CN104056614B - Construction and application of two-dimensional nanometer sheet and cerium oxide nanometer particle composite material - Google Patents
Construction and application of two-dimensional nanometer sheet and cerium oxide nanometer particle composite material Download PDFInfo
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- CN104056614B CN104056614B CN201410270197.0A CN201410270197A CN104056614B CN 104056614 B CN104056614 B CN 104056614B CN 201410270197 A CN201410270197 A CN 201410270197A CN 104056614 B CN104056614 B CN 104056614B
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Abstract
The invention relates to a method for assembling and constructing a novel composite functional material by a protonation transition metal composite oxide nanometer sheet and a cerium oxide nanometer particle. The method is characterized in that successful compounding of two sols can be realized under the mild condition, and has the advantages of simplicity in operation, uniformity in dispersing an object material, and the like. By taking HTiNbO5 nanometer sheet sol (which is prepared by performing proton exchange and stripping modification on lamellar composite oxide KTiNbO5 prepared by using a high-temperature solid-phase method) as the main body material and taking cerium oxide hydrosol as the object material, novel photocatalytic material e-HTiNbO5/CeO2 is prepared through compound assembling, and a spectrum response range of the photoelectric material is moved into a visible region from an ultraviolet light region. Ethanethiol is subjected to photocatalytic oxidation under static adsorption, and results indicate that compared with e-HTiNbO5 aggregate, the nanometer composite material has a more remarkable catalysis performance of degrading organic sulfides in a photocatalysis manner.
Description
Technical field
The present invention relates to a kind of simple to operate, guest materials finely dispersed preparation two dimension protonation titanium niobic acid nanometer sheet e-
htinbo5With one-dimensional cerium oxide ceo2Nanoparticle assembling builds method and the application of NEW TYPE OF COMPOSITE catalysis material.Belong to two dimension
Nanometer sheet builds the technical field of the method for composite photocatalyst material with 1-dimention nano particle assembling.It is mainly characterized by adopting and divides
Scattered nanometer sheet colloid material of main part and scattered oxide sol guest materials are controlled being combined, and build to visible light-responded
Photocatalysis composite functional material, and be applied to the photocatalytic oxidation degradation of organic sulfur compound in natural gas or biogas.
Background technology
Layered mixed oxide titanium columbate has high-ratio surface, interlayer ion interchangeability, electronics and proton conductive
The advantages of, can be modified obtaining new function material by methods such as ion exchange, organic intercalation and stripping restructuring
Material.These materials can be widely applied to photocatalysis, solid acid catalysis, modified electrode, solaode, fuel cell, lithium battery,
The aspects such as hydrogen storage, the material with nanometer chip architecture that particularly stripped restructuring modification obtains has high aspect ratio and can use
In biological implantation material, sensor, drug system etc..
In recent years the ion modification to lamellar compound, oxide pillars are concentrated mainly on to the research of layered photocatalyst material
Support and group are filled with acquisition new function catalysis material.Research shows, has the catalysis material such as titanate, titanium of layer structure
Niobates etc., by ion exchange, peeling off the method for modifying such as assembling can be with its catalytic performance of modulation so that this kind of layered photocatalyst
Agent has response in visible region, to obtain the photocatalyst just under visible light conditions with light-catalyzed reaction activity.
At present, the research of rare-earth metal catalyst and metal oxide nanoparticles composite photo-catalyst is also gradually closed
Note.Research shows: ce co-doping titanium dioxide photocatalyst can be degraded methyl orange under visible light；ce3+The tio of doping2Catalysis
Agent has preferable degradation effect to 2-mercaptobenzothiazole (mbt)；cu/ceo2Catalyst can be catalyzed so2It is oxidized to so3；Ce, si
The ce-si/tio of codope2There is photocatalytic activity under visible light.Layered titanoniobate etc. leads to as a class novel photocatalyst
Cross and can not only reduce the energy gap of synthesized material moreover it is possible to press down with the doping such as transition metal, alkali metal or rare earth ion
Photoinduced electron processed and hole in conjunction with therefore Layered titanoniobate is combined with rare-earth oxide ceria and urges as light
Agent has broad application prospects.
