CN105013520B - MHCF/TiO2Nano-composite catalyst and its preparation and application - Google Patents
MHCF/TiO2Nano-composite catalyst and its preparation and application Download PDFInfo
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Abstract
The invention provides a kind of preparation of transition metal hexacyanoferrate/nano titania composite catalyst：Using transition metal chloride or transition metal nitrate, potassium ferrocyanide, titanium dioxide as raw material, pass through chemical solution method in situ, by transition metal hexacyanoferrate (MHCF) growth in situ on titania nanoparticles surface, MHCF/TiO is obtained2Nano-composite catalyst.Present invention also offers a kind of MHCF/TiO2The method of nano-composite catalyst light Fenton concerted reaction degradable organic pollutant：In the dark reaction without light, MHCF can carry out degradable organic pollutant in the form of Fenton's reaction, and under ultraviolet light, titanium dioxide (photochemical catalyst) can produce electron hole pair, and electronics can accelerate in MHCF by H2O2The ferric reduction of oxidation, simultaneously, the electronics that MHCF receives titanium dioxide can also suppress the compound of photo-generate electron-hole, and then accelerate Fenton's reaction and photocatalysis process to produce the efficiency of hydroxyl radical free radical, and its synergy has extraordinary degradation efficiency to a variety of different organic pollutions.
Description
Technical field
The present invention relates to the preparation of transition metal hexacyanoferrate/nano titania composite catalyst, and its
Under the irradiation of ultraviolet light, photocatalysis and the method for heterogeneous Fenton's reaction concerted catalysis degraded Some Organic Pollutants.
Background technology
Transition metal hexacyanoferrate is that the Nomenclature Composition and Structure of Complexes changes very abundant metal organic framework compound, and companion
With the development of material science, constantly there is newcomer to be synthesized.Such compound is because itself having absorption, catalysis, light
Cause the various excellent physicochemical properties such as magnetic and be widely studied.Because it has efficient peroxidase activity, quilt
It is widely used in the fields such as hydrogen peroxide sensor.And Fenton's reaction is to be generated using ferric ion come catalyzing hydrogen peroxide
The method that hydroxyl isoreactivity species carry out degradable organic pollutant, if MHCF is used for sweet smell as an efficient class peroxidase
Reaction will certainly have an outstanding Fenton catalytic activity, but its relatively low dark reaction Fenton activity and its hardly possible separation at present
Characteristic also limit it and use.
One prominent advantage of photochemical catalyst is available with solar energy to produce hydroxyl radical free radical, in various light
In catalysis material, TiO2It is considered as the most active photochemical catalyst under ultraviolet light.Because its physical chemistry is stable
Property, low cost, it is repeatable utilize, nontoxic performance becomes one of catalysis material of current most study.But it is due to
TiO2With wider band gap (2.9eV), it is the focus studied at present that its photoresponse scope red shift is entered into visible region.
Recent research person is on MHCF, TiO2To H2O2Detection carried out substantial amounts of research, but on MHCF/TiO2
Do not had been reported that for photocatalysis or the research of Fenton's reaction.Therefore, a kind of new multi-functional MHCF/TiO is prepared2It is compound
Material, so as to further improve the efficiency of light-Fenton degradable organic pollutant, expands TiO2Visible light-responded region, increase is fragrant
Pause and react the Activity and stabill of pH scopes and reaction, and probe into the progress of its catalytic mechanism is deep, should to finding environment
The catalyst with preferable application potential has important theory and real value in.
The content of the invention
It is contemplated that preparing transition metal hexacyanoferrate (heterogeneous Fenton reagent) and titanium dioxide (photocatalysis
Agent) nano-composite catalyst, and find the synergy under ultraviolet light with best photocatalysis and Fenton's reaction
Proportioning, and then have an efficient degrading activity to a variety of different organic pollutions.
A kind of transition metal hexacyanoferrate/nano titania composite catalyst, the cyanogen of active constituent transition metal six
Close ferrite (MHCF) to be carried on titania support, transition metal hexacyanoferrate is in the load on titania support
Measure as the 1-25% of titanium dioxide quality.
Transition metal is Fe, Co, Ni, Cu, Zn or Mn；Composite catalyst particle diameter is 10-50 nanometers.
Its preparation process is as follows：
1) by 0.5-2g TiO2It is scattered in 10-50ml deionized waters, the K of proportioning needed for adding4[Fe(CN)6] mixing
Stir 20-120min；
2) transition metal chloride or transition metal nitrate of required proportioning are made into settled solution；Its transition metal
Ion molar concentration is 1-20mmol/L；
3) transition metal ions and K are pressed4[Fe(CN)6] mol ratio be 1-2, by step 2) resulting solution instill step 1)
The nano composite material of 20-120min generations is stirred in resulting solution；
4) static aging 12-20h；Centrifugation, solid matter washing, dry product.
