CN101518742B - Iron composition visible light photocatalyst composed of double-coordination functional group ligands and iron ions and preparation method and purpose thereof - Google Patents
Iron composition visible light photocatalyst composed of double-coordination functional group ligands and iron ions and preparation method and purpose thereof Download PDFInfo
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- CN101518742B CN101518742B CN2009100816748A CN200910081674A CN101518742B CN 101518742 B CN101518742 B CN 101518742B CN 2009100816748 A CN2009100816748 A CN 2009100816748A CN 200910081674 A CN200910081674 A CN 200910081674A CN 101518742 B CN101518742 B CN 101518742B
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Abstract
The invention relates to an iron composition visible light photocatalyst composed of double-coordination functional group ligands and iron ions and the preparation method and the purpose thereof. The iron composition visible light photocatalyst formed by ligand molecules with double-coordination functional groups and Fe<2+> ions or Fe<3+> ions is obtained by mixing a solution in which double-coordination functional group ligand molecules which are synchronously provided with nitrogen atom terminals and carboxyl terminals are dissolved and a Fe<2+> ion saline solution or Fe<3+> ion saline solution, wherein an electron shared by Fe<2+> ions and nitrogen atoms of the ligands forms a coordination bond, and the mol ratio of the ligand molecules to the Fe<2+> ions is 3:1; an electron shared by the Fe<3+> ions and carbonyl groups at the carbonyl group ends of the ligands forms a coordination bond, and the mol ratio of the ligand molecules to the Fe<3+> ions is 2:1. The iron composition visible light photocatalyst can effectively degrade and mineralize toxic and organic pollutants in water through activating oxygen in air, which is dissolved in water under the excitation of visible light.
Description
Technical field
The invention belongs to the visible-light photocatalyst field, particularly two coordination functional group parts and Fe
2+And Fe
3+Iron complex visible-light photocatalyst that ion makes up respectively and above-mentioned Preparation of catalysts method; And the airborne oxygen that above-mentioned catalyst is applied to dissolve in the activated water, thereby the toxic organic pollutant effectively in degraded and the mineralising water body.
Background technology
The Fenton reaction is a kind of advanced oxidization method, and its mechanism of action is Fe
2+Ion and H
2O
2Hybrid reaction under normal temperature, normal pressure generates hydroxyl radical free radical (OH) and Fe
3+Ion, the Fenton reaction is usually used in the polymerisation of free radical initiation, the hydroxylating and the water body purification reaction of aromatic, particularly aspect the advanced treating of waste water, with its organic pollution of eliminating chemical oxygen consumption (COC) (COD), colourity and bio-refractory efficiently, fast is characteristics, becomes the irreplaceable method of current other purification techniques.Wherein hydroxyl radical free radical has very high oxidizing potential (E=+2.8V (Vs NHE)), its can and most organic matter generation electrophilic addition reaction, substitution reaction and electron transfer reaction and oxidation operation is degraded.This is that the Fenton reaction is found to have obtained the lasting fundamental cause of using since the century.But, used a large amount of Fe in the reaction because this reaction belongs to dose response
2+Ion (and H
2O
2Deng molar dose), have a large amount of Fe in the system after feasible the processing
3+And the complex compound of coloured organic decomposition product, be difficult to eliminate.In addition, reaction generally need be carried out in less than 3 acid medium at pH, and H in the course of reaction
2O
2Utilization rate not high yet, limited the extensive use of this method.A great improvement---changes the Fenton oxidation reaction of dosage into the Fenton reaction of catalysis---can significantly reduce Fe in the reaction system
2+Content (from～10
-2M is reduced to～and 10
-5The M magnitude), therefore, needn't carry out precipitation process to the molysite that adds again.But wherein influence one step of key of catalytic cycle, i.e. Fe
3++ H
2O
2→ Fe
2++ OOH speed only is 0.001M
-1s
-1And main reaction Fe
2++ H
2O
2→ Fe
3++ OH+
-OH (76M
-1s
-1) compare the serious speed that reduces catalytic reaction, but also reduced H
2O
2Be decomposed into the efficient of OH.After this developed light and helped/the Fenton technology, this technology has greatly improved the oxidation efficiency of Fenton reagent.This type of document has " Journal of Molecular Catalysis magazine " to roll up the 77th page article " light of radiation of visible light helps/the Fenton degradation of dye " (Wu, K. in 1999 144; Xie, Y.; Zhao, J.; Hidaka, H.Photo-Fenton degradation of adye under visible light irradiaion, J.Mol.Catal.) and article " photochemistry of dyestuff is faded in the presence of iron ion and hydrogen peroxide " (Herrera, the F. of the 3145th page of " environmental science and the technology " of American Chemical Society 1999 33 volume; Kiwi, J.; Lopez, A.; Nadtochenko, V.Photochemicaldecoloration of Remazol Brilliant Blue and Uniblue A in the presence of Fe
3+AndH
2O
2, Environ.Sci.Technol.).Its basic principle is to utilize light-induced reaction with Fe (OH)
2+Fast restore is Fe