The method that the present invention is combined using two kinds of colloidal sols with heterogeneity electric charge, by one-dimensional cerium oxide nano particle and two
Dimension protonation titanium columbate nanometer sheet carries out the visible light-responded Photocatalysis Function Material of compound structure, and is applied to photocatalytic-oxidation
Change degraded organic sulfur compound.Using ethyl mercaptan as representative organic sulfur compound, result of study shows, this nano composite material has
The catalytic performance of obvious photocatalytic degradation organic sulfur compound.The method successfully by 1-dimention nano particle assembling in two-dimensional nano
Sheet matrix surface, and dispersed.
Content of the invention
The present invention relates to a kind of protonation composite transition metal oxide nanometer sheet and rare earth oxide cerium dioxide nano
Particle assembling builds NEW TYPE OF COMPOSITE Photocatalysis Function Material, that is, adopt the method for simple operationss by 1-dimention nano particle ceria
It is assembled in protonation composite transition metal oxide titanium niobic acid two-dimensional nano piece matrix surface, and dispersed.Prepared answers
The photocatalytic oxidation degradation removing of closing light catalysiss materials application organic sulfur compound in natural gas or biogas.The present invention carries
1-dimention nano particle has been supplied successfully to be assembled in two-dimensional nano piece matrix surface, and homodisperse method, and use it for energy
The purification of the fuel gas in the conversion process of source.Specifically include following steps:
(1) prepare 0.6mol l–1Hno3Solution 150ml is standby.
(2) use the 0.6mol l preparing in step (1)–1Hno3Solution prepares 0.25mol l–1ce(no3)3Solution
100ml.
(3) implement 1: measure the 20ml0.25mol l preparing in step (2)–1ce(no3)3Solution, adds 30%
Hydrogenperoxide steam generator, makes ce3+And h2o2The amount of material, than for 1:1.2, under conditions of being stirred continuously, is slowly added dropwise
0.02mol·l–1nh3·h2O solution is to ph between 4～5, you can generates the cerium oxide nano hydrosol of yellow, is designated as 1#.
Implement 2: measure the 20ml0.25mol l preparing in step (2)–1ce(no3)3Solution, adds 30% peroxide
Change hydrogen solution, make ce3+And h2o2The amount of material, than for 1:0.8, under conditions of being stirred continuously, is slowly added dropwise 0.02mol l– 1nh3·h2O solution ph is between 4～5, you can generates the cerium oxide nano hydrosol of yellow, is designated as 2#.
Implement 3: measure the 20ml0.25mol l preparing in step (2)–1ce(no3)3Solution, adds 30% peroxide
Change hydrogen solution, make ce 3+And h2o2The amount of material, than for 1:0.4, under conditions of being stirred continuously, is slowly added dropwise 0.02mol l– 1nh3·h2O solution ph is between 4～5, you can generates the cerium oxide nano hydrosol of yellow, is designated as 3#.
Implement 4: measure the 20ml0.25mol l preparing in step (2)–1ce(no3)3Solution, is not added with 30% peroxide
Change hydrogen solution, under conditions of being stirred continuously, be slowly added dropwise 0.02mol l–1nh3·h2O solution ph is between 4～5, you can
Generate the cerium oxide nano hydrosol of yellow, be designated as 4#.
(4) with titanium dioxide (tio2), niobium oxide (nb2o5) and potassium carbonate (k2co3) it is raw material, using high temperature solid-state method
Prepare predecessor ktinbo5Through h+Exchange the stratified material htinbo obtaining white powder5.
Take appropriate htinbo5In conical flask, plus appropriate amount of deionized water mix homogeneously, four fourths of 25% after Deca dilution
Base ammonium hydroxide (tbaoh) solution, conical flask, between 9～10, is then placed in constant temperature under 318k by the ph adjusting this mixed liquor
After vibration 5d, using high speed centrifuge, reacted emulsion is centrifuged, the upper strata colloidal sol obtaining is htinbo5Nanometer sheet is molten
Glue is standby, centrifuge speed 9000r min–1, centrifugation time 10min.
Take htinbo prepared in right amount5Nano-film sol, by 200ml0.05mol l–1Hno3Solution is with 20ml h–1Speed drops to htinbo5In nano-film sol, there is coagulation thing to occur, this coagulation thing is washed with deionized to no nitric acid
Residual, is vacuum dried under 333k, grinds and obtains final product htinbo5Nanometer sheet aggregation, is designated as e-htinbo5Aggregation.
