CN104897655B - A kind of method of Lacking oxygen in quick detection titanium oxide - Google Patents
A kind of method of Lacking oxygen in quick detection titanium oxide Download PDFInfo
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- CN104897655B CN104897655B CN201510346373.9A CN201510346373A CN104897655B CN 104897655 B CN104897655 B CN 104897655B CN 201510346373 A CN201510346373 A CN 201510346373A CN 104897655 B CN104897655 B CN 104897655B
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- titanium oxide
- lacking oxygen
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Abstract
The invention discloses a kind of method of Lacking oxygen in quick detection titanium oxide.Gas molecule ether and oxygen are first diffused into titania surface by this method；Because the Lacking oxygen of titania surface has the ability of strong adsorption of oxygen molecule, the oxygen of Lacking oxygen is adsorbed onto by capturing a super oxygen species (O of the free electron formation with compared with strong oxidizing property2 ‑), then, the ether molecule and O of chemical adsorption states2 ‑Acetaldehyde molecule (the CH of reaction generation excitation state3CHO*), the process that the acetaldehyde molecule of excitation state returns to ground state can produce certain energy, and the energy is discharged in optical form, and its luminous signal value is detected by chemiluminescent analyzer, the relation being directly proportional according to the amount of Lacking oxygen to luminous signal, obtains the value of Lacking oxygen in titanium oxide.This method has the advantages that equipment is simple, quick, easily operated.It has broad application prospects for the evaluation of the Lacking oxygen with widely studied meaning in defect oxide.
Description
Technical field
The invention belongs to titanium oxide catalyst research field, and in particular to a kind of Lacking oxygen of utilization titanium oxide is urged with ether
Change the correlation of luminescence-producing reaction, the method for Lacking oxygen in quick detection titanium oxide is carried out using ether as molecular probe.
Background technology
Titanium oxide is with very excellent optical characteristics, high chemical stability, heat endurance, nontoxicity and in nature
Middle storage capacity is big, and good development prospect is all shown in many fields.Research finds that the property of titanium oxide is not depended solely on
Its geometry and electronic structure, while also being influenceed by its defect sturcture.At present, many scientific workers endeavour
In the chemistry of titanium oxide defect, electricity and OPTICAL PROPERTIES, preferably to regulate and control the concentration of Lacking oxygen, so as to promote to urge
Change reaction.In the defect of these titanium oxide, Lacking oxygen is considered as the defect for having prominent Research Significance.Theoretical calculation and experiment
The Lacking oxygen characterized in display, titanium dioxide can be as light induced electron trap, so as to effectively strengthen its photocatalytic activity.Cause
This, the concentration of Lacking oxygen is for regulating and controlling the property of titanium oxide by suitable means with very heavy in effectively evaluating titanium oxide
The meaning wanted.
However, because Lacking oxygen has unstable, the low property of concentration, it is difficult to be detected to cause it.It is empty currently used for oxygen
The method of position detection mainly has surface titration method, electron paramagnetic spectrum (ESR), x-ray photoelectron spectroscopy method (XPS).For example：
The document of A.N.Petrov, Solid State Ionics 1995,80,189-199 uses surface titration method, and this method is biography
The Lacking oxygen qualitative and quantitative analysis method of system, it has the disadvantage to work as TiO2When catalyst color is deeper, titration end-point easily by
Disturb and produce certain error.Document Xu, X.Inorg.Chem.2015,54,1556-1562 utilize electron paramagnetic spectrum
(ESR) effective sign has been carried out to Lacking oxygen, but generally requirement of this method to system is higher, while needing specialty
Technical staff operation；Document Murray, C.B.J.Am.Chem.Soc.2012,134,6751-6761 use X-ray photoelectricity
Sub- spectroscopy (XPS), TiO can be characterized well by being combined using O 1s XPS2The Lacking oxygen on surface, but this method phase
Higher to cost, time-consuming, and which limits the extensive use of the technology.A kind of quick, easy evaluation titanium oxide of research
The method of middle Lacking oxygen is considerable.