2+Thereby, quicken the main catalytic reaction rate, solved the speed problem of rate determining step.But, therefore iron ion must also just can carry out in acid medium as the main body of catalytic cycle because system remains freely, secondly, except to the coloured dyestuff contaminant, must utilize the UV-irradiation could be effective to general organic pollutant degradation.This is to the serious restriction of Yan Youqi based on utilizing green energy resource such as solar energy, because ultraviolet light only accounts for about 3%, the spectrum of the overwhelming majority is in the visible region.For this reason, significant improvement---improvement that the catalysis form of iron is carried out---becomes the research forward position of the Fenton reaction of current catalysis, and at first " science " magazine nineteen ninety-five of the U.S. has been delivered B, Meunier etc. based on water-soluble sulfonic acid FePC catalysis H
2O
2Oxidation system (A.Sorokin, J.L.S é ris, B.Meunier, Science1995,268,1163～1166),, this system catalytic activity is just arranged as axial ligand although still needing volumetric concentration to be about 30% acetonitrile, but it has shown very high catalyzed conversion number (TON～10 in wide pH scope
2), its basic principle is that nitrogen 4 coordination structures of analog cytochrome P-450 make the high activity that this catalyst has.Thereafter, T.J.Collins etc. have developed the iron catalyst of another kind of non-heme part TAML, are published in (S.S.Gupta on " science " magazine of the U.S., M.Stadler, C.A.Noser, A.Ghosh, B.Steinhoff, D.Lenoir, C.P.Horwitz, K.-W.Schramm, T.J.Collins, Science 2002,296,326-328), this catalyst does not need acetonitrile to make axial ligand, has higher turn over number and transformation frequency (TON/s).But these catalyst system and catalyzings all can not activate molecular oxygen, and inevitably always is accompanied by the oxidative degradation of catalyst itself.Simple nitrogen is the rigid structure of part, on the one hand as center Fe activation H
2O
2Platform provide powerful support for the catalytic cycle of iron valence state, particularly when high valence iron turns back to the catalysis initial state, have the obviously higher oxidation-reduction potential (E of specific ionization
Fe3+/Fe2+High), oxidation H smoothly
2O
2, self be reduced to iron at a low price.Himself also participates in reaction as electron donor but then, becomes the radical cation of corproporphyrin ring, and the result is that rigid structure often causes and directly disassembles epoxidation, and the center iron of making forever loses corresponding coordination structure, thus inactivation.And the more general oxygenase of living things system mostly is non-heme structure (non-heme); except the nitrogen ligand of two histidines; it mainly is carboxyl coordination; flexible carboxyl coordination structure can be left away neatly during near catalytic active center or evades strong active group attack at substrate; protect self to be immune against attacks, keep the long-life.And such action is the alleviation H with coexistence in the biology enzyme system
2O
2, the OOH free radical antioxygen coenzyme mechanism (reversible oxidation of lipid quinone) carry out.At present, such chemical synthesis system also fails to synthesize.After this, other N that also has development such as U.S. scientist Lawrence Que
3, N
4And N
5The iron catalyst of structure all has extraordinary activation H
2O
2Even the catalytic capability of molecular oxygen, but reaction mostly needs reducing agent or carries out in organic solvent.Can infer that the oxidant of using this economy of molecular oxygen still all will have minimum danger to the oxidation Decomposition of catalyst to ecological environment, will become a kind of green oxidation technology of milder.
But vital problem does not still solve, and how to seek suitable organic ligand regulation and control and generates the reaction of Fe (II) complex compound by the reduction of Fe (III) complex compound, guarantees that promptly part can catch Fe fast
3+The destruction that can evade OH radical pair part to complex state again.In brief, one can make Fe
3+By complexing and fast restore are Fe fast
2+Fast free mechanism be the even more ideal pattern of present Fenton system.In addition, for keeping the stable of catalyst, the selection of part should guarantee that nitrogen is the rigid structure of part, provides powerful support for the catalytic cycle of iron valence state as the platform of center Fe (II) activation; Take into account Fe (III) and its coordination structure again and can evade strong active group attack, avoid catalysqt deactivation, the present invention just is based on such principle design.
Summary of the invention
The object of the present invention is to provide two coordination functional group parts and Fe
2+And Fe
3+The iron complex visible-light photocatalyst that ion makes up respectively.
A further object of the present invention is to provide two coordination functional group parts and Fe
2+And Fe
3+The preparation method of the iron complex visible-light photocatalyst that ion makes up respectively.
An also purpose of the present invention is two coordination functional group parts and Fe
2+And Fe
3+The iron complex visible-light photocatalyst that ion makes up respectively is applied to the oxidative degradation aspect of toxic organic pollutant, under radiation of visible light and in the aqueous solution of wide pH (pH4～8) scope, above-mentioned photochemical catalyst can utilize the airborne oxygen that dissolves in the water to generate high price (IV) the ferriferous oxide kind of high reaction activity sustainedly and stably, the airborne oxygen that under the exciting of visible light, dissolves in the activated water effectively degrade with the mineralising water body in toxic organic pollutant.
