CN108103525B - N doping carbon dots modify tungstic acid complex light electrode and preparation method thereof and decompose the application in water in photoelectrocatalysis - Google Patents

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

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CN108103525B
CN108103525B CN201711417939.8A CN201711417939A CN108103525B CN 108103525 B CN108103525 B CN 108103525B CN 201711417939 A CN201711417939 A CN 201711417939A CN 108103525 B CN108103525 B CN 108103525B
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complex light
carbon dots
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doping carbon
optoelectronic pole
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CN108103525A (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, the following steps are included: first generating WO 3 film on electro-conductive glass, obtain substrate, tungstic trioxide nano-slice optoelectronic pole is made through hydro-thermal, annealing in substrate again, then N doping carbon dots solution is prepared, N doping carbon dots are modified using dipping construction from part on tungstic trioxide nano-slice optoelectronic pole；The invention also discloses the complex light electrodes to decompose the application in water in photoelectrocatalysis.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 serious problem of tungstic acid surface charge recombination can also be reduced, 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 modify tungstic acid complex light electrode and preparation method thereof, He Guang 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 modification tungstic acid composite photoelectric Pole and preparation method thereof and the application in photoelectrocatalysis decomposition water.
Background technique
Currently, energy crisis is increasingly severe, how to develop and increasingly cause people using reproducible clean energy resource Concern.Solar energy storage level is very big and pollution-free in nature, is a kind of ideal renewable resource.Since 1972 by Fujishima reports TiO2Optoelectronic pole can use solar hydrogen making and provide clean, the green energy [A. Fujishima, K. Honda, Nature, 1972,238,37-38], utilize the transition metal oxide half of nanostructure Conductor material (such as TiO2, Fe2O3, WO3) this method of water generation hydrogen and oxygen is catalytically decomposed by optical electro-chemistry (PEC) It is considered as a kind of promising environmentally friendly route.
Metal semiconductor oxide tungstic acid (WO3) be widely used in photoelectricity as a kind of optical anode material and urge Change and decomposes in water reaction.WO3Belong to N-shaped indirect band-gap semiconductor, forbidden bandwidth is 2.5 ~ 2.8 eV and valence band current potential compares 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 WO3It is also a kind of inexpensive, nontoxic, environmental-friendly semiconductor material.Base In these excellent properties, WO3People are caused widely to study in fields such as light degradation, Driven by Solar Energy optical electro-chemistry.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 property of optoelectronic pole is still far below its theoretical value (~ 5 mA cm-2).How further to mention High WO3To light utilization efficiency and improves electron hole separative efficiency and become the focus of people's research problem.Studies have shown that passing through element Doping, selective doping semiconductor [T. Zhang, Z. L. Zhu, H. N. Chen, et al., Nanoscale, 2015,7,2933-2940.], construct nanostructure [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] electron transfer efficiency the methods of can be improved, reduce electron-hole It is compound to improving WO3Photoelectrocatalysis efficiency.
A nova of the carbon dots (CDs) as 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.).Pass through the size and selectivity of regulation and control carbon dots Hetero atom is adulterated, to adjust band gap (T. F. Yeh, C. Y. Teng, S. Chen and the H. Teng, Adv of carbon dots Mater, 2014,26,3297-3303).Using carbonitride and ethylenediamine as presoma, nitrogen is prepared for using the method for reflux and is mixed Miscellaneous carbon dots (NCDs), can it is significant improve CDs conductivity and electric charge transfer and electrolyte-electrode interaction, be conducive to It is catalyzed water decomposition under visible light illumination.The carbon dots of N doping have 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, to reach raising WO3The effect of photoelectrocatalysis efficiency.
Summary of the invention
Based on the deficiencies of the prior art, the object of the present invention is to provide N doping carbon dots 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 Point modification tungstic acid complex light electrode decomposes the application in water in photoelectrocatalysis.
