CN107149935B - A kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure - Google Patents
A kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000011258 core-shell material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 87
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 70
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 28
- 238000004140 cleaning Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 10
- 230000015556 catabolic process Effects 0.000 abstract description 63
- 238000006731 degradation reaction Methods 0.000 abstract description 63
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 58
- 229940043267 rhodamine b Drugs 0.000 abstract description 58
- 238000000034 method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 33
- 230000000694 effects Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920001021 polysulfide Polymers 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229910002552 Fe K Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
A kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure, it is related to a kind of preparation method of fenton catalyst.The invention aims to solve the problems, such as existing fenton catalyst degradation of organic substances low efficiency and multiple cycle performance degradation.Method: one, reaction solution is prepared；Two, the mixed liquor containing hydro-thermal reaction product is prepared；Three, it is centrifuged, obtains hydro-thermal reaction product；Four, it cleans, it is dry, obtain the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure.The more iron sulfide of efficient out-phase class fenton catalyst core-shell structure prepared by the present invention degradation rate of rhodamine B degradation in 30min reaches 97%.The present invention can get a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure.
Description
Technical field
The present invention relates to a kind of preparation methods of fenton catalyst.
Background technique
Chemical industry is made that great contribution as the pillars of the national economy, for rapid economic development, but consequently also brings
More and more pollution problems, such as water pollution, soil pollution and atmosphere pollution.In soil pollution and water pollution, with benzene
Phenol is the arene pollutant of representative, seriously endangers human body and ecological environment.Advanced catalytic oxidation (Fenton oxidation and class
Fenton oxidation) it reacts at normal temperatures and pressures, it is easy to operate, oxidability is strong, in soil remediation and treatment of Organic Wastewater application
It has a extensive future.And in current Fenton oxidation technology, fenton catalyst is not available under neutral system, and multiple cycle performance
Degradation, degradation rate reaches the 10% of first time when using for the second time.Therefore in the exploitation of efficient different-phase catalyst, valence is prepared
It is honest and clean be easy to get, large specific surface area and the high class fenton catalyst material of activity in water treatment field have important application value.
Summary of the invention
It is serious the invention aims to solve existing fenton catalyst degradation of organic substances low efficiency and multiple cycle performance
The problem of decline, and a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure is provided.
A kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure, it is specifically complete according to the following steps
At:
One, thiocarbamide and iron powder are added in dehydrated alcohol, then ultrasonic power be 60W under ultrasonic disperse 3min~
10min obtains reaction solution；
The quality of iron powder described in step 1 and the volume ratio of dehydrated alcohol are (0.3g~1g): 50mL；
The molar ratio of iron powder and thiocarbamide described in step 1 is (0.5~1.5): (0.3~3.5)；
Two, reaction solution obtained in step 1 is added in hydrothermal reaction kettle, then in the case where temperature is 180 DEG C~220 DEG C
Hydro-thermal reaction 20h~for 24 hours, obtain the mixed liquor containing hydro-thermal reaction product；
Three, the mixed liquor containing hydro-thermal reaction product is centrifuged in the case where centrifugal speed is 4000r/min~5000r/min
4min~6min removes supernatant, obtains hydro-thermal reaction product；
Four, first using deionized water to hydro-thermal reaction product cleaning 3 times~5 times obtained in step 3, nothing is reused
Water-ethanol dries at being finally 60 DEG C~80 DEG C in temperature to hydro-thermal reaction product cleaning 3 times~5 times, obtains efficient out-phase class
The more iron sulfide of fenton catalyst core-shell structure.
Advantages of the present invention:
One, the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure prepared by the present invention are degraded Luo Dan in 30min
The degradation rate of bright B reaches 97%；
Two, the partial size of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure prepared by the present invention is micron order；
Three, the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure prepared by the present invention are core-shell structure, Cong Tiebiao
Face starts to vulcanize, and most surface layer, which is formed, crystallizes good polysulfide crystal；
Four, degradation sieve can be used for multiple times in the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure prepared by the present invention
Red bright B, degradation rate reaches the 88%~90% of first time when using for the second time, and degradation rate reaches first time when using for the third time
77%~80%.
The present invention can get a kind of method for preparing the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure.
