CN104897655A - Method for rapidly detecting oxygen vacancy in titanium oxide - Google Patents
Method for rapidly detecting oxygen vacancy in titanium oxide Download PDFInfo
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- CN104897655A CN104897655A CN201510346373.9A CN201510346373A CN104897655A CN 104897655 A CN104897655 A CN 104897655A CN 201510346373 A CN201510346373 A CN 201510346373A CN 104897655 A CN104897655 A CN 104897655A
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- titanium dioxide
- oxygen
- lacking oxygen
- ceramic rod
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Abstract
The invention discloses a method for rapidly detecting an oxygen vacancy in titanium oxide. The method includes that gas molecule ether and oxygen are diffused to the titanium oxide surface; since the oxygen vacancy on the titanium oxide surface has strong capacity of adsorbing an oxygen molecule, the oxygen adsorbed to the oxygen vacancy forms a super-oxygen kind (O2<->) quite strong in oxidability by capturing a free electron, then, an ether molecule in the chemical adsorption state reacts with the O2<-> to form an acetaldehyde molecule (CH3CHO*) in the excited state, a certain energy can be produced in a process that the acetaldehyde molecule in the excited state returns to the ground state, and is released in a photology form, and a chemiluminescent analyzer detects a luminescence signal value of luminescence so as to obtain a value of the oxygen vacancy in the titanium oxide according to the direct proportion relation between the content of the oxygen vacancy and the luminescence signal. The method has the advantages of simple equipment, rapidity, easiness in operation and wide application prospect for assessment of the oxygen vacancy of extensive research significance in defective oxides.
Description
Technical field
The invention belongs to titanium oxide catalyst research field, be specifically related to a kind of correlativity utilizing the Lacking oxygen of titanium dioxide and ether catalytic luminescence to react, detect the method for Lacking oxygen in titanium dioxide using ether as molecular probe fast.
Background technology
Titanium dioxide has very excellent optical characteristics, high chemical stability, thermal stability, non-toxic and large in occurring in nature storage capacity, all demonstrates good development prospect in a lot of field.Research finds, the character of titanium dioxide not only depends on its geometry and electronic structure, is also subject to the impact of its defect sturcture simultaneously.At present, there is a lot of scientific workers to be devoted to the chemistry of titanium dioxide defect, electricity and OPTICAL PROPERTIES, better to regulate and control the concentration of Lacking oxygen, thus promoted catalytic reaction.In the defect of these titanium dioxide, Lacking oxygen is considered to the defect having outstanding Research Significance.Theory calculate and Experimental Characterization display, the Lacking oxygen in titania as light induced electron trap, thus effectively can strengthen its photocatalytic activity.Therefore, in effectively evaluating titanium dioxide, the concentration of Lacking oxygen has very important significance for the character by suitable means regulation and control titanium dioxide.
But because Lacking oxygen has instability, the character that concentration is low, causes it to be difficult to detected.The method detected for Lacking oxygen at present mainly contains surface titration method, electron paramagnetic spectrum (ESR), x-ray photoelectron spectroscopy method (XPS).Such as: A.N.Petrov, Solid State Ionics 1995,80, the 189-199 document adopts surface titration method, and the method is traditional Lacking oxygen qualitative and quantitative analysis method, and its shortcoming works as TiO
2when catalyst color is darker, titration end-point is easily interfered and produces certain error.Document Xu, X.Inorg.Chem.2015,54,1556-1562 utilize electron paramagnetic spectrum (ESR) to carry out effective sign to Lacking oxygen, but the requirement of usual this method to system is higher, need technical professional to operate simultaneously; Document Murray, C.B.J.Am.Chem.Soc.2012,134,6751-6761 adopt x-ray photoelectron spectroscopy method (XPS), utilize the XPS of O 1s to combine and well can characterize TiO
2the Lacking oxygen on surface, but this method relative cost is higher, and length consuming time, which limits the widespread use of this technology.The method studying Lacking oxygen in a kind of quick, easy evaluation titanium dioxide is considerable.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, provide the method for Lacking oxygen in a kind of quick detection titanium dioxide, the method is easy, quick, has higher actual application prospect.
