CN110182882A - One kind being based on Fe/FeS@SiO2Material goes the test method of trichloro ethylene in water removal - Google Patents

One kind being based on Fe/FeS@SiO2Material goes the test method of trichloro ethylene in water removal Download PDF

Info

Publication number
CN110182882A
CN110182882A CN201910384198.0A CN201910384198A CN110182882A CN 110182882 A CN110182882 A CN 110182882A CN 201910384198 A CN201910384198 A CN 201910384198A CN 110182882 A CN110182882 A CN 110182882A
Authority
CN
China
Prior art keywords
fes
sio
tce
deionized water
added
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910384198.0A
Other languages
Chinese (zh)
Inventor
李辉
相明辉
任路遥
司若凡
曹伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Shanghai for Science and Technology
Original Assignee
University of Shanghai for Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Shanghai for Science and Technology filed Critical University of Shanghai for Science and Technology
Priority to CN201910384198.0A priority Critical patent/CN110182882A/en
Publication of CN110182882A publication Critical patent/CN110182882A/en
Pending legal-status Critical Current

Links

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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention provides one kind to be based on Fe/FeS@SiO2Material goes the test method of trichloro ethylene in water removal, it is characterised in that specifically includes: step 1 prepares following material: step 2, preparation Fe/FeS, by 0.483g FeCl3·6H2O is dissolved in three-necked flask with 25mL deionized water and 45mL ethyl alcohol, and with 600rpm mechanical stirring；Step 3 prepares hollow mesopore silicon oxide spheres (HMSS)；Step 4 completes Fe/FeS@SiO2Preparation；For the TCE that degrades, degradation experiment is completed in serum bottle by step 5, Fe/FeS the and Fe/FeS@SiO2 prepared.In the present invention, Fe/FeS@SiO2The open duct of material and bigger specific surface area make it possible to the more TCE of absorption, increase TCE and the contact of Fe/FeS core, the special construction of yolk-eggshell material also takes full advantage of the whole surface of Fe/FeS core, so that the removal rate of TCE is significantly improved.