Core of the present invention is two coordination functional group parts and Fe
2+And Fe
3+The iron complex visible-light photocatalyst that ion makes up respectively is two coordination functional group parts and Fe when what use
2+During iron complex visible-light photocatalyst that ion makes up, Fe
2+The airborne oxygen that dissolves in the iron ion complex activated water generates high price (IV) iron complex active specy, and the high price of generation (IV) iron complex active specy self is reduced to Fe in the process of oxidative degradation and mineralising organic pollutant molecule
3+The iron ion complex promptly is two coordination functional group parts and Fe
3+The iron complex that ion makes up; When what use is two coordination functional group parts and Fe
3+During iron complex visible-light photocatalyst that ion makes up, this photochemical catalyst can quicken to influence one step of key (even the Fe of catalytic cycle
3+Quick complexing of quilt and fast restore are to Fe
2+), thereby the carrying out that quickens whole catalytic cycle.N atom end and Fe with ligand molecular of two coordination functional group
2+Be engaged in visible region bigger absorption is arranged, the airborne oxygen that this catalyst dissolves in can activated water under radiation of visible light generates high price (IV) iron complex active specy, and this high price (IV) iron complex active specy self is reduced to the Fe of Fe (III) valence state in the process of oxidative degradation and mineralising organic pollutant molecule
3+, the Fe that reduction generates
3+Cooperate by the H in the system with the c-terminus of ligand molecular fast with two coordination functional group
2O
2Fe (II) complex compound state is returned in reduction, thereby finishes whole circulation, and obviously, such catalytic cycle has following characteristics, and (1) catalyst ligand has N atomic unit end and carboxyl unit side, Fe simultaneously
2+And Fe
3+Be easy to carry out between the N of part atom end and c-terminus respectively reversible coordination conversion, this reversible coordination conversion has been stablized catalyst on the one hand, has avoided the oxidation Decomposition of part, has increased Fe (III) complex compound on the other hand by H
2O
2The driving force of Fe (II) complex compound is returned in reduction, thereby has accelerated the rapid reaction of Fenton system rate determining step; (2) the Fenton reaction condition has been expanded in the aqueous environment of wide pH (pH4～8) scope; (3) utilize have two coordination functional group ligand molecular respectively with Fe
3+And Fe
2+Special coordination functional structure (Fe
2+The nitrogen-atoms end coordination of ion and part, Fe
3+The c-terminus coordination of ion and part) quickened Fe
3+/ Fe
2+Catalytic cycle.The airborne oxygen that this photochemical catalyst can dissolve in activated water under the visible light generates high price (IV) iron complex active specy, therefore can be applied to smoothly in the reaction such as water body purification.
The iron complex visible-light photocatalyst that the of the present invention pair of coordination functional group part and iron ion make up is ligand molecular and the Fe with two coordination functional group
2+Ion or Fe
3+The complex that ion forms, wherein, the ligand molecular with two coordination functional group respectively with Fe
2+The mol ratio of ion is 3: 1; With Fe
3+The mol ratio of ion is 2: 1.
Described ligand molecular with two coordination functional group has nitrogen-atoms end and c-terminus simultaneously, and possesses and Fe
2+And Fe
3+The ability of dual coordination, i.e. Fe
2+Ion forms coordinate bond, Fe with the nitrogen-atoms shared electron of the ligand molecular with two coordination functional group
3+Ion forms coordinate bond with the carbonyl shared electron of the c-terminus of the ligand molecular with two coordination functional group.Ligand molecular with two coordination functional group has following structure:
Wherein A, B, C, D independently are H, OH, OCH
3Or C
5In the following aliphatic hydrocarbon any.
The preparation method of the iron complex visible-light photocatalyst that the of the present invention pair of coordination functional group part and iron ion make up may further comprise the steps:
(1). the ligand molecular that will have two coordination functional group according to the NaOH mol ratio be that 1: 2 ratio is dissolved in the NaOH aqueous slkali;
(2). solution that is dissolved with ligand molecular and Fe that step (1) is obtained with two coordination functional group
2+Ion salt solution mixes, and stirs, and obtains red mixed solution; Wherein, the ligand molecular and the Fe that have two coordination functional group
2+The mol ratio of ion is 3: 1; Or
Solution that is dissolved with ligand molecular and Fe that step (1) is obtained with two coordination functional group
3+Ion salt solution mixes, and stirs, and obtains colourless mixed solution; Wherein, the ligand molecular and the Fe that have two coordination functional group
3+The mol ratio of ion is 2: 1;
(3). the red or colourless mixed solution that step (2) is obtained refluxes, and becomes peony until the color of the mixed solution of redness by redness, then wine-colored solution is filtered; Or
Become faint yellowly until the color of colourless mixed solution by colourless, then flaxen solution is filtered;
The solid that obtains after filtering is carried out evaporate to dryness, the solid that obtains behind the evaporate to dryness is recrystallized in hot water, obtain two coordination functional group parts and Fe
2+Ion or Fe
3+The iron complex visible-light photocatalyst that ion makes up.
The temperature of described hot water is 60～90 ℃.
Described Fe
2+Ion salt solution is selected from a kind of in ferrous perchlorate, ferrous sulfate or the solution of ferrous chloride.
Described Fe
3+Ion salt solution is selected from a kind of in ferric perchlorate, ferric sulfate or the ferric chloride solution.