(5) implement 1: under conditions of standing, respectively to implement the 1# cerium oxide nano hydrosol obtaining in (3) as object
Material, is slowly added dropwise to the material of main part htinbo implementing acquisition in 45In nano-film sol, after concussion reaction 6h under 318k,
Using dust technology adjust ph to 5～6, and precipitate be not further added by after, under 318k continue concussion 6h, room temperature standing aging.With filter
Film sucking filtration separates, and sucking filtration is drained three times with the alcohol-water solution of 1:1 before terminating, and obtains cream solid, is vacuum dried under 333k
Obtain catalysis material, be designated as e-htinbo5/ceox-1#.
Implement 2: under conditions of standing, respectively to implement the 2# cerium oxide nano hydrosol obtaining in (3) for object material
Material, is slowly added dropwise to the material of main part htinbo implementing acquisition in 45In nano-film sol, after concussion reaction 6h under 318k, adopt
With dust technology adjust ph to 5～6, and precipitate be not further added by after, under 318k continue concussion 6h, room temperature standing aging.Use filter membrane
Sucking filtration separates, and sucking filtration is drained three times with the alcohol-water solution of 1:1 before terminating, and obtains cream solid, is vacuum dried under 333k
To catalysis material, it is designated as e-htinbo5/ceox-2#.
Implement 3: under conditions of standing, respectively to implement the 3# cerium oxide nano hydrosol obtaining in (3) for object material
Material, is slowly added dropwise to the material of main part htinbo implementing acquisition in 45In nano-film sol, after concussion reaction 6h under 318k, adopt
With dust technology adjust ph to 5～6, and precipitate be not further added by after, under 318k continue concussion 6h, room temperature standing aging.Use filter membrane
Sucking filtration separates, and sucking filtration is drained three times with the alcohol-water solution of 1:1 before terminating, and obtains cream solid, is vacuum dried under 333k
To catalysis material, it is designated as e-htinbo5/ceox-3#.
Implement 4: under conditions of standing, respectively to implement the 4# cerium oxide nano hydrosol obtaining in (3) for object material
Material, is slowly added dropwise to the material of main part htinbo implementing acquisition in 45In nano-film sol, after concussion reaction 6h under 318k, adopt
With dust technology adjust ph to 5～6, and precipitate be not further added by after, under 318k continue concussion 6h, room temperature standing aging.Use filter membrane
Sucking filtration separates, and sucking filtration is drained three times with the alcohol-water solution of 1:1 before terminating, and obtains cream solid, is vacuum dried under 333k
To catalysis material, it is designated as e-htinbo5/ceox-4#.
(6) prepared catalysis material in step (5) is carried out UV-Vis DRS spectrum (uv-vis drs) table
Levy.The optimal photocatalyst of photo absorption property is selected by characterization result.
The photophase feature of sample prepared by table 1
(7) take prepared e-htinbo in appropriate step (4)5Prepared having most preferably in aggregation and step (6)
The catalysis material of photo absorption property in 453k activation processing 1h, accurately weigh 50mg catalyst be positioned over 235ml () in quartz reactor, air atmosphere, em is respectively 2.87kpa and 3.17kpa with the initial partial pressure of steam,
Absorption 1h, the quartz reactor after absorption is placed in irradiation 1h under visible ray.Visible light source is that Xi'an is more limited than bright biotechnology
Company produces, and power is 500w.
Brief description
Fig. 1 is embodiment 1 preparation htinbo5Predecessor ktinbo used by nano-film sol5(a) and htinbo5The xrd of (b)
Collection of illustrative plates.The xd-3 type x-ray diffraction that the X-ray diffraction instrument being used produces for Beijing Puxi General Instrument Co., Ltd
Instrument.Experiment condition: copper target, pipe pressure: 35kv；Pipe flow: 30ma.
Fig. 2 is the e-htinbo that embodiment 1 is obtained5Aggregation (a) and e-htinbo5/ceo2The xrd collection of illustrative plates of (b).Institute
Using instrument and the same Fig. 1 of test condition.
Fig. 3 is the e-htinbo that embodiment 1 is obtained5Aggregation (a) and e-htinbo5/ceo2The raman spectrum of (b)
Figure.The in via-reflex type laser that the laser capture microdissection Confocal laser-scanning microscopy Yi Shi renishaw company being used produces shows
Micro- Confocal laser-scanning microscopy instrument.Laser source wavelength is 532nm, laser intensity 5mw.