To achieve the goals above, the technical solution adopted by the present invention are as follows:
A kind of preparation method of tungstic acid complex light electrode, comprising the following steps:
(1) wolframic acid and polyvinyl alcohol are added in hydrogenperoxide steam generator, it is molten to obtain seed layer to homogeneous solution is formed for stirring Liquid；Seed layer solution is coated on electro-conductive glass using spin-coating method, then 450 ~ 550 will be warming up to by the electro-conductive glass of coating DEG C, after heat preservation 1.5 ~ 3 hours, it is cooled to room temperature, obtains substrate；Wherein, the additional amount of wolframic acid is 70 ~ 80 in hydrogenperoxide steam generator G/L, polyvinyl alcohol additional amount be 20 ~ 40 g/L；
(2) hydrogenperoxide steam generator of wolframic acid, oxalic acid, urea, hydrochloric acid are added in acetonitrile, stirring to formation homogeneous solution, Obtain hydro-thermal reaction liquid；Substrate obtained by step (1) is placed in hydro-thermal reaction liquid, in 160 ~ 200 DEG C hydro-thermal reaction 1 ~ 6 hour, Taken out after being cooled to room temperature, it is washed, dry, then at 450 ~ 550 DEG C keep the temperature 1.5 ~ 3 hours after, be cooled to room temperature, obtain three oxygen Change tungsten 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) urea is obtained into carbonitride by calcining, carbonitride is uniformly mixed with ethylenediamine, after reflux 10 ~ 15 hours, PH value of solution is adjusted to being in neutrality, by dialysis, obtains N doping carbon dots solution；
(4) tungstic trioxide nano-slice optoelectronic pole obtained by step (2) is placed in N doping carbon dots solution obtained by step (3), Impregnate 20 ~ after forty minutes, take out and it is dry to get.
Preferably, spin-coating method described in step (1) is specially by seed layer solution drop coating on electro-conductive glass, and revolving speed is It 2000 ~ 3500 revs/min, maintains 20 ~ 40 seconds, as a spin coating period, spin coating periodicity totally 5 ~ 20 times, each spin coating period The drop coating amount of interior seed liquor is 50 ~ 120 μ L/cm2。
Preferably, the concentration of hydrogenperoxide steam generator described in step (1) is 25 ~ 35 wt%.
Preferably, in the hydrogenperoxide steam generator of wolframic acid described in step (2) wolframic acid concentration be 0.04 ~ 0.06 mol/L, The concentration of hydrogen peroxide is 1.4 ~ 2 mol/L.
Preferably, calcining described in step (3) comprises the concrete steps that: being first warming up to 500 ~ 600 with the rate of 3 ~ 6 DEG C/min DEG C, 2.5 ~ 3.5 hours are kept the temperature, is then cooled to room temperature with the rate of 3 ~ 6 DEG C/min.
Preferably, carbonitride mixes with ethylenediamine and is formed by the concentration of carbonitride in mixed liquor and is in the step (3) 1.5~2.5 g/L。
Preferably, pH value of solution is adjusted in step (3) use concentrated hydrochloric acid.
Preferably, electro-conductive glass described in step (1) is fluorine-doped tin oxide electro-conductive glass.
Tungstic acid complex light electrode is modified using the N doping carbon dots that the above method is prepared.
Above-mentioned N doping carbon dots modification tungstic acid complex light electrode decomposes the application in water in photoelectrocatalysis.
The electro-conductive glass is ordinary commercial products.
Tungstic acid is grown in conductive glass surface using the method for hydrothermal synthesis by the present invention, 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 and photoproduction of optoelectronic pole The transfer efficiency of carrier is improved, and the electric conductivity of complex light electrode is effectively improved, and can also reduce tungstic acid surface The serious problem of charge recombination finally improves the complex light electrode photoelectric to improve the photoelectrocatalysis efficiency of tungstic acid The efficiency of water is catalytically decomposed.