The of the present invention pair of coordination functional group part and Fe
2+And Fe
3+The iron complex visible-light photocatalyst that ion makes up respectively can effectively utilize visible light, and utilize the airborne oxygen that dissolves in the water to generate high price (IV) iron complex active specy, this high price (IV) iron complex active specy self is reduced to Fe (III) valence state, Fe thereupon in the process of oxidative degradation and mineralising organic pollutant molecule
3+Ion cooperates then by H with the c-terminus of the ligand molecular with two coordination functional group fast
2O
2Reduction is returned Fe (II) complex compound and is finished whole circulation.The contribution of the iron complex visible-light photocatalyst maximum of of the present invention pair of coordination functional group structure is Fe
2+The airborne oxygen that the ionic complex visible-light photocatalyst can dissolve in the activated water under the exciting of visible light effectively degrade and the mineralising water body in toxic organic pollutant; And Fe
3+The ionic complex visible-light photocatalyst can be at H
2O
2Effect generate down Fe
2+Ionic complex visible-light photocatalyst, the airborne oxygen that under the exciting of visible light, dissolves in the activated water effectively degrade and the mineralising water body in toxic organic pollutant.
Photochemical catalyst of the present invention can be used for the purified treatment of organic pollution in industrial wastewater and the city domestic sewage.
Described organic pollution comprises azo dyes (No. two oranges), ALIZARIN YELLOW GG, peacock green, rhodamine B, acridine orange, 2,4-dichloro-phenol, phthalic acid, salicylic acid etc.
The ligand molecular with two coordination functional group in the photochemical catalyst of the present invention has and Fe simultaneously
2+The nitrogen of coordination (N) atomic unit end coordination site position and and Fe
3+The carboxyl unit side coordination site position of coordination, Fe
2+And Fe
3+Can be according to Fe in the course of reaction
2+/ Fe
3+Each stage of ionic catalysis circulation is carried out the coordination conversion at the nitrogen-atoms end and the c-terminus of the ligand molecular with two coordination functional group flexibly, makes Fe
3+Can be Fe (II) complex compound by quick complexing and fast restore, the rate determining step of accelerating the Fenton reaction be rapid.The airborne oxygen that photochemical catalyst of the present invention dissolves in can activated water under visible light, utilize the oxidant of this economy of molecular oxygen effectively degrade and the mineralising water body in toxic organic pollutant, ecological environment is still all had great scientific meaning to the oxidation Decomposition of pollutant.
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Description of drawings
Fig. 1. the concentration of the embodiment of the invention 1 is 1 * 10
-4No. two orange dye discoloration water bodys of M are at visible light (the photocatalytic degradation design sketch under the irradiation of λ＞420nm).
Fig. 2. the concentration of the embodiment of the invention 2 is 1 * 10
-4No. two orange dye discoloration water bodys of M are at visible light (the photocatalytic degradation design sketch under the irradiation of λ＞420nm).
Fig. 3. the concentration of the embodiment of the invention 3 is 1 * 10
-4No. two orange dyestuffs and the concentration of M are 1 * 10
-42 of M, 4-dichloro-phenol polluted-water is at visible light (the photocatalytic activity design sketch of mineralising separately under the irradiation of λ＞420nm).
Fig. 4. the photochemical catalyst (4 * 10 of the embodiment of the invention 7
-6M) No. two oranges (1 * 10 of continuous 5 oxidative degradation of circulation in the aqueous solution of pH=6.0
-4M) photocatalytic activity is design sketch as a result.
The photochemical catalyst (4 * 10 of Fig. 5 a. embodiment of the invention 8
-6M) (under the irradiation of λ＞420nm), under aerobic (air) and anaerobic (removing air) condition, carry out No. two oranges (1 * 10 of photocatalytic degradation respectively at visible light
-4M) contrast effect figure.
The photochemical catalyst (4 * 10 of Fig. 5 b. embodiment of the invention 8
-6M) (under the irradiation of λ＞420nm), under aerobic (air) and anaerobic (removing air) condition, carry out photocatalytic degradation 2 respectively, 4-dichloro-phenol (1 * 10 at visible light
-4M) contrast effect figure.
Fig. 6. the photochemical catalyst (4 * 10 of the embodiment of the invention 9
-6M) visible light (under the irradiation of λ＞420nm), No. two oranges 1 * 10 of photocatalytic degradation in the aqueous solution of different pH values (pH=4.0,6.0,8.0) respectively
-4The contrast effect figure of M.
Fig. 7. the photochemical catalyst (4 * 10 of Comparative Examples 1
-6M) at visible light (photocatalytic degradation 2 under the irradiation of λ＞420nm), 4-dichloro-phenol (1 * 10
-4The degraded contrast effect figure of experimental result M) and general Fenton reaction.
