CN105336498A - Novel and stable g-C3N4/NiO photoelectric cathode preparation method - Google Patents

Novel and stable g-C3N4/NiO photoelectric cathode preparation method Download PDF

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CN105336498A
CN105336498A CN201510686192.0A CN201510686192A CN105336498A CN 105336498 A CN105336498 A CN 105336498A CN 201510686192 A CN201510686192 A CN 201510686192A CN 105336498 A CN105336498 A CN 105336498A
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fto
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CN105336498B (en
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董玉明
陈艳美
王光丽
蒋平平
赵辉
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Jiangnan University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a novel and stable g-C3N4/NiO photoelectric hydrogen production electrode preparation method, and belongs to the technical field of inorganic chemistry and photoelectrocatalysis. The g-C3N4 light absorber is nonmetal and is made of nontoxic and easily available materials. The preparation method solves the problem that in the prior art, usually a toxic cadmium metal chalcogenide as the light absorber, and utilizes the g-C3N4 as the photoelectric cathode light absorption agent and cocatalyst for the first time. The preparation method includes: 1 taking FTO electro-conductive glass as the substrate and using a hydrothermal method to prepare ordered NiO films; and 2 immersing the NiO/FTO electrode obtained by the last step in the saturated thiourea solution for 4h, and then placing the NiO/FTO electrode in a muffle furnace for calcining for 2h by 500DEG C, and then taking out and obtaining the g-C3N4/NiO/FTO electrode. The preparation method is simple and easy to operate and is good for large-scale application.

Description

A kind of g-C of novel stabilising 3n 4the preparation method of/NiO photocathode
Technical field
The invention belongs to semiconductor photoelectrocatalysielectrode and decompose aquatic products hydrogen technical field, relate to a kind of preparation method of novel photocathode.
Background technology
In the past few decades, the energy and environmental problem have become one of most important and most popular theme in the world.Compare and fossil fuel, Hydrogen Energy has higher calorific value as a kind of fuel of environmental sound, almost higher than four times of methane.Due to this possibility producing a kind of clean energy resource carrier and do not have carbon dioxide to produce, decomposing aquatic products hydrogen and attracted considerable attention, is also the opportunity in energy storage field.The most effectively to produce one of hydrogen mode be photoelectric decomposition aquatic products hydrogen, and this mode can catch and store solar energy in the simplest chemical bond and generate without any pollutant.Generally speaking, photoelectric decomposition water device is made up of two kinds of different optoelectronic poles: photocathode and photo cathode, reduction and the oxidation reaction of water occur respectively under sunlight.No matter photo cathode or photocathode are made up of three components usually, n-type semiconductor or p-type semiconductor, sensitising agent and co-catalyst.
For an optoelectronic pole, light absorber is its key components, and the semiconductor of its sensitization broad stopband available is coupled with a kind of co-catalyst again, can be used for promoting the generation of chemical energy on electrode.Organic dyestuff, is the sensitising agent that the first generation occurs, but when carrying out sensitized photoelectrodes with it, due to the desorb of dye molecule or the leaching of catalyst, is easy to degrade.The sulphur system cadmium compound occurred subsequently can make full use of full spectrum sunlight because it has suitable energy gap, and preparation method is simple, applied range, and changes light abstraction width by the size controlling particle, therefore likely replaces organic dyestuff.But, because the toxic of cadmium element and earth's crust content do not enrich, thus limit the extensive use of cadmium system chalcogen compound.Therefore, develop a kind of novel, nontoxic, at a low price, effective and stable light absorber is significant.In addition, in order to accelerate electro transfer, reduce the compound in electronics and hole and improve hydrogen generation efficiency, certain co-catalyst is also necessary.
Recent years, a kind of novel non-metal optical catalyst g-C 3n 4potential using value due to it has attracted the attention of a lot of research worker, and it may be used for photocatalysis Decomposition aquatic products hydrogen, photocatalysis degradation organic contaminant and photocatalysis organic synthesis.G-C 3n 4have suitable energy gap can absorbing wavelength at the light of 450nm.In addition, g-C 3n 4have excellent chemistry and thermodynamic stability and outstanding characteristic electron.In Photocatalyzed Hydrogen Production, based on g-C 3n 4photochemical catalyst much studied.Recently, again You Liangge seminar g-C 3n 4as eelctro-catalyst, under lower overpotential, illustrate excellent catalytic activity.In sum, g-C 3n 4not only can be used as sensitising agent and also can make the catalytic activity that co-catalyst improves system.But, relevant g-C at present 3n 4the research of the Optical Electro-Chemistry aspect of sensitized photoelectrodes is also less.Based on this, we intend to design one g-C 3n 4the photocathode of sensitization, for decomposing aquatic products hydrogen.Nickel oxide (NiO), as a kind of p-type semiconductor, is identified a kind of substrate of outstanding conduction hole.Having one can effectively transfer to hole in NiO compared with the valence band electromotive force of NiO corrigendum, therefore the present invention with this bi-material construct a kind of novel with stable composite type photocathode for photoelectric decomposition aquatic products hydrogen.