The method, using ether molecule as probe, utilizes the TiO of metal ion mixing
2and the TiO that hydrogen is heat treated
2catalytic activity and the correlativity of its Lacking oxygen content, detect the Lacking oxygen of titanium dioxide in conjunction with gas catalysis luminescence fast, and then screening and assessment carried out to the catalytic activity of titanium dioxide.Under gaseous state, first, gas molecule ether and oxygen are diffused into titania surface; The Lacking oxygen of titania surface has the ability of stronger adsorption of oxygen molecule, and the oxygen being adsorbed onto Lacking oxygen can form by catching a free electron the super oxygen kind (O had compared with strong oxidizing property
2 -), then, the ether molecule of chemical adsorption states and O
2 -reaction generates the acetaldehyde molecule (CH of excited state
3cHO
*), the process that the acetaldehyde molecule of excited state gets back to ground state can produce certain energy, and this energy discharges with the form of optics, and is detected by photomultiplier amplifying signal.Being directly proportional to luminous signal according to the amount of Lacking oxygen in titanium dioxide, by measuring the power of luminous signal, realizing the quick detection of Lacking oxygen in titanium dioxide, applicable titanium oxide catalyst can be screened simultaneously.
Detect the device of Lacking oxygen in titanium dioxide as shown in Figure 1, its air pump, vaporizer, quartz ampoule are connected by silicone tube, and quartz ampoule is placed in chemiluminescent analyzer; Have a detachable ceramic rod in quartz ampoule, a contact transformer heats to ceramic rod; Chemiluminescent analyzer is connected with computer.
In titanium dioxide, the concrete method of testing of Lacking oxygen is as follows:
A. titanium dioxide powder is added in deionized water the slurries being made into 0.50-0.55g/mL, be evenly coated on ceramic rod, the thickness of coating is 0.45-0.50mm.
Described titanium dioxide is doped with M metallic ion, and M is one of Cu, Fe, Co, Cr ion, and the doping of M accounts for TiO
2mass percentage be 0.5%-2.0% and under 250 DEG C of-400 DEG C of hydrogen atmospheres the titanium dioxide of calcination process 30-60 minute.
B. treat that the slurries on steps A ceramic rod are micro-dry, ceramic rod is loaded in the quartz ampoule of chemiluminescent analyzer device inside; Removing pneumatic pump in water, with the air after activated carbon filtration as reaction carrier gas, coutroi velocity, at 200-300mL/min, makes the surface by ceramic rod in quartz ampoule of Uniform gas flow velocity; Impose the voltage of 100-110V with contact transformer to ceramic rod, the temperature of ceramic rod is risen to the temperature 150-200 DEG C of detection;
C. rising temperature device in unlatching vaporizer makes temperature rise to 150-200 DEG C, 0.1 mole of diethyl ether solution is injected vaporizer, air in pneumatic pump flows through vaporizer and brings the ether of wherein vaporizing into quartz ampoule, titanium dioxide on ether and ceramic rod reacts and produces luminescence, by chemiluminescent analyzer image data, record and analyze data.According to the phenomenon that the amount of Lacking oxygen in titanium dioxide is directly proportional to the luminous signal that reaction produces, thus the height of Lacking oxygen content in titanium oxide catalyst can be compared.
Described vaporizer is that outside has the volume of heating jacket to be the canister of 1-2mL.
Fig. 2 display be the catalytic luminescence signal of the Cu adulterated TiOx of different quality mark, along with increasing of Cu doping content, chemiluminescence signal value presents the trend first raising and reduce afterwards, and this trend is consistent with the variation tendency of the content of Lacking oxygen in the adulterated TiOx of Cu shown in table 1 sample; Fig. 3 display be Cu, Fe, Co, Cr tetra-catalytic luminescence signal of titanium dioxide of metal ion species doping, wherein Cu/TiO
2luminous signal is the highest, is followed successively by Co/TiO
2, Fe/TiO
2, Cr/TiO
2; Fig. 4 display be the chemiluminescence signal of titanium dioxide sample under hydrogen atmosphere after different temperatures calcination process, chemiluminescence signal intensity presents increase tendency along with the rising of sintering temperature.
The invention has the beneficial effects as follows: adopt ether to carry out the method for Lacking oxygen in Fast Evaluation titanium dioxide as molecular probe, this method is easy, quick, and equipment is simple simultaneously, cost is low, the reaction time is short, can be widely used in the evaluation of Lacking oxygen in titanium dioxide.
Accompanying drawing explanation
The reaction unit figure that in Fig. 1 titanium oxide catalyst, Lacking oxygen is evaluated.