Description

One kind being based on Fe/FeS@SiO2Material goes the test method of trichloro ethylene in water removal
Technical field
The present invention relates to a kind of methods for removing trichloro ethylene, more particularly to a kind of Fe/FeS@SiO2 material that is based on to remove The test method of trichloro ethylene in water.
Background technique
Chlorohydrocarbon (Volatile chlorinated hydrocarbons, VCHs) is widely used to industrial production. It is unexpected to leak and the unreasonable storage disposition and discharge of chlorinated hydrocabon all be caused serious during Chemical Manufacture Underground water pollution.Trichloro ethylene (TCE) is one of most commonly detected chlorinated hydrocabon in underground water, as a kind of potent carcinogenic Substance, it can be continuously present in during natural degradation.TCE has three to cause effect, i.e. teratogenesis, carcinogenic, mutagenesis.TCE etc. Organo-chlorine pollutant is exposed to human body for a long time to cause very big influence to the healthy and safe of people itself.
Currently, the method for removing TCE from water mainly includes physical absorption, biodegrade and electronation oxidation.In recent years Come, nano zero valence iron technology causes domestic and international researcher to the degradation application of chlorohydrocarbon and widely pays close attention to.Wherein, sodium sulfide Rice Zero-valent Iron (Fe/FeS) have biggish specific surface area, stronger conductive capability and convenient and fast Magneto separate characteristic, therefore by Wider concern.It has been proved that vulcanization nano zero valence iron achieves in the degradation to chlorohydrocarbon better than nano zero valence iron Effect.But vulcanizing nano zero valence iron is the electronic selection for improving nano zero valence iron, is transmitted to electronics more Pollutant.However, it does not improve the agglomeration traits of nano zero valence iron.Vulcanize nano zero valence iron in the mistake of processing pollutant Can still it reunite in journey, to influence its effect for removing pollutant.
Summary of the invention
The purpose of the present invention is how to verify Fe/FeS@SiO2The open duct of material and bigger specific surface area can It adsorbs more TCE, so that the removal rate of TCE is significantly improved.
The technical solution of the present invention is to provide one kind to be based on Fe/FeS@SiO2Material goes the test of trichloro ethylene in water removal Method, it is characterised in that specifically include:
Step 1, prepares following material: Iron(III) chloride hexahydrate FeCl at step 13·6H2O, mass percent > 99%；Ammonia Water NH4OH, mass percent 25~28%；Cetyl trimethylammonium bromide CTAB, mass percent > 99%；Positive silicic acid second Ester TEOS, mass percent 28%；Sodium borohydride NaBH4, mass percent > 96%；Natrium carbonicum calcinatum Na2CO3, quality percentage Number 99.8%；And trichloro ethylene, mass percent > 99%；And sodium dithionite Na2S2O4；
Step 2, preparation Fe/FeS, by 0.483g FeCl3·6H2O is dissolved in three with 25mL deionized water and 45mL ethyl alcohol In mouth flask, and with 600rpm mechanical stirring；
Step 3 prepares hollow mesopore silicon oxide spheres (HMSS)；
Step 4 completes Fe/FeS@SiO2Preparation, by synthetic hollow mesopore silicon oxide and 0.483g FeCl3· 6H2It is dissolved in three-necked flask after O deionized water and ethyl alcohol mixing, under nitrogen protection stirs suspension strongly 15min, then by 0.340g NaBH4With 0.005g Na2S2O4It is dispersed in the 30mL deionized water in beaker, and passes through Longer BQ50-1J-A peristaltic pump is with 1.5mLmin-1It is added in three-necked flask；Under these conditions, after 30min, synthesis Contain 0.1g Fe0Fe/FeS@SiO2；
For the TCE that degrades, degradation experiment is completed in serum bottle by step 5, Fe/FeS the and Fe/FeS@SiO2 prepared.
Further, in step 2, by 0.340g NaBH4With 0.005g Na2S2O4The 30mL being dispersed in beaker go from In sub- water, and by Longer BQ50-1J-A peristaltic pump with 1.5mLmin-1It is added in three-necked flask；Under these conditions, After 30min, synthesis contains 0.1g Fe0Fe/FeS.
Further, step 3 the following steps are included:
Step 3.1, the 3.15mL ammonia spirit in 74mL ethyl alcohol, 10mL deionized water and mass percent 25~28% Mixture in be added 6ml TEOS, then by solution stir 1 hour to obtain SiO2；
Step 3.2,0.050g SiO2Be added to 0.075g CTAB containing 25mL deionized water, 15mL ethyl alcohol and 0.275mL NH4In the three-necked flask of OH, mixture is stirred at 600 rpm 0.5 hour；
0.125mL TEOS is added in flask, and passes through after mixture is stirred for 4 h at 300 rpm by step 3.3 Product is collected by centrifugation；
Step 3.4, by 0.212g Na2CO3It is added in the suspension of above-mentioned product, is vigorously stirred 10h at 50 DEG C Afterwards, it collects particle and is washed 3 times with ethyl alcohol and deionized water respectively, obtain hollow mesopore silicon oxide.
Further, step 5 the following steps are included:
The TCE aqueous solution of 100mL and material containing 0.1g Fe0 are added in serum bottle, serum bottle by step 5.1 It is put in after sealing on homemade roller and is reacted with the revolving speed of 15rmin-1；1mL water sample is taken at regular intervals, is passed through Concentration is measured after 0.22 μm of membrane filtration；