As far as our knowledge goes, at present also not about g-C 3n 4the report that photocathode produces hydrogen is coupled as with NiO.In the present invention, we use water heat transfer NiO electrode, and then with simple thermal polymerization method g-C 3n 4with NiO electrode coupling.Under light illumination, g-C 3n 4/ NiO electrode can obtain higher photocurrent response value at 0V (vsRHE), 10 times of this value the chances are independent NiO electrode and be independent g-C 3n 420 times of electrode big.In addition, we have studied the charge transfer characteristic of this catalytic process with photic fluorescence analysis and impedance spectrum, have also been made certain discussion to the mechanism that the photoelectric properties of this combination electrode improve.
Summary of the invention
The object of the present invention is to provide a kind of novel product hydrogen photocathode g-C 3n 4the preparation method of/NiO and its product hydrogen application, this electrode has very high stability in long-time course of reaction.Under illumination, g-C 3n 4/ NiO electrode can obtain higher photocurrent response value at 0V (vsRHE), 10 times of this value the chances are independent NiO electrode and be independent g-C 3n 420 times of electrode big.The electrode be produced illustrates preferably catalytic activity, long stability and higher faradic efficiency and preparation method is simple.
Object of the present invention can be achieved through the following technical solutions:
Employing hydro thermal method, thermal polymerization prepare g-C 3n 4/ NiO electrode, step is made up of 3 steps.
(1) surface preparation of FTO electro-conductive glass
FTO electro-conductive glass first successively at absolute ethyl alcohol, soak two hours in acetone, and then in the aqueous isopropanol of 2mol/L potassium hydroxide, add hot reflux 30min;
(2) hydro thermal method prepares NiO/FTO electrode
FTO glass is put into 0.25mol/LNi (NO 3) 26H 2in the mixed aqueous solution of O and 0.25mol/L hexamethylenetetramine, 100 DEG C of heating 12min, take out, by washed with de-ionized water, dry, and to be placed in Muffle furnace 450 DEG C of calcining 2h, NiO/FTO electrode;
(3) thermal polymerization is adopted to prepare g-C 3n 4/ NiO photocathode
Above-mentioned obtained NiO/FTO electrode is immersed in saturated thiourea solution and soaks 4h, taking-up is dried, and afterwards the NiO/FTO electrode of upper for absorption thiocarbamide is placed in tube furnace, at N 2under atmosphere, 500 DEG C of calcining 2h, take out to obtain g-C 3n 4/ NiO/FTO.
Product hydrogen electrode g-C as above 3n 4/ NiO/FTO can be applicable to photoelectrocatalysis and produces hydrogen.
In order to illustrate that the present invention proposes the necessity of NiO in preparation method, we have also prepared control sample.The method same for above-mentioned (3) prepares pure g-C 3n 4sample, this sample by electrophoretic deposition on FTO.Detailed process is as follows: first a certain amount of thiocarbamide is placed in porcelain boat, is then placed in tube furnace, at N 2under atmosphere, 500 DEG C of calcinings 2h, the g-C taking out pure 3n 4sample; Then g-C 3n 4with Mg (NO 3) 26H 2o is blended in aqueous isopropanol, and obtained electrophoresis liquid, FTO is done negative electrode, and platinum guaze does anode, and electrophoresis 1min under the voltage of 160V, can obtain g-C 3n 4/ FTO electrode.
Remarkable advantage of the present invention is:
(1), after this electrode adopts simple hydro thermal method to prepare NiO, reusable heat polymerization is by g-C 3n 4at NiO on the surface, preparation method is simple in load.
(2) NiO is a kind of well p-type semiconductor, and has good thermal stability and chemical stability.
(3) g-C 3n 4as a kind of novel metalloid and nontoxic light absorbent, there is comparatively suitable energy gap, and earth's crust rich content, be a kind of potential light-sensitive material.
(4) electrode prepared by the present invention is used for the hydrogen manufacturing of photoelectric decomposition water, and reaction is efficient, simple to operate, cheap practical, and the electrode of preparation has very high stability, has very high practical value and application prospect.
