CN108103525A - N doping carbon dots modification tungstic acid complex light electrode and preparation method thereof and the application in photoelectrocatalysis decomposes water - Google Patents

N doping carbon dots modification tungstic acid complex light electrode and preparation method thereof and the application in photoelectrocatalysis decomposes water Download PDF

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CN108103525A
CN108103525A CN201711417939.8A CN201711417939A CN108103525A CN 108103525 A CN108103525 A CN 108103525A CN 201711417939 A CN201711417939 A CN 201711417939A CN 108103525 A CN108103525 A CN 108103525A
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complex light
tungstic acid
light electrode
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carbon dots
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CN108103525B (en
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孔维倩
张晓凡
周燕南
刘会利
张守仁
杨保成
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Huanghe Science and Technology College
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Abstract

The invention discloses a kind of tungstic acid complex light electrodes and preparation method thereof, comprise the following steps：WO 3 film is first generated on electro-conductive glass, obtain substrate, tungstic trioxide nano-slice optoelectronic pole is made through hydro-thermal, annealing in substrate again, then prepares N doping carbon dots solution, using dipping construction from part modification N doping carbon dots on tungstic trioxide nano-slice optoelectronic pole；The invention also discloses application of the complex light electrode in photoelectrocatalysis decomposes water.NCDs/WO produced by the present invention3The electric conductivity of optoelectronic pole and the transfer efficiency of photo-generated carrier are improved, effectively improve the electric conductivity of complex light electrode, the problem of tungstic acid surface charge recombination is serious can also be reduced, so as to improve the photoelectrocatalysis efficiency of tungstic acid, the efficiency of the composite photoelectric aurora electrocatalytic decomposition water is finally improved.

Description

N doping carbon dots modifies tungstic acid complex light electrode and preparation method thereof and in light Application in electrocatalytic decomposition water
Technical field
The invention belongs to optoelectronic materials technologies, and in particular to a kind of N doping carbon dots modifies tungstic acid composite photoelectric Pole and preparation method thereof and the application in photoelectrocatalysis decomposes water.
Background technology
At present, energy crisis is increasingly severe, how to develop and increasingly causes people using reproducible clean energy resource Concern.Solar energy storage level is very big and pollution-free in nature, is a kind of preferable renewable resource.Since 1972 by Fujishima reports TiO2Optoelectronic pole can utilize solar hydrogen making to provide clean, the green energy [A. Fujishima, K. Honda, Nature, 1972,238,37-38], the transition metal oxide half of nanostructured is utilized Conductor material（Such as TiO2, Fe2O3, WO3）Pass through optical electro-chemistry（PEC）This method of water generation hydrogen and oxygen is catalytically decomposed It is considered as a kind of promising environmentally friendly route.
Metal semiconductor oxide tungstic acid（WO3）It has been widely used in photoelectricity as a kind of light anode material to urge Change and decompose in water reaction.WO3Belong to n-type indirect band-gap semiconductor, energy gap compares for 2.5 ~ 2.8 eV and valence band current potential It is high（3.0 eV vs. RHE）.In addition, compared with other metal semiconductor materials, WO3With some unique optical electro-chemistry Matter.For example, WO3Nearly 12% solar spectral absorption can be absorbed, hole-diffusion length is about 150 nmWO3There is higher electricity Sub- transport efficiency（12 cm2 V-1 s-1）.Meanwhile WO3And a kind of inexpensive, nontoxic, environmental-friendly semi-conducting material.Base In these excellent properties, WO3In fields such as light degradation, Driven by Solar Energy optical electro-chemistry people is caused widely to study.Although In this way, WO3It is slow to be still limited by its hole dynamics, electric charge transfer is relatively slow at semiconductor/electrolyte interface and electronics-sky Cave is quickly compound, therefore, WO3The PEC properties of optoelectronic pole are still far below its theoretical value（~5 mA cm-2）.How further to carry High WO3To light utilization efficiency and improve electron hole separative efficiency and become the focus of people's research problem.Research shows to pass through element Doping, selective doping semiconductor [T. Zhang, Z. L. Zhu, H. N. Chen, et al., Nanoscale, 2015,7,2933-2940.], construct nanostructured [P. M. Rao, L. Cai, C. Liu, et al., Nano Lett. 2014,14,1099-1105.] and carbon-based material modification [W. N. Shi, X. F. Zhang, J. Brillet, Et al., Carbon, 2016,105,387-393] the methods of, can improve electron transfer efficiency, reduce electron-hole It is compound so as to improving WO3Photoelectrocatalysis efficiency.