Fig. 4 and Fig. 5 is the e-htinbo that embodiment 1 is obtained respectively5Aggregation (a) and e-htinbo5/ceo2(b)
Tem picture.The ht7700 type transmission electron microscope that the transmission electron microscope being used produces for Hitachi, Ltd.
Fig. 6 is the e-htinbo that embodiment 1 is obtained5The bet curve of aggregation.The specific surface area being used and aperture are divided
Beckman coulter sa3100 type specific surface area and Porosimetry that analyzer produces for Beckman Coulter Inc. of the U.S..
Fig. 7 is the e-htinbo prepared by embodiment 15/ceo2Bet curve.The instrument being used and the same Fig. 6 of condition.
Fig. 8 is the e-htinbo obtained in embodiment 15The thermal analysis curve of aggregation.The thermogravimetric synchronization discrepancy being used
Hot thermal analyzer is the sta449c type tg-dsc synchronous solving of the limited production of the resistance to instrument manufacturing of speeding of Germany.Temperature elevating range: room
Temperature～800 DEG C, heating rate: 10k min–1.
Fig. 9 is the e-htinbo prepared by embodiment 15/ceo2Thermal analysis curve.The instrument being used and condition are with figure
7.
Figure 10 is the e-htinbo prepared by embodiment 15Aggregation (a) and e-htinbo5/ceo2The ultraviolet-visible of (b)
Diffuse spectrogram.The ultraviolet-visible spectrophotometer being used is the tu- that Beijing Pu Xi all purpose instrument company limited produces
1901 dual-beam ultraviolet-visible spectrophotometers, reference: baso4.
Figure 11 is the e-htinbo before and after static adsorption-light-catalyzed reaction in embodiment 15Aggregation (1) and e-htinbo5/
ceo2(2) ft-tr spectrogram.Wherein, (a) fresh sample；Sample after (b) static adsorption-visible light catalytic.Used
Fourier transformation infrared spectrometer is the vector33 Fourier transformation infrared spectrometer that German Brooker company produces, and scans model
Enclose: 4000cm–1～400cm–1, scanning times: 32, resolution: 4cm–1.
Specific embodiment
Example that specific complex group accommodate nano composite material is given below.Wherein, embodiment 1 is most preferably modified result
Embodiment, and prepared material is represented by e-htinbo5/ceo2.
Embodiment 1
Step 1
1. prepare 0.6mol l–1Hno5Solution 150ml is standby.
2. accurately weigh 10.856g ce (no3)3·6h2O, with the 0.6mol l of step 1. middle preparation–1Hno5Solution
Prepare 0.25mol l–1ce(no3)3Solution 100ml.
3. measure step 2. in the 20ml0.25mol l for preparing–1ce(no3)3Solution, adds 30% hydrogen peroxide
Solution, makes ce3+And h2o2The amount of material, than for 1:1.2, under conditions of being stirred continuously, is slowly added dropwise 0.02mol l–1nh3·
h2Between o solution 60～150ml, now the ph of solution system is 4～5, you can generate the cerium oxide nano hydrosol of yellow.
Step 2
1. accurately weigh 1.553g tio2, 2.576g nb2o5And 1.477g k2co3Mix in agate mortar, with no
Water-ethanol is tuned into pasty state, is ground to ethanol and substantially volatilizees completely.
2. by step 1. in ground mixture be placed in thermostatic drying chamber, 353k is dried completely, about 10h.
3. by step, 2. gained pressed powder takes out, and more than 30min is ground in cooling.
4. by step 3. in ground mixture be transferred in corundum crucible and transfer in temperature programming resistance furnace, first
With 5k min–1Programming rate be warmed up to 1073k, then with 1k min–1Programming rate be warmed up to 1373k constant temperature 24h, from
So it is cooled to room temperature.
5. by after step 4. EP (end of program), product is taken out and is scattered in appropriate amount of deionized water, filtering and washing to filtrate is in
Neutrality, dries then at 353k and white powdery solids ktinbo is obtained5, yield is about 90%.
Step 3
1. weigh 3.000g ktinbo5In 50ml conical flask, add 30ml2mol l–1Hno3Solution is permanent in 318k
Temperature vibration.
2. after reaction 24h, by step 1. in mixed solution take out standing 4h, careful separation adds after going out supernatant
The fresh 2mol l of 30ml–1Hno3Solution.
3. repeat step 2. 3 times.