Accompanying drawing explanation
Fig. 1 is that the SEM of the made electrode of embodiment 1 schemes (a) NiO/FTO and (b) g-C 3n 4/ NiO/FTO; C () TEM schemes; D () HRTEM schemes.
Fig. 2 is the XPS figure of the made electrode of embodiment 1: (a) overall diagram; (b) Ni2p; C) O1s; (d) C1s; (e) N1s.
Fig. 3 is the made g-C of embodiment 2 3n 4(A) UV-vis abosrption spectrogram (illustration is holder gram curve) of/NiO/FTO electrode; (B) three kinds of electrode chrono-amperometric comparison diagrams.
Fig. 4 be under embodiment 3 made electrode illumination condition in different electrolyte solution electric current variation diagram in time: (a) applied voltage E=-0.2VvsRHE is at N 2saturated Na 2sO 4(0.1mol/L) in electrolyte; B () applied voltage E=0VvsRHE is at the Na of the saturation of the air 2sO 4(0.1mol/L) in electrolyte.
Fig. 5 is product hydrogen content comparison diagram at different conditions in (a) three kinds of electrode 4h in embodiment 4; (b) g-C 3n 4/ NiO/FTO electrode under applied voltage E=-0.2VvsRHE at Na 2sO 4(0.1mol/L) electric charge and electric current variation diagram in time in electrolyte; (c) g-C 3n 4/ NiO/FTO electrode is at Na 2sO 4(0.1mol/L) electric current-potential change figure under light and no light condition is being had in electrolyte.
Fig. 6 is the trans cis photoisomerization figure of (A) three kinds of electrodes in embodiment 5; (B) three kinds of electrodes are at Na 2sO 4(0.1mol/L) Nyquist diagram in electrolyte.
The g-C of Fig. 7 for proposing in embodiment 6 3n 4/ NiO/FTO electrode H_2-producing mechanism figure.
Embodiment
Below in conjunction with the drawings and specific embodiments, preparation process of the present invention, sign and the performance test results are further described, but catalyst provided by the invention is not restricted to following case study on implementation.
Embodiment 1
A kind of g-C 3n 4the preparation method of/NiO/FTO photocathode, its concrete steps are:
(1) surface preparation of FTO electro-conductive glass
FTO electro-conductive glass first successively at absolute ethyl alcohol, soak two hours in acetone, and then in the aqueous isopropanol of 2mol/L potassium hydroxide, add hot reflux 30min;
(2) hydro thermal method prepares NiO/FTO electrode
FTO glass is put into 0.25mol/LNi (NO 3) 26H 2in the mixed aqueous solution of O and 0.25mol/L hexamethylenetetramine, 100 DEG C of heating 12min, take out, by washed with de-ionized water, dry, and to be placed in Muffle furnace 450 DEG C of calcining 2h, NiO/FTO electrode;
(3) thermal polymerization is adopted to prepare g-C 3n 4the NiO combination electrode of sensitization
Above-mentioned obtained NiO/FTO electrode is immersed in saturated thiourea solution and soaks 4h, taking-up is dried, and afterwards the NiO/FTO electrode of upper for absorption thiocarbamide is placed in tube furnace, at N 2under atmosphere, 500 DEG C of calcining 2h, take out to obtain g-C 3n 4/ NiO/FTO.
Fig. 1 is its ESEM, transmission electron microscope picture, and contrast from Fig. 1 (a) and 1 (b), independent NiO presents the alveolate texture of porous, g-C 3n 4nanometer sheet is loaded on electrode after NiO/FTO, and obviously great changes will take place for electrode surface, and electrode surface comparison of ingredients closely with consistent, and is evenly dispersed in whole NiO substrate.The composition of electrode surface is scraped from FTO, has done low power transmission and high power transmission characterizes, as shown in Fig. 1 (c) He 1 (d).Can find out have lamellar morphology to occur from low power transmission plot (c), be defined as polymer g-C 3n 4.And lattice 0.24nm and 0.21nm occurred in high power transmission plot corresponds respectively to (111) and (200) crystal face of NiO.Fig. 2 is its XPS collection of illustrative plates, and by inquiry XPS database and with reference to reporting document, and above-mentioned analysis can to determine in the present invention by hydro thermal method and the made photocathode composition of thermal polymerization it is g-C 3n 4/ NiO.
Embodiment 2
Investigate g-C 3n 4the photoelectrochemical behaviour of/NiO/FTO photocathode, and under similarity condition and only containing the g-C of single component 3n 4/ FTO, NiO/FTO electrode contrast.
