CN106938340A - A kind of preparation method and its usage of the halogenation oxygen bismuth of bismuth metal auto-dope - Google Patents
A kind of preparation method and its usage of the halogenation oxygen bismuth of bismuth metal auto-dope Download PDFInfo
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Abstract
The invention provides a kind of preparation method and its usage of the halogenation oxygen bismuth of bismuth metal auto-dope, carry out as steps described below：First, weigh the ionic liquid containing halogen to be put into the reactor of polytetrafluoroethyllining lining, secondly, add ethylene glycol, and fully dissolved；Glucose and five water bismuth nitrates are added in reactor again, stirred to well mixed；Constant temperature thermal response is carried out, room temperature is naturally cooled to after completion of the reaction；Solid product is washed through alcohol, washed, centrifuges, is dried to obtain the halogenation oxygen bismuth material of bismuth metal auto-dope.Electrode material used in the present invention is the halogenation oxygen bismuth of the bismuth metal auto-dope responded in visible region, explores its superior photoelectric properties, has widened application of the halogenation bismuthyl material in photoelectric field, also have found a kind of new material for Photoelectric Detection.
Description
Technical field
The present invention design optical electro-chemistry Material Field, refer in particular to a kind of halogenation oxygen bismuth of bismuth metal auto-dope preparation method and
Its purposes.
Background technology
In recent years, optical electro-chemistry (PEC), as a kind of technology newly developed, is paid close attention to by the whole world, is widely used in light
Xie Shui, contaminant degradation, the field such as solar energy conversion and bio-sensing.Photoelectrochemical process is the process of photoproduction electricity, i.e., photosensitive
Under light illumination, electronics is excited material, and electric charge is transmitted in the way of electro transfer and produces electrochemistry letter to electrode surface
Number process.When irradiation light energy is equal to or more than the energy of semiconductor band gap (Eg), electronics (e-) being stimulated jumped by valence band
Adjourn and hole (h is then produced in conduction band, valence band+), electronics is efficiently separated with hole, just realizes photoelectric conversion, with photoelectrochemical
Learn and optical electro-chemistry reaction occurs after active material light is excited, so as to form photovoltage or photoelectric current.PhotoelectrochemicalTechnique Technique
Light harvesting is upgraded in one with electrochemical techniques, shows a superior selectivity, portability, miniaturization, the advantages of cheap.
Halogenation oxygen bismuth (BiOX, X=Cl, Br, I), aoxidizes semiconductor, with preferable photo electric as a kind of laminated metal
Can, open the new way of novel visible response photoelectric material research, thus the focus as social concerns.But they have
Have efficiency of light absorption low, electric charge transfer speed is slow and light induced electron with hole to the higher probability of recombination the shortcomings of, seriously limit
Its photoelectric properties.Therefore, it is necessary to propose improved method to improve the separative efficiency of photo-generate electron-hole pair, enter one
Step widens the practical application of its optical electro-chemistry.It is wherein metal-doped to greatly improve BiOX (X=as a kind of effective method
Cl, Br, I) photoelectric properties.It points out that metal nanoparticle, such as gold, silver, and platinum have the interface of a Schottky barrier,
It is conducive to the separation of electric transmission and electron-hole pair as an electron trap.Similar, bismuth metal shows height
Anisotropic Fermi surface, the mean free path of long carrier, low, the small carrier effective mass of carrier density, and
The features such as less band gap, and it is with low cost, nontoxic (Z.K.Cui, Y.G.Zhang, S.L.Li, S.X.Ge,
Catal.Commun.72(2015)97-100.).At present, there is document report bismuth metal deposit on semiconductor light-catalyst surface,
Such as Bi/BiOI (C.Chang, L.Y.Zhu, Y.Fu, X.L.Chu, Chem.Eng.J.233 (2013) 305-314), Bi/TiO2
(H.Y.Li, J.F.Liu, J.J.Qian, Q.Y.Li, J.J.Yang, Chin.J.Catal.35 (9) (2014) 1578-1589),
With Bi/BiOCl (M.C.Gao, D.F.Zhang, X.P.Pu, K.Y.Ding, H.Li, T.T.Zhang, H.Y.Ma,
Sep.Purif.Technol.149 (27) (2015) 288-294), substantially increase the electronics in catalyst and the separation in hole
Efficiency, improves the photoelectric properties of composite.So far, using solvent heat one-step synthesis method Bi/BiOX (X=Cl, Br, I),
And inquire into its photoelectric properties and not yet have been reported that.