1 is pneumatic pump, and 2 is vaporizer, and 3 is chemiluminescent analyzer, and 4 is computer, and 5 is quartz ampoule, and 6 is ceramic heating bar, and 7 is transformer.
The corresponding diagram of Cu doping and catalytic luminescence signal in titanium dioxide in Fig. 2 embodiment 1.
The corresponding diagram of the metallic ion adulterated in titanium dioxide in Fig. 3 embodiment 2 and catalytic luminescence signal.
The sintering temperature of titanium dioxide in hydrogen and the corresponding diagram of catalytic luminescence signal in Fig. 4 embodiment 3.
Embodiment
Embodiment 1
Adopt experimental provision described in Fig. 1.
A. plain TiO is got
2and the TiO of 1.0%, 1.5%, 2.0%Cu doping
2powder adds deionized water for stirring evenly respectively, is made into the slurries of 0.50g/mL; To be spread upon on ceramic rod and thickness is about 0.50mm, ceramic rod is inserted in quartz ampoule, 105V voltage is imposed to ceramic rod, then with silica gel in pneumatic pump, the air that charcoal treatment is crossed is as the carrier gas ventilation 30min reacted, and gas flow rate is 250mL/min, when the temperature of ceramic rod reaches 170 DEG C, starting vaporizer heat riser, is 170 DEG C to temperature of vaporization chamber.Ensure the stable operation of chemiluminescent analyzer.
B. the diethyl ether solution of 25 μ L 0.1mol/L is injected vaporizer, be loaded into quartz ampoule and Cu/TiO on ceramic rod by the air in pneumatic pump
2go up and chemisorption oxygen reaction on a catalyst, produce luminous, by chemiluminescent analyzer image data.As shown in Figure 2, the strong and weak size of chemiluminescence signal is result: TiO
2<1.0%Cu/TiO
2<1.5%Cu/TiO
2>2.0%Cu/TiO
2, along with the increase luminous signal of Cu doping increases, when doping is 1.5%, chemiluminescence signal reaches maximal value; Continue to increase doping to 2.0%, chemiluminescence signal reduces.Illustrate that variation tendency and in the titanium dioxide Lacking oxygen content of luminous signal intensity along with Cu doping is consistent with the variation tendency of Cu doping, draw the conclusion of the relation that the content of luminous signal intensity and Lacking oxygen is proportionate thus.
Comparative example 1
Plain TiO in Example 1
2be respectively 1.0%, 1.5% with Cu doping massfraction, 2.0% powder adopts traditional XPS analysis method to carry out contrast test:
Use Thermo ESCALAB 250 instrument, get the above-mentioned powder of 30-60mg and put into transition chamber after compressing tablet respectively, vacuumize and after supplementing nitrogen three times, sample proceeded in glove box main body, reinstall reactor, carry out pre-service; After pre-service, sheet sample is taken out from reactor, adhere on sample stage with conducting resinl, proceed to energy spectrometer evacuated chamber under nitrogen atmosphere and carry out vacuumizing process, treat that vacuum tightness is higher than 10
-4after Pa, then proceed to energy spectrometer analysis room and detect.According to XPS data test result, following formula (Vo: Lacking oxygen) is utilized to calculate Cu/TiO
2the percentage composition of middle Lacking oxygen:
The percentage of Lacking oxygen=[(Ti atomic percentage × 4) – (Lattice Oxygen atomic percentage × 2)] * sensitivity factor }/2 × 100.
(Wagner,C.D.；Moulder,J.F.；Davis,L.E.；Riggs,W.M.Perkin-Elmer Corporation:Eden Prairie,MN,1979；You,M.；Kim,T.G.；Sung,Y.M.Growth Des.2010,10,983-987)
The results are shown in Table 1:
Table 1
As shown in Table 1, in the titanium dioxide of the different Cu dopings come detected by XPS method, the variation tendency of Lacking oxygen amount is TiO
2<1.0%Cu/TiO
2<1.5%Cu/TiO
2>2.0%Cu/TiO
2, this result and Fig. 2 to survey chemiluminescence signal variation tendency be the same.It can thus be appreciated that, the relation that the content of chemiluminescence signal intensity and Lacking oxygen is proportionate.The method applied in the present invention is consistent with the testing result of traditional XPS method.