Fig. 3 (a) is the made g-C of embodiment 1 3n 4the UV-vis abosrption spectrogram of/NiO/FTO electrode, as can be seen from the figure, g-C 3n 4absorption edge at about 440nm, its energy gap is by gram curve calculation of the holder in illustration, and namely the extended line of linear segment on the holder gram curve corresponding to it and the intersection point of abscissa are g-C 3n 4energy gap value.In addition, can also as seen from the figure, the absorption in visible-range of independent NiO is very weak, and g-C 3n 4/ NiO combination electrode shows stronger absorbability on the contrary within the scope of 350-460nm.From above result: g-C 3n 4the absworption peak of/NiO combination electrode is compared and is moved to longer wavelength direction with independent NiO electrode, also shows g-C 3n 4the light absorptive of/NiO combination electrode obtains certain raising.
We also test the photocurrent response of brand-new electrode.With 0.10mol/LNa 2sO 4for electrolyte solution, Ag/AgCl electrode is used as reference electrode, platinum guaze as to electrode, prepared g-C 3n 4/ NiO/FTO, g-C 3n 4/ FTO, NiO/FTO electrode as work electrode, electrolyte solution CH 4/ N 2mist degassed, remove wherein O 2, with the xenon lamp of 300W for light source have studied g-C 3n 4and the separation of photogenerated charge and electron interaction between NiO.As can be seen from Fig. 3 (b), g-C 3n 4/ NiO/FTO electrode, under the applied voltage of 0VvsRHE, can obtain 0.02mAcm -2current density, be approximately g-C 3n 420 times of/FTO electrode, 10 times of NiO/FTO electrode, this result describes g-C 3n 4favourable with the combination of NiO for the photoelectric properties improving electrode.
Embodiment 3
The Photoelectrochemical stabilization of an electrode is concerning most important a photoelectricity produces hydrogen system, and therefore, we have investigated made electrode g-C 3n 4the long-time stability of/NiO/FTO.
With 0.10mol/LNa 2sO 4for electrolyte solution, Ag/AgCl electrode is used as reference electrode, platinum guaze as to electrode, prepared g-C 3n 4/ NiO/FTO electrode as work electrode, electrolyte solution CH 4/ N 2mist degassed, remove wherein O 2, then measure its electrochemical stability with CHI600E electrochemical instrument.
Fig. 4 (a) and (b) represent g-C respectively 3n 4/ NiO/FTO electrode is with CH 4/ N 2saturatedly to scheme over time with electric current in the electrolyte solution of the saturation of the air.As can be seen from the figure our made electrodes electric current under these two conditions can keep long stability (10h).It should be noted that density of photocurrent that this electrode reaches in the electrolyte of the saturation of the air far away higher than with CH 4/ N 2in saturated electrolyte, its reason is that light induced electron not only can to reduce proton (H in the electrolyte of the saturation of the air 2) can also oxygen (O in reductive water 2).But the above results shows g-C 3n 4/ NiO/FTO electrode can keep good stability containing oxygen and non-containing in oxygen electrolyte.In addition, we also test 200 times by cyclic voltammetry to this electrode, and unanimously and substantially identical, also the stability of provable electrode is very good for curve shape.To be shown by above embodiment 1,2 and 3 result, we prepared a kind of novel, nontoxic, at a low price, the photocathode of effective and good stability.
Embodiment 4
Investigate made g-C 3n 4product hydrogen factor and the product hydrogen faradic efficiency of/NiO/FTO electrode.
With 0.10mol/LNa 2sO 4for electrolyte solution, Ag/AgCl electrode is used as reference electrode, platinum guaze as to electrode, prepared g-C 3n 4/ NiO/FTO, g-C 3n 4/ FTO, NiO/FTO electrode as work electrode, electrolyte solution CH 4/ N 2mist degassed, remove wherein O 2, then measure its photoelectric properties with CHI600E electrochemical instrument.
As shown in Fig. 5 (a), only having under light source existent condition, three electrodes all do not have hydrogen to produce, and show that light source is the necessary condition of producing hydrogen; Only having under applied voltage existent condition, g-C 3n 4/ FTO electrode does not detect hydrogen, and two other electrode all can only detect trace hydrogen; Under light and the simultaneous situation of electricity, g-C 3n 4/ FTO electrode does not detect hydrogen, and NiO/FTO electrode detection goes out a small amount of hydrogen, g-C 3n 4/ NiO/FTO electrode detection has gone out a large amount of hydrogen.Above result shows, light and electricity are g-C 3n 4/ NiO/FTO photocathode produces the essential condition of hydrogen, and it is compared and creates maximum hydrogen-producing speed with two other electrode, is due to g-C 3n 4being separated and transfer of electric charge is conducive to the synergy of NiO.In addition, we also compare electrode at the curve chart having electric current-electromotive force under light and no light condition, as we know from the figure, the photoelectric current of electrode obtained by us acquired by under illumination condition, far away higher than in dark reaction, shows that electrode obtained by us is a kind of well photocathode.
