Alpha-ferric oxide polystyrene composite fibre, preparation method and its in photocatalytic degradation benzeneApplication in phenolic compoundTechnical field
The invention belongs to fiber preparation and phenol compound degradation technique fields, and in particular to a kind of alpha-ferric oxide is poly-Styrene composite fibre, preparation method and its application in Photocatalytic Degradation of Phenol class compound.
Background technique
With the fast development of society and industry, water pollution has become one of the problem for seriously endangering human survival.ItsIn, phenol pollutant is present in ore refining, dyestuff, drug more and produces in the waste water of industry, because of its stable structure, has oneThe features such as fixed carcinogenicity and be concerned.Photocatalysis contaminant degradation technology because the features such as its is efficient, cheap, environmentally protective byGradually cause extensive concern.The key of photocatalysis technology is the exploitation of the photochemical catalyst of efficient stable.Existing commercialCatalysis material P25 (TiO2), although showing good photocatalysis performance, the optical response range of material is narrow, solar energyUtilization rate is lower.Therefore, it is still necessary to further being researched and developed to the catalyst for degradation of phenol class compound.
Summary of the invention
Present invention aims to overcome that prior art defect, a kind of alpha-ferric oxide composite polystyrene fiber, preparation are providedMethod and its application in Photocatalytic Degradation of Phenol class compound.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of alpha-ferric oxide polystyrene composite fibre comprising following steps:
1) by the butanol solution of ferric nitrate in 120 DEG C of -160 DEG C of heat preservation 12-36h, cooled to room temperature, be centrifuged,It washs, be dried to obtain α-Fe2O3Powder；
2) by α-Fe2O3Powder is cleaned by ultrasonic with dehydrated alcohol under nitrogen atmosphere, is then placed in PS fiber magnetic agitation0.5-3 hours, finally under nitrogen atmosphere in60In Co- gamma-rays device, 25-35 kGy irradiation radiation treatment 6-12 is controlledHour, it is washed, be drying to obtain α-Fe2O3/ PS composite fibre.
Specifically, 8-12g ferric nitrate can be taken to be dissolved in 40mL-80mL n-butanol and obtaining ferric nitrate just in step 1)Butanol solution.Preferably, step 1) specifically: 1) weigh 8-12g ferric nitrate (Fe (NO3)3•9H2O), it is added to 40mL-80mLIn n-butanol, stirring and dissolving obtains dark red solution, is poured into 100ml polytetrafluoro reaction kettle, 5-10 DEG C/min is warming up to120 DEG C -160 DEG C and after keeping the temperature 12-36h, cooled to room temperature, 8000rpm centrifuge separation obtains red powder, anhydrous secondAlcohol washing centrifugation 5 times, powder is placed in vacuum drying oven, obtains α-after 40 DEG C of heat preservation drying under the conditions of vacuum 0.8-0.9MPaFe2O3Powder (average grain diameter 9.5-52.5 nm).
Specifically, 0.02-0.10 g α-Fe can be taken in step 22O3Powder is surpassed with 100-180ml dehydrated alcoholSound cleaning, PS fiber additive amount are 0.2-1.0 g.Preferably, step 2 specifically: measure 100-180ml dehydrated alcohol and be placed inIn 250ml glass sample bottle, after leading to nitrogen 15min with 100ml/min flow velocity, α-Fe is weighed2O3Powder 0.02-0.10 g, is poured intoIn glass sample bottle and bottle cap is covered, sealed membrane seal bottle cap surrounding is placed in supersonic cleaning machine 400W ultrasound 20min.Weigh PSFiber 0.2-1.0 g is put into glass sample bottle, sealing, after magnetic agitation 0.5-3 hours, leads to nitrogen with 100ml/min flow velocity15min, seal glass sample bottle.Glass sample bottle is placed in one60In Co- gamma-rays device, 25-35 kGy irradiation spoke is controlledAccording to processing 6-12 hours.After radiation treatment, composite fibre is taken out, after eluting sample with 200ml dehydrated alcohol, is put into vacuumIn baking oven, after controlling heat preservation 6-12 hours of 35 DEG C of 0.9MPa pressure, α-Fe is obtained2O3/ PS composite material.