A kind of MHCF/TiO2Nano-composite catalyst is used for light-Fenton Synergistic degradation Some Organic Pollutants, its specific step
Suddenly it is：
Under the irradiation of ultraviolet light, photocatalysis-Fenton's reaction synergy, a variety of organic contaminations of efficient catalytic degraded are produced
Thing.
Under the irradiation of ultraviolet light, by prepared MHCF/TiO2In H2O2In the presence of carry out organic pollutant degradation, two
Titanium oxide (photochemical catalyst) light induced electron can accelerate in MHCF by H2O2The ferric reduction of oxidation, meanwhile, MHCF receives dioxy
The compound of its photo-generate electron-hole can also be suppressed by changing the electronics of titanium, produce the synergy of photocatalysis and Fenton's reaction, efficiently
Catalytic degradation Some Organic Pollutants.
Light-Fenton Synergistic degradation organic pollution condition：Room temperature, catalyst concn 1g/L, RhB concentration 12mg/L, H2O2
The concentration 0.4mol/L aqueous solution, 27w uviol lamps are apart from liquid level 10cm height.
The organic pollution is：Rhodamine B (RhB), salicylic acid, isoamyl diketone or one kind in m-methyl phenol or two
More than kind.
The invention has the advantages that：
1) under the irradiation of ultraviolet light, ferric iron produces light Fenton collaboration effect in titanium dioxide photoproduction electron reduction MHCF
Really, its degradable organic pollutant efficiency is increased substantially；
2) program is simple and easy to apply, and prepared catalyst has good stability and recycles performance.
Brief description of the drawings
Fig. 1 is embodiment 1-5 XRD spectra, it can be found that as transition metal hexacyanoferrate is supported from spectrogram
The raising of amount, the diffraction maximum of its (200) crystal face gradually strengthens；
Fig. 2 is MHCF/TiO prepared by embodiment 32The high resolution electron microscopy photo of nano-composite catalyst, it can be seen that mistake
It is the surface that titanium dioxide granule is grown in the short grained form of nanometer to cross metal hexacyanoferrate；
Fig. 3 is embodiment 1-5 differences MHCF/TiO2Activity under the dark reaction Fenton activity and ultraviolet light of loading
Figure.It can be seen that in the case of without light, the reactivity of catalyst increases with the raising of MHCF loadings.
Under the assistance of ultraviolet light, its light-Fenton activity is further improved, and therefore, it can prove that photochemical catalyst and its surface are heterogeneous
The concerted catalysis effect of Fenton reagent；
And it is seen that in MHCF/TiO2When mol ratio is 1/60, it has had highest concerted catalysis degraded effect
Rate, further improves loading, and its concerted catalysis effect starts reduction；
Fig. 4 is the gained MHCF/TiO of embodiment 32Degraded of the nano-composite catalyst to a variety of different organic pollutions is imitated
Rate.We have found that it has very high degrading activity to salicylic acid, isoamyl diketone and m-methyl phenol；
Fig. 5 is the gained MHCF/TiO of embodiment 32The recycling performance of nano-composite catalyst.As can be seen that circulation makes
Remained unchanged with its degrading activity to RhB after 4 times and be maintained at 95% or so.Illustrate that it has and recycle performance well.
Embodiment
Embodiment 1
0.95g titanium dioxide (P25) is scattered in 15ml deionized waters and stirred, 0.0254g K are added4[Fe
(CN)6] continue stir 30min obtain solution a, 0.024g iron chloride is dissolved in 15ml deionized water obtained solution b, by solution b
It is slowly dropped in a and continues to stir 30min, aging 20h.Prepare MHCF/ TiO2The nanometer of=1/200 (mol ratio) is answered
Condensation material (by electron microscopic observation, its particle diameter is 20-50 nanometers).Centrifuge washing is dried (20-80 degrees Celsius of drying) and used afterwards
In light-Fenton concerted catalysis active testing (dark reaction condition：Catalyst concn 1g/L, RhB concentration 12mg/L, H2O2Concentration
The 0.4mol/L aqueous solution.Light Fenton's reaction condition：Ultraviolet light is added on the basis of dark reaction：27w black light lamps are apart from liquid level
10cm height), after 30min, its RhB dark reactions activity of degrading is that the activity under 22%, ultraviolet light is 58%.