Detailed description of the invention
Fig. 1 is the curve graph of rhodamine B degradation, in Fig. 11 be iron powder rhodamine B degradation curve, 2 make for embodiment one
The curve of the standby efficient more iron sulfide rhodamine B degradations of out-phase class fenton catalyst core-shell structure, 3 height prepared for embodiment two
Imitate the curve of the more iron sulfide rhodamine B degradations of out-phase class fenton catalyst core-shell structure, the 4 efficient out-phase prepared for embodiment three
The curve of the more iron sulfide rhodamine B degradations of class fenton catalyst core-shell structure, the 5 efficient out-phase class Fentons prepared for example IV
The curve of the more iron sulfide rhodamine B degradations of catalyst core shell structure；
Fig. 2 is XRD spectra, the 1 efficient out-phase class fenton catalyst core-shell structure mostly vulcanization prepared for example IV in Fig. 2
The XRD curve of iron, " ◆ " are Fe7S8Characteristic peak, 2 be Fe7S8Standard x RD curve；
Fig. 3 is that the SEM of iron powder schemes；
Fig. 4 is the SEM figure of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of example IV preparation；
Fig. 5 is to show that the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of example IV preparation amplify 5000 times
SEM figure；
Fig. 6 is that the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of example IV preparation amplify 10000 times
SEM figure；
Fig. 7 is that the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of example IV preparation amplify 20000 times
SEM figure；
Fig. 8 is to show the more iron sulfide amplifications 20000 of the efficient out-phase class fenton catalyst core-shell structure of example IV preparation
SEM figure again；
Fig. 9 is the curve graph of rhodamine B degradation three times, in Fig. 91 be first time rhodamine B degradation curve, 2 be second
The curve of secondary rhodamine B degradation, 3 be the curve of third time rhodamine B degradation.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of more iron sulfide of efficient out-phase class fenton catalyst core-shell structure
Preparation method is specifically realized by the following steps:
One, thiocarbamide and iron powder are added in dehydrated alcohol, then ultrasonic power be 60W under ultrasonic disperse 3min~
10min obtains reaction solution；
The quality of iron powder described in step 1 and the volume ratio of dehydrated alcohol are (0.3g~1g): 50mL；
The molar ratio of iron powder and thiocarbamide described in step 1 is (0.5~1.5): (0.3~3.5)；
Two, reaction solution obtained in step 1 is added in hydrothermal reaction kettle, then in the case where temperature is 180 DEG C~220 DEG C
Hydro-thermal reaction 20h~for 24 hours, obtain the mixed liquor containing hydro-thermal reaction product；
Three, the mixed liquor containing hydro-thermal reaction product is centrifuged in the case where centrifugal speed is 4000r/min~5000r/min
4min~6min removes supernatant, obtains hydro-thermal reaction product；
Four, first using deionized water to hydro-thermal reaction product cleaning 3 times~5 times obtained in step 3, nothing is reused
Water-ethanol dries at being finally 60 DEG C~80 DEG C in temperature to hydro-thermal reaction product cleaning 3 times~5 times, obtains efficient out-phase class
The more iron sulfide of fenton catalyst core-shell structure.
The advantages of present embodiment:
One, the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of present embodiment preparation are degraded in 30min
The degradation rate of rhodamine B reaches 97%；
Two, the partial size of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of present embodiment preparation is micron
Grade；
Three, the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of present embodiment preparation are core-shell structure, from
Iron surface starts to vulcanize, and most surface layer, which is formed, crystallizes good polysulfide crystal；
Four, drop can be used for multiple times in the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of present embodiment preparation
Rhodamine B is solved, degradation rate reaches the 88%~90% of first time when using for the second time, and degradation rate reaches first when using for the third time
Secondary 77%~80%.
Present embodiment can get a kind of method for preparing the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: iron powder described in step 1
Partial size be 4 μm~8 μm.Other steps are same as the specific embodiment one.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: institute in step 1
The quality for the iron powder stated and the volume ratio of dehydrated alcohol are (0.3g~0.56g): 50mL.Other steps and specific embodiment one
Or two is identical.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: institute in step 1
The quality for the iron powder stated and the volume ratio of dehydrated alcohol are (0.56g~1g): 50mL.Other steps and specific embodiment one to
Three is identical.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: institute in step 1
The molar ratio of the iron powder and thiocarbamide stated is (0.5~1.5): (0.3~2).Other steps are identical as specific embodiment one to four.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: institute in step 1
The molar ratio of the iron powder and thiocarbamide stated is (0.5~1.5): (0.3~0.5).Other steps and one to five phase of specific embodiment
Together.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: will in step 1
Thiocarbamide and iron powder are added in dehydrated alcohol, then ultrasonic disperse 3min~5min in the case where ultrasonic power is 60W, obtain reaction solution.