The content of the invention
The present invention is directed to propose a kind of preparation method of the halogenation oxygen bismuth of bismuth metal auto-dope.In contrast to BiOX (X=Cl,
Br, I) monomer, bismuth metal introducing accelerate composite electric charge transfer, promote photo-generate electron-hole to efficiently separating,
And obtain more excellent photoelectric properties.
The technical solution adopted by the present invention is：
A kind of preparation method of the halogenation oxygen bismuth of bismuth metal auto-dope, is carried out as steps described below：
First, weigh the ionic liquid containing halogen to be put into the reactor of polytetrafluoroethyllining lining, secondly, add second two
Alcohol, and fully dissolved；Glucose and five water bismuth nitrates are added in reactor again, stirred to well mixed；Carry out permanent
Warm reaction, naturally cools to room temperature after completion of the reaction；Solid product is washed through alcohol, washed, is centrifuged, bismuth gold is dried to obtain
Belong to the halogenation oxygen bismuth of auto-dope, be designated as Bi/BiOX, wherein, X is Cl, Br or I.
Prepare halogenation oxygen bismuth monomer identical with the halogenation oxygen bismuth method for preparing bismuth metal auto-dope, be simply added without grape
Sugar：First, weigh the ionic liquid containing halogen to be put into polytetrafluoroethyllining lining reactor, secondly, add ethylene glycol, go forward side by side
Row fully dissolving；It is another to add five water bismuth nitrates in reactor, and continue stirring until well mixed；Constant temperature thermal response is carried out,
Room temperature is naturally cooled to after completion of the reaction；Solid product is washed through alcohol, washed, centrifuges, is dried to obtain halogenation oxygen bismuth monomer,
BiOX is designated as, wherein, X is Cl, Br or I.
The described ionic liquid containing halogen, ethylene glycol, the amount ratio of glucose and five water bismuth nitrates are 1mmol：
20mL：0.1~1.0g：1mmol.
The described ionic liquid containing halogen is the 1- cetyl -3- methylimidazole villaumites containing chlorine source
([C16mim] Cl), the 1- cetyl -3- methylimidazoles bromide ([C16mim] Br) containing bromine source or the 1- fourths containing propiodal
Base -3- methylimidazoles salt compounded of iodine ([Bmim] I).
The temperature of the constant temperature thermal response is 140-160 DEG C, and the reaction time is 24h；Described drying temperature is 50 DEG C, is done
The dry time is 12h.
The halogenation oxygen bismuth of prepared bismuth metal auto-dope is used to prepare modified electrode, by optical electro-chemistry detection to chlorobenzene
Phenol (4-CP), Ciprofloxacin (CIP) or phenol.
In described optical electro-chemistry detection, the preparation method of modified electrode is：
Step 1, ITO electro-conductive glass pre-processed：By ITO electro-conductive glass respectively in deionized water, ethanol successively
It is cleaned by ultrasonic after half an hour, is repeatedly rinsed with deionized water；Then electro-conductive glass is put into the NaOH aqueous solution, boiled, and protected
Hold 30 minutes, cleaned and dried up stand-by with deionized water；
Step 2, prepare modified electrode：The halogenation oxygen bismuth of bismuth metal auto-dope is distributed in deionized water, ultrasonic disperse,
The suspension stablized；Then, take on the ITO electro-conductive glass that suspended drop-coated pre-processes in step 1, natural drying at room temperature
It is stand-by afterwards；Obtained modified electrode is denoted as Bi/BiOX-ITO.