Carbon dots（CDs）As a nova of nano material, due to they have it is at low cost, it is environmental-friendly, and have Good chemical stability and receive much attention（H. T. Li, X. D. He, Z. H. Kang, et al., Angew. Chem. Int. Ed., 2010, 49, 4430-4434.）.By the size and selectivity that adjust and control carbon dots Hetero atom is adulterated, so as to adjust the band gap of carbon dots（T. F. Yeh, C. Y. Teng, S. Chen and H. Teng, Adv Mater, 2014, 26, 3297-3303）.Using carbonitride and ethylenediamine as presoma, it is prepared for nitrogen using the method for reflux and mixes Miscellaneous carbon dots（NCDs）, can it is significant improve CDs electrical conductivity and electric charge transfer and electrolyte-electrode interaction, be conducive to Water decomposition is catalyzed under visible light illumination.The carbon dots of N doping has been widely used in terms of photocatalysis and light degradation, but with Semiconductor is conjointly employed in photoelectrocatalysis and is rarely reported.Based on the photoelectric property that NCDs is excellent, NCDs is used to modify WO3It helps In the electric conductivity for improving material, it is expected to improve the separative efficiency of carrier, prevents the compound of electron-hole, improved so as to reach WO3The effect of photoelectrocatalysis efficiency.
The content of the invention
Based on the deficiencies of the prior art, object of the present invention is to provide N doping carbon dotss to modify tungstic acid complex light Electrode（NCDs/WO3Optoelectronic pole）, tungsten trioxide photoelectrode is modified by the carbon dots of N doping, the photoelectricity for improving tungstic acid is urged Change efficiency.
The present invention also provides the preparation methods and nitrogen-doped carbon of N doping carbon dots modification tungstic acid complex light electrode Application of the point modification tungstic acid complex light electrode in photoelectrocatalysis decomposes water.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of preparation method of tungstic acid complex light electrode, comprises the following steps：
（1）Wolframic acid and polyvinyl alcohol are added in hydrogenperoxide steam generator, stirring obtains Seed Layer solution to homogeneous solution is formed； Seed Layer solution is coated on using spin-coating method on electro-conductive glass, then 450 ~ 550 DEG C will be warming up to by the electro-conductive glass of coating, After when heat preservation 1.5 ~ 3 is small, it is cooled to room temperature, obtains substrate；Wherein, the addition of wolframic acid is 70 ~ 80 g/ in hydrogenperoxide steam generator L, the addition of polyvinyl alcohol is 20 ~ 40 g/L；
（2）The hydrogenperoxide steam generator of wolframic acid, oxalic acid, urea, hydrochloric acid are added in acetonitrile, stirring is obtained to homogeneous solution is formed Hydro-thermal reaction liquid；By step（1）Gained substrate is placed in hydro-thermal reaction liquid, when 160 ~ 200 DEG C of hydro-thermal reactions 1 ~ 6 are small, cooling Taken out after to room temperature, it is washed, dry, then at 450 ~ 550 DEG C of heat preservations 1.5 ~ 3 it is small when after, be cooled to room temperature, obtain tungstic acid Nanometer sheet optoelectronic pole；Wherein, the molar ratio of wolframic acid, oxalic acid, urea, HCl and acetonitrile is（6~9）:（10~20）:（15~25）: （100~200）:（1×104~1.5×104）；
（3）By urea by calcining obtain carbonitride, carbonitride is uniformly mixed with ethylenediamine, reflux 10 ~ 15 it is small when after, adjusting PH value of solution, by dialysis, obtains N doping carbon dots solution to being in neutrality；
（4）By step（2）Gained tungstic trioxide nano-slice optoelectronic pole is placed in step（3）In gained N doping carbon dots solution, impregnate 20 ~ after forty minutes, take out and it is dry to get.