Other steps are identical as specific embodiment one to six.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: will in step 2
Reaction solution obtained in step 1 is added in hydrothermal reaction kettle, then temperature be 180 DEG C~200 DEG C at hydro-thermal reaction 20h~
22h obtains hydro-thermal reaction product.Other steps are identical as specific embodiment one to seven.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: will in step 2
Reaction solution obtained in step 1 is added in hydrothermal reaction kettle, then temperature be 200 DEG C~220 DEG C at hydro-thermal reaction 22h~
For 24 hours, hydro-thermal reaction product is obtained.Other steps are identical as specific embodiment one to eight.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: first in step 4
It is anti-to hydro-thermal that dehydrated alcohol first is reused to hydro-thermal reaction product cleaning 3 times~4 times obtained in step 3 using deionized water
It answers product cleaning 3 times~4 times, is dried at being finally 60 DEG C~70 DEG C in temperature, obtain efficient out-phase class fenton catalyst nucleocapsid
The more iron sulfide of structure.Other steps are identical as specific embodiment one to nine.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure is specifically pressed
What following steps were completed:
One, thiocarbamide and 0.56g iron powder are added in 50mL dehydrated alcohol, then the ultrasonic disperse in the case where ultrasonic power is 60W
5min obtains reaction solution；
The molar ratio of iron powder and thiocarbamide described in step 1 is 1:0.5；
The partial size of iron powder described in step 1 is 6 μm；
Two, reaction solution obtained in step 1 is added in hydrothermal reaction kettle, then temperature be 200 DEG C at hydro-thermal reaction
For 24 hours, hydro-thermal reaction product is obtained；
Three, the mixed liquor containing hydro-thermal reaction product is centrifuged 5min in the case where centrifugal speed is 4000r/min, removes supernatant
Liquid obtains hydro-thermal reaction product；
Four, first using deionized water to hydro-thermal reaction product cleaning 3 times obtained in step 3, dehydrated alcohol is reused
To hydro-thermal reaction product cleaning 3 times, is dried at being finally 60 DEG C in temperature, obtain efficient out-phase class fenton catalyst core-shell structure
More iron sulfide.
Embodiment two: a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure is specifically pressed
What following steps were completed:
One, thiocarbamide and 0.56g iron powder are added in 50mL dehydrated alcohol, then the ultrasonic disperse in the case where ultrasonic power is 60W
5min obtains reaction solution；
The molar ratio of iron powder and thiocarbamide described in step 1 is 1:2；
The partial size of iron powder described in step 1 is 6 μm；
Two, reaction solution obtained in step 1 is added in hydrothermal reaction kettle, then temperature be 200 DEG C at hydro-thermal reaction
For 24 hours, hydro-thermal reaction product is obtained；
Three, the mixed liquor containing hydro-thermal reaction product is centrifuged 5min in the case where centrifugal speed is 4000r/min, removes supernatant
Liquid obtains hydro-thermal reaction product；
Four, first using deionized water to hydro-thermal reaction product cleaning 3 times obtained in step 3, dehydrated alcohol is reused
To hydro-thermal reaction product cleaning 3 times, is dried at being finally 60 DEG C in temperature, obtain efficient out-phase class fenton catalyst core-shell structure
More iron sulfide.
Embodiment three: a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure is specifically pressed
What following steps were completed:
One, thiocarbamide and 0.56g iron powder are added in 50mL dehydrated alcohol, then the ultrasonic disperse in the case where ultrasonic power is 60W
5min obtains reaction solution；
The molar ratio of iron powder and thiocarbamide described in step 1 is 1:3；
The partial size of iron powder described in step 1 is 6 μm；
Two, reaction solution obtained in step 1 is added in hydrothermal reaction kettle, then temperature be 200 DEG C at hydro-thermal reaction
For 24 hours, hydro-thermal reaction product is obtained；
Three, the mixed liquor containing hydro-thermal reaction product is centrifuged 5min in the case where centrifugal speed is 4000r/min, removes supernatant
Liquid obtains hydro-thermal reaction product；
Four, first using deionized water to hydro-thermal reaction product cleaning 3 times obtained in step 3, dehydrated alcohol is reused
To hydro-thermal reaction product cleaning 3 times, is dried at being finally 60 DEG C in temperature, obtain efficient out-phase class fenton catalyst core-shell structure
More iron sulfide.