In step 1, the concentration of the described NaOH aqueous solution is 0.1~1mol/L.
In step 2, prepared turbid liquid concentration is 1.0mg/mL；The drop coating is on the ITO electro-conductive glass of pretreatment
Suspension be 70 μ L.
In order to which (Bi/BiOX, X=Cl, Br, the I)-ITO modified electrodes prepared with above-mentioned preparation method compare, by class
(BiOX, X=Cl, Br, I)-ITO modified electrodes are made like method.
Bi/BiOX (X=Cl, Br, I) material that above-mentioned preparation method is prepared is inquired into using electrochemical workstation
Photoelectric properties.
Inquire into photoelectrochemical behaviour specific method be：By phosphate buffer move into sample cell in, using modified electrode as
Working electrode, platinum electrode is as to electrode, and saturation Ag/AgCl electrodes are fitted into sample cell as reference electrode；By highlighted
Spend xenon lamp source of parallel light system instrument and illumination is carried out to working electrode, current signal is produced on the working electrode (s；Current signal leads to
Cross electrochemical workstation and be sent to computer and be converted into data signal, show as photocurrent response.
Wherein, described phosphate buffer solution is mutual by configuring 0.1mol/L sodium dihydrogen phosphate and disodium hydrogen phosphate
Adjust, pH value is made for 7.0.Its concentration is 0.1mol/L.
The present invention has the advantage that：
(1) Bi/BiOX (X=Cl, Br, I) material prepared by the present invention be can be by portion using the reproducibility of glucose
Divide the bismuth ion (Bi with positive trivalent3+) it is reduced into bismuth metal.And there is no the generation of carbon in whole reaction system, this explanation Portugal
Grape sugar is not converted to carbon.
(2) electrode material used in the present invention is the Bi/BiOX (X=Cl, Br, I) responded in visible region, is explored
Its superior photoelectric properties, has widened application of the halogenation bismuthyl material in photoelectric field, also have found one kind for Photoelectric Detection
New material.
(3) detection means used in the present invention has higher detection sensitivity, and cost consumption is low, and portability is small-sized
The advantages of change.
(4) the halogenation oxygen bismuth material of the bismuth metal auto-dope prepared by can be effectively used for parachlorophenol (4-CP), and ring third is husky
Star (CIP), and phenol etc. optical electro-chemistry detection, with obvious practicality.
Brief description of the drawings
Fig. 1 is the synthesis schematic diagram of Bi/BiOX (X=Cl, Br, I) material.
Fig. 2 is X-ray diffraction (XRD) figure of Bi/BiOX (X=Cl, Br, I) material.
Fig. 3 is transmission electron microscope (TEM) figure of Bi/BiOX (X=Cl, Br, I) material, wherein (a) is Bi/BiOCl, (b) is
Bi/BiOBr, (c) is Bi/BiOI.
Fig. 4 is solid uv drses (DRS) figure of Bi/BiOX (X=Cl, Br, I) material.
Fig. 5 is AC impedance (EIS) figure of Bi/BiOX (X=Cl, Br, I) material.
Fig. 6 is modified electrode (Bi/BiOX, X=Cl, Br, I)-ITO and (BiOX, X=Cl, Br, I)-ITO photoelectric current
Figure, wherein (a) is Bi/BiOCl (curve I) and BiOCl (curve II), (b) is Bi/BiOBr (curve I) and BiOBr (curves
II), (c) is Bi/BiOI (curve I) and BiOI (curve II).
Fig. 7 is the photosignal response diagram that modified electrode Bi/BiOI-ITO detects phenol, wherein figure a is different dense for detection
The photoelectricity flow graph obtained by phenol is spent, figure b is the linear relationship chart of phenol concentration-photoelectric current increment.
