CN102029163A - Catalase catalyst analog as well as preparation method and application thereof - Google Patents
Catalase catalyst analog as well as preparation method and application thereof Download PDFInfo
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- CN102029163A CN102029163A CN200910272236XA CN200910272236A CN102029163A CN 102029163 A CN102029163 A CN 102029163A CN 200910272236X A CN200910272236X A CN 200910272236XA CN 200910272236 A CN200910272236 A CN 200910272236A CN 102029163 A CN102029163 A CN 102029163A
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Abstract
The invention provides a catalase catalyst analog which is bismuth ferrite. The preparation method comprises the following steps of: dissolving raw materials of ferric nitrate and bismuth nitrate in ethylene glycol monomethyl ether; adding a complexant and a dispersant to prepare sol and further obtain gel; calcining the obtained gel at high temperature; and postprocessing the obtained gel to obtain BiFeO3 catalase catalyst analog. The catalase catalyst analog has simple preparation process, low cost and stable chemical activity. Because the catalase catalyst analog can be subjected to magnetic recovery, the catalase catalyst can be reused many times, thereby overcoming the defects that the traditional catalase catalyst analog is synthesized in a mode wastes time, labor and money, is unstable and is hard to recover during application and the like. The catalase catalyst analog can serve as the substitute product of the natural catalase, can be used for detecting and analyzing H2O2 content in food samples, biological samples and environment samples and can be used for degrading and mineralizing organic pollutants.
Description
Technical field
The present invention relates to the quasi-enzyme catalytic field, particularly many ferrimagnets ferrous acid bismuth (BiFeO
3) have a catalatic catalytic activity of class, it can be under nearly neutral, room temperature and the no special external energy condition of (referring to ultrasonic, heating using microwave, high light irradiation etc.) effective activation hydrogen peroxide (H
2O
2) produce the hydroxy radical of strong oxidizing property, thus make organic pollutant degradation and mineralising, and the detection and the water that can be applicable to content of hydrogen peroxide pollute processing.
Technical background
Environmental pollution particularly water pollution is one of focal issue of restriction China economic development.Microbial method is modal sewage water treatment method, but owing to contain a large amount of high toxicities, the organic pollution of difficult degradation in many industrial wastewaters, can cause the microorganism can't normal growth even death and losing efficacy when handling this class waste water with traditional microbial method.In recent years, people attempt the optically catalytic TiO 2 technology is used to handle industrial wastewater, but because existing photocatalysis technology exists utilization ratio of optical energy and the low inferior deficiency of quantum efficiency, thereby seriously limited its actual application value.
Classical Fenton reaction (Fe
2+And H
2O
2) can produce a large amount of hydroxy radicals with strong oxidizing property ability, be widely used in the processing of waste water.But also there are some problems in actual applications in the method, only is applicable to pH less than 3 acid system as Fenton reaction, and Fe
2+Be depleting agents, cause the generation of a large amount of iron mud, thereby make that last handling process is an effort again consuming time.And then people's various new improvement technology that begin one's study.Utilize ultraviolet light or direct current to quicken Fe if any the people
3+Be converted into Fe
2+, so that improve the cyclic utilization rate of Fenton reaction, but this light Fenton or Fenton technology still exist in actual application problems such as energy consumption is big, disposal cost height.Zhao advances just to wait people (Ji, H.; Song, W.; Chen, C.; Yuan, H.; Ma, W.; Zhao, J.Environ.Sci.Technol.2007,41,5103-5107.) with organic ligand and Fe
3+Or Fe
2+Coordination generates organic coordination compound, and these organic coordination compounds are immobilized on ion exchange resin.Utilize it that absorbing of visible light (or sunshine) realized Fe
3+To Fe
2+Conversion, but this system still needs to consume external energy, keeps Fe
3+With Fe
2+Circulation, reach effective activation H
2O
2Purpose.