Embodiment 2
0.95g titanium dioxide (P25) is scattered in 15ml deionized waters and stirred, 0.048g K are added4[Fe
(CN)6] continue stir 30min obtain solution a, 0.0507g iron chloride is dissolved in 15ml deionized water obtained solution b, by solution b
It is slowly dropped in a and continues to stir 30min, aging 20h.Prepare MHCF/ TiO2The nanometer of=1/100 (mol ratio) is answered
Condensation material.Centrifuge washing is used for light-Fenton concerted catalysis active testing (dark reaction condition after drying：Catalyst concn 1g/L,
RhB concentration 12mg/L, H2O2The concentration 0.4mol/L aqueous solution.Light Fenton's reaction condition：Added on the basis of dark reaction ultraviolet
Light：27w black light lamps are apart from liquid level 10cm height).After 30min, under its RhB dark reactions activity of degrading is 54%, ultraviolet light
Activity be 83%.
Embodiment 3
0.95g titanium dioxide (P25) is scattered in 15ml deionized waters and stirred, 0.0845g K are added4[Fe
(CN)6] continue stir 30min obtain solution a, 0.0721g iron chloride is dissolved in 15ml deionized water obtained solution b, by solution b
It is slowly dropped in a and continues to stir 30min, aging 20h.Prepare MHCF/ TiO2=1/60 (mol ratio) it is nano combined
Material.Centrifuge washing is used for light-Fenton concerted catalysis active testing (dark reaction condition after drying：Catalyst concn 1g/L, RhB
Concentration 12mg/L, H2O2The concentration 0.4mol/L aqueous solution.Light Fenton's reaction condition：Ultraviolet light is added on the basis of dark reaction：
27w black light lamps are apart from liquid level 10cm height).After 30min, under its RhB dark reactions activity of degrading is 81%, ultraviolet light
Activity is 95%.
Embodiment 4
0.95g titanium dioxide (P25) is scattered in 15ml deionized waters and stirred, 0.169g K are added4[Fe
(CN)6] continue stir 30min obtain solution a, 0.16g iron chloride is dissolved in 15ml deionized water obtained solution b, solution b is delayed
Slow be added drop-wise in a continues to stir 30min, aging 20h.Prepare MHCF/ TiO2The nano combined material of=1/30 (mol ratio)
Material.Centrifuge washing is used for light-Fenton concerted catalysis active testing (dark reaction condition after drying：：Catalyst concn 1g/L, RhB are dense
Spend 12mg/L, H2O2The concentration 0.4mol/L aqueous solution.Light Fenton's reaction condition：Ultraviolet light is added on the basis of dark reaction：27w
Black light lamp is apart from liquid level 10cm height).After 30min, its RhB dark reactions activity of degrading is the activity under 86%, ultraviolet light
For 96%.
Embodiment 5
0.95g titanium dioxide (P25) is scattered in 15ml deionized waters and stirred, 0.338g K are added4[Fe
(CN)6] continue stir 30min obtain solution a, 0.32g iron chloride is dissolved in 15ml deionized water obtained solution b, solution b is delayed
Slow be added drop-wise in a continues to stir 30min, aging 20h.Prepare MHCF/ TiO2The nano combined material of=1/15 (mol ratio)
Material.Centrifuge washing is used for light-Fenton concerted catalysis active testing (dark reaction condition after drying：Catalyst concn 1g/L, RhB are dense
Spend 12mg/L, H2O2The concentration 0.4mol/L aqueous solution.Light Fenton's reaction condition：Ultraviolet light is added on the basis of dark reaction：27w
Black light lamp is apart from liquid level 10cm height).After 30min, its RhB dark reactions activity of degrading is the activity under 96%, ultraviolet light
For 96%.
In aforesaid way, MHCF/TiO2It can be come out, and then recycled by centrifuging after use.With
It is upper described, it is only one of embodiment of the present invention, but protection scope of the present invention is not limited thereto, and it is any to be familiar with sheet
The technical staff in field disclosed herein technical scope in, without the variation and replacement of inventive concept, all should wrap
It is contained within protection domain.Therefore, protection scope of the present invention should be determined by the scope of protection defined in the claims.
Claims (7)
1.MHCF/TiO2Nano-composite catalyst, it is characterised in that：
Active constituent transition metal hexacyanoferrate (MHCF) is carried on titania support, transition metal Hexacyanoferrate
Salt is in the 1-25% that the load capacity on titania support is titanium dioxide quality；
Its preparation process is as follows：
1) by 0.5-2g TiO2It is scattered in 10-50ml deionized waters, the K of proportioning needed for adding4[Fe(CN)6] mix
20-120min；
2) transition metal chloride or transition metal nitrate of required proportioning are made into settled solution；Its transition metal ions
Molar concentration is 1-20mmol/L；
3) transition metal ions and K are pressed4[Fe(CN)6] mol ratio 1-2, by step 2) resulting solution instill step 1) gained it is molten
The nano composite material of 20-120min generations is stirred in liquid；
4) static aging 12-20h；Centrifugation, solid matter washing, dry product.