Example IV: a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure is specifically pressed
What following steps were completed:
One, thiocarbamide and 0.56g iron powder are added in 50mL dehydrated alcohol, then the ultrasonic disperse in the case where ultrasonic power is 60W
5min obtains reaction solution；
The molar ratio of iron powder and thiocarbamide described in step 1 is 0.5:2；
The partial size of iron powder described in step 1 is 6 μm；
Two, reaction solution obtained in step 1 is added in hydrothermal reaction kettle, then temperature be 200 DEG C at hydro-thermal reaction
For 24 hours, hydro-thermal reaction product is obtained；
Three, the mixed liquor containing hydro-thermal reaction product is centrifuged 5min in the case where centrifugal speed is 4000r/min, removes supernatant
Liquid obtains hydro-thermal reaction product；
Four, first using deionized water to hydro-thermal reaction product cleaning 3 times obtained in step 3, dehydrated alcohol is reused
To hydro-thermal reaction product cleaning 3 times, is dried at being finally 60 DEG C in temperature, obtain efficient out-phase class fenton catalyst core-shell structure
More iron sulfide.
Embodiment one, embodiment two, embodiment three are identical with example IV iron powder described in step 1.
The Degrading experiment one of rhodamine B degradation: sieve for being 0.6g/L by the concentration that 30mg iron powder is added to 50mL rhodamine B
It in red bright B aqueous solution, stirs evenly, adds the H that 34 μ L concentration are 6mmol/L2O2Solution is stirred for uniformly, then at room temperature
0min~30min is reacted, degradation effect is as shown in figure 1 shown in curve 1；
The Degrading experiment two of rhodamine B degradation: efficient out-phase class fenton catalyst nucleocapsid prepared by 30mg embodiment one
The concentration that the more iron sulfide of structure are added to 50mL rhodamine B is to stir evenly, add in the rhodamine B aqueous solution of 0.6g/L
34 μ L concentration are the H of 6mmol/L2O2Solution is stirred for uniformly, then reacts 0min~30min, degradation effect such as Fig. 1 at room temperature
Shown in middle curve 2；
The Degrading experiment three of rhodamine B degradation: efficient out-phase class fenton catalyst nucleocapsid prepared by 30mg embodiment two
The concentration that the more iron sulfide of structure are added to 50mL rhodamine B is to stir evenly, add in the rhodamine B aqueous solution of 0.6g/L
34 μ L concentration are the H of 6mmol/L2O2Solution is stirred for uniformly, then reacts 0min~30min, degradation effect such as Fig. 1 at room temperature
Shown in middle curve 3；
The Degrading experiment four of rhodamine B degradation: efficient out-phase class fenton catalyst nucleocapsid prepared by 30mg embodiment three
The concentration that the more iron sulfide of structure are added to 50mL rhodamine B is to stir evenly, add in the rhodamine B aqueous solution of 0.6g/L
34 μ L concentration are the H of 6mmol/L2O2Solution is stirred for uniformly, then reacts 0min~30min, degradation effect such as Fig. 1 at room temperature
Shown in middle curve 4；
The Degrading experiment five of rhodamine B degradation: efficient out-phase class fenton catalyst nucleocapsid prepared by 30mg example IV
The concentration that the more iron sulfide of structure are added to 50mL rhodamine B is to stir evenly, add in the rhodamine B aqueous solution of 0.6g/L
34 μ L concentration are the H of 6mmol/L2O2Solution is stirred for uniformly, then reacts 0min~30min, degradation effect such as Fig. 1 at room temperature
Shown in middle curve 5；
Fig. 1 is the curve graph of rhodamine B degradation, in Fig. 11 be iron powder rhodamine B degradation curve, 2 make for embodiment one
The curve of the standby efficient more iron sulfide rhodamine B degradations of out-phase class fenton catalyst core-shell structure, 3 height prepared for embodiment two
Imitate the curve of the more iron sulfide rhodamine B degradations of out-phase class fenton catalyst core-shell structure, the 4 efficient out-phase prepared for embodiment three
The curve of the more iron sulfide rhodamine B degradations of class fenton catalyst core-shell structure, the 5 efficient out-phase class Fentons prepared for example IV
The curve of the more iron sulfide rhodamine B degradations of catalyst core shell structure；
Fig. 1 is different catalysts rhodamine B degradation 30min removal rate curve, and the rising of curve 1 is due in uncomfortable pH
Micron iron cannot function as the catalyst of class Fenton's reaction under system, contain a small amount of iron powder in solution, centrifugation can not completely remove.