Since the eighties in last century, had and discovered in vital movement with the ferro element to be that the catalase of activated centre atom can activate H under room temperature, no external energy and nearly neutral condition
2O
2Yet, time-consuming, the effort, expensive of these natural catalatic purge processes, and its environment tolerance is very limited, in use and easy inactivation, thereby can not be directly used in waste water control.Be that the substitute that the Environmental Chemistry men of representative are devoted to develop native catalase always is used to activate H with Meunier
2O
2, they have developed a kind of ferrous phthalocyanine complex, can effectively activate H in the mixed solvent of acetonitrile and water under room temperature condition
2O
2, and degraded (Sorokin, the J.L. of realization chlorophenol pollutant; Seris, J.L.; Meunier, B.Science 1995,268,1163-1165.).But if make water make solvent separately, the degraded of chlorophenols will obviously be suppressed, thereby limit this system in the actual environment Application of Sewage.People such as American scholar Collins have developed a kind of huge ring organic coordination compound of tetramine base (commodity are called Fe-TAML) of iron, and this catalyst can activate H efficiently under the condition of the aqueous solution, nearly neutral pH, room temperature and no external energy
2O
2, and can be with the rapid mineralising of organic pollution (Collins, T.J.Acc.Chem.Res.2002,35,782-790 and Gupta, S.S.; Stadler, M.; Noser, C.A.; Ghosh, A.; Steinhoff, B.; Lenoir, D.; Horwitz, C.P.; Schramm, K.; Collins, T.J.Science 2002,296,326-328.).Though this type of catalyst shows excellent performance aspect catalytic activity, but its preparation process complexity, cost be very high, be difficult to recycle, and this catalyst is originally as organic compound, the hydroxy radical oxidation that is produced in can be in the process of degraded and inactivation by system, even the dissociation of ligand reaction takes place and lost efficacy (Polshin, V. under lower pH condition; Popescu, D.L.; Fischer, A.; Chanda, A.; Homer, D.C.; Beach, E.S.; Henry, J.; Qian, Y.L.; Horwitz, C.P.; Lente, G.; Fabian, I.; Munck, E.; Bominaar, E.L.; Ryabov, A.D.; Collins, T.J.J.Am.Chem.Soc.2008,130,4497-4506.).Therefore, develop the class hydrogen peroxide enzyme catalyst that the gentle anti-hydroxy radical ability of a kind of service condition is strong, the preparation method simple, be easy to recycle, have crucial economy and social value aspect industry and the sanitary wastewater improvement.
Summary of the invention
Task of the present invention provides a kind catalase catalyst, it is very simple and reliable to make it have preparation process, but raw material is cheap and easy to get, the stable magnetic recovery of chemism, can be at the aqueous solution, room temperature, near neutral and do not introduce under any special external energy condition of (referring to ultrasonic, heating using microwave, high light irradiation etc.) effectively activation H
2O
2Produce the characteristics such as hydroxy radical of strong oxidizing property, with overcome prior art when the synthetic class hydrogen peroxide enzyme catalyst hydrogen peroxide catalyzed dose of effort, time-consuming, expensive and native catalase or existing class in use instability, be difficult to deficiency such as recovery.
Realize that technical scheme of the present invention is:
This kind catalase catalyst provided by the invention is the ferrous acid bismuth, and what use when the ferrous acid bismuth is used as class hydrogen peroxide enzyme catalyst is ferrous acid bismuth meal end.
The present invention activates H with the ferrous acid bismuth as class catalase catalyst
2O
2,, thereby realize H in food, biology or the environmental sample in order to the hydroxy radical oxidizing ferment substrate of generation strong oxidizing property
2O
2Content detection is analyzed, and described zymolyte is benzoic acid, cumarin, P-hydroxybenzoic acid, aniline, o-phenylenediamine or 3,3,5,5-tetramethyl benzidine etc.
The present invention with the ferrous acid bismuth as class hydrogen peroxide enzyme activation H
2O
2Realize oxidative degradation and mineralising with the hydroxy radical that produces strong oxidizing property to environmental organic pollutant, said herein environmental organic pollutant comprises: class organic pollutions such as organic dyestuff, endocrine interferon, antibiotic and machine chloro pesticide, and wherein organic dyestuff comprises materials such as rhodamine, methyl orange, malachite green and methylene blue; The endocrine interferon comprises materials such as nonyl phenol, bisphenol-A and estrone; Antibiotic comprises materials such as tetracycline, terramycin and chloramphenicol; Organo-chlorine pesticide comprises materials such as hexachloro-benzene, toxaphene and DDT.