Embodiment 2
Get the Cu that massfraction is 1.0%, Co, Fe, Cr tetra-metal ion species doping TiO
2.Other steps are with embodiment 1, and test result is shown in Fig. 3, and the strong and weak size of chemiluminescence signal is: Cu/TiO
2>Co/TiO
2>Fe/TiO
2>Cr/TiO
2.
Embodiment 3
By TiO undoped in embodiment 1
2powder difference 250 DEG C in a hydrogen atmosphere, 300 DEG C, 350 DEG C, 400 DEG C of calcination process 2h, the sample obtained is designated as H-250 respectively, H-300, H-350, H-400.Other steps are with embodiment 1, and test result is shown in Fig. 4, and the strong and weak size of chemiluminescence signal is: H-400>H-350>H-300GreatT.Grea T.GTH-250.
Claims (3)
1. detect a method for Lacking oxygen in titanium dioxide fast, the concrete method of testing changing Lacking oxygen in titanium is as follows:
A. titanium dioxide powder is added in deionized water the slurries being made into 0.50-0.55g/mL, be evenly coated on ceramic rod, the thickness of coating is 0.45-0.50mm;
B. treat that the slurries on steps A ceramic rod are micro-dry, ceramic rod is loaded in the quartz ampoule of chemiluminescent analyzer device inside; Removing pneumatic pump in water, with the air after activated carbon filtration as reaction carrier gas, coutroi velocity, at 200-300mL/min, makes the surface by ceramic rod in quartz ampoule of Uniform gas flow velocity; Impose the voltage of 100-110V with contact transformer to ceramic rod, the temperature of ceramic rod is risen to the temperature 150-200 DEG C of detection;
C. rising temperature device in unlatching vaporizer makes temperature rise to 150-200 DEG C, 0.1 mole of diethyl ether solution is injected vaporizer, air in pneumatic pump flows through vaporizer and brings the ether of wherein vaporizing into quartz ampoule, titanium dioxide on ether and ceramic rod reacts and produces luminescence, detects its luminous signal value by chemiluminescent analyzer.
2. the method for Lacking oxygen in quick detection titanium dioxide according to claim 1, it is characterized in that the titanium dioxide described in steps A is doped with M metallic ion, M is one of Cu, Fe, Co, Cr ion, and the doping of M accounts for TiO
2mass percentage be 0.5%-2.0%, this iron oxide is through the titanium dioxide of under 250 DEG C of-400 DEG C of hydrogen atmospheres calcination process 30-60 minute.
3. the method for Lacking oxygen in quick detection titanium dioxide according to claim 1, is characterized in that the relation be directly proportional to luminous signal according to the amount of Lacking oxygen, and the luminous signal value obtained from step C obtains the qualitative value of Lacking oxygen titanium dioxide indirectly.
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Cited By (2)
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| CN109115940A (en) * | 2018-10-22 | 2019-01-01 | 北京科技大学 | A kind of iodine number method measuring oxygen vacancy concentration in bismuth ferrite based leadless piezoelectric ceramics |
| CN111693590A (en) * | 2020-06-03 | 2020-09-22 | 同济大学 | Device and method for measuring gas oxidability |
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| US8502343B1 (en) * | 2010-11-17 | 2013-08-06 | The University Of Toledo | Nanoelectric memristor device with dilute magnetic semiconductors |
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| CN104609467A (en) * | 2015-01-21 | 2015-05-13 | 武汉理工大学 | Photoinduced red-turning titanium oxide as well as preparation method and application thereof |
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| US8502343B1 (en) * | 2010-11-17 | 2013-08-06 | The University Of Toledo | Nanoelectric memristor device with dilute magnetic semiconductors |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109115940A (en) * | 2018-10-22 | 2019-01-01 | 北京科技大学 | A kind of iodine number method measuring oxygen vacancy concentration in bismuth ferrite based leadless piezoelectric ceramics |
| CN109115940B (en) * | 2018-10-22 | 2020-12-22 | 北京科技大学 | Iodine amount method for determining oxygen vacancy concentration in bismuth ferrite-based lead-free piezoelectric ceramic |
| CN111693590A (en) * | 2020-06-03 | 2020-09-22 | 同济大学 | Device and method for measuring gas oxidability |
| CN111693590B (en) * | 2020-06-03 | 2021-05-11 | 同济大学 | Device and method for measuring gas oxidability |
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