The above two o'clock causes absorbance to go up not down；It is anti-to class Fenton from curve 2,3,4 and 5 as can be seen that the ratio with sulphur increases
The catalytic effect answered is obviously improved.When example IV preparation, removal rate has reached 97, and the proportional speed for being further added by sulphur has
It is promoted, but it is little to react final removal rate variation.
Fig. 2 is XRD spectra, the 1 efficient out-phase class fenton catalyst core-shell structure mostly vulcanization prepared for example IV in Fig. 2
The XRD curve of iron, " ◆ " are Fe7S8Characteristic peak, 2 be Fe7S8Standard x RD curve.
Fig. 3 is that the SEM of iron powder schemes；
Fig. 4 is the SEM figure of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of example IV preparation；
It is about 10 μm from unreacted iron powder partial size known to Fig. 3 and Fig. 4, the partial size after reaction is increased slightly but remains
Micron order.
Fig. 5 is to show that the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of example IV preparation amplify 5000 times
SEM figure；
Fig. 6 is that the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of example IV preparation amplify 10000 times
SEM figure；
Fig. 7 is that the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of example IV preparation amplify 20000 times
SEM figure；
Fig. 8 is to show the more iron sulfide amplifications 20000 of the efficient out-phase class fenton catalyst core-shell structure of example IV preparation
SEM figure again.
From Fig. 5~Fig. 8 it is found that the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of example IV preparation are core
Shell structure vulcanizes since iron surface, and most surface layer, which is formed, crystallizes good polysulfide crystal；
Table 1 is the spot scan power spectrum of the more iron sulfide crystal faces of efficient out-phase class fenton catalyst of example IV preparation in Fig. 5
(EDS) result tested；
Table 1
| Element | Mass fraction % | Atomic percent % |
| S K | 41.42 | 55.19 |
| FeK | 58.58 | 44.81 |
| Totals | 100.00 | 100.00 |
Table 2 is the shell spot scan power spectrum of the efficient more iron sulfide of out-phase class fenton catalyst of example IV preparation in Fig. 5
(EDS) result tested；
Table 2
| Element | Mass fraction % | Atomic percent % |
| S K | 43.25 | 57.03 |
| Fe K | 56.75 | 42.97 |
| Totals | 100.00 | 100.00 |
Table 3 is the kernel spot scan power spectrum of the efficient more iron sulfide of out-phase class fenton catalyst of example IV preparation in Fig. 5
(EDS) result tested；
Table 3
| Element | Mass fraction % | Atomic percent % |
| S K | 21.07 | 31.74 |
| Fe K | 78.93 | 68.26 |
| Totals | 100.00 | 100.00 |
The cyclic test one of rhodamine B degradation: efficient out-phase class fenton catalyst nucleocapsid prepared by 30mg example IV
The concentration that the more iron sulfide of structure are added to 50mL rhodamine B is to stir evenly, add in the rhodamine B aqueous solution of 0.6g/L
34 μ L concentration are the H of 6mmol/L2O2Solution is stirred for uniformly, then reacts 0min~30min, degradation effect such as Fig. 9 at room temperature
Shown in middle curve 1；
The cyclic test two of rhodamine B degradation: by rhodamine B degradation water in the cyclic test one of 30mg rhodamine B degradation
The more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of example IV preparation after solution 30min take out, and use distillation
Water cleans 5 times, then is dried in vacuo 10h at being 60 DEG C in temperature, obtains the efficient out-phase class Fenton of second of rhodamine B degradation
The more iron sulfide of catalyst core shell structure；The efficient out-phase class fenton catalyst core-shell structure of second of rhodamine B degradation is more
The concentration that iron sulfide is added to 50mL rhodamine B is to stir evenly in the rhodamine B aqueous solution of 0.6g/L, it is dense to add 34 μ L
Degree is the H of 6mmol/L2O2Solution is stirred for uniformly, then reacts 0min~30min, curve in degradation effect such as Fig. 9 at room temperature
Shown in 2；
The cyclic test three of rhodamine B degradation: by rhodamine B degradation water in the cyclic test two of 30mg rhodamine B degradation
The more iron sulfide of the efficient out-phase class fenton catalyst core-shell structure of second of rhodamine B degradation after solution 30min take out, and make
5 times wash with distilled water, then it is dried in vacuo 10h at being 60 DEG C in temperature,
Obtain the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of third time rhodamine B degradation；By third
The more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of secondary rhodamine B degradation are added to the concentration of 50mL rhodamine B
To stir evenly in the rhodamine B aqueous solution of 0.6g/L, the H that 34 μ L concentration are 6mmol/L is added2O2Solution is stirred for
It is even, then 0min~30min is reacted at room temperature, degradation effect is as shown in curve 3 in Fig. 9.