Embodiment
With reference to specific implementation example, the present invention will be further described, so that those skilled in the art more fully understand
The present invention, but protection scope of the present invention is not limited to following examples.
Embodiment 1：
(1) preparation of bismuthyl chloride monomer material is that solvent thermal reaction one-step method is made：First, 1mmol 1- ten is weighed
Six alkyl -3- methylimidazole villaumites ([C16Mim] Cl) ionic liquid be put into 25mL polytetrafluoroethyllining lining reactor, its
Secondary, the ethylene glycol solution for pipetting 20mL is put into kettle, and is fully dissolved.The another five water bismuth nitrates by 1mmol add kettle
In, and continue to stir half an hour, it is extremely well mixed.Room temperature is naturally cooled to after reaction 24h under the conditions of 160 DEG C；To finally it produce
Thing is washed through alcohol, is washed, and is centrifuged, and BiOCl is obtained in drying 12h at 50 DEG C.
(2) preparation of the bismuthyl chloride material of bismuth metal auto-dope is that five water bismuth nitrate systems are reduced by glucose
：First, 1mmol 1- cetyl -3- methylimidazole villaumites ([C is weighed16Mim] Cl) ionic liquid be put into the poly- of 25mL
In tetrafluoroethene liner reactor, secondly, the ethylene glycol solution for pipetting 20mL is put into kettle, and is fully dissolved.Separately will
0.1g glucose and the water bismuth nitrates of 1mmol five is added in kettle, and continues to stir half an hour, extremely well mixed.In 160 DEG C of bars
Room temperature is naturally cooled to after reacting 24h under part.Final product is washed through alcohol, washed, is centrifuged, is obtained in drying 12h at 50 DEG C
To Bi/BiOCl.
(3) preparation of modified electrode：ITO electro-conductive glass preprocessing process first, by ITO electro-conductive glass respectively go from
It is cleaned by ultrasonic successively after half an hour in sub- water, ethanol, is repeatedly rinsed with deionized water.Then electro-conductive glass is put into 0.1mol/L
In the NaOH aqueous solution, boiled, and kept for 30 minutes, cleaned and dried up stand-by with deionized water.Configure 1mol/L Bi/
The BiOCl aqueous solution, puts it into and ultrasonic disperse is carried out in ultrasonic machine, the suspension stablized.Then, 70 μ L suspensions are taken
Drop coating is on the ITO electro-conductive glass of pretreatment, and room temperature is stand-by after drying up naturally.Obtained modified electrode is denoted as Bi/BiOCl-
ITO.In order to which the Bi/BiOCl-ITO prepared with above-mentioned preparation method is compared, BiOCl-ITO modifications are made by similar approach
Electrode.
(4) optical electro-chemistry detection method and condition：
Light source is derived from high brightness xenon lamp source of parallel light system instrument, and (CHF-XM35-500W, Beijing is smooth with 500W xenon lamps
Open up Science and Technology Ltd.) as visible light source.The ultraviolet light of xenon lamp is filtered with 400nm optical filters.Electrochemistry experiment uses CHI
660B electrochemical workstations (Shanghai Chen Hua Instrument Ltd.), utilize traditional three-electrode system：Modified electrode is work electricity
Pole, platinum electrode is that, to electrode, saturation Ag/AgCl electrodes are reference electrode (all current potentials are both with respect to SCE).Electrochemistry experiment
Carried out in room temperature, phosphate buffer solution (0.1mol/L, pH=7.0), current potential is 0V (vs SCE).EIS experiment containing
5mmol/L Fe(CN)6 3-/4-0.1mol/L KCl solution in carry out, frequency range is 0.01Hz~10kHz, and initial potential is
0.24V, AC amplitude is 5mV.