The specific embodiment
Above-mentioned 4,4 '-dicarboxyl-2,2 '-the bipyridine ligand molecule is that 1: 2 ratio is dissolved in the NaOH aqueous slkali according to mol ratio, to be dissolved with 4,4 '-dicarboxyl-2,2 '-solution of bipyridine ligand molecule and ferrous perchlorate's solution is according to 3: 1 mixed in molar ratio, stirs, and obtains red mixed solution.Then, the mixed solution of the redness 20 minutes colors until mixed solution that reflux are become peony by redness, then wine-colored solution is filtered, the solid that obtains after filtering is carried out evaporate to dryness, the solid that obtains behind the evaporate to dryness is recrystallized in 80 ℃ of hot water, obtain Fe
2+The ionic complex visible-light photocatalyst.
The photochemical catalyst (4 * 10 of gained
-6M) under radiation of visible light, be used for the neutral aqueous solution catalytic degradation toxic pollutant azo dyes (No. two oranges) of pH=6.0.The concentration of No. two orange dyestuffs in simulation sewage is 1 * 10
-4M, the photocatalytic degradation effect under visible light (luminous intensity is 110 milliwatt/square centimeters) irradiation as shown in Figure 1.
Curve 1: no photochemical catalyst and H
2O
2Blank illumination penetrate reaction.
Curve 2: illumination is penetrated but is not had the system of photochemical catalyst, H
2O
2: 2 * 10
-3M.
Curve 3: described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, dark reaction.
Curve 4: described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, illumination is penetrated.
Illumination experiment condition a: halogen lamp is placed in the double glazing condensation sleeve pipe, on every side around recirculated cooling water.(λ＞420nm) places the chuck outside to excise the following light of 420nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.
Above-mentioned 4,4 '-dicarboxyl-2,2 '-the bipyridine ligand molecule is that 1: 2 ratio is dissolved in the NaOH aqueous slkali according to mol ratio, to be dissolved with 4,4 '-dicarboxyl-2,2 '-solution of bipyridine ligand molecule and ferric perchlorate's solution is according to 2: 1 mixed in molar ratio, stirs, and obtains colourless mixed solution.Then, colourless mixed solution refluxed to be become faint yellowly until the color of mixed solution by colourless in 20 minutes, then flaxen solution was filtered, and the solid that obtains after filtering is carried out evaporate to dryness, and the solid that obtains behind the evaporate to dryness is recrystallized in 80 ℃ of hot water, obtained Fe
3+The ionic complex visible-light photocatalyst.
The photochemical catalyst (4 * 10 of gained
-6M) under radiation of visible light, be used for the aqueous solution catalytic degradation toxic pollutant azo dyes (No. two oranges) of pH=8.0.The concentration of No. two orange dyestuffs in simulation sewage is 1 * 10
-4M, the photocatalytic degradation effect under visible light (luminous intensity is 110 milliwatt/square centimeters) irradiation as shown in Figure 2.
Curve 1: no photochemical catalyst and H
2O
2Blank light reaction.
Curve 2: illumination is penetrated but is not had the system of photochemical catalyst, H
2O
2: 2 * 10
-3M.
Curve 3: described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, dark reaction.
Curve 4: described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, illumination is penetrated.
Illumination experiment condition a: halogen lamp is placed in the double glazing condensation sleeve pipe, on every side around recirculated cooling water.(λ＞420nm) places the chuck outside to excise the following light of 420nm fully and guarantee that reaction only carries out under visible light for cut-off type optical filter.
The photochemical catalyst (4 * 10 of embodiment 1
-6M) (luminous intensity is 110 milliwatt/square centimeters, and λ＞420nm) the following concentration that contains that is used for mineralising pH=4.0 of irradiation is 1 * 10 at visible light
-4No. two oranges and the concentration of M are 1 * 10
-42 of M, the aqueous solution of 4-dichloro-phenol, No. two oranges of mineralising and 2, the photocatalytic activity result of 4-dichloro-phenol is as shown in Figure 3.
1: No. two orange of curve: 1 * 10
-4M, described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, illumination is penetrated.
Curve 2:2,4-dichloro-phenol: 1 * 10
-4M, described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, illumination is penetrated.
Above-mentioned 4,4 '-dicarboxyl-3,3 '-dimethyl-2,2 '-the bipyridine ligand molecule is that 1: 2 ratio is dissolved in the NaOH aqueous slkali according to mol ratio, will be dissolved with 4,4 '-dicarboxyl-3,3 '-dimethyl-2,2 '-solution of bipyridine ligand molecule and ferrous perchlorate's solution is according to 3: 1 mixed in molar ratio, stirs, and obtains red mixed solution.Then, the mixed solution of the redness 30 minutes colors until mixed solution that reflux are become peony by redness, then wine-colored solution is filtered, the solid that obtains after filtering is carried out evaporate to dryness, the solid that obtains behind the evaporate to dryness is recrystallized in 60 ℃ of hot water, obtain Fe
2+The ionic complex visible-light photocatalyst.
This photochemical catalyst is at catalytic degradation toxic pollutant 2, and effect is obvious in the reaction of 4-dichloro-phenol, and the concentration of photochemical catalyst is 4 * 10 in the regulation system
-6M, H
2O
2Concentration be 2 * 10
-3M, 2, the concentration of 4-dichloro-phenol is 1 * 10
-4M, mixed solution pH value is 6.0, (luminous intensity is 110 milliwatt/square centimeters at visible light, the irradiation of λ＞420nm) reaction 6 hours down, reaction finishes the back catabolite to be measured by high pressure liquid chromatography HPLC, 80% 2,4-dichloro-phenol is degraded, and mineralization rate is about 30%.