Detailed description of the invention
Fig. 1 is 1 gained WO of embodiment3Optoelectronic pole and NCDs/WO3The TEM of optoelectronic pole schemes；
Fig. 2 is 1 gained NCDs/WO of embodiment3The XPS map of optoelectronic pole；
Fig. 3 is 1 gained WO of embodiment3Optoelectronic pole and NCDs/WO3The UV-vis map 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 incident photon-to-electron conversion efficiency 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 keep technical purpose of the invention, technical scheme and beneficial effects clearer, combined with specific embodiments below Technical solution of the present invention is further illustrated, but the embodiment is intended to explain the present invention, and should not be understood as pair Limitation of the invention, in the examples where no specific technique or condition is specified, according to the literature in the art described technology or Condition is carried out according to product description.
There is fluorine-doped tin oxide electro-conductive glass (FTO electro-conductive glass) purchased from Wuhan lattice solar energy science and technology in following embodiments Limit company, with a thickness of 2.2mm, resistance is 14 Ω, light transmittance 90%.The temperature control heating platform is using German import PZ28-3TD Titanium-base thermal station and PR 5-3T cyclelog.
Embodiment 1
A kind of preparation method of N doping carbon dots modification tungstic acid complex light electrode, comprising 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, make its shape At homogeneous solution, seed layer solution is obtained；FTO electro-conductive glass is successively passed through into acetone, dehydrated alcohol and each ultrasound of deionized water After 15 minutes, with being dried with nitrogen；Then FTO electro-conductive glass is placed in the rotating disk of spin coating instrument, pipettes 100 with liquid-transfering gun For μ L seed layer solution drop coating on electro-conductive glass, coated area is fixed as 1 × 1.5 cm2, revolving speed is 3000 revs/min, maintains 30 Second, as a spin coating period, spin coating periodicity totally 10 times, colorless film is coated on FTO electro-conductive glass；It will pass through again The FTO electro-conductive glass of coating 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 protected It after holding 2 hours, is cooled to room temperature, obtains substrate；Wherein, the concentration of hydrogenperoxide steam generator is 34 wt%；
It (2) is 6 mol/L by the hydrogenperoxide steam generator of 3 mL wolframic acids, 0.02 g oxalic acid, 0.02 g urea, 0.5 mL concentration Hydrochloric acid is added in 12.5 mL acetonitriles, and lasting stirring makes solid be completely dissolved to form homogeneous solution, obtains hydro-thermal reaction liquid；By water Thermal response liquid is transferred in reaction kettle liner, and substrate obtained by step (1) is inserted into hydro-thermal reaction liquid, anti-in 180 DEG C of hydro-thermals It answers 2 hours, is taken out after being cooled to room temperature, through milli-Q water, is dried with nitrogen, then be placed on temperature control titanium-base warm table, with 5 DEG C/min heating rate be warming up to 500 DEG C, after being kept for 2 hours, be cooled to room temperature, obtain tungstic trioxide nano-slice optoelectronic pole (WO3Optoelectronic pole)；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, are then placed in Muffle furnace and are warming up to 550 with the heating rate of 5 DEG C/min DEG C, then 3 h of constant temperature is cooled to room temperature again with the rate of 5 DEG C/min, finally obtain the carbonitride (C of powder3N4)；By 0.02 g Carbonitride is uniformly mixed with 10 mL ethylenediamines, and 12 h that flow back under conditions of 80 DEG C obtain yellow solution, and acquired solution is used Dense HCl(wt 37%) neutralize, then again by the solution after neutralization with semi-permeable membrane (MWCO 1000) carry out dialysis can be obtained it is pure Pure N doping carbon dots (NCDs) solution can be obtained；
(4) tungstic trioxide nano-slice optoelectronic pole obtained by step (2) is placed in N doping carbon dots solution obtained by step (3), After impregnating 30 minutes, takes 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, comprising 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, make its shape At homogeneous solution, seed layer solution is obtained；FTO electro-conductive glass is successively passed through into acetone, dehydrated alcohol and each ultrasound of deionized water After 15 minutes, with being dried with nitrogen；Then FTO electro-conductive glass is placed in the rotating disk of spin coating instrument, pipettes 50 with liquid-transfering gun For μ L seed layer solution drop coating on electro-conductive glass, coated area is fixed as 1 × 1.5 cm2, revolving speed is 2000 revs/min, maintains 30 Second, as a spin coating period, spin coating periodicity totally 10 times, colorless film is coated on FTO electro-conductive glass；It will pass through again The FTO electro-conductive glass of coating is placed on temperature control titanium-base warm table, is warming up to 500 DEG C with 5 DEG C/min of heating rate, is protected It after holding 1.5 hours, is cooled to room temperature, obtains substrate；Wherein, the concentration of hydrogenperoxide steam generator is 25 wt%；