Class catalase Preparation of catalysts method provided by the invention may further comprise the steps:
(1) presses Fe (NO
3)
39H
2O and Bi (NO
3)
35H
2The mol ratio of O is that 1: 1 ratio is dissolved in it in EGME solution, with EGME solution and used Fe (NO
3)
39H
2The mol ratio of the iron atom among the O is 8～160: 1, is preferably 10～30: 1, and more preferably 20: 1 ratio is determined the consumption of EGME solution, is to stir 5～60min under 25～60 ℃ of conditions in temperature, with 0.1～6mol L
-1HNO
3The pH to 4 of regulator solution～7;
(2) in the solution that step (1) obtains, add complexant, with complexant and the used Fe (NO of step (1)
3)
39H
2The mol ratio of the iron atom among the O is 0.1～5: 1, is preferably 1～3: 1, and more preferably 1: 1 ratio is determined the consumption of complexant, adds dispersant again, with dispersant and the used Fe (NO of step (1)
3)
39H
2The mol ratio of iron atom is 5～100: 1 among the O, be preferably 10～20: 1, more preferably 15: 1 ratio is determined the consumption of dispersant, stirs 10～100min and obtain pitchy colloidal sol under temperature is 25～150 ℃, keeps 5～40h to obtain gel then under 100 ℃ of conditions;
(3) the gel roasting 5～50min on electric furnace that step (2) is obtained transfers to then in the Muffle furnace and to be 400～600 ℃ in temperature and to keep obtaining in 2～10 hours graininess class catalase catalyst B iFeO down
3
With the prepared graininess class of step (3) catalase catalyst B iFeO
3Obtain Powdered class catalase catalyst B iFeO through grinding
3, can be during concrete operations with the prepared graininess BiFeO of step (3)
3Class hydrogen peroxide enzyme catalyst places mortar, promptly obtains Powdered BiFeO through repeatedly grinding
3Class hydrogen peroxide enzyme catalyst.
The complexant that adds in the above-mentioned steps (2) is any one or two kinds in oxalic acid, ethylenediamine tetra-acetic acid (EDTA), nitrilotriacetic acid (NTA), ethylenediamine, bipyridyl and the Phen, when the complexant that adds was two kinds, the ratio between them was arbitrarily.The dispersant that adds in the above-mentioned steps (2) is a kind of in ethylene glycol, polyethylene glycol and the glycerine or two kinds, and when the dispersant that adds was two kinds, the ratio between them was arbitrarily.
The powdery product that has confirmed the present invention's preparation by Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction characterization methods such as (XRD) is BiFeO really
3, seeing Fig. 1 and Fig. 2, Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the pulverulent solids product of the inventive method preparation for Fourier transform infrared spectroscopy (FT-IR) figure of the powdery product of the inventive method preparation, Fig. 2.As can be seen from Figure 1, the prepared product of the present invention is at 553 and 443 centimetres
-1The place has two tangible infrared absorption peaks, represents the stretching vibration of Fe-O and the flexural vibrations of O-Fe-O respectively.As can be seen from Figure 2, the prepared product of the present invention has typical perovskite structure, does not have the generation of iron oxide and bismuth oxide dephasign, its result and BiFeO
3Standard x RD spectrogram (JCPDS File No.20-169) unanimity proves that the product that the present invention makes is BiFeO really
3
Record its intensity of magnetization-magnetic field intensity (M-H) curve by magnetometer, obtaining its saturation magnetization is 2.2 electromagnetic unit/gram (emu g
-1); See Fig. 3, Fig. 3 is the magnetic hysteresis regression curve collection of illustrative plates of the powdery product of the inventive method preparation, and as can be seen from Figure 3, its saturation magnetization of the prepared product of the present invention is 2.2emu g
-1, after externally-applied magnetic field removes, its intensity of magnetization will be classified as zero, illustrate that the prepared product of the present invention has superparamagnetism.