Preferably, step（1）Described in spin-coating method be specially on electro-conductive glass by Seed Layer solution drop coating, rotating speed is It 2000 ~ 3500 revs/min, maintains 20 ~ 40 seconds, as a spin coating cycle, spin coating periodicity totally 5 ~ 20 times, each spin coating cycle The drop coating amount of interior seed liquor is 50 ~ 120 μ L/cm2。
Preferably, step（1）Described in hydrogenperoxide steam generator concentration be 25 ~ 35 wt%.
Preferably, step（2）Described in wolframic acid hydrogenperoxide steam generator in wolframic acid concentration for 0.04 ~ 0.06 mol/L, The concentration of hydrogen peroxide is 1.4 ~ 2 mol/L.
Preferably, step（3）Described in calcine comprise the concrete steps that：First 500 ~ 600 are warming up to the rate of 3 ~ 6 DEG C/min DEG C, when heat preservation 2.5 ~ 3.5 is small, then it is cooled to room temperature with the rate of 3 ~ 6 DEG C/min.
Preferably, the step（3）The concentration that middle carbonitride mixes carbonitride in formed mixed liquor with ethylenediamine is 1.5~2.5 g/L。
Preferably, step（3）Middle adjusting pH value of solution uses concentrated hydrochloric acid.
Preferably, step（1）Described in electro-conductive glass be fluorine-doped tin oxide electro-conductive glass.
The N doping carbon dots being prepared using the above method modifies tungstic acid complex light electrode.
Application of the above-mentioned N doping carbon dots modification tungstic acid complex light electrode in photoelectrocatalysis decomposes water.
The electro-conductive glass is ordinary commercial products.
Tungstic acid is grown in conductive glass surface by the present invention using the method for hydrothermal synthesis, then by N doping carbon dots Modification is in tungstic acid semiconductor material surface, under the effect of N doping carbon dots, NCDs/WO3The electric conductivity of optoelectronic pole and photoproduction The transfer efficiency of carrier is improved, and effectively improves the electric conductivity of complex light electrode, can also reduce tungstic acid surface The problem of charge recombination is serious so as to improve the photoelectrocatalysis efficiency of tungstic acid, finally improves the complex light electrode photoelectric The efficiency of water is catalytically decomposed.
Description of the drawings
Fig. 1 is 1 gained WO of embodiment3Optoelectronic pole and NCDs/WO3The TEM figures of optoelectronic pole；
Fig. 2 is 1 gained NCDs/WO of embodiment3The XPS collection of illustrative plates of optoelectronic pole；
Fig. 3 is 1 gained WO of embodiment3Optoelectronic pole and NCDs/WO3The UV-vis collection of illustrative plates of optoelectronic pole；
Fig. 4 is 1 gained WO of embodiment3Optoelectronic pole and NCDs/WO3The linear sweep voltammetry curve of optoelectronic pole；
Fig. 5 is 1 gained WO of embodiment3Optoelectronic pole and NCDs/WO3The electricity conversion curve of optoelectronic pole；
Fig. 6 is 1 gained WO of embodiment3Optoelectronic pole and NCDs/WO3The electrochemical impedance spectroscopy of optoelectronic pole.
Specific embodiment
In order to make the technical purpose of the present invention, technical solution and advantageous effect clearer, with reference to specific embodiment Technical scheme is further illustrated, but the embodiment is intended to explain the present invention, and it is not intended that right The limitation of the present invention, in the examples where no specific technique or condition is specified, according to the described technology of document in the art or Condition is carried out according to product description.