The content of the invention
The purpose of the present invention is to overcome that of the prior art not enough there is provided a kind of side of Lacking oxygen in quick detection titanium oxide
Method, this method is easy, quick, with higher actual application prospect.
This method utilizes the TiO of metal ion mixing using ether molecule as probe2And the heat treated TiO of hydrogen2
Catalytic activity and its Lacking oxygen content correlation, lighted with reference to gas catalysis and carry out the Lacking oxygen of quick detection titanium oxide, entered
And the catalytic activity to titanium oxide carries out screening and assessment.Under gaseous state, first, gas molecule ether and oxygen are diffused into oxygen
Change titanium surface；The Lacking oxygen of titania surface has the ability of stronger adsorption of oxygen molecule, and the oxygen for being adsorbed onto Lacking oxygen can
With by capturing a super oxygen species (O of the free electron formation with compared with strong oxidizing property2 -), then, the ether of chemical adsorption states
Molecule and O2 -Acetaldehyde molecule (the CH of reaction generation excitation state3CHO*), the process that the acetaldehyde molecule of excitation state returns to ground state can be produced
Raw certain energy, the energy is discharged in optical form, and amplifies signal detection by photomultiplier.According to titanium oxide
The amount of middle Lacking oxygen is directly proportional to luminous signal, by determining the power of luminous signal, realizes the quick of Lacking oxygen in titanium oxide
Detection, while suitable titanium oxide catalyst can be screened.
Detect the device of Lacking oxygen in titanium oxide as shown in figure 1, its air pump, vaporizer, quartz ampoule pass through silicone tube
Connection, quartz ampoule is placed in chemiluminescent analyzer；There is a detachable ceramic rod in quartz ampoule, a contact transformer is to pottery
Porcelain rod is heated；Chemiluminescent analyzer is connected with computer.
The specific method of testing of Lacking oxygen is as follows in titanium oxide：
A., titanium dioxide powder is added to the slurries that 0.50-0.55g/mL is made into deionized water, ceramic rod is uniformly coated to
On, the thickness of coating is 0.45-0.50mm.
Described titanium oxide is doped with M metal ions, and M is one of Cu, Fe, Co, Cr ions, and M doping is accounted for
TiO2Weight/mass percentage composition be 0.5%-2.0% and by calcination process under 250 DEG C of -400 DEG C of hydrogen atmospheres 30-60 minutes
Titanium oxide.
B. treat that the slurries on step A ceramic rods are micro- dry, the quartz ampoule that ceramic rod is loaded inside chemiluminescent analyzer device
In；The water in air pump, the air after being filtered through activated carbon are removed as the carrier gas of reaction, coutroi velocity is in 200-300mL/
Min so that the surface by ceramic rod in quartz ampoule of Uniform gas flow velocity；With contact transformer 100- is imposed to ceramic rod
110V voltage, the temperature of ceramic rod is risen to 150-200 DEG C of the temperature of detection；
C. opening liter temperature device in vaporizer makes temperature rise to 150-200 DEG C, and 0.1 mole of diethyl ether solution injection is vaporized
In room, the air in air pump flows through vaporizer and brings the ether wherein vaporized into quartz ampoule, ether and the oxygen on ceramic rod
Change titanium react and produce luminous, by chemiluminescent analyzer gathered data, record simultaneously analyze data.According to Lacking oxygen in titanium oxide
The phenomenon that is directly proportional of luminous signal that is produced to reaction of amount so that in comparable titanium oxide catalyst Lacking oxygen content height
It is low.
Described vaporizer is the canister that the outside volume for having heating mantle is 1-2mL.
The catalytic luminescence signal of the Cu adulterated TiOxes of different quality containing is shown in Fig. 2, with Cu doping contents
Increase, chemiluminescence signal value is presented in the trend for first raising and reducing afterwards, this trend and Cu adulterated TiOxes sample shown in table 1
The variation tendency of the content of Lacking oxygen is consistent；Cu, Fe, Co, the titanium oxide of the metal ion species of Cr tetra- doping is shown in Fig. 3
Catalytic luminescence signal, wherein Cu/TiO2Luminous signal highest, is followed successively by Co/TiO2, Fe/TiO2, Cr/TiO2；What Fig. 4 was shown
The chemiluminescence signal of the titanium oxide sample under hydrogen atmosphere after different temperatures calcination process, chemiluminescence signal intensity with
Increase tendency is presented in the rise of sintering temperature.