2. according to nano-composite catalyst described in claim 1, it is characterised in that：
Transition metal is Fe, Co, Ni, Cu, Zn or Mn；
Composite catalyst particle diameter is 10-50 nanometers.
3. the preparation method of nano-composite catalyst described in a kind of claim 1 or 2, it is characterised in that：
Its preparation process is as follows：
1) by 0.5-2g TiO2It is scattered in 10-50ml deionized waters, the K of proportioning needed for adding4[Fe(CN)6] mix
20-120min；
2) transition metal chloride or transition metal nitrate of required proportioning are made into settled solution；Its transition metal ions
Molar concentration is 1-20mmol/L；
3) transition metal ions and K are pressed4[Fe(CN)6] mol ratio 1-2, by step 2) resulting solution instill step 1) gained it is molten
The nano composite material of 20-120min generations is stirred in liquid；
4) static aging 12-20h；Centrifugation, solid matter washing, dry product.
4. the MHCF/TiO described in a kind of claim 1 or 22The application of nano-composite catalyst, it is characterised in that：
Described MHCF/TiO2Nano-composite catalyst is used for light-Fenton Synergistic degradation organic pollution.
5. according to the application of nano-composite catalyst described in claim 4, it is characterised in that：
Under the irradiation of ultraviolet light, by prepared MHCF/TiO2In H2O2In the presence of carry out organic pollutant degradation, titanium dioxide
Titanium light induced electron can accelerate in MHCF by H2O2The ferric reduction of oxidation, meanwhile, the electronics that MHCF receives titanium dioxide also may be used
To suppress the compound of its photo-generate electron-hole, the synergy of photocatalysis and Fenton's reaction is produced, efficient catalytic degraded is a variety of to be had
Organic pollutants.
6. according to the application of nano-composite catalyst described in claim 4, it is characterised in that：
Light-Fenton Synergistic degradation organic pollution condition：Room temperature, catalyst concn 1g/L, RhB concentration 12mg/L, H2O2Concentration
The 0.4mol/L aqueous solution, 27w uviol lamps are apart from liquid level 10cm height.
7. according to the application of nano-composite catalyst described in claim 4,5 or 6, it is characterised in that：
The organic pollution is：Rhodamine B (RhB), salicylic acid, isoamyl diketone or one kind in m-methyl phenol or two kinds with
On.
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| CN109701667A (en) * | 2019-01-09 | 2019-05-03 | 山西大学 | A kind of photochemical catalyst and preparation method thereof |
| CN110180600B (en) * | 2019-04-28 | 2021-09-24 | 太原科技大学 | Preparation method and application of photocatalyst for treating organic wastewater |
| CN110624560B (en) * | 2019-09-17 | 2020-08-04 | 吉林师范大学 | FeVO for photo-Fenton combined catalysis4/TiO2Porous catalyst membrane layer material and preparation method thereof |
| CN113044912A (en) * | 2019-12-26 | 2021-06-29 | 中国科学院广州能源研究所 | Method for rapidly degrading organic pollutants in water |
| CN112889841B (en) * | 2021-01-26 | 2022-04-15 | 张斌翔 | Virus killing spray special for photocatalytic apatite coating technology |
| CN115703077B (en) * | 2021-08-10 | 2024-05-14 | 中国科学院大连化学物理研究所 | PB@MoS2Application of catalyst in heterogeneous Fenton-like reaction |
| CN114160153A (en) * | 2021-11-27 | 2022-03-11 | 北京工业大学 | Method for degrading monatomic transition group element photocatalyst of organic medicine |
| CN115920895B (en) * | 2022-12-30 | 2023-07-28 | 西安理工大学 | photo-Fenton transition metal monoatomic catalyst and preparation method and application thereof |
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| CN102962063A (en) * | 2011-09-01 | 2013-03-13 | 苏州科技学院 | Preparation of Prussian blue photo-Fenton catalyst and method for degrading organic pollutant |
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| FR2828818B1 (en) * | 2001-08-22 | 2003-12-05 | Commissariat Energie Atomique | SOLID COMPOSITE MATERIAL FIXING MINERAL POLLUTANTS, PROCESS FOR PREPARING THE SAME, AND METHOD FOR FIXING MINERAL POLLUTANTS EMPLOYING THE SAME |
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| CN102962063A (en) * | 2011-09-01 | 2013-03-13 | 苏州科技学院 | Preparation of Prussian blue photo-Fenton catalyst and method for degrading organic pollutant |
Non-Patent Citations (1)
| Title |
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| "Electrocatalytic Oxidation of Hydrazine Based on NiHCF@TiO2 Core-Shell Nanoparticles Modified GCE";S. Jancy Sophia，et al;《Int. J. Electrochem. Sci.》;20120801;第7卷;第2.4节 * |
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