Specifically, PS fiber is obtained through following step in step 2: by polystyrene powder, dimethylformamide and chlorineAfter benzene mixing, is reacted 4-8 hours in 60-75 DEG C of return stirring, then cool to room temperature, obtain PS spinning solution, then through Static SpinningSilk to get.
Wherein, the mixed proportion of polystyrene powder, dimethylformamide and chlorobenzene are as follows: take 6.0-15.0 g polystyrenePowder, 80-110mL dimethylformamide and 20-40mL chlorobenzene are mixed；Electrospinning conditions are as follows: spinning solution promotesSpeed is 0.15-0.50ml/min, voltage 18.0-23.5 kV, receives distance 14-18cm, spinning machine operational window humidity 45-75%, 15-25 DEG C of temperature.
The present invention provides the alpha-ferric oxide polystyrene composite fibres being prepared using above-mentioned preparation method.
The present invention also provides above-mentioned alpha-ferric oxide polystyrene composite fibres in Photocatalytic Degradation of Phenol class compoundApplication.
Application the present invention also provides above-mentioned alpha-ferric oxide polystyrene composite fibre as oil adsorbent.
In the present invention, bloodstone (α-Fe2O3) it is not only a kind of green, cheap semiconductor, and can effectively absorb 30One of ~ 37% solar energy, therefore become ideal photochemical catalyst.Secondly, in the photocatalytic process, the recycling of catalyst andBeing recycled also becomes its one of important investigation factor in actual use.Composite fibre solar energy utilization ratio of the present inventionHigh, low in cost, photocatalysis high concentration phenols degrading activity height, stable structure, and the composite fibre is for a variety of oiliness objectsMatter and organic pollutant show good adsorption capacity, have extensively in the fields such as sanitary wastewater processing and Industrial Wastewater TreatmentApplication prospect.
Compared to the prior art, beneficial effects of the present invention:
The present invention has been respectively synthesized the Fe of polymolecularity using dissolution thermal method and method of electrostatic spinning2O3Material and high-specific surface area(BET method measures specific surface area and is greater than 160m2/ g) polystyrene (PS) fiber, and Fe is obtained by gamma-ray irradiation method2O3/PS composite material.The Fe2O3/ PS composite material has good oily adsorption capacity, to automobile engine oil, pumping fluid, edible peanutThe adsorbance of oil reaches 141.6,139.4 and 138.0 g/g；It is illumination 1 hour at visible light (nm of λ > 400) simultaneously, respectively96.2 % and 89.2 % are reached to the catalysis degradation modulus of 20 mg/L 4- chlorophenols and 10 mg/L 4- nitrophenols.By 6 timesAfter circulation, Photocatalytic Degradation Property is all larger than 78 %, and catalyst recovery yield reaches 99.2 %.
Detailed description of the invention
Fig. 1 is Fe in Examples 1 and 22O3- 1(a) and Fe2O3(illustration is sample to the nano particle transmission electron microscope picture of -2 (b)Product grain size distribution)；
Fig. 2 be 1 step 1) of embodiment preparation gained PS fiber scanning electron microscope (SEM) photograph (illustration is high power scanning electron microscope (SEM) photograph, PS fiberThere are a large amount of pleated structures on surface)；
Fig. 3 is that embodiment 1 prepares gained Fe2O3/ PS-1 composite fibre scanning electron microscope (SEM) photograph (illustration be high power scanning electron microscope (SEM) photograph,Fe2O3- 1 particle is evenly distributed on PS fiber surface)；
Fig. 4 is that embodiment 2 prepares gained Fe2O3/ PS-2 composite fibre scanning electron microscope (SEM) photograph (illustration be high power scanning electron microscope (SEM) photograph,Fe2O3- 2 particles are evenly distributed on PS fiber surface)；
Fig. 5 is that Examples 1 and 2 prepare gained Fe2O3/ PS-1 and Fe2O3The XRD spectrum of/PS-2 sample；
Fig. 6 is photocatalytic degradation device schematic diagram；
Fig. 7 is the degradation property figure of different sample visible light photocatalysis 4-CP (a) and 4-NP (b)；
Fig. 8 is that embodiment 2 obtains Fe2O3Degradation efficiency figure in/PS-2 composite fibre photocatalysis circulation experiment；
Fig. 9 is adsorbance of the different samples to automobile engine oil, peanut oil, pumping fluid.