Step 5.2, using the pattern and structure of SEM and tem observation material, utilize XRD determining material substance composition and brilliant Body structure；Use XPS analysis material surface element；Using FT-IR measurement Fe/FeS@SiO2Surface functional group；It is analyzed using EDS The Elemental redistribution of material.
The beneficial effects of the present invention are:
(1) FT-IR atlas analysis, XRD and the test results such as XPS characterization and SEM and TEM observation show preparation Fe/FeS@SiO2Material has yolk-eggshell structure.The particle diameter distribution of material is the experiment proves that added mesoporous hollow silica After shell, reunite and reduce, in aqueous solution, the average grain diameter of particle is 11.89 μm, less than 29.00 μm not wrapped up.
It (2) is 10mgL in initial concentration-1In solution, add containing 0.1g Fe0Iron sulphur than the Fe/FeS@for 30 SiO2In the case of, the removal rate of TCE is 90.75% after reaction 180min, compared with 66.06% when not wrapping up silica shell, Removal effect significantly improves.
(3)Fe/FeS@SiO2The open duct of material and bigger specific surface area make it possible to the more TCE of absorption, Increase TCE and the contact of Fe/FeS core, the special construction of yolk-eggshell material also takes full advantage of the entire of Fe/FeS core Surface, so that the removal rate of TCE is significantly improved.
Detailed description of the invention
Fig. 1 is Fe/FeS@SiO2The FTIR spectrogram of material；
Fig. 2 is Fe/FeS@SiO2The XPS characterization result of the XRD spectra of material, XPS characterization result sum；
Fig. 3 is SEM, TEM and SEM-Mapping result of material；
Fig. 4 is Fe/FeS and Fe/FeS@SiO2Grain size distribution；
The effect picture that Fig. 5 removes TCE for the molar ratio of iron and sulphur；
Fig. 6 is Fe/FeS@SiO2, tri- kinds of materials of Fe/FeS and HMSS are to the removal efficiency of TCE；
Fig. 7 is that different initial concentrations influence the removal of TCE；
Fig. 8 is Fe/FeS@SiO2The XRD spectra of material；
Fig. 9 is Fe/FeS@SiO2SEM and TEM figure after material degradation TCE.
Specific embodiment
Technical solution of the present invention is described in detail below with reference to attached drawing 1-9.
As shown in Figure 1, this embodiment offers one kind to be based on Yolk@Shell structure Fe/FeS@SiO2Material goes to remove water The test method of middle trichloro ethylene, specifically includes:
Step 1, prepares following material: Iron(III) chloride hexahydrate FeCl at step 13·6H2O, mass percent > 99%；Ammonia Water NH4OH, mass percent 25~28%；Cetyl trimethylammonium bromide CTAB, mass percent > 99%；Positive silicic acid second Ester TEOS, mass percent 28%；Sodium borohydride NaBH4, mass percent > 96%；Natrium carbonicum calcinatum Na2CO3, quality percentage Number 99.8%；And trichloro ethylene, mass percent > 99%；And sodium dithionite Na2S2O4；
Test instrument: scanning electron microscope (JSM-6360LV, Japanese JEOL company)；Transmission electron microscope (JEM-1400, Japanese JEOL company)；X-ray powder diffraction instrument (D/max 2550V, Rigaku company, the U.S.)；X-ray electricity Sub- energy depressive spectroscopy (Axis Ultra DLD, Kratos company, the U.S.)；Fourier transformation infrared spectrometer (Nicolet 6700, U.S. Buddhist nun high-tensile strength company)；Energy dispersive spectrometry (EDAX TEAM Apollo, Yi Dakesi Co., Ltd, the U.S.).
Step 2, preparation Fe/FeS, by 0.483g FeCl3·6H2O is dissolved in three with 25mL deionized water and 45mL ethyl alcohol In mouth flask, and with 600rpm mechanical stirring；
By 0.340g NaBH4With 0.005g Na2S2O4It is dispersed in the 30mL deionized water in beaker, and passes through Longer BQ50-1J-A peristaltic pump is with 1.5mLmin-1It is added in three-necked flask；Under these conditions, after 30min, synthesis Contain 0.1g Fe0Fe/FeS.
Step 3 prepares hollow mesopore silicon oxide spheres (HMSS)
Step 3.1,74mL ethyl alcohol, 10mL deionized water and mass percent be 25~28% 3.15mL ammonium hydroxide it is molten 6ml TEOS is added in the mixture of liquid, solution is then stirred 1 hour to obtain SiO2。
Step 3.2,0.050g SiO2Be added to 0.075g CTAB containing 25mL deionized water, 15mL ethyl alcohol and 0.275mL NH4In the three-necked flask of OH, mixture is stirred at 600 rpm 0.5 hour.
0.125mL TEOS is added in flask, and passes through after mixture is stirred for 4h at 300 rpm by step 3.3 Product is collected by centrifugation.
Step 3.4, by 0.212g Na2CO3It is added in the suspension of above-mentioned product, is vigorously stirred 10h at 50 DEG C Afterwards, it collects particle and is washed 3 times with ethyl alcohol and deionized water respectively, obtain hollow mesopore silicon oxide.
Step 4 completes Fe/FeS@SiO2Preparation, by synthetic hollow mesopore silicon oxide and 0.483g FeCl3· 6H2It is dissolved in three-necked flask after O deionized water and ethyl alcohol mixing, under nitrogen protection stirs suspension strongly 15min, then by 0.340g NaBH4With 0.005g Na2S2O4It is dispersed in the 30mL deionized water in beaker, and passes through Longer BQ50-1J-A peristaltic pump is with 1.5mLmin-1It is added in three-necked flask.Under these conditions, after 30min, synthesis Contain 0.1g Fe0Fe/FeS@SiO2。
For the TCE that degrades, degradation experiment is completed in serum bottle by step 5, Fe/FeS the and Fe/FeS@SiO2 prepared.
The TCE aqueous solution of 100mL and material containing 0.1g Fe0 are added in serum bottle, serum bottle by step 5.1 It is put in after sealing on homemade roller and is reacted with the revolving speed of 15rmin-1.1mL water sample is taken at regular intervals, is passed through Concentration is measured after 0.22 μm of membrane filtration.