Next, we have investigated the faradic efficiency of this electrode.As shown in Fig. 5 (b), be-0.2VvsRHE at applied voltage, the linear increase of quantity of electric charge increase in time, after the experimental period of 4h, 0.13C by the total charge dosage of electrode, corresponding to the hydrogen output of 0.65 μm of ol, coincide by the hydrogen output 0.64 μm of ol ten points measured by gas-chromatography with us, show that the faradic efficiency of the product hydrogen of this electrode is close to 100%.
Embodiment 5
Investigate made g-C 3n 4the H_2-producing mechanism of/NiO/FTO electrode.
In a lot of research, fluorescence analysis is used to disclose catching, shift and being separated of electric charge carrier, and also can be used to research light induced electron and hole effect in the semiconductors, its reason is fluorescent emission is the compound coming from free charge.At this, we have been g-C 3n 4/ NiO/FTO, g-C 3n 4the fluorometric investigation (excitation wavelength 325nm) of/FTO, NiO/FTO tri-kinds of electrodes.Can find out from Fig. 6 (a), pure g-C 3n 4emission peak at 440nm, this value and g-C 3n 4energy gap value be consistent.With independent g-C 3n 4contrast, g-C 3n 4the fluorescence signal of/NiO obviously weakens, this is because the compound ability in light induced electron and hole is inhibit greatly, also shows that the electronics excited can at g-C 3n 4and fast transfer between NiO.
Electrochemical impedance spectroscopy can be used to Study of Catalyst g-C 3n 4/ NiO and proton H +between the transfer process of electronics, and total product hydrogen activity of electrode depends on charge transfer resistance (R ct), and R ctpass through g-C 3n 4/ NiO electrode and H +between the resistance at interface depend on semicircle diameter in low-frequency range.Can find out from Fig. 6 (b), with independent NiO and g-C 3n 4electrode is compared, g-C 3n 4/ NiO combination electrode shows has minimum R ct, show g-C 3n 4this environment of/NiO is more conducive to electro transfer to electrolyte.Above result indicates g-C 3n 4the recombination rate in electronics and hole is reduced with the combination of NiO.
Based on above research, we have proposed a kind of possible H_2-producing mechanism.As shown in Figure 7, g-C 3n 4/ NiO electrode under light illumination, becomes excitation state, and the hole of the electronics and oxidation state that create reproducibility is respectively at valence band VB and conduction band CB, and NiO is difficult to be excited due to its wider energy gap.Oxidizability hole is by the valence band of direct NiO afterwards, is then consumed by the electronics of external circuit.Meanwhile, the H+ of electronics rapidly and in electrolyte of reproducibility reacts and generates hydrogen, and the compound that result also in electronics and hole weakens.

Claims (2)

1. a g-C 3n 4the preparation method of/NiO photocathode, is characterized in that preparation process is carried out as follows:
(1) surface preparation of FTO electro-conductive glass
FTO electro-conductive glass first successively at absolute ethyl alcohol, soak two hours in acetone, and then in the aqueous isopropanol of 2mol/L potassium hydroxide, add hot reflux 30min;
(2) hydro thermal method prepares NiO/FTO electrode
FTO glass is put into 0.25mol/LNi (NO 3) 26H 2in the mixed aqueous solution of O and 0.25mol/L hexamethylenetetramine, 100 DEG C of heating 12min, take out, by washed with de-ionized water, dry, and to be placed in Muffle furnace 450 DEG C of calcining 2h, NiO/FTO electrode;
(3) thermal polymerization is adopted to prepare g-C 3n 4/ NiO photocathode
Above-mentioned obtained NiO/FTO electrode is immersed in saturated thiourea solution and soaks 4h, taking-up is dried, and afterwards the NiO/FTO electrode of upper for absorption thiocarbamide is placed in tube furnace, at N 2under atmosphere, 500 DEG C of calcining 2h, take out to obtain g-C 3n 4/ NiO/FTO.
2. a kind of g-C according to claim 1 3n 4the preparation method of/NiO photocathode, it is characterized in that the method raw materials used be nontoxic and the inorganic nickel of cheapness and thiocarbamide.
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