Embodiment 2：
(1) preparation of bismuthyl bromide monomer material is that solvent thermal reaction one-step method is made：First, 1mmol 1- ten is weighed
Six alkyl -3- methylimidazole bromides ([C16Mim] Br) ionic liquid be put into 25mL polytetrafluoroethyllining lining reactor, its
Secondary, the ethylene glycol solution for pipetting 20mL is put into kettle, and is fully dissolved.The another five water bismuth nitrates by 1mmol add kettle
In, and continue to stir half an hour, it is extremely well mixed.Room temperature is naturally cooled to after reaction 24h under the conditions of 140 DEG C；To finally it produce
Thing is washed through alcohol, is washed, and is centrifuged, and BiOBr is obtained in drying 12h at 50 DEG C.
(2) preparation of the bismuthyl bromide material of bismuth metal auto-dope is that five water bismuth nitrate systems are reduced by glucose
：First, 1mmol 1- cetyl -3- methylimidazole bromides ([C is weighed16Mim] Br) ionic liquid be put into the poly- of 25mL
In tetrafluoroethene liner reactor, secondly, the ethylene glycol solution for pipetting 20mL is put into kettle, and is fully dissolved.Separately will
1.0g glucose and the water bismuth nitrates of 1mmol five is added in kettle, and continues to stir half an hour, extremely well mixed.In 160 DEG C of bars
Room temperature is naturally cooled to after reacting 24h under part.Final product is washed through alcohol, washed, is centrifuged, is obtained in drying 12h at 50 DEG C
To Bi/BiOBr.
(3) preparation of modified electrode：ITO electro-conductive glass preprocessing process first, by ITO electro-conductive glass respectively go from
It is cleaned by ultrasonic successively after half an hour in sub- water, ethanol, is repeatedly rinsed with deionized water.Then electro-conductive glass is put into 0.1mol/L
In the NaOH aqueous solution, boiled, and kept for 30 minutes, cleaned and dried up stand-by with deionized water.Configure 1mol/L Bi/
The BiOBr aqueous solution, puts it into and ultrasonic disperse is carried out in ultrasonic machine, the suspension stablized.Then, 70 μ L suspensions are taken
Drop coating is on the ITO electro-conductive glass of pretreatment, and room temperature is stand-by after drying up naturally.Obtained modified electrode is denoted as Bi/BiOBr-
ITO.In order to which the Bi/BiOBr-ITO prepared with above-mentioned preparation method is compared, BiOBr-ITO modifications are made by similar approach
Electrode.
(4) optical electro-chemistry detection method and condition：
Light source is derived from high brightness xenon lamp source of parallel light system instrument, and (CHF-XM35-500W, Beijing is smooth with 500W xenon lamps
Open up Science and Technology Ltd.) as visible light source.The ultraviolet light of xenon lamp is filtered with 400nm optical filters.Electrochemistry experiment uses CHI
660B electrochemical workstations (Shanghai Chen Hua Instrument Ltd.), utilize traditional three-electrode system：Modified electrode is work electricity
Pole, platinum electrode is that, to electrode, saturation Ag/AgCl electrodes are reference electrode (all current potentials are both with respect to SCE).Electrochemistry experiment
Carried out in room temperature, phosphate buffer solution (0.1mol/L, pH=7.0), current potential is 0V (vs SCE).EIS experiment containing
5mmol/L Fe(CN)6 3-/4-0.1mol/L KCl solution in carry out, frequency range is 0.01Hz~10kHz, and initial potential is
0.24V, AC amplitude is 5mV.
Embodiment 3：
(1) preparation of bismuthyl iodide monomer material is that solvent thermal reaction one-step method is made：First, 1mmol 1- fourths are weighed
The ionic liquid of base -3- methylimidazoles salt compounded of iodine ([Bmim] I) is put into 25mL polytetrafluoroethyllining lining reactor, secondly, is moved
Take 20mL ethylene glycol solution to be put into kettle, and fully dissolved.The another five water bismuth nitrates by 1mmol are added in kettle, and
Half an hour is persistently stirred, it is extremely well mixed.Room temperature is naturally cooled to after reaction 24h under the conditions of 160 DEG C；By final product through alcohol
Wash, wash, centrifuge, BiOI is obtained in drying 12h at 50 DEG C.