Fluorine-doped tin oxide electro-conductive glass in following embodiments（FTO electro-conductive glass）Have purchased from Wuhan lattice solar energy science and technology Limit company, thickness 2.2mm, resistance be 14 Ω, light transmittance 90%.The temperature control heating platform is using German import PZ28-3TD Titanium-base thermal station and PR 5-3T cyclelogs.
Embodiment 1
A kind of preparation method of N doping carbon dots modification tungstic acid complex light electrode, comprises the following steps：
（1）2.5 g wolframic acids and 1.0 g polyvinyl alcohol are added in 34 mL hydrogenperoxide steam generators, are stirred overnight, are formed it into Even solution obtains Seed Layer solution；FTO electro-conductive glass is passed through into acetone, absolute ethyl alcohol and each ultrasonic 15 points of deionized water successively After clock, dried up with nitrogen；Then FTO electro-conductive glass is placed in the rotating disk of spin coating instrument, 100 μ L is pipetted with liquid-transfering gun For Seed Layer solution drop coating on electro-conductive glass, coated area is fixed as 1 × 1.5 cm2, rotating speed is 3000 revs/min, is maintained 30 seconds, As a spin coating cycle, spin coating periodicity totally 10 times is coated with colorless film on FTO electro-conductive glass；To through again and painting The FTO electro-conductive glass covered is placed on temperature control titanium-base warm table, is warming up to 450 DEG C with 5 DEG C/min of heating rate, is kept 2 After hour, it is cooled to room temperature, obtains substrate；Wherein, the concentration of hydrogenperoxide steam generator is 34 wt%；
（2）It is 6 mol/L hydrochloric acid by the hydrogenperoxide steam generator of 3 mL wolframic acids, 0.02 g oxalic acid, 0.02 g urea, 0.5 mL concentration It adds in 12.5 mL acetonitriles, lasting stirring makes solid be completely dissolved to form homogeneous solution, obtains hydro-thermal reaction liquid；Hydro-thermal is anti- Liquid is answered to be transferred in reaction kettle liner, and by step（1）It is small in 180 DEG C of hydro-thermal reactions 2 in gained substrate insertion hydro-thermal reaction liquid When, it is taken out after being cooled to room temperature, dries up through milli-Q water, nitrogen, then be placed on temperature control titanium-base warm table, with 5 DEG C/minute The heating rate of clock is warming up to 500 DEG C, keep 2 it is small when after, be cooled to room temperature, obtain tungstic trioxide nano-slice optoelectronic pole（WO3Light Electrode）；Wherein, the concentration of wolframic acid is 0.05 mol/L in the hydrogenperoxide steam generator of wolframic acid, the concentration of hydrogen peroxide is 1.7 mol/L；
（3）10 g urea are put into crucible, is then placed in Muffle furnace and is warming up to 550 DEG C with the heating rate of 5 DEG C/min, perseverance 3 h of temperature, are then cooled to room temperature again with the rate of 5 DEG C/min, finally obtain the carbonitride of powder（C3N4）；0.02 g is nitrogenized Carbon is uniformly mixed with 10 mL ethylenediamines, and 12 h that flow back under conditions of 80 DEG C obtain yellow solution, by acquired solution with dense HCl（wt 37%）It neutralizes, then again by the solution semi-permeable membrane after neutralization（MWCO 1000）Being dialysed, it is pure to can obtain It can obtain pure N doping carbon dots（NCDs）Solution；
（4）By step（2）Gained tungstic trioxide nano-slice optoelectronic pole is placed in step（3）In gained N doping carbon dots solution, impregnate After 30 minutes, take out and dried in 60 DEG C of baking oven and modify tungstic acid complex light electrode to get N doping carbon dots（NCDs/ WO3Optoelectronic pole）.