It (2) is 6 by the hydrogenperoxide steam generator of 3 mL wolframic acids, 0.018 g oxalic acid, 0.018 g urea, 0.4 mL concentration Mol/L hydrochloric acid is added in 12 mL acetonitriles, and lasting stirring is completely dissolved solid and forms homogeneous solution, obtains hydro-thermal reaction liquid； Hydro-thermal reaction liquid is transferred in reaction kettle liner, and substrate obtained by step (1) is inserted into hydro-thermal reaction liquid, in 160 DEG C of water It thermal response 6 hours, takes out after being cooled to room temperature, through milli-Q water, is dried with nitrogen, then be placed on temperature control titanium-base warm table On, 500 DEG C are warming up to 5 DEG C/min of heating rate, after being kept for 1.5 hours, is cooled to room temperature, obtains tungsten trioxide nano Piece optoelectronic pole (WO3Optoelectronic pole)；Wherein, the concentration of wolframic acid is 0.04 mol/L, hydrogen peroxide in the hydrogenperoxide steam generator of wolframic acid Concentration be 1.4 mol/L；
(3) 10 g urea are put into crucible, are then placed in Muffle furnace and are warming up to 500 with the heating rate of 5 DEG C/min DEG C, then 3 h of constant temperature is cooled to room temperature again with the rate of 5 DEG C/min, finally obtain the carbonitride (C of powder3N4)；By 0.015 G carbonitride 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%) neutralize, then again by the solution after neutralization with semi-permeable membrane (MWCO 1000) carry out dialysis can be obtained it is pure Net can be obtained pure N doping carbon dots (NCDs) solution；
(4) tungstic trioxide nano-slice optoelectronic pole obtained by step (2) is placed in N doping carbon dots solution obtained by step (3), It impregnates after ten minutes, takes 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, comprising 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, make its shape At homogeneous solution, seed layer solution is obtained；FTO electro-conductive glass is successively passed through into acetone, dehydrated alcohol and each ultrasound of deionized water After 15 minutes, with being dried with nitrogen；Then FTO electro-conductive glass is placed in the rotating disk of spin coating instrument, pipettes 120 with liquid-transfering gun For μ L seed layer solution drop coating on electro-conductive glass, coated area is fixed as 1 × 1.5 cm2, revolving speed is 3500 revs/min, maintains 30 Second, as a spin coating period, spin coating periodicity totally 10 times, colorless film is coated on FTO electro-conductive glass；It will pass through again The FTO electro-conductive glass of coating 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 protected It after holding 3 hours, is cooled to room temperature, obtains substrate；Wherein, the concentration of hydrogenperoxide steam generator is 34 wt%；
It (2) is 6 mol/ by the hydrogenperoxide steam generator of 3 mL wolframic acids, 0.036 g oxalic acid, 0.03 g urea, 0.6 mL concentration L hydrochloric acid is added in 12 mL acetonitriles, and lasting stirring is completely dissolved solid and forms homogeneous solution, obtains hydro-thermal reaction liquid；By water Thermal response liquid is transferred in reaction kettle liner, and substrate obtained by step (1) is inserted into hydro-thermal reaction liquid, anti-in 200 DEG C of hydro-thermals It answers 1 hour, is taken out after being cooled to room temperature, through milli-Q water, is dried with nitrogen, then be placed on temperature control titanium-base warm table, with 5 DEG C/min heating rate be warming up to 550 DEG C, after being kept for 1.5 hours, be cooled to room temperature, obtain tungstic trioxide nano-slice photoelectricity Pole (WO3Optoelectronic pole)；Wherein, in the hydrogenperoxide steam generator of wolframic acid wolframic acid concentration be 0.06 mol/L, hydrogen peroxide concentration For 2 mol/L；
(3) 10 g urea are put into crucible, are then placed in Muffle furnace and are warming up to 600 with the heating rate of 5 DEG C/min DEG C, then 3 h of constant temperature is cooled to room temperature again with the rate of 5 DEG C/min, finally obtain the carbonitride (C of powder3N4)；By 0.025 G carbonitride 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%) neutralize, then again by the solution after neutralization with semi-permeable membrane (MWCO 1000) carry out dialysis can be obtained it is pure Net can be obtained pure N doping carbon dots (NCDs) solution；
(4) tungstic trioxide nano-slice optoelectronic pole obtained by step (2) is placed in N doping carbon dots solution obtained by step (3), After impregnating 80 minutes, takes 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 carry out TEM characterization, as a result respectively as Fig. 1 (a), (b) shown in.By Fig. 1 (a) it is found that prepared WO3Photoelectricity and be lamellar structure, thickness is about 15-30 nm；By Fig. 1 (b) It is found that WO3NCDs is firmly adhered to WO after impregnating in NCDs solution3Surface.