BiFeO of the present invention
3The class catalase can replace native catalase (as the horseradish catalase) to be used for H
2O
2Detection.Particularly, BiFeO of the present invention
3Class catalase powder can effectively activate H
2O
2Produce the hydroxy radical of strong oxidizing property, and can be fast with multiple colourless hydrogen peroxide zymolyte (as 3,3,5, the 5-tetramethyl benzidine, o-phenylenediamine, aniline etc.) oxidation generates the product with different colours, or not fluorescent zymolyte (as cumarin, bipyridyl, benzoic acid etc.) oxidation is generated fluorescence-causing substance.Utilize the changing value and the H of these substrates absorbance or fluorescence intensity in the fermentoid oxidation reaction process
2O
2There is linear relationship between the concentration, can be used for H in food, environment and the biological sample
2O
2The check and analysis of content.
Because BiFeO of the present invention
3The class catalase can be in room temperature, near neutral and do not introduce under any special external energy situation of (referring to ultrasonic, heating using microwave, high light irradiation etc.) effectively activation H
2O
2Produce the hydroxy radical of strong oxidizing property, thereby can be fast and degraded even the various toxic organic pollutants of mineralising effectively.These toxic pollutants comprise the organic dyestuff (as rhodamine, methyl orange, methylene blue etc.) of various bio-refractories, endocrine interferon (as nonyl phenol, bisphenol-A, estrone etc.) and organo-chlorine pesticide (as hexachloro-benzene, toxaphene, DDT etc.), antibiotic (as tetracycline, terramycin, chloramphenicol etc.) etc.
BiFeO provided by the invention
3Class hydrogen peroxide enzyme catalyst can and not introduced under any special external energy condition of (referring to ultrasonic, heating using microwave, high light irradiation etc.) effectively activation H in room temperature, nearly neutral pH
2O
2Produce the hydroxy radical of strong oxidizing property, the common zymolyte of hydroxy radical oxidation that can this strong oxidizing property is used for H
2O
2The check and analysis of content also can be widely used in the degraded and the mineralising of organic pollution in the environment.
BiFeO provided by the invention
3Class hydrogen peroxide enzyme catalyst can be a raw material with commercially available ferric nitrate and bismuth nitrate directly, and preparation technology is simple, does not have harsh synthesis condition requirement, and is with low cost.Reuse but synthetic catalyst is stable, nontoxic, application pH scope is wide, pollutant is had high clearance magnetic recovery.These advantages have guaranteed that such hydrogen peroxide enzyme catalyst can remove and the mineralising organic pollution efficiently, thus the environmental pollution of effectively administering these pollutants and being caused.
As everyone knows, native catalase is at catalytic activation H
2O
2The aspect has best catalytic activity, and the class hydrogen peroxide enzyme catalyst that the present invention makes can reach the catalytic activity identical with native catalase, can be at the aqueous solution, room temperature, near neutral and do not introduce under any special external energy condition of (referring to ultrasonic, heating using microwave, high light irradiation etc.) effectively activation H
2O
2Produce the hydroxy radical of strong oxidizing property, thus degraded and the various organic pollutions of mineralising fast.Therefore, BiFeO provided by the invention
3Class hydrogen peroxide enzyme catalyst is in the waste water control industry value that is widely used, and in addition, as the substitute products of native catalase, this type of enzyme catalyst also can be used for H in food, biology and the environmental sample
2O
2The check and analysis of content.
Description of drawings
Fig. 1 is the FT-IR collection of illustrative plates of the powdery product of the inventive method preparation, and its ordinate is a transmitance, abscissa be wave number (centimetre
-1).As can be seen from Figure 1, the prepared product of the present invention is 553 and 443cm
-1Have two tangible infrared absorption peaks, represent the stretching vibration of Fe-O and the flexural vibrations of O-Fe-O respectively.