Step 5.2, using the pattern and structure of SEM and tem observation material, utilize XRD (radioactive source Cu K α) to measure material Expect material composition and crystal structure；Use XPS (radioactive source Al K α) analysis of material surface-element；Using FT-IR measurement Fe/ FeS@SiO2Surface functional group；The Elemental redistribution of material is analyzed using EDS.
In the step, institute's water sampling is added in 5mL extraction flask, 3 min of 2mL n-hexane oscillation extraction is added, takes Layer liquid 1mL is covered tightly in 2mL sample injection bottle with polytetrafluoroethylene (PTFE) bottle cap.Using Agilent company of the U.S. GC=7890A type gas phase Chromatograph measures TCE content: 1.4 μm of DB-VRX columns of the μ m of 60m × 250, ECD detector, autosampler, split ratio are 20:1, sample volume are 1 μ L.In 75 DEG C of constant temperature test samples, injector temperature is 240 DEG C, and detector temperature is 260 DEG C, and carrier gas is nitrogen Gas, purity >=99.99%.
Test result analysis:
1、Fe/FeS@SiO2The morphological analysis of material
As shown in Figure 1, the figure is Fe/FeS@SiO2The FTIR spectrogram of material.It will be seen from figure 1 that 3462 cm-1Width It is attributable to the stretching vibration of adsorbed water molecule and the O-H of aquation silanol group with peak.1620cm-1The small peak of wave band can return Because in the H-O-H bending vibration of adsorbed water molecule.With 1062 and 457cm-1Centered on frequency band be Si-O-Si stretching vibration, Si-O-Si is the characteristic peak of the mesopore silicon oxide of synthesis.In experiment before, we are surveyed by nitrogen adsorption-detachment assays Fe/FeS@SiO is determined2The specific surface area of material is 85m2·g-1, average pore size 5nm also demonstrates the silica shell of synthesis With mesoporous.
As shown in Fig. 2 (a), which is Fe/FeS@SiO2The XRD spectra of material is being Fe positioned at 44.6 ° of diffraction maximums0 (110) body-centered cubic (JCPDS no.06-0696).And it is then related with hollow mesopore silicon oxide spheres in 22.8 ° of diffraction maximums.Not It detects and the Fe in card (JCPDS no.6-0696)0Other relevant diffraction maximums, it may be possible to since HMSS shell covers Iron core.After being reacted with TCE, Fe0Diffraction maximum disappear, and occur the characteristic peak of magnetic iron ore at 35 °, this shows to react Fe/FeS@SiO in journey2Fe/FeS core in material, which is corroded, generates the oxide of iron.
As shown in Fig. 2 (b), which is Fe/FeS@SiO2The XPS characterization result of material.Silicon, oxygen, carbon are the masters of the substance Constituent is wanted, iron content is low.The peak of carbon is related with amorphous carbon, and agraphitic carbon is one layer of thin carbonaceous material, usually sudden and violent It is exposed on the surface of most of samples of air and finds, and the peak value of oxygen and silicon is then from HMSS.Because the addition of sulphur source compared with Few, the content of S element is very low, so in Fe/FeS and Fe/FeS@SiO2S element is not shown in the full spectrogram of the XPS of material Peak.But it can be seen that S from the spectrum analysis of S2p2-Presence, thus it is speculated that know as FeS.The XPS spectrum figure of Fe/FeS is compared, Fe/FeS@SiO2The peak of iron obviously weakens in the XPS spectrum figure of material, illustrates that Fe/FeS has been wrapped in HMSS substantially.
2, the Electronic Speculum of material and power spectrum interpretation of result
As shown in figure 3, the figure is Fe/FeS and Fe/FeS@SiO2SEM and TEM image.Fig. 3 (a) is Fe/FeS SEM figure, it can be seen from the figure that Fe/FeS particle is spherical in shape, surface is smooth.It is worth noting that, iron-based material is solid due to it Some magnetic and high surface energy and be easy aggregation, this is their major defects in soil and groundwater processing application. Fe/FeS remains the spherical-like morphology of particle after by the covering of HMSS shell, but due to external HMSS shell, magnetic between Fe/FeS particle Property interaction weaken, agglomeration significantly reduces, and particle is in bead single one by one, as shown in Fig. 3 (b).Fig. 3 (c) Fe/FeS@SiO is shown2The apparent yolk-eggshell structure of material.Fe/FeS@SiO2Black core in material corresponds to Fe/FeS, and the shell of grey then corresponds to HMSS.In TEM image it will be clear that gap between core and shell, then tie Fig. 3 (d) SEM-Mapping is closed, can prove Fe/FeS@SiO2Material is successfully prepared.
3, the particle diameter distribution of material
Fe/FeS the and Fe/FeS@SiO prepared2Material carries out grain with 2000 type laser particle instrument of Mastersizer Diameter analysis, decentralized medium is deionized water.Particle diameter distribution result is as shown in Figure 4.As seen from the figure, Fe/FeS@SiO2Material Average grain diameter be 11.89 μm, much smaller than the Fe/FeS (29.00 μm) for not wrapping up mesopore silicon oxide shell.In conjunction with SEM figure it is found that After having wrapped up mesopore silicon oxide shell, intergranular reunion is significantly reduced.
4, iron sulphur compares the influence of TCE removal