Embodiment 5
The photochemical catalyst of embodiment 1 is not only to No. two oranges and 2, the degraded of 4-dichloro-phenol has positive effect, and water miscible dyestuff ALIZARIN YELLOW GG, peacock green, rhodamine B, acridine orange, water soluble organic substance phthalic acid or salicylic degraded also had positive effect, concentration is 5 * 10
-6This photochemical catalyst of M is used for visible light, and (luminous intensity is 110 milliwatt/square centimeters, the irradiation of λ＞420nm) is the catalytic degradation of above-mentioned organic pollution in the neutral aqueous solution of pH=6.0 down, substrate self has obtained bigger mineralization rate (total organic carbon removing rate) when degraded takes place, and the mineralization rate during degradation of substrates 90% (refers to that pollutant is converted into CO in the degradation process
2Percentage) be listed in table 1.The be degraded concentration of pollutant of increasing has obtained higher turn over number (molal quantity that refers to 1 mol catalyst conversion pollutant molecule), and is as shown in table 1:
Table 1
Above-mentioned 4,4 '-dicarboxyl-2-methyl-2 '-hydroxyl-3 '-ethyl-2,2 '-the bipyridine ligand molecule is that 1: 2 ratio is dissolved in the NaOH aqueous slkali according to mol ratio, to be dissolved with 4,4 '-dicarboxyl-2-methyl-2 '-hydroxyl-3 '-ethyl-2,2 '-solution of bipyridine ligand molecule and ferrous perchlorate's solution stirs according to 3: 1 mixed in molar ratio, obtains red mixed solution.Then, the color that the mixed solution of redness is refluxed until mixed solution becomes peony by redness, then wine-colored solution is filtered, and the solid that obtains after filtering is carried out evaporate to dryness, and the solid that obtains behind the evaporate to dryness is recrystallized in 90 ℃ of hot water, obtains Fe
2+The ionic complex visible-light photocatalyst.
This photochemical catalyst visible light (luminous intensity is 110 milliwatt/square centimeters, effective catalytic degradation dyestuff rhodamine B under the irradiation of λ＞420nm), the concentration of the photochemical catalyst in the system is 2 * 10
-6M, H
2O
2Concentration be 2 * 10
-3The concentration of M, rhodamine B is 1 * 10
-4M, the pH value of mixed solution is 6.0, and visible light irradiation down reacted 12 hours, and 95% rhodamine B is degraded, and mineralization rate is about 35%.
Embodiment 7
According to the illumination experiment condition of embodiment 1, with the photochemical catalyst (4 * 10 of embodiment 1
-6M) No. two oranges (1 * 10 of continuous 5 oxidative degradation of circulation in the aqueous solution of pH=6.0
-4M/ time) the photocatalytic activity result as shown in Figure 4.This photochemical catalyst is under radiation of visible light, at H
2O
2(2 * 10
-3M) have degradation results demonstration down, through reusing 5 times, photocatalyst activity changes without any conspicuousness.
The photochemical catalyst (4 * 10 of embodiment 1
-6M) (luminous intensity is 110 milliwatt/square centimeters, and λ＞420nm) irradiation is following, and carrying out photocatalytic degradation concentration in the neutral aqueous solution of the pH=6.0 under aerobic (air) and anaerobic (removing air) condition respectively is 1 * 10 at visible light
-4No. two oranges and the concentration of M are 1 * 10
-42 of M, the contrast effect of 4-dichloro-phenol, the result is shown in Fig. 5 (a) and Fig. 5 (b).
Photochemical catalyst (4 * 10 under (air) and the oxygen free condition under Fig. 5 (a), the aerobic conditions
-6M) No. two oranges (1 * 10 of degraded under radiation of visible light
-4M) contrast effect figure.
1: No. two orange of curve: 1 * 10
-4M, described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, anaerobic, illumination is penetrated.
2: No. two oranges of curve: 1 * 10
-4M, described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, aerobic, illumination is penetrated.
Photochemical catalyst (4 * 10 under (air) and the oxygen free condition under Fig. 5 (b), the aerobic conditions
-6M) under radiation of visible light, degrade 2,4-dichloro-phenol (1 * 10
-4M) contrast effect figure.
Curve 1:2,4-dichloro-phenol: 1 * 10
-4M, described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, anaerobic, illumination is penetrated.
Curve 2:2,4-dichloro-phenol: 1 * 10
-4M, described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, aerobic, illumination is penetrated.
In addition, with this photochemical catalyst (4 * 10
-6M) be used for the aqueous solution catalytic degradation 2 of pH=6.0 under visible light, 4-dichloro-phenol (1 * 10
-4M), experimental result shows: if in course of reaction limit border ring aerating oxygen in reaction system, promptly strengthen the oxygen of the top of solution in the reaction system and press, also can accelerate the speed of degradation of substrates.Photochemical catalyst (4 * 10
-6M) and H
2O
2(2 * 10
-3M) in the reaction system of Cun Zaiing, under the aerating oxygen condition, radiation of visible light 430 minutes, 2,4-dichloro-phenol has degraded about 90%.