Fig. 2 is the XRD figure spectrum of the powdery product of the inventive method preparation, and its ordinate is a diffracted intensity, and abscissa is angle of diffraction (degree).As can be seen from Figure 2, the prepared product of the present invention has typical perovskite structure, does not have the generation of iron oxide and bismuth oxide dephasign, its result and BiFeO
3Standard x RD spectrogram (JCPDS File No.20-169) unanimity proves that the product that the present invention synthesizes is BiFeO really
3
Fig. 3 is the magnetic hysteresis regression curve collection of illustrative plates of the powdery product of the inventive method preparation, and its ordinate is specific magnetization (electromagnetic unit/gram), and abscissa is magnetic field intensity (oersted).As can be seen from Figure 3, its saturation magnetization of the prepared product of the present invention is 2.2emu g
-1, after externally-applied magnetic field removes, its intensity of magnetization will be classified as zero, illustrate that the prepared product of the present invention has superparamagnetism.
Fig. 4 is BiFeO of the present invention
3Class hydrogen peroxide enzyme activation H
2O
2Oxybenzene formic acid detects H
2O
2The fluorescence spectrum figure of content, ordinate are different H
2O
2The fluorescence intensity of the fluorescence-causing substance that is generated under the concentration; Abscissa is wavelength (nanometer), and (interior illustration is for measuring H
2O
2The calibration curve collection of illustrative plates, ordinate is the fluorescence intensity of the fluorescence-causing substance that generates; Abscissa is H
2O
2Concentration (every liter of micromole)).This figure illustrates BiFeO of the present invention
3Class hydrogen peroxide enzyme catalyst can effectively activate H
2O
2, can be advantageously used in low concentration H
2O
2The detection of content.
Fig. 5 is BiFeO of the present invention
3Class hydrogen peroxide enzyme activation H
2O
2The ultraviolet-visible spectrogram that fades of degraded rhodamine, ordinate is an absorbance, and abscissa is wavelength (nanometer), and (interior illustration is different system oxidative degradation organic dyestuff rhodamines, the independent H of curve 1 representative
2O
2The degraded rhodamine, the independent BiFeO of curve 2 representatives
3The degraded rhodamine, curve 3 is represented BiFeO
3-H
2O
2System degraded rhodamine, ordinate are the dyestuff residual concentration and the ratio of its initial concentration; Abscissa is reaction time (branch)).This figure illustrates the BiFeO that the present invention makes
3Class hydrogen peroxide enzyme catalyst can effectively activate H
2O
2, can be advantageously used in the rhodamine degraded of organic pollution in the environment.
The specific embodiment
Embodiment 1: use BiFeO of the present invention
3Class catalase catalyst activation H
2O
2Come Oxybenzene formic acid to be used for indirect determination H
2O
2Content
With the 5mg BiFeO that makes
3Pulverulent solids joins in the 10mL distilled water, and ultrasonic dispersion 1min is with isopyknic 1.0mmol L
-1The benzoic acid aqueous solution, add H again
2O
2(ultimate density is 2.0 * 10
-8～2.0 * 10
-5Mol L
-1).At this moment, the substrate benzoic acid can be generated the hyperfluorescence material by catalytic oxidation, and the maximum emission wavelength of its fluorescence-causing substance is 405nm.Behind reaction 15min, it is centrifugal to get the 2mL reactant liquor rapidly, and the supernatant after centrifugal is taken out, and measures the fluorescence intensity of supernatant at the 405nm place on sepectrophotofluorometer.This BiFeO
3Class catalase catalyst system and catalyzing is at the changing value and the H of 405nm place fluorescence intensity
2O
2Concentration is 2.0 * 10
-8～2.0 * 10
-5Mol L
-1Scope internal memory linear relationship is seen Fig. 4.In addition, we choose native catalase (is example with the horseradish catalase) as catalyst replacement BiFeO
3The class catalase repeats this experiment, and the result shows changing value and the H of horseradish catalase catalyst system and catalyzing in 405nm place fluorescence intensity
2O
2Concentration is 2.0 * 10
-8～2.0 * 10
-5Mol L
-1Also deposit linear relationship in the scope.The class hydrogen peroxide enzyme catalyst that this control experiment explanation the present invention makes can reach the catalytic activity identical with native catalase.Utilize BiFeO provided by the invention
3Class hydrogen peroxide enzyme catalyst can effectively activate H
2O
2Excellent properties, can be advantageously used in low concentration H in the actual samples such as food, environment and biology
2O
2The check and analysis of content.