Embodiment 2
A kind of preparation method of N doping carbon dots modification tungstic acid complex light electrode, comprises the following steps：
（1）2.4 g wolframic acids and 0.7 g polyvinyl alcohol are added in 34 mL hydrogenperoxide steam generators, are stirred overnight, are formed it into Even solution obtains Seed Layer solution；FTO electro-conductive glass is passed through into acetone, absolute ethyl alcohol and each ultrasonic 15 points of deionized water successively After clock, dried up with nitrogen；Then FTO electro-conductive glass is placed in the rotating disk of spin coating instrument, 50 μ L kinds is pipetted with liquid-transfering gun For sublayer solution drop coating on electro-conductive glass, coated area is fixed as 1 × 1.5 cm2, rotating speed is 2000 revs/min, is maintained 30 seconds, with This is a spin coating cycle, spin coating periodicity totally 10 times, and colorless film is coated on FTO electro-conductive glass；Coating will be passed through again FTO electro-conductive glass be placed on temperature control titanium-base warm table, be warming up to 500 DEG C with 5 DEG C/min of heating rate, keep 1.5 After hour, it is cooled to room temperature, obtains substrate；Wherein, the concentration of hydrogenperoxide steam generator is 25 wt%；
（2）It is 6 mol/L salt by the hydrogenperoxide steam generator of 3 mL wolframic acids, 0.018 g oxalic acid, 0.018 g urea, 0.4 mL concentration Acid is added in 12 mL acetonitriles, and lasting stirring is completely dissolved solid and forms homogeneous solution, obtains hydro-thermal reaction liquid；By hydro-thermal Reaction solution is transferred in reaction kettle liner, and by step（1）In gained substrate insertion hydro-thermal reaction liquid, in 160 DEG C of hydro-thermal reactions 6 Hour, taken out after being cooled to room temperature, dry up, then be placed on temperature control titanium-base warm table through milli-Q water, nitrogen, with 5 DEG C/ Minute heating rate be warming up to 500 DEG C, keep 1.5 it is small when after, be cooled to room temperature, obtain tungstic trioxide nano-slice optoelectronic pole （WO3Optoelectronic pole）；Wherein, the concentration of wolframic acid is 0.04 mol/L in the hydrogenperoxide steam generator of wolframic acid, the concentration of hydrogen peroxide is 1.4 mol/L；
（3）10 g urea are put into crucible, is then placed in Muffle furnace and is warming up to 500 DEG C with the heating rate of 5 DEG C/min, perseverance 3 h of temperature, are then cooled to room temperature again with the rate of 5 DEG C/min, finally obtain the carbonitride of powder（C3N4）；0.015 g is nitrogenized Carbon is uniformly mixed with 10 mL ethylenediamines, and 12 h that flow back under conditions of 80 DEG C obtain yellow solution, by acquired solution with dense HCl（wt 37%）It neutralizes, then again by the solution semi-permeable membrane after neutralization（MWCO 1000）Being dialysed, it is pure to can obtain It can obtain pure N doping carbon dots（NCDs）Solution；
（4）By step（2）Gained tungstic trioxide nano-slice optoelectronic pole is placed in step（3）In gained N doping carbon dots solution, impregnate After ten minutes, take out and dried in 60 DEG C of baking oven and modify tungstic acid complex light electrode to get N doping carbon dots（NCDs/ WO3Optoelectronic pole）.