By the molar ratio of iron and sulphur be 75,30,15,7.5 contain 0.1g Fe0Fe/FeS be added to be equipped with respectively The 10mgL of 100ml-1In the serum bottle of TCE solution, it is put into roller and is reacted after sealing.Research iron and sulphur rub You compare the influence of TCE removal, as a result as shown in Figure 5.As seen from the figure, with the continuous reduction of Fe/S, the removal of TCE takes the lead in Increase, it is rear to reduce, and as Fe/S=30, TCE removal efficiency is maximum, is 90.75%.RAJAJAYAVEL et al. vulcanization Nano zero valence iron degradation TCE has also obtained similar result[21].Higher or lower Fe/S will lead to the reduction of removal rate. Existing document points out that the concrete reason of the conclusion is because of the reduction with Fe/S, and more FeS are in Fe0Surface Creation, from And reduce the active site on surface, it is suppressed that the dissolution of iron core, to reduce material to the removal efficiency of TCE.Institute The Fe/S used with subsequent experimental is for 30.
5, Fe/FeS@SiO2 and Fe/FeS remove TCE Contrast on effect
Fig. 6 is Fe/FeS@SiO2, tri- kinds of materials of Fe/FeS and HMSS are to the removal efficiency of TCE.Under normal temperature and pressure, reaction After 180min, the Fe/FeS of 0.1g is 10mgL to initial concentration-1TCE solution removal efficiency be 66.06%.And in phase Under same reaction condition, the Fe/FeS for having wrapped up hollow mesopore silicon oxide shell is 90.75% to the removal efficiency of TCE.Illustrate to wrap After having wrapped up in HMSS, the ability of material removal pollutant is had been significantly improved.Meanwhile to HMSS removal TCE effect also into It has gone research, only 6.5% or so has been removed under the same conditions.Illustrate Fe/FeS@SiO2It is mainly logical to the removal of TCE Cross reduction reaction.
6, TCE initial concentration influences removal TCE
0.1g Fe will be contained0, Fe/S ratio be 30 Fe/FeS@SiO2Add respectively to TCE initial concentration be 10,20, 30, in the solution of 40mg/L, as a result as shown in Figure 7.As seen from the figure, TCE initial concentration is 10mgL-1When, Fe/FeS@SiO2 It is best to the removal effect of TCE, there is 90.75% TCE to be removed in 3 hours.And when TCE initial concentration is 40mgL-1 When, Fe/FeS@SiO2Worst to the removal effect of TCE, only 69.75% TCE is removed.This explanation is in other conditions phase With in the case where, the removal effect of TCE is deteriorated with the increase of TCE concentration.Known to analysis: the active sites on the surface Fe/FeS Point is limited, and the increase of the concentration of TCE can aggravate competition of the TCE molecule to the active site on the surface Fe/FeS, finally make Removal rate reduces.
7, Fe/FeS@SiO2 dosage influences removal TCE
0.05,0.1,0.2,0.3g Fe will be contained respectively0Fe/FeS@SiO2Being added to TCE initial concentration is 10mg L-1Solution in, degradation results are as shown in Figure 8.It can be seen from the figure that when dosage is 0.05g, Fe/FeS@SiO2It is right The effect of TCE is worst, removal rate 81.00%.When dosage is 0.3g, Fe/FeS@SiO2It is best to the effect of TCE, two Hour can substantially remove TCE.Should the result shows that, under the same conditions, the removal effect of TCE with dosage increase And gradually improve.Known to analysis: the increase of dosage is also increased and is connect with pollutant TCE so that active site increases Contacting surface product, to improve the removal efficiency of TCE.
8, Fe/FeS@SiO2 material degradation TCE action principle is analyzed
Fig. 9 is Fe/FeS@SiO2SEM and TEM figure after material degradation TCE.Schemed by SEM it is found that particle is obvious after reacting Become larger and be packed together, and there are also spicule generations on surface, it can be speculated for ferriferous oxide in conjunction with XRD diagram.In addition. From TEM image as can be seen that reaction after Fe/FeS@SiO2In Fe/FeS core disappear, and have sheet in particle surface Ferriferous oxide generates.This illustrates Fe/FeS@SiO2In the reaction process with TCE, mainly Fe/FeS core is reacted with TCE, and It is oxidized to the surface that shell is attached to after ferriferous oxide dissolves out.It existing goes in conjunction with experiment before and about Fe/FeS Except the research report of TCE, Fe/FeS@SiO can be speculated2The absorption degradation mechanism of material.Firstly, Fe/FeS@SiO2Shell Porous network enhances the ability of its adsorbed target contaminant molecule, while target contaminant can pass through mesoporous channel system The active site on Fe/FeS core surface is penetrated by HMSS shell.Secondly, yolk-eggshell structure serves as " nano-reactor frame Frame ", and different from core shell nanoparticles, there is very big gap between core and shell, this whole surface for allowing for core can be with It is come into full contact with pollutant.Third, the HMSS shell being wrapped on the surface Fe/FeS can prevent passivation and the group of particle It is poly-, to improve the degradation efficiency of TCE.
Although the principle of the present invention is described in detail above in conjunction with the preferred embodiment of the present invention, this field It is to be understood by the skilled artisans that above-described embodiment is only the explanation to exemplary implementation of the invention, not to the present invention The restriction of scope.Details in embodiment is simultaneously not meant to limit the scope of the invention, without departing substantially from spirit of the invention In the case where range, any equivalent transformation based on technical solution of the present invention, simple replacement etc. obviously change, It falls within the scope of the present application.