Embodiment 9
The photochemical catalyst (4 * 10 of embodiment 1
-6M), (luminous intensity is 110 milliwatt/square centimeters, λ＞420nm) shine down, No. two oranges 1 * 10 of photocatalytic degradation in the aqueous solution of different pH values (pH=4.0,6.0,8.0) respectively at visible light
-4The contrast effect of M as shown in Figure 6.
1: No. two orange of curve: 1 * 10
-4M, described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, illumination is penetrated, pH=4.0.
2: No. two oranges of curve: 1 * 10
-4M, described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, illumination is penetrated, pH=6.0.
3: No. two oranges of curve: 1 * 10
-4M, described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, illumination is penetrated, pH=8.0.
As shown in Figure 6, described photochemical catalyst (4 * 10
-6M) under radiation of visible light, respectively all can be in the aqueous solution of different pH values (pH=4.0,6.0,8.0) to No. two oranges 1 * 10
-4M effectively degrades.
Comparative Examples 1
The photochemical catalyst (4 * 10 of embodiment 1
-6M) (luminous intensity is 110 milliwatt/square centimeters, and λ＞420nm) the following concentration that contains that is used for photocatalytic degradation pH=6.0 of irradiation is 1 * 10 at visible light
-42 of M, the neutral aqueous solution of 4-dichloro-phenol, photocatalytic degradation 2, the degraded contrast effect of the experimental result of 4-dichloro-phenol and general Fenton reaction is as shown in Figure 7.
Curve 1: the blank light reaction of no photochemical catalyst and hydrogen peroxide.
Curve 2:Fenton reaction (luminous intensity is 110 milliwatt/square centimeters, λ＞420nm), ferrous perchlorate: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, illumination is penetrated.
Curve 3: described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, dark reaction.
Curve 4: described photochemical catalyst: 4 * 10
-6M, H
2O
2: 2 * 10
-3M, illumination is penetrated.
Comparative Examples 2
Get any one and ferrous perchlorate in above-mentioned 5 kinds of compounds respectively, wherein, any one in above-mentioned 5 kinds of compounds and ferrous perchlorate's mol ratio is 3: 1, then according to the synthetic corresponding 5 kinds of iron nitrogen complex photochemical catalysts of the preparation method of embodiment 1.
5 kinds of prepared photochemical catalysts are used for visible light, and (luminous intensity is 110 milliwatt/square centimeters, and λ＞420nm) shining down, the concentration that contains of pH=6.0 is 1 * 10
-4No. two oranges and the concentration of M are 1 * 10
-42 of M, the neutral aqueous solution of 4-dichloro-phenol, No. two oranges of catalyzing oxidizing degrading organic pollution and 2,4-dichloro-phenol, above-mentioned 5 kinds of photochemical catalysts are compared with photochemical catalyst of the present invention does not have the photocatalytic degradation activity.
Comparative Examples 3
Get above-mentioned 2 kinds of compounds and ferrous perchlorate's mixed dissolution, stir then, obtain photochemical catalyst, wherein, compound (1): compound (2): ferrous perchlorate's mol ratio is 3: 3: 1.
Prepared photochemical catalyst is used for visible light, and (luminous intensity is 110 milliwatt/square centimeters, and λ＞420nm) shining down, the concentration that contains of pH=6.0 is 1 * 10
-4No. two oranges and the concentration of M are 1 * 10
-42 of M, the neutral aqueous solution of 4-dichloro-phenol, No. two oranges of catalyzing oxidizing degrading organic pollution and 2,4-dichloro-phenol, above-mentioned photochemical catalyst are compared with catalyst of the present invention does not have the photocatalytic degradation activity yet.
Comparative Examples 4
(luminous intensity is 110 milliwatt/square centimeters, and the irradiation of λ＞420nm) produces heat and the thermal response that causes, has carried out in 40 ℃ of water-baths (air) photochemical catalyst (photochemical catalyst of embodiment 1: 4 * 10 under the aerobic conditions in order to get rid of visible light
-6M) No. two oranges (1 * 10 of degradable organic pollutant
-4M) and 2,4-dichloro-phenol (1 * 10
-4M) dark reaction, pH=6.0, H
2O
2: 2 * 10
-3M.Experimental result shows: under the dark reaction condition of heating, less change has taken place in concentration of substrate in the reaction time, substantially can get rid of the degradation of substrates that is caused by thermal response thus in the reaction time, promptly the degraded mineralising major part of substrate is that photocatalytic activity by photochemical catalyst of the present invention causes in the reaction time internal reaction system.
Claims (6)
1. the iron complex visible-light photocatalyst of two coordination functional group parts and iron ion structure, it is characterized in that: described iron complex visible-light photocatalyst is ligand molecular and the Fe with two coordination functional group
2+Ion or Fe
3+The complex that ion forms, wherein:
Described ligand molecular with two coordination functional group has nitrogen-atoms end and c-terminus simultaneously, and it has formula (I) structure; Fe
2+Ion forms coordinate bond, the ligand molecular of two coordination functional group and Fe with the nitrogen-atoms shared electron of the ligand molecular with two coordination functional group
2+The mol ratio of ion is 3: 1; Fe
3+Ion forms coordinate bond, ligand molecular and Fe with two coordination functional group with the carbonyl shared electron of the c-terminus of the ligand molecular with two coordination functional group
3+The mol ratio of ion is 2: 1;
Wherein A, B, C, D independently are H, OH, OCH
3Or C
5In the following aliphatic group any one.