Fig. 9 is the curve graph of rhodamine B degradation three times, in Fig. 91 be first time rhodamine B degradation curve, 2 be second
The curve of secondary rhodamine B degradation, 3 be the curve of third time rhodamine B degradation.
As can be seen from Figure 9, it drops for second of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure of example IV preparation
The degradation rate of solution rhodamine B reaches 84.79%, and performance reaches the 88.73% of first time, the degradation of third time rhodamine B degradation
Rate reaches 74.11%, and performance reaches the 77.55% of first time, it was demonstrated that the efficient out-phase class fenton catalyst of example IV preparation
The more iron sulfide cycle performances of core-shell structure are good.
Embodiment five: a kind of preparation method of the efficient more iron sulfide of out-phase class fenton catalyst, specifically according to the following steps
It completes:
One, thiocarbamide and 0.56g iron powder are added in 50mL dehydrated alcohol, then the ultrasonic disperse in the case where ultrasonic power is 60W
5min obtains reaction solution；
The molar ratio of iron powder and thiocarbamide described in step 1 is 0.81:1；
The partial size of iron powder described in step 1 is 6 μm；
Two, reaction solution obtained in step 1 is added in hydrothermal reaction kettle, then temperature be 200 DEG C at hydro-thermal reaction
For 24 hours, hydro-thermal reaction product is obtained；
Three, the mixed liquor containing hydro-thermal reaction product is centrifuged 5min in the case where centrifugal speed is 4000r/min, removes supernatant
Liquid obtains hydro-thermal reaction product；
Four, first using deionized water to hydro-thermal reaction product cleaning 3 times obtained in step 3, dehydrated alcohol is reused
To hydro-thermal reaction product cleaning 3 times, is dried at being finally 60 DEG C in temperature, obtain efficient out-phase class fenton catalyst and vulcanize more
Iron.
Embodiment six: a kind of preparation method of the efficient more iron sulfide of out-phase class fenton catalyst, specifically according to the following steps
It completes:
One, thiocarbamide and 0.56g iron powder are added in 50mL dehydrated alcohol, then the ultrasonic disperse in the case where ultrasonic power is 60W
5min obtains reaction solution；
The molar ratio of iron powder and thiocarbamide described in step 1 is 0.75:1；
The partial size of iron powder described in step 1 is 6 μm；
Two, reaction solution obtained in step 1 is added in hydrothermal reaction kettle, then temperature be 200 DEG C at hydro-thermal reaction
For 24 hours, hydro-thermal reaction product is obtained；
Three, the mixed liquor containing hydro-thermal reaction product is centrifuged 5min in the case where centrifugal speed is 4000r/min, removes supernatant
Liquid obtains hydro-thermal reaction product；
Four, first using deionized water to hydro-thermal reaction product cleaning 3 times obtained in step 3, dehydrated alcohol is reused
To hydro-thermal reaction product cleaning 3 times, is dried at being finally 60 DEG C in temperature, obtain efficient out-phase class fenton catalyst and vulcanize more
Iron.