(2) preparation of the bismuthyl iodide material of bismuth metal auto-dope is that five water bismuth nitrate systems are reduced by glucose
：First, the ionic liquid for weighing 1mmol 1- butyl -3- methylimidazoles salt compounded of iodine ([Bmim] I) is put into 25mL polytetrafluoroethyl-ne
In alkene liner reactor, secondly, the ethylene glycol solution for pipetting 20mL is put into kettle, and is fully dissolved.The another Portugal by 0.5g
Grape sugar and the water bismuth nitrates of 1mmol five are added in kettle, and continue to stir half an hour, extremely well mixed.Reacted under the conditions of 140 DEG C
Room temperature is naturally cooled to after 24h.Final product is washed through alcohol, washed, is centrifuged, Bi/ is obtained in drying 12h at 50 DEG C
BiOI。
(3) preparation of modified electrode：ITO electro-conductive glass preprocessing process first, by ITO electro-conductive glass respectively go from
It is cleaned by ultrasonic successively after half an hour in sub- water, ethanol, is repeatedly rinsed with deionized water.Then electro-conductive glass is put into 0.1mol/L
In the NaOH aqueous solution, boiled, and kept for 30 minutes, cleaned and dried up stand-by with deionized water.Configure 1mol/L Bi/
The BiOI aqueous solution, puts it into and ultrasonic disperse is carried out in ultrasonic machine, the suspension stablized.Then, the 70 suspended drops of μ L are taken
It is applied on the ITO electro-conductive glass of pretreatment, room temperature is stand-by after drying up naturally.Obtained modified electrode is denoted as Bi/BiOI-ITO.
In order to which the Bi/BiOI-ITO prepared with above-mentioned preparation method is compared, BiOI-ITO modified electrodes are made by similar approach.
(4) Bi/BiOI-ITO prepared by can be used for parachlorophenol (4-CP), the inspection of Ciprofloxacin (CIP) and phenol
Survey, the present invention is by taking phenol as an example：The preparation of target detection thing phenol：4ng mL are respectively configured-1,12ng mL-1,20ng mL-1,
36ng mL-1,52ng mL-1,80ng mL-1,120ng mL-1,200ng mL-1,400ng mL-1,600ng mL-1,800ng
mL-1,1400ng mL-1,1660ng mL-1,2200ng mL-1,2600ng mL-1The phenol of isoconcentration, it is to be detected.
(5) optical electro-chemistry detection method and condition：
Light source is derived from high brightness xenon lamp source of parallel light system instrument, and (CHF-XM35-500W, Beijing is smooth with 500W xenon lamps
Open up Science and Technology Ltd.) as visible light source.The ultraviolet light of xenon lamp is filtered with 400nm optical filters.Electrochemistry experiment uses CHI
660B electrochemical workstations (Shanghai Chen Hua Instrument Ltd.), utilize traditional three-electrode system：Modified electrode is work electricity
Pole, platinum electrode is that, to electrode, saturation Ag/AgCl electrodes are reference electrode (all current potentials are both with respect to SCE).Electrochemistry experiment
Carried out in room temperature, phosphate buffer solution (0.1mol/L, pH=7.0), current potential is 0V (vs SCE).EIS experiment containing
5mmol/L Fe(CN)6 3-/4-0.1mol/L KCl solution in carry out, frequency range is 0.01Hz~10kHz, and initial potential is
0.24V, AC amplitude is 5mV.
Fig. 1 is the synthesis schematic diagram of Bi/BiOX (X=Cl, Br, I) material.Prepared by the present invention Bi/BiOX (X=Cl,
Br, I) material be according to the schematic diagram scheme preparation.Prepare the ionic liquid that is used during Bi/BiOCl for 1- cetyls-
3- methylimidazole villaumites ([C16Mim] Cl), it is 1- cetyl -3- methylimidazoles to prepare the ionic liquid used during Bi/BiOBr
Bromide ([C16Mim] Br), it is 1- butyl -3- methylimidazoles salt compounded of iodine ([Bmim] I) to prepare the ionic liquid used during Bi/BiOI.