Claims (4)

1. one kind is based on Fe/FeS@SiO2Material goes the test method of trichloro ethylene in water removal, it is characterised in that specifically includes:
Step 1 prepares following material: Iron(III) chloride hexahydrate FeCl3·6H2O, mass percent > 99%；Ammonium hydroxide NH4OH, matter Measure percentage 25~28%；Cetyl trimethylammonium bromide CTAB, mass percent > 99%；Ethyl orthosilicate TEOS, quality Percentage 28%；Sodium borohydride NaBH4, mass percent > 96%；Natrium carbonicum calcinatum Na2CO3, mass percent 99.8%；With Trichloro ethylene, mass percent > 99%；And sodium dithionite Na2S2O4；
Step 2, preparation Fe/FeS, by 0.483g FeCl3·6H2O 25mL deionized water and 45mL ethyl alcohol are dissolved in three mouthfuls of burnings In bottle, and with 600rpm mechanical stirring；
Step 3 prepares hollow mesopore silicon oxide spheres (HMSS)；
Step 4 completes Fe/FeS@SiO2Preparation, by synthetic hollow mesopore silicon oxide and 0.483g FeCl3·6H2O With being dissolved in three-necked flask after deionized water and ethyl alcohol mixing, suspension is stirred into 15min strongly under nitrogen protection, then will 0.340g NaBH4With 0.005g Na2S2O4It is dispersed in the 30mL deionized water in beaker, and by peristaltic pump with 1.5mL min-1It is added in three-necked flask；Under these conditions, after 30min, synthesis contains 0.1g Fe0Fe/FeS@SiO2；
Step 5, Fe/FeS the and Fe/FeS@SiO prepared2For the TCE that degrades, degradation experiment is completed in serum bottle.
2. according to claim 1 be based on Fe/FeS@SiO2Material goes the test method of trichloro ethylene in water removal, feature It is: in step 2, by 0.340g NaBH4With 0.005g Na2S2O4It is dispersed in the 30mL deionized water in beaker, and passes through Peristaltic pump is with 1.5mLmin-1It is added in three-necked flask；Under these conditions, after 30min, synthesis contains 0.1g Fe0Fe/ FeS。
3. according to claim 1 be based on Fe/FeS@SiO2Material goes the test method of trichloro ethylene in water removal, feature Be: step 3 the following steps are included:
Step 3.1,74mL ethyl alcohol, 10mL deionized water and mass percent 25~28% 3.15mL ammonia spirit mixing 6ml TEOS is added in object, solution is then stirred 1 hour to obtain SiO2；
Step 3.2,0.050g SiO2It is added to 0.075g CTAB containing 25mL deionized water, 15mL ethyl alcohol and 0.275mL NH4In the three-necked flask of OH, mixture is stirred at 600 rpm 0.5 hour；
0.125mL TEOS is added in flask step 3.3, and is received after mixture is stirred for 4h at 300 rpm by centrifugation Collect product；
Step 3.4, by 0.212g Na2CO3It is added in the suspension of above-mentioned product, after being vigorously stirred 10h at 50 DEG C, collects Particle is simultaneously washed 3 times with ethyl alcohol and deionized water respectively, obtains hollow mesopore silicon oxide.
4. according to claim 1 be based on Fe/FeS@SiO2Material goes the test method of trichloro ethylene in water removal, feature Be: step 5 the following steps are included:
The TCE aqueous solution of 100mL and material containing 0.1g Fe0 are added in serum bottle by step 5.1, after serum bottle sealing It is put on homemade roller and is reacted with the revolving speed of 15rmin-1；1mL water sample is taken at regular intervals, through 0.22 μm of filter membrane Concentration is measured after filtering；
Step 5.2, using the pattern and structure of SEM and tem observation material, utilize XRD determining material substance composition and crystal knot Structure；Use XPS analysis material surface element；Using FT-IR measurement Fe/FeS@SiO2Surface functional group；Material is analyzed using EDS The Elemental redistribution of material.
CN201910384198.0A 2019-05-09 2019-05-09 One kind being based on Fe/FeS@SiO2Material goes the test method of trichloro ethylene in water removal Pending CN110182882A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910384198.0A CN110182882A (en) 2019-05-09 2019-05-09 One kind being based on Fe/FeS@SiO2Material goes the test method of trichloro ethylene in water removal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910384198.0A CN110182882A (en) 2019-05-09 2019-05-09 One kind being based on Fe/FeS@SiO2Material goes the test method of trichloro ethylene in water removal