Specific embodiment
Technical solution of the present invention is further discussed in detail with reference to embodiments, but protection scope of the present inventionIt is not limited thereto.
Embodiment 1
A kind of preparation method of alpha-ferric oxide polystyrene composite fibre, specifically comprises the following steps:
1) 8.0g polystyrene (PS) powder is weighed, 72ml dimethylformamide is measured by PS and stirs swelling, add chlorobenzene28mL, agitating and heating flows back 4 hours under the conditions of 75 DEG C, then cools to room temperature to obtain PS spinning solution；Spinning solution is injectedIn 25ml glass syringe, using No. 7 stainless steel syringe needles, it is 0.36 mL/min, 19 kV of voltage in fltting speed, receives distance17 cm, spinning machine operational window humidity 45% carry out electrostatic spinning under conditions of 25 DEG C of temperature and obtain PS fiber (see figure 2)；
2) 8.08g ferric nitrate (Fe (NO is weighed3)3•9H2O it) is added in 50mL n-butanol, it is molten to obtain kermesinus for stirring and dissolvingLiquid is poured into 100ml polytetrafluoro reaction kettle, after 5 DEG C/min is warming up to 120 DEG C and keeps the temperature 12h, cooled to room temperature,8000rpm centrifuge separation obtains red powder, dehydrated alcohol washing centrifugation 5 times, powder is placed in vacuum drying oven, in vacuum40 DEG C of heat preservation drying obtain Fe under the conditions of 0.9MPa2O3- 1 powder (average grain diameter: 11.5 nm are shown in Fig. 1)；
3) it measures 100ml dehydrated alcohol to be placed in 250ml glass sample bottle, after leading to nitrogen 15min with 100ml/min flow velocity, claimTake the Fe that step 2 obtains2O30.03 g of -1 powder, pours into glass sample bottle and covers bottle cap, sealed membrane seal bottle cap surrounding,It is placed in supersonic cleaning machine 400W ultrasound 20min.It weighs 0.4 g of PS fiber that step 1) obtains to be put into glass sample bottle, seal,After 30 min of magnetic agitation, nitrogen 15min, seal glass sample bottle are led to 100ml/min flow velocity.Glass sample bottle is placed inOne60In Co- gamma-rays device, control 30 kGy irradiation radiation treatment 8 hours.After radiation treatment, directly with tweezers fromComposite fibre is taken out in bottle, after eluting sample with 200ml dehydrated alcohol, is put into vacuum drying oven, controls 35 DEG C of 0.9MPa pressureAfter heat preservation 6 hours, Fe is obtained2O3/ PS-1 complex fiber material.
Embodiment 2
A kind of preparation method of alpha-ferric oxide polystyrene composite fibre, specifically comprises the following steps:
1) 9.5g polystyrene (PS) powder is weighed, 100ml dimethylformamide is measured by PS and stirs swelling, add chlorobenzene20mL, agitating and heating flows back 6 hours under the conditions of 65 DEG C, it then cools to room temperature to obtain PS spinning solution；Spinning solution is injectedIn 25ml glass syringe, using No. 7 stainless steel syringe needles, it is 0.20 ml/min, 20 kV of voltage in fltting speed, receives distance18 cm, spinning machine operational window humidity 65% carry out electrostatic spinning under conditions of 18 DEG C of temperature and obtain PS fiber；
2) 12g ferric nitrate (Fe (NO is weighed3)3•9H2O it) is added in 70mL n-butanol, stirring and dissolving obtains dark red solution, willIt is poured into 100ml polytetrafluoro reaction kettle, after 10 DEG C/min is warming up to 130 DEG C and keeps the temperature for 24 hours, cooled to room temperature,8000rpm centrifuge separation obtains red powder, dehydrated alcohol washing centrifugation 5 times, powder is placed in vacuum drying oven, in vacuum40 DEG C of heat preservation drying obtain Fe under the conditions of 0.9MPa2O3- 2 powders (average grain diameter: 16.7 nm are shown in Fig. 1)；
3) it measures 150ml dehydrated alcohol to be placed in 250ml glass sample bottle, after leading to nitrogen 15min with 100mL/min flow velocity, claimTake the Fe that step 2 obtains2O30.02 g of -2 powder, pours into glass sample bottle and covers bottle cap, sealed membrane seal bottle cap surrounding,It is placed in supersonic cleaning machine 400W ultrasound 20min.It weighs 0.5 g of PS fiber that step 1) obtains to be put into glass sample bottle, seal,After 30 min of magnetic agitation, after leading to nitrogen 15min with 100mL/min flow velocity, seal glass sample bottle.Glass sample bottle is placed inOne60In Co- gamma-rays device, control 28 kGy irradiation radiation treatment 6 hours.After radiation treatment, directly with tweezers fromComposite fibre is taken out in bottle, after eluting sample with 200ml dehydrated alcohol, sample is put into vacuum drying oven, control 0.9MPa pressureAfter 35 DEG C of power keep the temperature 6 hours, Fe is obtained2O3/ PS-2 complex fiber material.