2. the preparation method of the iron complex visible-light photocatalyst that makes up of according to claim 1 pair of coordination functional group part and iron ion is characterized in that this method may further comprise the steps:
(1). the ligand molecular that will have two coordination functional group according to the NaOH mol ratio be that 1: 2 ratio is dissolved in the NaOH aqueous slkali;
(2). solution that is dissolved with ligand molecular and Fe that step (1) is obtained with two coordination functional group
2+Ion salt solution mixes, and stirs, and obtains red mixed solution; Wherein, the ligand molecular and the Fe that have two coordination functional group
2+The mol ratio of ion is 3: 1; Or
Solution that is dissolved with ligand molecular and Fe that step (1) is obtained with two coordination functional group
3+Ion salt solution mixes, and stirs, and obtains colourless mixed solution; Wherein, the ligand molecular and the Fe that have two coordination functional group
3+The mol ratio of ion is 2: 1;
(3). the red or colourless mixed solution that step (2) is obtained refluxes, and becomes peony until the color of the mixed solution of redness by redness, then wine-colored solution is filtered; Or
Become faint yellowly until the color of colourless mixed solution by colourless, then flaxen solution is filtered;
The solid that obtains after filtering is carried out evaporate to dryness, the solid that obtains behind the evaporate to dryness is recrystallized in hot water, obtain two coordination functional group parts and Fe
2+Ion or Fe
3+The iron complex visible-light photocatalyst that ion makes up.
3. method according to claim 2 is characterized in that: the temperature of described hot water is 60～90 ℃.
4. method according to claim 2 is characterized in that: described Fe
2+Ion salt solution is selected from a kind of in ferrous perchlorate, ferrous sulfate or the solution of ferrous chloride.
5. method according to claim 2 is characterized in that: described Fe
3+Ion salt solution is selected from a kind of in ferric perchlorate, ferric sulfate or the ferric chloride solution.
6. the purposes of the iron complex visible-light photocatalyst that makes up of according to claim 1 pair of coordination functional group part and iron ion is characterized in that: described Fe
2+The airborne oxygen that the ionic complex visible-light photocatalyst dissolves in the activated water under the exciting of visible light effectively degrade and the mineralising water body in toxic organic pollutant;
Described Fe
3+The ionic complex visible-light photocatalyst is at H
2O
2Effect generate down Fe
2+Ionic complex visible-light photocatalyst, the airborne oxygen that under the exciting of visible light, dissolves in the activated water effectively degrade and the mineralising water body in toxic organic pollutant.
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| CN104084235B (en) * | 2013-04-01 | 2016-05-25 | 中国科学院化学研究所 | There is iron complex photochemical catalyst of the coordination bonding of the hydrocarbon key of selective oxidation secondary and its preparation method and application |
| CN105268479B (en) * | 2015-11-10 | 2017-09-05 | 安徽理工大学 | The preparation method of high efficiency photocatalyst based on iron and Phen |
| CN108686333B (en) * | 2017-04-07 | 2021-03-12 | 南开大学 | Method for photocatalytic degradation of phosphate compounds based on micro/nano coordination polymer |
| CN109142254A (en) * | 2018-10-24 | 2019-01-04 | 华侨大学 | A kind of multiwave length spectro photometric detection method based on Fenton oxidation ABTS chromogenic assay content of hydrogen peroxide |
| CN110683993B (en) * | 2019-10-16 | 2022-11-04 | 黄冈师范学院 | Preparation method and application of ferrous phthalhydrazide |
| CN116675323B (en) * | 2023-07-03 | 2023-10-31 | 江苏省南京环境监测中心 | Light-mediated Fenton iron mud recycling process |
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| CN1386581A (en) * | 2001-05-18 | 2002-12-25 | 中国科学院化学研究所 | Bionic visible light solid-phase catalyst and its preparing process |
| CN1552524A (en) * | 2003-06-05 | 2004-12-08 | 中国科学院化学研究所 | Selective oxidative light catalyst and preparing method thereof |
| CN101152633A (en) * | 2006-09-25 | 2008-04-02 | 中国科学院化学研究所 | Visible light photocatalyst for constructing nitrogen and iron complex with hydrogen-like quinone and uses of the same |
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| CN1386581A (en) * | 2001-05-18 | 2002-12-25 | 中国科学院化学研究所 | Bionic visible light solid-phase catalyst and its preparing process |
| CN1552524A (en) * | 2003-06-05 | 2004-12-08 | 中国科学院化学研究所 | Selective oxidative light catalyst and preparing method thereof |
| CN101152633A (en) * | 2006-09-25 | 2008-04-02 | 中国科学院化学研究所 | Visible light photocatalyst for constructing nitrogen and iron complex with hydrogen-like quinone and uses of the same |
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