Embodiment 3
A kind of preparation method of N doping carbon dots modification tungstic acid complex light electrode, comprises the following steps：
（1）2.7 g wolframic acids and 1.3 g polyvinyl alcohol are added in 34 mL hydrogenperoxide steam generators, are stirred overnight, are formed it into Even solution obtains Seed Layer solution；FTO electro-conductive glass is passed through into acetone, absolute ethyl alcohol and each ultrasonic 15 points of deionized water successively After clock, dried up with nitrogen；Then FTO electro-conductive glass is placed in the rotating disk of spin coating instrument, 120 μ L is pipetted with liquid-transfering gun For Seed Layer solution drop coating on electro-conductive glass, coated area is fixed as 1 × 1.5 cm2, rotating speed is 3500 revs/min, is maintained 30 seconds, As a spin coating cycle, spin coating periodicity totally 10 times is coated with colorless film on FTO electro-conductive glass；To through again and painting The FTO electro-conductive glass covered is placed on temperature control titanium-base warm table, is warming up to 550 DEG C with 5 DEG C/min of heating rate, is kept 3 After hour, it is cooled to room temperature, obtains substrate；Wherein, the concentration of hydrogenperoxide steam generator is 34 wt%；
（2）It is 6 mol/L salt by the hydrogenperoxide steam generator of 3 mL wolframic acids, 0.036 g oxalic acid, 0.03 g urea, 0.6 mL concentration Acid is added in 12 mL acetonitriles, and lasting stirring is completely dissolved solid and forms homogeneous solution, obtains hydro-thermal reaction liquid；By hydro-thermal Reaction solution is transferred in reaction kettle liner, and by step（1）In gained substrate insertion hydro-thermal reaction liquid, in 200 DEG C of hydro-thermal reactions 1 Hour, taken out after being cooled to room temperature, dry up, then be placed on temperature control titanium-base warm table through milli-Q water, nitrogen, with 5 DEG C/ Minute heating rate be warming up to 550 DEG C, keep 1.5 it is small when after, be cooled to room temperature, obtain tungstic trioxide nano-slice optoelectronic pole （WO3Optoelectronic pole）；Wherein, the concentration of wolframic acid is 0.06 mol/L in the hydrogenperoxide steam generator of wolframic acid, the concentration of hydrogen peroxide is 2 mol/L；
（3）10 g urea are put into crucible, is then placed in Muffle furnace and is warming up to 600 DEG C with the heating rate of 5 DEG C/min, perseverance 3 h of temperature, are then cooled to room temperature again with the rate of 5 DEG C/min, finally obtain the carbonitride of powder（C3N4）；0.025 g is nitrogenized Carbon is uniformly mixed with 10 mL ethylenediamines, and 12 h that flow back under conditions of 80 DEG C obtain yellow solution, by acquired solution with dense HCl（wt 37%）It neutralizes, then again by the solution semi-permeable membrane after neutralization（MWCO 1000）Being dialysed, it is pure to can obtain It can obtain pure N doping carbon dots（NCDs）Solution；
（4）By step（2）Gained tungstic trioxide nano-slice optoelectronic pole is placed in step（3）In gained N doping carbon dots solution, impregnate After 80 minutes, take out and dried in 60 DEG C of baking oven and modify tungstic acid complex light electrode to get N doping carbon dots（NCDs/ WO3Optoelectronic pole）.
Characterization and detection
To WO made from embodiment 13Optoelectronic pole and NCDs/WO3Optoelectronic pole carries out TEM characterizations, as a result respectively such as Fig. 1（a）、（b） It is shown.By Fig. 1（a）It understands, prepared WO3Photoelectricity and for lamellar structure, thickness is about 15-30 nm；By Fig. 1（b）It can Know, WO3NCDs is firmly adhered to WO after being impregnated in NCDs solution3Surface.
In order to further prove NCDs and WO3It is effectively combined, by prepared NCDs/WO3Complex light electrode carries out XPS is characterized, and the results are shown in Figure 2.As can be observed from Figure, NCDs/WO3Complex light electrode contains W（32~40 eV）, C （280~290 eV）, N（395~405 eV）And O（522~535 eV）Four kinds of elements of element, can be with NCDs/WO3It is contained Element is corresponding, illustrates that by the method impregnated NCDs/WO can be successfully prepared3Optoelectronic pole.
Fig. 3 is WO3Light anode and NCDs/WO3The ultraviolet-visible absorption spectroscopy of complex light electrode.As seen from Figure 2, WO3Optoelectronic pole has very strong absorption in short wavelength region（λ<450 nm）, but modify WO by NCDs3After optoelectronic pole, NCDs/ WO3Absorption intensity in the range of entire uv-vis spectra is improved.Experiment shows to modify WO with NCDs3Light anode can be with Enhance WO3Optoelectronic pole improves WO to the absorption intensity of sunlight3To the utilization ratio of light.