Embodiment 2: use BiFeO of the present invention
3Class catalase catalyst activation H
2O
2Come the oxidation cumarin to be used for indirect determination H
2O
2Content
With the 5mg BiFeO that makes
3Pulverulent solids joins in the 10mL distilled water, and ultrasonic dispersion 1min is with isopyknic 0.5mmol L
-1The cumarin aqueous solution, add H again
2O
2(ultimate density is 6.0 * 10
-8～5.0 * 10
-5Mol L
-1).At this moment, the substrate cumarin can be generated hyperfluorescence material umbelliferone by catalytic oxidation, and the maximum emission wavelength of its fluorescence-causing substance is 456nm.Behind reaction 10min, it is centrifugal to get the 2mL reactant liquor rapidly, and the supernatant after centrifugal is taken out, and measures the fluorescence intensity of supernatant at the 456nm place on sepectrophotofluorometer.This BiFeO
3Class catalase catalyst system and catalyzing is at the changing value and the H of 456nm place fluorescence intensity
2O
2Concentration is 6.0 * 10
-8～5.0 * 10
-5Mol L
-1Scope internal memory linear relationship.Utilize BiFeO of the present invention
3Class hydrogen peroxide enzyme catalyst can effectively activate H
2O
2Excellent properties, can be advantageously used in low concentration H in the actual samples such as food, environment and biology
2O
2The check and analysis of content.
Embodiment 3: use BiFeO
3Class catalase catalyst activation H
2O
2Come oxidation 3,3,5, the 5-tetramethyl benzidine is used for indirect determination H
2O
2Content
With the 5mg BiFeO that makes
3Pulverulent solids joins in the 5mL distilled water, and ultrasonic dispersion 1min is with isopyknic 1mmol L
-13,3,5,5-tetramethyl benzidine aqueous solution adds H again
2O
2(ultimate density is 5.0 * 10
-7～2.0 * 10
-4Mol L
-1).At this moment, substrate 3,3,5, the 5-tetramethyl benzidine can be generated blue product by catalytic oxidation, and the maximum absorption wavelength of its blue product is 650nm.Behind reaction 15min, it is centrifugal to get the 2mL reactant liquor rapidly, and the supernatant after centrifugal is taken out, and measures the absorbance of supernatant at the 650nm place on ultraviolet-visible spectrophotometer.This BiFeO
3Class catalase catalyst system and catalyzing is at the changing value and the H of 650nm place absorbance
2O
2Concentration is 5.0 * 10
-72.0 * 10
-4Mol L
-1Scope internal memory linear relationship.Utilize BiFeO of the present invention
3Class hydrogen peroxide enzyme catalyst can effectively activate H
2O
2Excellent properties, can be advantageously used in low concentration H in the actual samples such as food, environment and biology
2O
2The check and analysis of content.
Embodiment 4: use BiFeO of the present invention
3Class catalase catalyst activation H
2O
2Come the oxidation o-phenylenediamine to be used for indirect determination H
2O
2Content
With the 5mg BiFeO that makes
3Pulverulent solids joins in the 5mL distilled water, and ultrasonic dispersion 1min is with isopyknic 2.0mmol L
-1The o-phenylenediamine aqueous solution, add H again
2O
2(ultimate density is 8.0 * 10
-7～4.0 * 10
-4Mol L
-1).At this moment, the substrate o-phenylenediamine can be generated orange product by catalytic oxidation, and the maximum absorption wavelength of its orange product is 410nm.Behind reaction 15min, it is centrifugal to get the 2mL reactant liquor rapidly, and the supernatant after centrifugal is taken out, and measures the absorbance of supernatant at the 410nm place on ultraviolet-visible spectrophotometer.This BiFeO
3Class catalase catalyst system and catalyzing is at the changing value and the H of 410nm place absorbance
2O
2Concentration is 8.0 * 10
-7～4.0 * 10
-4Mol L
-1Scope internal memory linear relationship.Utilize BiFeO of the present invention
3Class hydrogen peroxide enzyme catalyst can effectively activate H
2O
2Excellent properties, can be advantageously used in low concentration H in the actual samples such as food, environment and biology
2O
2The check and analysis of content.