The beneficial effects of the invention are as follows：Using ether as molecular probe come the side of Lacking oxygen in Fast Evaluation titanium oxide
Method, this method is easy, quick, while equipment is simple, low cost, reaction time are short, can be widely applied to oxygen in titanium oxide empty
The evaluation of position.
Brief description of the drawings
The reaction unit figure that Lacking oxygen is evaluated in Fig. 1 titanium oxide catalysts.
1 is air pump, and 2 be vaporizer, and 3 be chemiluminescent analyzer, and 4 be computer, and 5 be quartz ampoule, and 6 be ceramic heat
Rod, 7 be transformer.
In Fig. 2 embodiments 1 in titanium oxide Cu dopings and catalytic luminescence signal corresponding diagram.
The corresponding diagram of the metal ion adulterated in Fig. 3 embodiments 2 in titanium oxide and catalytic luminescence signal.
The corresponding diagram of sintering temperature of the titanium oxide in hydrogen and catalytic luminescence signal in Fig. 4 embodiments 3.
Embodiment
Embodiment 1
Using experimental provision described in Fig. 1.
A. the TiO undoped is taken2And the TiO of 1.0%, 1.5%, 2.0%Cu doping2Powder is separately added into deionized water
In stir, be made into 0.50g/mL slurries；It is applied on ceramic rod and thickness about 0.50mm, ceramic rod is inserted
Into quartz ampoule, 105V voltages are imposed to ceramic rod, then with through silica gel in air pump, the treated air of activated carbon is as anti-
The carrier gas ventilation 30min answered, gas flow rate is 250mL/min, when the temperature of ceramic rod reaches 170 DEG C, starts vaporizer liter
Warm device, is 170 DEG C to temperature of vaporization chamber.Ensure the stable operation of chemiluminescent analyzer.
B. 25 μ L 0.1mol/L diethyl ether solution is injected in vaporizer, quartz ampoule is loaded into simultaneously by the air in air pump
Cu/TiO on ceramic rod2The oxygen reaction of upper and chemisorbed on a catalyst, produces and lights, by chemiluminescent analyzer
Gathered data.As a result as shown in Fig. 2 chemiluminescence signal power size is：TiO2<1.0%Cu/TiO2<1.5%Cu/TiO2>
2.0%Cu/TiO2, with the increase luminous signal increase of Cu dopings, when doping is 1.5%, chemiluminescence signal reaches
Maximum；Continue to increase doping to 2.0%, chemiluminescence signal reduction.Illustrate luminous signal intensity with Cu dopings
Variation tendency is consistent with the variation tendency of Cu dopings with Lacking oxygen content in titanium oxide, it follows that luminous signal intensity
The conclusion for the relation being proportionate with the content of Lacking oxygen.
Comparative example 1
The TiO undoped in Example 12It is respectively 1.0%, 1.5%, 2.0% powder with Cu doping mass fractions
Contrast test is carried out using traditional XPS analysis method：
Using the instruments of Thermo ESCALAB 250, take the above-mentioned powder of 30-60mg to be put into transition chamber after compressing tablet respectively, take out true
It is empty and supplement after nitrogen three times, sample is transferred in gloves box main body, reactor is reloaded into, is pre-processed；Pretreatment is finished
Afterwards, sheet sample is taken out from reactor, be glued to conduction on sample stage, energy disperse spectroscopy evacuated chamber is transferred under nitrogen atmosphere
Vacuumize process is carried out, treats that vacuum is higher than 10-4After Pa, then it is transferred to energy spectrometer analysis room and is detected.According to XPS data tests
As a result, equation below (Vo is utilized：Lacking oxygen) calculate Cu/TiO2The percentage composition of middle Lacking oxygen：
The percentage of Lacking oxygen=[(Ti atomic percentage × 4)-(Lattice Oxygen atomic percentage × 2)] * sensitivity because
Son }/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)
It the results are shown in Table 1：
Table 1
As shown in Table 1, the variation tendency of Lacking oxygen amount is in the titanium oxide for the different Cu dopings come detected by XPS methods
TiO2<1.0%Cu/TiO2<1.5%Cu/TiO2>2.0%Cu/TiO2, this result and Fig. 2 survey chemiluminescence signal change
Trend is the same.It follows that the relation that chemiluminescence signal intensity and the content of Lacking oxygen are proportionate.The present invention is adopted
Method is consistent with the testing result of traditional XPS methods.