CHI 760E electrochemical workstations are used in experiment（Shanghai Chen Hua Instrument Ltd.）, three-electrode system research WO3 And NCDs/WO3The photoelectrocatalysis of optoelectronic pole decomposes aqueous energy, wherein using platinized platinum as to electrode, saturated calomel electrode is reference electricity Pole, photoelectricity extremely working electrode prepared by experiment, electrolyte are 1 mol/L H2SO4Solution.Lead to before test into electrolyte solution Enter high-purity N2To remove dissolved oxygen therein, duration of ventilation is 30 min.The spectrum of approximate sunlight in order to obtain, makes in experiment The 500 W xenon lamps with application AM 1.5G optical filters are light source（CEL-S500, middle religion Jin Yuan）, and calibrate its optical power density and be 100 mW cm-2.In experiment, photocurrent testing is linear scan cyclic voltammetry, and potential test scope is 0.2 V~1.2 V vs. SCE sweep speed as 10 mV s-1.The electrochemical impedance spectroscopy of electrode is tested under illumination condition（EIS）For Electrode The variations such as the front and rear interfacial charge transfer resistance of modification, capacitance.
In the test system for decomposing water in photoelectrocatalysis, photoelectric current be a kind of direct reflection semiconductor to the absorption of photon and The means of testing of Utilization ability.Fig. 4 is WO3And NCDs/WO3Optoelectronic pole is under illumination condition（100 mW cm-2, AM 1.5G）Institute The linear sweep voltammetry curve measured.In 1.0 V（vs. SCE）Under the conditions of, with WO3It compares, NCDs/WO3The photoelectric current of optoelectronic pole Add 1.92 times.With continuing to increase for voltage, WO3Optoelectronic pole is in 0.9 V（vs. SCE）Electric current has basically reached saturation （0.62 mA cm-2）, and NCDs/WO3The electric current of optoelectronic pole is still continuously increased with the increase of voltage, is finally reached current saturation （1.19 mA cm-2）.The experimental results showed that NCDs greatly improves WO3The saturation current of optoelectronic pole, so as to be more advantageous to WO3 Photoelectrocatalysis decomposes the progress of water reaction.
In order to study WO3And NCDs/WO3The electricity conversion of optoelectronic pole at different wavelengths（IPCE）, with three electrode bodies The IPCE measured under different wave length is tied up under the voltage of 1.0 V vs SCE, and experimental result is as shown in Figure 5.It can from Fig. 5 It arrives, NCDs/WO3In the range of entire wavelength region（360~500 nm）IPCE efficiency be above WO3Optoelectronic pole.The result with Ultraviolet absorpting spectrum result is consistent.
In order to further study transfer process of the charge on semiconductor/electrolyte interface, WO is tested3Optoelectronic pole and NCDs/WO3Optoelectronic pole is under illumination conditions（100 mW cm-2, AM 1.5G）Electrochemical impedance spectroscopy.As shown in fig. 6, NCDs/ WO3The semicircle of optoelectronic pole is less than WO3Optoelectronic pole illustrates NCDs/WO3The interfacial charge transfer resistance that optoelectronic pole has is smaller, should As a result NCDs/WO is also illustrated3Optoelectronic pole has the separation of better photo-generated carrier and faster interfacial charge transfer process.
After testing, the NCDs/WO obtained by embodiment 23The photoelectric current of optoelectronic pole is higher than the WO obtained by embodiment 23Photoelectricity Pole, the NCDs/WO obtained by embodiment 33The photoelectric current of optoelectronic pole is higher than the WO obtained by embodiment 33Optoelectronic pole.