Embodiment 5: use BiFeO of the present invention
3Class catalase catalyst activation H
2O
2Come the oxidative degradation rhodamine
In 50mL concentration is 20 μ mol L
-1The rhodamine aqueous solution in add 25mg BiFeO
3Pulverulent solids, ultrasonic dispersion 1min, dark condition stir 30min down and reach the adsorption/desorption balance.Adding 0.5mL concentration then is 1.0mol L
-1H
2O
2Solution, it is centrifugal to get the 2mL reactant liquor every 15min, and the supernatant after centrifugal is taken out, and measures the absorbance (see figure 5) of its supernatant at the 554nm place on ultraviolet-visible spectrophotometer.Find that this type of hydrogen peroxide enzyme catalyst fades the whole oxidations of organic dyestuff rhodamine within 1.5h, and the further mineralising of energy, behind reaction 2h, its total organic carbon (TOC) has descended 90%.The BiFeO that utilizes the present invention to make
3Class hydrogen peroxide enzyme catalyst can effectively activate H
2O
2Excellent properties, can be advantageously used in the degraded and the mineralising of organic pollution in the environment.
Embodiment 6: use BiFeO of the present invention
3Class catalase catalyst activation H
2O
2Come oxidative degradation DDT
In 50mL concentration is 100 μ mol L
-1The DDT aqueous solution in add 25mg BiFeO
3Pulverulent solids, ultrasonic dispersion 1min, dark condition stir 30min down and reach the adsorption/desorption balance.Adding 1.0mL concentration then is 1.0mol L
-1H
2O
2Solution, it is centrifugal to get the 2mL reactant liquor every 20min, and the supernatant after centrifugal is taken out, and measures its supernatant concentration under HPLC.Find that this type of hydrogen peroxide enzyme catalyst effectively removes DDT within 5h, and further mineralising, behind reaction 8h, its total organic carbon (TOC) has descended 73%.The BiFeO that utilizes the present invention to make
3Class hydrogen peroxide enzyme catalyst can effectively activate H
2O
2Excellent properties, can be advantageously used in the degraded and the mineralising of organic pollution in the environment.
Embodiment 7: use BiFeO
3Class catalase catalyst activation H
2O
2Come the oxidative degradation bisphenol-A
In 50mL concentration is 1.0mmol L
-1The bisphenol-A aqueous solution in add 50mg BiFeO
3Pulverulent solids, ultrasonic dispersion 1min, dark condition stir 30min down and reach the adsorption/desorption balance.Adding 1.0mL concentration then is 2.0mol L
-1H
2O
2Solution, it is centrifugal to get the 2mL reactant liquor every 20min, and the supernatant after centrifugal is taken out, and measures its supernatant concentration under HPLC.Find that this type of hydrogen peroxide enzyme catalyst effectively removes bisphenol-A within 3h, and further mineralising, behind reaction 6h, its total organic carbon amount (TOC) has descended 76%.The BiFeO that utilizes the present invention to make
3Class hydrogen peroxide enzyme catalyst can effectively activate H
2O
2Excellent properties, can be advantageously used in the degraded and the mineralising of organic pollution in the environment.
Application examples 8: use BiFeO
3Class catalase catalyst activation H
2O
2Come the oxidative degradation tetracycline
In 50mL concentration is 0.8mmol L
-1The tetracycline aqueous solution in add 50mg BiFeO
3Pulverulent solids, ultrasonic dispersion 2min, dark condition stir 30min down and reach the adsorption/desorption balance.Adding 1.0mL concentration then is 2.0mol L
-1H
2O
2Solution, it is centrifugal to get the 2mL reactant liquor every 30min, and the supernatant after centrifugal is taken out, and measures its supernatant concentration under HPLC.Find that this type of hydrogen peroxide enzyme catalyst effectively removes tetracycline within 4h, and further mineralising, behind reaction 6h, its total organic carbon (TOC) has descended 70%.The BiFeO that utilizes the present invention to make
3Class hydrogen peroxide enzyme catalyst can effectively activate H
2O
2Excellent properties, can be advantageously used in the degraded and the mineralising of organic pollution in the environment.