Fig. 2 is X-ray diffraction (XRD) figure of Bi/BiOX (X=Cl, Br, I) material.Bi/BiOX prepared by the present invention
The XRD characterize datas of (X=Cl, Br, I) material are as shown in Figure 2.Found in the XRD spectrum of compound in Fig. 2 (a, b, c)
Metal Bi characteristic peak, illustrates that the water bismuth nitrate of part five is successfully converted into bismuth metal by glucose.In addition XRD peak shape is sharp
It is sharp, illustrate that prepared material has preferable crystallinity.
Fig. 3 is transmission electron microscope (TEM) figure of Bi/BiOX (X=Cl, Br, I) material.It can be seen from Fig. 3 (a, b, c)
Go out, bismuth metal uniform particle is distributed on the surface of halogenation oxygen bismuth.
Fig. 4 is solid uv drses (DRS) figure of Bi/BiOX (X=Cl, Br, I) material.From Fig. 4 (a, b, c)
It can be seen that the halogenation oxygen bismuth of bismuth metal modification all has wider ABSORPTION EDGE than each self-corresponding monomer.In addition compound is can
There is stronger absorption in Jian Guang areas, illustrate that its absorbing properties preferably, is conducive to the separation in light induced electron and hole, made it have
Preferable photoelectric properties.
Fig. 5 is AC impedance (EIS) figure of Bi/BiOX (X=Cl, Br, I) material.The resistance of material prepared by the present invention
Value is detected by carrying out AC impedance to working electrode, further studies Bi/BiOX (X=Cl, Br, I) material transfer electronics
Ability, the resistance of Bi/BiOX (X=Cl, Br, I) material is lower, illustrates that it shifts the ability of electronics stronger, can effectively by
Photo-generate electron-hole is to separation.From Fig. 5 (a, b, c) as can be seen that Bi/BiOCl resistance is less than BiOCl monomers, Bi/BiOBr
Resistance be less than BiOBr monomers, same Bi/BiOI resistance is less than BiOI monomers, the halogenation oxygen of this explanation bismuth metal modification
Bismuth has stronger electron transmission ability.The introducing of bismuth metal accelerates the transfer of electric charge, promotes light induced electron and hole
Separation, makes compound have more preferable photoelectric properties.
Fig. 6 is modified electrode (Bi/BiOX, X=Cl, Br, I)-ITO and (BiOX, X=Cl, Br, I)-ITO photoelectric current
Figure.Under light irradiation, the response of electrode pair light prepared by different materials is different, and the photo-current intensity of generation is also different.Therefore can be with
Produce the photoelectric current of varying strength according to different operating electrode to illustrate that different materials respond the difference of light, the stronger theory of photoelectric current
The separative efficiency in bright working electrode light induced electron and hole under light illumination is higher.From Fig. 6 (a, b, c) as can be seen that institute of the present invention
The compound of preparation has higher photocurrent values than corresponding monomer, and the introducing of this explanation bismuth metal accelerates turning for electric charge
Move, promote the separation in light induced electron and hole, make compound that there are more preferable photoelectric properties, this result and AC impedance
(EIS) figure result is coincide.These results illustrate that Bi/BiOX (X=Cl, Br, I) material is expected to be used in optical electro-chemistry detection.