Fig. 1 is Fe in Examples 1 and 22O3- 1 and Fe2O3- 2 nano particle transmission electron microscope picture.As can be seen from Figure:Fe2O3- 1 and Fe2O3- 2 samples are made of nano particle, and particle diameter distribution substantially conforms to normal distribution, and average grain diameter is respectively aboutFor 11.5nm and 16.7nm.
Fig. 2 is the scanning electron microscope (SEM) photograph that 1 step 1) of embodiment prepares gained PS fiber.As seen from the figure: PS fiber is continuous micro-Meter level fiber, average fibre diameter are about 1.3 μm, and fiber surface has a large amount of fold holes, and BET method measures specific surface area and is about186.9 m2/g。
Fig. 3 and 4 is respectively Examples 1 and 2 preparation gained Fe2O3/ PS-1 and Fe2O3The scanning electron microscope (SEM) photograph of/PS-2.By schemingIt can be seen that: the uniform Fe of PS fiber surface of surface folding hole2O3Little particle, since nano particle exists during irradiation reactionAgglomeration, therefore its partial size showed is greater than Fe2O3The partial size measured in transmission electron microscope.
Fig. 5 is that Examples 1 and 2 prepare gained Fe2O3/ PS-1 and Fe2O3The XRD spectrum of/PS-2 sample.As seen from the figure:Fe2O3- 1 and Fe2O3- 2 sample diffraction peak positions and intensity and α-Fe2O3Standard diagram (PDF No:01-087-1166) is identical,Therefore, the iron oxide that step 2 obtains is α-Fe2O3；Fe2O3/ PS-1 and Fe2O3In/PS-2 map, it is located at 20oThe width of left and rightPeak is consistent with the diffraction maximum of PS fiber, remaining diffraction maximum position is identical as iron oxide sample diffraction peak position, therefore Fe2O3/PS material is only by α-Fe2O3It is formed with PS.
Photocatalysis test:
Photocatalytic degradation device can be found in Fig. 6, and concrete operations are as follows: by 0.1 g composite fibre (m0) tile and be fixed on oneOn polytetrafluoro bracket, making its light-receiving area is about 3.5*3.5 cm2, the fiber after fixation is placed in reactor, 200ml is addedIt simulates sewage (20 mg/mL 4- chlorophenol 4-CP or 10 mg/mL 4- nitrophenol 4-NP), logical cooling water control outside reactor3 DEG C of sewage temperature processed, with 10mL/min flow velocity blowing air.Reactor is placed in dark room conditions, after magnetic agitation 30min, is beatenThe 300 W Xe arc lamp of source (Beijing CEL-HXF300 CEAULIGHT Co., Ltd, China) that opens the light is used as light source, and exposure light passes through purpleOuter optical filter (nm of λ > 400) obtains visible exposure light.3 ml solution, 8000rpm centrifugation are taken from catalyst system every 10minAfter 3min, 279 nm and 317 nm are chosen using ultraviolet-visible spectrophotometer (Agilent Varian Cary-300) respectivelyFor test wavelength, the concentration C of 4- chlorophenol and 4- nitrophenol is detectedx, before darkroom is turned on light after adsorbing, solution concentration is denoted asC0, calculate contaminant degradation rate=Cx/C0× 100%, the catalytic performance test of sample carries out 3 times in parallel, calculates average degradation rate meterFor the catalyst catalytic performance.