Finally illustrate, in the present invention, preparing the parameter of electrode can adjust in respective range, it will be apparent that afflux Body, semi-conducting material, graphene and cocatalyst materials can make corresponding replacement or modified.Above example only to Illustrate technical scheme and unrestricted, although having been carried out by referring to the preferred embodiment of the present invention to the present invention Description, it should be appreciated by those of ordinary skill in the art that various change can be made to it in the form and details Become, the spirit and scope of the present invention limited without departing from the appended claims.

Claims (10)

1. a kind of preparation method of N doping carbon dots modification tungstic acid complex light electrode, which is characterized in that comprise the following steps：
（1）Wolframic acid and polyvinyl alcohol are added in hydrogenperoxide steam generator, stirring obtains Seed Layer solution to homogeneous solution is formed； Seed Layer solution is coated on using spin-coating method on electro-conductive glass, then 450 ~ 550 DEG C will be warming up to by the electro-conductive glass of coating, After when heat preservation 1.5 ~ 3 is small, it is cooled to room temperature, obtains substrate；Wherein, the addition of wolframic acid is 70 ~ 80 g/ in hydrogenperoxide steam generator L, the addition of polyvinyl alcohol is 20 ~ 40 g/L；
（2）The hydrogenperoxide steam generator of wolframic acid, oxalic acid, urea, hydrochloric acid are added in acetonitrile, stirring is obtained to homogeneous solution is formed Hydro-thermal reaction liquid；By step（1）Gained substrate is placed in hydro-thermal reaction liquid, when 160 ~ 200 DEG C of hydro-thermal reactions 1 ~ 6 are small, cooling Taken out after to room temperature, it is washed, dry, then at 450 ~ 550 DEG C of heat preservations 1.5 ~ 3 it is small when after, be cooled to room temperature, obtain tungstic acid Nanometer sheet optoelectronic pole；Wherein, the molar ratio of wolframic acid, oxalic acid, urea, HCl and acetonitrile is（6~9）:（10~20）:（15~25）: （100~200）:（1×104~1.5×104）；
（3）By urea by calcining obtain carbonitride, carbonitride is uniformly mixed with ethylenediamine, reflux 10 ~ 15 it is small when after, adjusting PH value of solution, by dialysis, obtains N doping carbon dots solution to being in neutrality；
（4）By step（2）Gained tungstic trioxide nano-slice optoelectronic pole is placed in step（3）In gained N doping carbon dots solution, impregnate After 10 ~ 80 minutes, take out and it is dry to get.
2. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：Step（1）Described in Spin-coating method is specially on electro-conductive glass by Seed Layer solution drop coating, and rotating speed is 2000 ~ 3500 revs/min, is maintained 20 ~ 40 seconds, with This is a spin coating cycle, and spin coating periodicity totally 5 ~ 15 times, the drop coating amount of seed liquor is 50 ~ 120 μ L/ in each spin coating cycle cm2。
3. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：Step（1）Described in The concentration of hydrogenperoxide steam generator is 25 ~ 35 wt%.
4. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：Step（2）Described in The concentration of wolframic acid is 0.04 ~ 0.06 mol/L in the hydrogenperoxide steam generator of wolframic acid, the concentration of hydrogen peroxide is 1.4 ~ 2 mol/L.
5. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：Step（3）Described in Calcining comprises the concrete steps that：500 ~ 600 DEG C first are warming up to the rate of 3 ~ 6 DEG C/min, when heat preservation 2.5 ~ 3.5 is small, then with 3 ~ 6 DEG C/rate of min is cooled to room temperature.
6. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：The step（3）In The concentration that carbonitride mixes carbonitride in formed mixed liquor with ethylenediamine is 1.5 ~ 2.5 g/L.
7. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：Step（3）Middle adjusting PH value of solution uses concentrated hydrochloric acid.
8. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：Step（1）Described in Electro-conductive glass is fluorine-doped tin oxide electro-conductive glass.
9. the N doping carbon dots modification tungstic acid complex light electrode being prepared using any the method for claim 1 ~ 8.
10. application of the N doping carbon dots modification tungstic acid complex light electrode in photoelectrocatalysis decomposes water described in claim 9.
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