Claims (10)
1. a kind catalase catalyst is characterized in that, such hydrogen peroxide enzyme catalyst is the ferrous acid bismuth.
2. the ferrous acid bismuth is as the application of class hydrogen peroxide enzyme catalyst.
3. the ferrous acid bismuth is activating H as the class catalase
2O
2Realize H in food, biology or the environmental sample with the hydroxy radical oxidizing ferment substrate that produces strong oxidizing property
2O
2Application during content detection is analyzed.
4. ferrous acid bismuth according to claim 3 is activating H as the class catalase
2O
2Realize H in food, biology or the environmental sample with the hydroxy radical oxidizing ferment substrate that produces strong oxidizing property
2O
2Application during content detection is analyzed is characterized in that described zymolyte is benzoic acid, cumarin, P-hydroxybenzoic acid, aniline, o-phenylenediamine or 3,3,5, the 5-tetramethyl benzidine.
5. the ferrous acid bismuth is activating H as the class catalase
2O
2Realize the oxidative degradation of environmental organic pollutant and the application in the mineralising with the hydroxy radical that produces strong oxidizing property.
6. ferrous acid bismuth according to claim 5 is activating H as the class catalase
2O
2Realize the oxidative degradation of environmental organic pollutant and the application in the mineralising be is characterized in that said environmental organic pollutant is organic dyestuff, endocrine interferon, antibiotic or organo-chlorine pesticide with the hydroxy radical that produces strong oxidizing property.
7. ferrous acid bismuth according to claim 6 is activating H as the class catalase
2O
2Realize the oxidative degradation of environmental organic pollutant and the application in the mineralising be is characterized in that described organic dyestuff is rhodamine, methyl orange, malachite green or methylene blue with the hydroxy radical that produces strong oxidizing property; Described endocrine interferon is nonyl phenol, bisphenol-A or estrone; Described antibiotic is tetracycline, terramycin or chloramphenicol; Described machine chloro pesticide is hexachloro-benzene, toxaphene or DDT.
8. a kind catalase Preparation of catalysts method may further comprise the steps:
(1) presses Fe (NO
3)
39H
2O and Bi (NO
3)
35H
2The mol ratio of O is that 1: 1 ratio is dissolved in it in EGME solution, with EGME solution and used Fe (NO
3)
39H
2The mol ratio of the iron atom among the O is 8～160: 1, is preferably 10～30: 1, and more preferably 20: 1 ratio is determined the consumption of EGME solution, is to stir 5～60min under 25～60 ℃ of conditions in temperature, with 0.1～6mol L
-1HNO
3The pH to 4 of regulator solution～7;
(2) in the solution that step (1) obtains, add complexant, with complexant and the used Fe (NO of step (1)
3)
39H
2The mol ratio of the iron atom among the O is 0.1～5: 1, is preferably 1～3: 1, and more preferably 1: 1 ratio is determined the consumption of complexant, adds dispersant again, with dispersant and the used Fe (NO of step (1)
3)
39H
2The mol ratio of iron atom is 5～100: 1 among the O, be preferably 10～20: 1, more preferably 15: 1 ratio is determined the consumption of dispersant, stirs 10～100min and obtain pitchy colloidal sol under temperature is 25～150 ℃, keeps 5～40h to obtain gel then under 100 ℃ of conditions;
(3) the gel roasting 5～50min on electric furnace that step (2) is obtained transfers to then in the Muffle furnace and to be 400～600 ℃ in temperature and to keep 2～10h to obtain graininess class catalase catalyst B iFeO down
3
9. class catalase Preparation of catalysts method according to claim 5, it is characterized in that, the complexant that adds in the step (2) is any one or two kinds in oxalic acid, ethylenediamine tetra-acetic acid (EDTA), nitrilotriacetic acid (NTA), ethylenediamine, bipyridyl and the Phen, when the complexant that adds was two kinds, the ratio between them was arbitrarily.
10. class catalase Preparation of catalysts method according to claim 5, it is characterized in that, the dispersant that adds in the step (2) is a kind of in ethylene glycol, polyethylene glycol and the glycerine or two kinds, and when the dispersant that adds was two kinds, the ratio between them was arbitrarily.
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