In order to further prove NCDs and WO3It is effectively combined, by prepared NCDs/WO3Complex light electrode carries out XPS characterization, as a result as shown in Figure 2.As can be observed from Figure, NCDs/WO3Complex light electrode contains the eV of W(32 ~ 40), C (280 ~ 290 eV), the eV of N(395 ~ 405) and the eV of O(522 ~ 535) four kinds of elements of element, it can be with NCDs/WO3It is contained Element is corresponding, illustrates that NCDs/WO can be successfully prepared by the method for dipping3Optoelectronic 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 (nm of λ < 450) in short wavelength region, but modifies WO by NCDs3After optoelectronic pole, NCDs/ WO3Absorption intensity in entire ultraviolet-visible spectral limit 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 efficiency of light.
WO is studied with CHI 760E electrochemical workstation (Shanghai Chen Hua Instrument Ltd.), three-electrode system in experiment3 And NCDs/WO3The photoelectrocatalysis of optoelectronic pole decomposes aqueous energy, wherein being to electrode with platinized platinum, saturated calomel electrode is reference electricity Pole, tests prepared photoelectricity extremely working electrode, and electrolyte is 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 It is light source (CEL-S500, middle religion Jin Yuan) with the 500 W xenon lamps for applying AM 1.5G optical filter, and calibrates its optical power density and be 100 mW cm-2.In experiment, photocurrent testing is linear scan cyclic voltammetry, and potential test range is 0.2 V~1.2 V vs. SCE, sweeping speed is 10 mV s-1.The electrochemical impedance spectroscopy (EIS) that electrode is tested under illumination condition is used for Electrode Modify the variations such as interfacial charge transfer resistance, the capacitor of front and back.
In the test system that photoelectrocatalysis decomposes water, photoelectric current be a kind of directly reflection semiconductor to the absorption of photon and The means of testing of Utilization ability.Fig. 4 is WO3And NCDs/WO3Optoelectronic pole (100 mW cm under illumination condition-2, AM 1.5G) and 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 Increase 1.92 times.With continuing to increase for voltage, WO3Optoelectronic pole is in 0.9 V(vs. SCE) electric current 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, to be more advantageous to WO3 Photoelectrocatalysis decomposes the progress of water reaction.
In order to study WO3And NCDs/WO3The incident photon-to-electron conversion efficiency (IPCE) of optoelectronic pole at different wavelengths, with three electrode bodies The IPCE measured under different wave length under the voltage of 1.0 V vs SCE is tied up to, experimental result is as shown in Figure 5.It can from Fig. 5 It arrives, NCDs/WO3The IPCE efficiency of (360 ~ 500 nm) is above WO within the scope of entire wavelength region3Optoelectronic 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 (100 mW cm under illumination conditions-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 and faster interfacial charge transfer process of better photo-generated carrier.