Embodiment seven: a kind of preparation method of the efficient more iron sulfide of out-phase class fenton catalyst, specifically according to the following steps
It completes:
One, thiocarbamide and 0.56g iron powder are added in 50mL dehydrated alcohol, then the ultrasonic disperse in the case where ultrasonic power is 60W
5min obtains reaction solution；
The molar ratio of iron powder and thiocarbamide described in step 1 is 2.15:1；
The partial size of iron powder described in step 1 is 6 μm；
Two, reaction solution obtained in step 1 is added in hydrothermal reaction kettle, then temperature be 200 DEG C at hydro-thermal reaction
For 24 hours, hydro-thermal reaction product is obtained；
Three, the mixed liquor containing hydro-thermal reaction product is centrifuged 5min in the case where centrifugal speed is 4000r/min, removes supernatant
Liquid obtains hydro-thermal reaction product；
Four, first using deionized water to hydro-thermal reaction product cleaning 3 times obtained in step 3, dehydrated alcohol is reused
To hydro-thermal reaction product cleaning 3 times, is dried at being finally 60 DEG C in temperature, obtain efficient out-phase class fenton catalyst and vulcanize more
Iron.
Claims (10)
1. a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure, it is characterised in that a kind of efficiently different
What the preparation method of the similar more iron sulfide of fenton catalyst core-shell structure was specifically realized by the following steps:
One, thiocarbamide and iron powder are added in dehydrated alcohol, then ultrasonic disperse 3min~10min in the case where ultrasonic power is 60W, are obtained
To reaction solution；
The quality of iron powder described in step 1 and the volume ratio of dehydrated alcohol are (0.3g~1g): 50mL；
The molar ratio of iron powder and thiocarbamide described in step 1 is (0.5~1.5): (0.3~3.5)；
Two, reaction solution obtained in step 1 is added in hydrothermal reaction kettle, then temperature be 180 DEG C~220 DEG C at hydro-thermal
Reaction 20h~for 24 hours, obtain the mixed liquor containing hydro-thermal reaction product；
Three, by the mixed liquor containing hydro-thermal reaction product centrifugal speed be 4000r/min~5000r/min under be centrifuged 4min~
6min removes supernatant, obtains hydro-thermal reaction product；
Four, first using deionized water to hydro-thermal reaction product cleaning 3 times~5 times obtained in step 3, anhydrous second is reused
Alcohol dries at being finally 60 DEG C~80 DEG C in temperature to hydro-thermal reaction product cleaning 3 times~5 times, obtains efficient out-phase class Fenton
The more iron sulfide of catalyst core shell structure.
2. a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure according to claim 1,
It is characterized in that the partial size of iron powder described in step 1 is 4 μm~8 μm.
3. a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure according to claim 1,
It is characterized in that the quality of iron powder described in step 1 and the volume ratio of dehydrated alcohol are (0.3g~0.56g): 50mL.
4. a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure according to claim 1,
It is characterized in that the quality of iron powder described in step 1 and the volume ratio of dehydrated alcohol are (0.56g~1g): 50mL.
5. a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure according to claim 1,
It is characterized in that the molar ratio of iron powder described in step 1 and thiocarbamide is (0.5~1.5): (0.3~2).
6. a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure according to claim 1,
It is characterized in that the molar ratio of iron powder described in step 1 and thiocarbamide is (0.5~1.5): (0.3~0.5).
7. a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure according to claim 1,
It is characterized in that thiocarbamide and iron powder are added in dehydrated alcohol in step 1, then the ultrasonic disperse in the case where ultrasonic power is 60W
3min~5min obtains reaction solution.
8. a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure according to claim 1,
It is characterized in that reaction solution obtained in step 1 is added in hydrothermal reaction kettle in step 2, then temperature be 180 DEG C~
Hydro-thermal reaction 20h~22h at 200 DEG C, obtains the mixed liquor containing hydro-thermal reaction product.
9. a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure according to claim 1,
It is characterized in that reaction solution obtained in step 1 is added in hydrothermal reaction kettle in step 2, then temperature be 200 DEG C~
Hydro-thermal reaction 22h at 220 DEG C~for 24 hours, obtain the mixed liquor containing hydro-thermal reaction product.
10. a kind of preparation method of the more iron sulfide of efficient out-phase class fenton catalyst core-shell structure as described in claim 1,
It is characterized in that in step 4 first using deionized water to hydro-thermal reaction product cleaning 3 times~4 times obtained in step 3, then makes
With dehydrated alcohol to hydro-thermal reaction product cleaning 3 times~4 times, dries, obtain efficiently different at being finally 60 DEG C~70 DEG C in temperature
The similar more iron sulfide of fenton catalyst core-shell structure.
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