Publications (1)

Publication Number Publication Date
CN110182882A true CN110182882A (en) 2019-08-30

Family

ID=67714297

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910384198.0A Pending CN110182882A (en) 2019-05-09 2019-05-09 One kind being based on Fe/FeS@SiO2Material goes the test method of trichloro ethylene in water removal

Country Status (1)

Country Link
CN (1) CN110182882A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69221329D1 (en) * 1991-09-03 1997-09-04 Mobil Oil Corp REMOVAL OF CYANIDE FROM WATER
CN1772363A (en) * 2004-11-11 2006-05-17 中国科学院化学研究所 Template process of preparing hollow ball and composite hollow ball
CN105582913B (en) * 2014-10-22 2018-01-23 中国科学院大连化学物理研究所 One kind has yolk eggshell structure Pt@SiO2The preparation method of catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69221329D1 (en) * 1991-09-03 1997-09-04 Mobil Oil Corp REMOVAL OF CYANIDE FROM WATER
CN1772363A (en) * 2004-11-11 2006-05-17 中国科学院化学研究所 Template process of preparing hollow ball and composite hollow ball
CN105582913B (en) * 2014-10-22 2018-01-23 中国科学院大连化学物理研究所 One kind has yolk eggshell structure Pt@SiO2The preparation method of catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LUYAO REN.ETAL: "Yolk-shell Fe/FeS@SiO2 particles with enhanced dispersibility，transportability and degradation of TBBPA", 《CATALYSIS TODAY》 *
XIAOLIANG FANG.ETAL: "A cationic surfactant assisted selective etching strategy to hollow mesoporous silica spheres", 《THE ROYAL SOCIETY OF CHEMISTRY》 *