Through detecting, NCDs/WO obtained by embodiment 23The photoelectric current of optoelectronic pole is higher than WO obtained by embodiment 23Photoelectricity Pole, NCDs/WO obtained by embodiment 33The photoelectric current of optoelectronic pole is higher than WO obtained by embodiment 33Optoelectronic pole.
Finally, it is stated that the parameter for preparing electrode can adjust in respective range, it will be apparent that afflux in the present invention Body, semiconductor material, graphene and cocatalyst materials can make corresponding replacement or modified.Above embodiments only to Illustrate technical solution of the present invention rather than limit, although having been carried out to the present invention by referring to the preferred embodiment of 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, without departing from the spirit and scope of the present invention defined by the appended claims.

Claims (6)

1. a kind of preparation method of N doping carbon dots modification tungstic acid complex light electrode, which 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 electro-conductive glass using spin-coating method, then 450 ~ 550 DEG C will be warming up to by the electro-conductive glass of coating, After heat preservation 1.5 ~ 3 hours, it is cooled to room temperature, obtains substrate；Wherein, the additional amount of wolframic acid is 70 ~ 80 g/ in hydrogenperoxide steam generator L, the additional amount of polyvinyl alcohol is 20 ~ 40 g/L；
(2) 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；Substrate obtained by step (1) is placed in hydro-thermal reaction liquid, in 160 ~ 200 DEG C hydro-thermal reaction 1 ~ 6 hour, it is cooling Taken out after to room temperature, it is washed, dry, then at 450 ~ 550 DEG C keep the temperature 1.5 ~ 3 hours 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) urea is obtained into carbonitride by calcining, carbonitride is uniformly mixed with ethylenediamine, flows back 10 under conditions of 80 DEG C After ~ 15 hours, pH value of solution is adjusted to being in neutrality, by dialysis, obtains N doping carbon dots solution；
(4) tungstic trioxide nano-slice optoelectronic pole obtained by step (2) is placed in N doping carbon dots solution obtained by step (3), is impregnated After 10 ~ 80 minutes, take out and it is dry to get；
Electro-conductive glass described in step (1) is fluorine-doped tin oxide electro-conductive glass, and with a thickness of 2.2mm, resistance is 14 Ω, light transmission Rate is 90%；
It is 1.5 ~ 2.5 g/L that carbonitride, which mixes with ethylenediamine and is formed by the concentration of carbonitride in mixed liquor, in the step (3)；
Calcining described in step (3) comprises the concrete steps that: first 500 ~ 600 DEG C are warming up to the rate of 3 ~ 6 DEG C/min, heat preservation 2.5 ~ It 3.5 hours, is then cooled to room temperature with the rate of 3 ~ 6 DEG C/min.
2. the preparation method of complex light electrode according to claim 1, it is characterised in that: the tool of spin-coating method described in step (1) Body is by seed layer solution drop coating on electro-conductive glass, and revolving speed is 2000 ~ 3500 revs/min, is maintained 20 ~ 40 seconds, as one In the spin coating period, spin coating periodicity totally 5 ~ 15 times, the drop coating amount of seed liquor is 50 ~ 120 μ L/cm in each spin coating period2。
3. the preparation method of complex light electrode according to claim 1, it is characterised in that: hydrogen peroxide described in step (1) The concentration of solution is 25 ~ 35 wt%.
4. the preparation method of complex light electrode according to claim 1, it is characterised in that: the mistake of wolframic acid described in step (2) The concentration of wolframic acid is 0.04 ~ 0.06 mol/L in hydrogen peroxide solution, the concentration of hydrogen peroxide is 1.4 ~ 2 mol/L.
5. the N doping carbon dots modification tungstic acid complex light electrode being prepared using any the method for claim 1 ~ 4.
6. N doping carbon dots described in claim 5, which modify tungstic acid complex light electrode, decomposes the application in water in photoelectrocatalysis.
CN201711417939.8A 2017-12-25 2017-12-25 N doping carbon dots modify tungstic acid complex light electrode and preparation method thereof and decompose the application in water in photoelectrocatalysis Expired - Fee Related CN108103525B (en)

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