as photochemical catalyst, it shows most
Strong photocatalytic activity, illumination reaction 60min is up to 96% to MB degradation efficiency, illustrates the Ta obtained in embodiment 23N5/C
Fiber photocatalyst has optimal visible light photocatalysis active.
Ta is recycled in experiment two3N5It is molten that composite fibre (sample of embodiment 2) has carried out 4 visible light photocatalytic degradation MB
The experiment (Fig. 4) of liquid.Each illumination 60min, and be all to carry out under the same test conditions, by 3 continuous photocatalysis
Degrading experiment, its photocatalytic degradation efficiency becomes 89%, the sample of illustrated example 2 by 96% to the 4th circulation circulated for the first time
Photocatalytic activity substantially do not reduce, with metastable photocatalytic activity.
Claims (10)
1. a kind of Ta3N5The preparation method of/C composite fibre photochemical catalysts, it is characterised in that：Comprise the steps：
Ta3N5Spinning solution preparation process：Soluble tantalum salt is added in Polymer Solution, 2~12h is stirred, obtains institute
State Ta3N5Spinning solution, wherein, the Polymer Solution by polyvinylpyrrolidone, absolute ethyl alcohol, DMF and
Acetic acid is mixed, and the volume ratio of the absolute ethyl alcohol, DMF and acetic acid is (3~4)：1：1；Described
Ta3N5In spinning solution, the mass percent concentration of the PVP is 5~10wt%, and the mass percent of the soluble tantalum salt is dense
Spend for 5~15wt%；
Ta2O5Fiber preparation process：By the Ta3N5Spinning solution carries out electrostatic spinning processing, obtains composite fibre；Again will be described multiple
Condensating fiber carries out calcination processing, obtains the Ta2O5Fiber；
Ta3N5Nanofiber preparation process：By the Ta2O5Fiber carries out nitrogen treatment, obtains Ta3N5Nanofiber；
Hydro-thermal reaction mixed system preparation process：By the Ta3N5Nanofiber is added in glucose solution, is stirred place
Reason, mixing time is 3h, obtains the hydro-thermal reaction mixed system；In the hydro-thermal reaction mixed system, the Ta3N5Nanometer
The content of fiber is 5g/L；In the glucose solution, the concentration of the glucose is 0.1mol/L；
Hydro-thermal reaction and subsequent processing steps：The hydro-thermal reaction mixed system is subjected to hydro-thermal reaction, hydro-thermal reaction production is obtained
Thing, wherein, the temperature of the hydro-thermal reaction is 180 DEG C, and the time is 12h；The hydro-thermal reaction product is carried out at centrifugation successively
Reason, washing process and drying and processing, product after being dried；
Calcining step：Product after the drying is subjected to calcination processing, Ta is obtained3N5/ C composite fibre photochemical catalysts, wherein, institute
The temperature for stating calcination processing is 800 DEG C, and heating rate is 3 DEG C/min, and calcination time is 5h, is entered under nitrogen or argon
OK.
2. Ta according to claim 13N5The preparation method of/C composite fibre photochemical catalysts, it is characterised in that：
The volume ratio of the absolute ethyl alcohol, N,N-dimethylformamide and acetic acid is 3：1：1.
3. Ta according to claim 13N5The preparation method of/C composite fibre photochemical catalysts, it is characterised in that：The Ta3N5Spin
In silk liquid, the mass percent concentration of the soluble tantalum salt is 10wt%.
4. Ta according to claim 13N5The preparation method of/C composite fibre photochemical catalysts, it is characterised in that：The polyethylene
The molecular weight of pyrrolidones is 1300000.
5. Ta according to claim 13N5The preparation method of/C composite fibre photochemical catalysts, it is characterised in that：
The Ta3N5In spinning solution preparation process, the soluble tantalum salt be butanol tantalum, ethanol tantalum, tantalic chloride, isopropanol tantalum,
One or more in sulfuric acid tantalum.
6. Ta according to claim 13N5The preparation method of/C composite fibre photochemical catalysts, it is characterised in that：
The Ta2O5In fiber preparation process, in the calcination processing, temperature is 500~800 DEG C, and the time is 2~15h.
7. Ta according to claim 13N5The preparation method of/C composite fibre photochemical catalysts, it is characterised in that：
The Ta3N5In nanofiber preparation process, the temperature of the nitrogen treatment is 750~900 DEG C, and the time is 4~15h；Institute
Nitrogen treatment is stated to carry out in ammonia atmosphere.
8. Ta according to claim 13N5The preparation method of/C composite fibre photochemical catalysts, it is characterised in that：
In the hydro-thermal reaction and subsequent processing steps, the hydro-thermal reaction is carried out in the reactor of polytetrafluoroethylene (PTFE) material,
Compactedness of the hydro-thermal reaction mixed system in the reactor is 60-90%.
9. Ta according to claim 83N5The preparation method of/C composite fibre photochemical catalysts, it is characterised in that：The hydro-thermal is anti-
It is 80% to answer compactedness of the mixed system in the reactor.
10. the Ta according to any one of claim 1-93N5The Ta that the preparation method of/C composite fibre photochemical catalysts is obtained3N5/
C composite fibre photochemical catalysts, it is characterised in that：The Ta3N5The shape characteristic of/C composite fibre photochemical catalysts is：The Ta3N5
The surface of nanofiber is uniformly wrapped up by one layer of C film, forms Ta3N5/ C nano fibre structure.
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