Fig. 7 is the photosignal response diagram that modified electrode Bi/BiOI-ITO detects phenol, wherein figure a is different dense for detection
The photoelectricity flow graph obtained by phenol is spent, figure b is the linear relationship chart of phenol concentration-photoelectric current increment.From figure 7 it can be seen that with
The increase of phenol concentration, Bi/BiOI-ITO photo-signal is gradually reduced.The detector have two ranges of linearity for 4~
16ng mL–1With 16~2600ng mL–1, corresponding linear equation is i respectively0- i=7.528*10–4+1.7*10–3*c/ng
mL–1(R2=0.9979, cPhenol:4~16ng mL–1)；i0- i=3.512*10–2+1.889*10–4c/ng mL–1(R2=
0.9984,cPhenol:16~2600ng mL–1), test limit is 1.3ng mL–1。
Claims (8)
1. the preparation method of the halogenation oxygen bismuth of a kind of bismuth metal auto-dope, it is characterised in that carry out as steps described below：
First, weigh the ionic liquid containing halogen to be put into the reactor of polytetrafluoroethyllining lining, secondly, add ethylene glycol,
And fully dissolved；Glucose and five water bismuth nitrates are added in reactor again, stirred to well mixed；Carry out constant temperature heating
Reaction, naturally cools to room temperature after completion of the reaction；Solid product is washed through alcohol, washed, is centrifuged, bismuth metal is dried to obtain certainly
The halogenation oxygen bismuth of doping, is designated as Bi/BiOX, wherein, X is halogen.
2. the preparation method of the halogenation oxygen bismuth of a kind of bismuth metal auto-dope according to claim 1, it is characterised in that described
The ionic liquid containing halogen, ethylene glycol, the amount ratio of glucose and five water bismuth nitrates be 1mmol：20mL：0.1~1.0g：
1mmol。
3. the preparation method of the halogenation oxygen bismuth of a kind of bismuth metal auto-dope according to claim 1, it is characterised in that described
The ionic liquid containing halogen be the 1- cetyl -3- methylimidazole villaumites containing chlorine source, the 1- hexadecanes containing bromine source
Base -3- methylimidazoles bromide or the 1- butyl -3- methylimidazole salt compounded of iodine containing propiodal.
4. the preparation method of the halogenation oxygen bismuth of a kind of bismuth metal auto-dope according to claim 1, it is characterised in that described
The temperature of constant temperature thermal response is 140~160 DEG C, and the reaction time is 24h；Described drying temperature is 50 DEG C, and drying time is
12h。
5. the purposes of the halogenation oxygen bismuth of bismuth metal auto-dope prepared by the method described in Claims 1 to 4 any one, its feature
Be that the halogenation oxygen bismuth of prepared bismuth metal auto-dope is used to prepare modified electrode, by optical electro-chemistry detect parachlorophenol,
Ciprofloxacin or phenol.
6. the purposes of the halogenation oxygen bismuth of bismuth metal auto-dope according to claim 5, it is characterised in that described modification electricity
The preparation method of pole is：
Step 1, ITO electro-conductive glass pre-processed：By ITO electro-conductive glass respectively in deionized water, ethanol it is ultrasonic successively
Clean after half an hour, repeatedly rinsed with deionized water；Then electro-conductive glass is put into the NaOH aqueous solution, boiled, and keep 30
Minute, cleaned and dried up stand-by with deionized water；
Step 2, prepare modified electrode：The halogenation oxygen bismuth of bismuth metal auto-dope is distributed in deionized water, ultrasonic disperse is obtained
Stable suspension；Then, take on the ITO electro-conductive glass that suspended drop-coated pre-processes in step 1, treated after natural drying at room temperature
With；Obtained modified electrode is denoted as Bi/BiOX-ITO.
7. the purposes of the halogenation oxygen bismuth of bismuth metal auto-dope according to claim 6, it is characterised in that described in step 1
The NaOH aqueous solution concentration be 0.1~1mol/L.
8. the purposes of the halogenation oxygen bismuth of bismuth metal auto-dope according to claim 6, it is characterised in that made in step 2
Standby turbid liquid concentration is 1.0mg/mL；The drop coating is 70 μ L in the suspension on the ITO electro-conductive glass of pretreatment.
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