4. the step mixed liquor that 3. middle reaction terminates is taken out, filtering and washing to filtrate is in neutrality, dries system then at 353k
Obtain white powdery solids htinbo5, yield is about 86%.
Step 4
1. weigh 1.000g htinbo5In 250ml conical flask, add 50ml deionized water.
2. TBAH (tbaoh) solution pipetting 1.0ml25% is scattered in 150ml deionized water.
3. by step 2. middle dilution after tbaoh solution be slowly added dropwise to step 1. in mixed liquor in and in Deca process
In shake up for several times manually, after completion of dropwise addition, the ph of mixed liquor is between 9～10.
4. by step 3. in mixed liquor be transferred in gas bath constant temperature oscillator, constant temperature oscillation 5d under 318k.
5. by step, 4. middle reaction terminates the emulsion centrifugation obtaining, and the upper strata colloidal sol obtaining is htinbo5Receive
Rice film sol.Centrifuge speed 9000r min–1, centrifugation time 10min.
6. by step 5. in the lower floor solid that is centrifugally separating to obtain take out and be scattered in about 200ml deionized water, Deca
25% TBAH (tbaoh) solution adjusts ph between 9～10, constant temperature oscillation 5d under 318k.
7. repeat step 5. with step 6. twice, merges the upper strata htinbo isolating every time5Nano-film sol.
8. take appropriate by step 7. in prepared htinbo5Nano-film sol 600ml, with about 20ml h–1Speed Deca
By 200ml0.05mol l–1Hno3Solution is to htinbo5In nano-film sol, white coagulation thing is had to occur, by this coagulation thing
It is washed with deionized to no nitric acid residual, is vacuum dried under 333k, grind and obtain final product htinbo5Nanometer sheet aggregation, is designated as e-
htinbo5Aggregation.
Step 5
1. measure prepared cerium oxide nano hydrosol 67ml, under conditions of standing, be slowly added dropwise made to 207ml
Standby htinbo5In nano-film sol.
2. by the mixed liquor of step 1. middle acquisition, after being placed in concussion 6h under 318k, adjust ph to 6 with dust technology, in 318k
Lower continuation concussion 6h, room temperature stands aging more than 24h.
3. by step 2. in product with filter membrane sucking filtration separate, sucking filtration terminate before drain three with the alcohol-water solution of 1:1
Secondary, obtain cream solid, vacuum drying, grinding, that is, obtain in visible light-responded catalysis material e- under 333k
htinbo5/ceo2.
Step 6
1. take the e-htinbo of 100mg preparation5Aggregation and the catalysis material e- with optimal photo absorption property
htinbo5/ceo2In 453k activation processing 1h.
2. respectively precise 50mg 1. in the catalyst sample handled well be positioned over 235ml () stone
In English reactor, air atmosphere, em is respectively 2.87kpa and 3.17kpa with the initial partial pressure of steam, adsorbs 1h.
3. step after 2. middle absorption terminates, the quartz reactor after absorption is placed in irradiation 1h under visible ray.Visible light source
Xi'an produces than bright bio tech ltd, and power is 500w.
Embodiment 2
Specific implementation steps are substantially the same manner as Example 1, and institute's difference is to add in the step 1 of embodiment 1
30% hydrogenperoxide steam generator, makes ce3+And h2o2The amount of material is than for 1:0.8.
Embodiment 3
Specific implementation steps are substantially the same manner as Example 1, and institute's difference is to add in the step 1 of embodiment 1
30% hydrogenperoxide steam generator, makes ce3+And h2o2The amount of material is than for 1:0.4.
Embodiment 4
Specific implementation steps are substantially the same manner as Example 1, and institute's difference is to be not added with the step 1 of embodiment 1
30% hydrogenperoxide steam generator.
Claims (2)
1. a kind of protonation composite oxides nano-film sol and ceria (ceo2) Nano sol assembling structure composite photocatalyst
The method of material is it is characterised in that by a certain proportion of htinbo5Nano-film sol and ceo2It is anti-that colloidal sol carries out mixing at normal temperatures
Should a period of time after, adjust mixed system ph so that complex is separated out completely, separate, washing, be dried after obtain under visible light
The catalysis material e-htinbo of response5/ceo2.
2. the photocatalysis composite e-htinbo that method as claimed in claim 1 obtains5/ceo2It is applied to natural gas, biology
The absorption of the organic sulfur compound in gas is removed with the photochemical catalytic oxidation under visible radiation.
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