Comparative experiments: with business photocatalyst P25 (TiO2) it is contrast sample, 0.1g P25, which is weighed, in 200ml simulates sewageAfter ten minutes, dark place magnetic agitation 20min, reactor leads to 3 DEG C of cooling water control sewage temperature to middle ultrasonic disperse outside, with 10mL/Min flow velocity blowing air.Illumination reaction test mode identical with fiber is then used, is evaluated under P25 radiation of visible light to 4-CPWith the degradation property of 4-NP pollutant.
Circulation experiment: the catalytic solution after above-mentioned test being poured out, catalyst is changed without, and rejoins new simulationSewage evaluates the degradation catalytic activity of sample by the above process.After experiment, catalyst, 8000rpm centrifugation are taken out with tweezers5 minutes abjection surface water is put into vacuum drying oven after being impregnated with 50ml ethyl alcohol, 35 DEG C drying 6 hours at pressure 0.9MPa, claimsCatalyst weight m is recorded again1, calculate catalyst recovery yield=m1/m0×100% 。
Material light catalysis activity is as shown in fig. 7, P25, PS fiber, Fe2O3- 1 and Fe2O3- 2 samples to 4-CP and 4-NP allThere is certain adsorption capacity, but under visible light (nm of λ > 400) irradiation, P25 and PS fiber does not have catalytic degradation performance substantially,Fe2O3- 1 and Fe2O3The catalytic degradation performance of -2 samples is again smaller than 35%, and Fe2O3/ PS-1 and Fe2O3The dark adsorption capacity of/PS-2There is promotion by a relatively large margin with Photocatalytic Degradation Property, wherein Fe2O3Illumination 1 is small under visible light for/PS-1 composite fibreWhen, 96.2 % and 89.2 % are respectively reached to the catalysis degradation modulus of 20 mg/L 4-CP and 10 mg/L 4-NP, in visible lightLower catalytic performance is significantly larger than commercialized P25 catalysis material.After 6 circulations, Photocatalytic Degradation Property is all larger than 78 %,Catalyst recovery yield reaches 99.2 %(and sees Fig. 8).
Oily absorption property test:
Weigh 0.2g Fe2O3- 1 and Fe2O3- 2, PS fiber, Fe2O3/ PS-1 composite fibre and Fe2O3/ PS-2 composite fibre is placedIn 100ml oily (automobile engine oil, peanut oil, pumping fluid), after mechanical stirring 10min, after taking out the hanging 2min of fiber, analysisBalance claims its weight.Using formula Q=(m1-m0)/m0Calculate material oil absorption (m1For fibre weight after oil suction, m0For fiber usePreceding weight, Q are the fiber oil absorption).
Absorption result is shown in Fig. 9.It can be seen that Fe in figure2O3- 1 and Fe2O3- 2 samples show weaker oily absorption property,Single PS fiber is only 44.2,45.4 and 34.1 g/g to the maximal absorptive capacity of automobile engine oil, pumping fluid, edible peanut oil；And composite fibre makes its oily adsorption capacity have biggish mention relative to PS fiber due to the fiber surface structure of its coarse complexityIt rises, Fe2O3/ PS-1 composite fibre respectively reaches 141.6 to the maximal absorptive capacity of automobile engine oil, pumping fluid, edible peanut oilG/g, 139.4 g/g and 138.0 g/g.
It in summary it can be seen: Fe of the present invention2O3/ PS composite fibre photocatalysis high concentration phenols degrading activity is high, structure is steadyIt is fixed, and the composite fibre shows good adsorption capacity for a variety of oily matters and organic pollutant, in sanitary wastewaterThe fields such as processing and Industrial Wastewater Treatment have a wide range of applications.