Similar Documents

Publication Publication Date Title
Abd Elkodous et al. Nanocomposite matrix conjugated with carbon nanomaterials for photocatalytic wastewater treatment
Bastami et al. Activated carbon from carrot dross combined with magnetite nanoparticles for the efficient removal of p-nitrophenol from aqueous solution
Pirveysian et al. Synthesis and characterization of sulfur functionalized graphene oxide nanosheets as efficient sorbent for removal of Pb2+, Cd2+, Ni2+ and Zn2+ ions from aqueous solution: a combined thermodynamic and kinetic studies
Jin et al. Nickel nanoparticles encapsulated in porous carbon and carbon nanotube hybrids from bimetallic metal-organic-frameworks for highly efficient adsorption of dyes
Maleki et al. Polyamidoamine dendrimer functionalized iron oxide nanoparticles for simultaneous electrochemical detection of Pb2+ and Cd2+ ions in environmental waters
Ptaszkowska-Koniarz et al. Removal of rhodamine B from water by modified carbon xerogels
Lima et al. Comparison of acidic leaching using a conventional and ultrasound-assisted method for preparation of magnetic-activated biochar
Cui et al. Electrochemical sensor based on ZIF-8@ dimethylglyoxime and β-cyclodextrin modified reduced graphene oxide for nickel (II) detection
Yang et al. Improving reductive performance of zero valent iron by H2O2/HCl pretreatment: a case study on nitrate reduction
Li et al. High performance cobalt nanoparticle catalysts supported by carbon for ozone decomposition: the effects of the cobalt particle size and hydrophobic carbon support
Zhao et al. Effect of ceria morphology on the activity of MnO x/CeO 2 catalysts for the catalytic combustion of chlorobenzene
Huang et al. Efficient catalytic activity and bromate minimization over lattice oxygen-rich MnOOH nanorods in catalytic ozonation of bromide-containing organic pollutants: Lattice oxygen-directed redox cycle and bromate reduction
Asadpour-Zeynali et al. A novel voltammetric sensor for mercury (II) based on mercaptocarboxylic acid intercalated layered double hydroxide nanoparticles modified electrode
JP3390649B2 (en) Spherical carbon material and method for producing the same
Amesh et al. High capacity amidic succinic acid functionalized mesoporous silica for the adsorption of uranium
dos Santos Morales et al. Vortex-assisted magnetic solid-phase extraction of cadmium in food, medicinal herb, and water samples using silica-coated thiol-functionalized magnetic multiwalled carbon nanotubes as adsorbent
Hussain et al. Synthesis of functionalized mesoporous Ni-SBA-16 decorated with MgO nanoparticles for Cr (VI) adsorption and an effective catalyst for hydrodechlorination of chlorobenzene
Mahamallik et al. Photo-Fenton process in a Co (II)-adsorbed micellar soft-template on an alumina support for rapid methylene blue degradation
Zhao et al. Preparation of hydrogen sulfide adsorbent derived from spent Fenton-like reagent modified biochar and its removal characteristics for hydrogen sulfide
Zhang et al. Preparation of magnetic flower-like molybdenum disulfide hybrid materials for the extraction of organophosphorus pesticides from environmental water samples
Shen et al. Manganese containing oxides catalytic ozonation in aqueous solution: catalytic mechanism on acid sites
Elías et al. Tailoring the stability and photo-Fenton activity of Fe-modified nanostructured silicates by tuning the metal speciation from different synthesis conditions
Rashwan et al. A novel catalyst of ceria-nanorods loaded on carbon xerogel for catalytic wet oxidation of methyl green dye
Huang et al. The synergetic effect of a structure-engineered mesoporous SiO 2–ZnO composite for doxycycline adsorption
Zhu et al. MoS2-modified MIL-53 (Fe) for synergistic adsorption-photocatalytic degradation of tetracycline

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20190830

RJ01 Rejection of invention patent application after publication