Embodiment 2
Take Cu, Co, Fe that mass fraction is 1.0%, the TiO of the metal ion species of Cr tetra- doping2.Other step be the same as Examples
1, test result is shown in Fig. 3, and chemiluminescence signal power size is：Cu/TiO2>Co/TiO2>Fe/TiO2>Cr/TiO2。
Embodiment 3
By undoped TiO in embodiment 12250 DEG C in a hydrogen atmosphere of powder difference, 300 DEG C, 350 DEG C, 400 DEG C of roastings
Processing 2h is burnt, obtained sample is designated as H-250, H-300, H-350, H-400 respectively.Other step be the same as Examples 1, test result
See Fig. 4, chemiluminescence signal power size is：H-400>H-350>H-300>H-250.
Claims (3)
1. the specific method of testing of Lacking oxygen is as follows in the method for Lacking oxygen, titanium oxide in a kind of quick detection titanium oxide：
A., titanium dioxide powder is added to the slurries that 0.50-0.55g/mL is made into deionized water, is uniformly coated on ceramic rod, is applied
The thickness covered is 0.45-0.50mm；
B. treat that the slurries on step A ceramic rods are micro- dry, ceramic rod is fitted into the quartz ampoule inside chemiluminescent analyzer device；Remove
The water gone in air pump, the air after being filtered through activated carbon as reaction carrier gas, coutroi velocity in 200-300mL/min,
So that Uniform gas flow velocity pass through the surface of ceramic rod in quartz ampoule；Impose 100-110V's to ceramic rod with contact transformer
Voltage, the temperature of ceramic rod is risen to 150-200 DEG C of the temperature of detection；
C. opening liter temperature device in vaporizer makes temperature rise to 150-200 DEG C, and 25 μ L, 0.1 mole of diethyl ether solution is injected into vapour
Change in room, the air in air pump flows through vaporizer and bring the ether wherein vaporized on quartz ampoule, ether and ceramic rod into
Titanium oxide is reacted and produces luminous, and its luminous signal value is detected by chemiluminescent analyzer.
2. the method for Lacking oxygen in quick detection titanium oxide according to claim 1, it is characterized in that the oxidation described in step A
Titanium is doped with M metal ions, and M is one of Cu, Fe, Co, Cr ions, and M doping accounts for TiO2Weight/mass percentage composition be
0.5%-2.0%, the titanium oxide is by the calcination process titanium oxide of 30-60 minutes under 250 DEG C of -400 DEG C of hydrogen atmospheres.
3. the method for Lacking oxygen in quick detection titanium oxide according to claim 1, it is characterized in that according to the amount of Lacking oxygen
The relation being directly proportional to luminous signal, the luminous signal value obtained from step C obtain titanium oxide indirectly in Lacking oxygen qualitative value.
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| US8502343B1 (en) * | 2010-11-17 | 2013-08-06 | The University Of Toledo | Nanoelectric memristor device with dilute magnetic semiconductors |
| CN103265067A (en) * | 2013-05-03 | 2013-08-28 | 上海中科高等研究院 | Processing method for enhancing electrochemical performances of TiO2 electrode |
| 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 |
| CN103265067A (en) * | 2013-05-03 | 2013-08-28 | 上海中科高等研究院 | Processing method for enhancing electrochemical performances of TiO2 electrode |
| 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 |
Non-Patent Citations (2)
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| Development of a Gas Sensor Utilizing Chemiluminescence on Nanosized Titanium Dioxide;Yongfa Zhu等;《Anal. Chem》;20020101;第74卷(第1期);第120-124页 * |
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