CN104593814A - Photoelectrochemical hydrogen evolution electrode of MoS2 modified silicon nanowire array, preparation method, and electrode system based on photoelectrochemical hydrogen evolution electrode - Google Patents
Photoelectrochemical hydrogen evolution electrode of MoS2 modified silicon nanowire array, preparation method, and electrode system based on photoelectrochemical hydrogen evolution electrode Download PDFInfo
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- 229910052961 molybdenite Inorganic materials 0.000 title abstract description 8
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title abstract description 8
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 241
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- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 238000006555 catalytic reaction Methods 0.000 claims description 6
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
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- 238000001228 spectrum Methods 0.000 description 4
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 3
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention discloses a photoelectrochemical hydrogen evolution electrode based on an MoS2 modified silicon nanowire array, a preparation method of the photoelectrochemical hydrogen evolution electrode, and an electrode system using the photoelectrochemical hydrogen evolution electrode. The photoelectrochemical hydrogen evolution electrode of the MoS2 modified silicon nanowire array comprises a silicon nanowire array and MoS2 nano particle clusters, high-temperature hypoxic calcination is performed on a former reactant (ammonium thiomolybdate) by adopting a pyrolysis technique, so that the MoS2 nano particle clusters are compounded on the surface of the silicon nanowire array so as to enhance the photochemical hydrogen evolution property of the silicon nanowire array instead of noble metal catalysts; because the photoelectrochemical hydrogen evolution electrode does not need to use noble metal, the cost is low, and the photoelectrochemical hydrogen evolution electrode can be used in industry on a large scale.
Description
Technical field
The invention belongs to electrochemical field, be specifically related to MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, also relate to MoS
2modify the preparation method of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and the three-electrode system containing this electrode.
Background technology
The energy that the Hydrogen Energy obtained by water of decomposition or hydrocarbon polymer can be used as the mankind, and adopt decomposing water with solar energy to be desirable solution routes to obtain these energy.From the angle analysis of thermodynamics and kinetics, there is larger obstruction in direct photolysis water, makes this process be difficult to realize in practice, and become the emphasis that global scientific research personnel captures.The intervention of electrochemical catalyst or photoelectrochemistry catalyzer can reduce the kinetics obstruction of photolysis water greatly, noble metal catalyst, wherein most is representational is exactly Pt, because of advantages such as its high conductivity, low overpotential of hydrogen evolution and high stabilities, becomes the focus catalyzer being applied to water of decomposition.But mass-producing comercial operation, the high consumption just necessary workout cost problem of catalyzer, so the cost of precious metal becomes the basic factor limiting its commercialization process.Finding suitable alternative catalysts is that scientific circles make great efforts the direction of research always for many years.Transient metal sulfide MoS
2, for precious metal, be exactly a kind of cheapness, the material of rich reserves, but MoS
2once be considered to be not suitable for as liberation of hydrogen material, because the MoS of lumphy structure
2electrolysis hydrogen efficiency is low.But along with the progress of science and technology, the especially high speed development of nano fabrication technique, this theory is faced with huge challenge and change.Therefore, MoS is improved further
2hydrogen Evolution Performance is the effective way of alternative noble metal catalyst, can reduce costs, and reserves also more horn of plenty.
Summary of the invention
In view of this, an object of the present invention is to provide MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, by two single metal auxiliary catalysis without electroetching legal system for high-sequential and perpendicular to the silicon nanowire array of substrate, then adopt pyrolysis technique directly forerunner's reactant ammonium thiomolybdate to be carried out high temperature roasting and make MoS
2be compound in silicon nanowire array surface, thus improve silicon nanowire array Hydrogen Evolution Performance; Two of object of the present invention is to provide MoS
2modify the preparation method of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, the method preparation is simple, is convenient to large-scale production; Three of object of the present invention is to provide containing MoS
2modify the three-electrode system of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, this three-electrode system can be directly used in photoelectrochemistry liberation of hydrogen.
For achieving the above object, following technical scheme is provided:
Based on MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, comprise conductive substrates and be compounded in the silicon nanowire array in conductive substrates, described silicon nanowire array surface recombination has MoS
2nano particle cluster.
Preferably, in described silicon nanowires permutation, the diameter of single silicon nanowires is 200-600 nanometer, and length is 5-10 micron, and the distance between centers of tracks of each nano wire is 0.8-1.2 micron.Silicon nanowires of the present invention can ensure that photogenerated charge can transfer to substrate and form watt current.
Preferably, described MoS
2the particle diameter of nano particle cluster is 200-500 nanometer, and its total surface area is equivalent to 40 ~ 50% of silicon nanowire array surface-area.MoS of the present invention
2nano particle cluster can keep photogenerated charge to be effectively transferred to solid-liquid interface, is the more reactive behavior site that hydrionic reduction provides simultaneously, and does not affect the extinction of substrate.
Preferably, described conductive substrate is copper sheet, and described nano-wire array is bonded by conductive silver glue and copper base, and described copper base is also coated with epoxy resin sealing insulation layer outward.
Further, described silicon nanowire array adopts two single metal auxiliary catalysis standby without electroetching legal system, described MoS
2nano particle cluster adopts pyrolysis technique to be compound in silicon nanowire array surface.
It is described based on MoS that the present invention also provides one to prepare
2modify the preparation method of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, it is characterized in that, comprise the steps:
1) silicon nanowires permutation is prepared: specifically comprise:
A) Wafer Cleaning: get silicon chip and carry out supersound washing with deionized water, dehydrated alcohol, acetone and SPM solution according to this;
B) deposited catalyst: the mixing solutions silicon chip after cleaning being placed in 3 ~ 5mol/L hydrofluoric acid and 1 ~ 10mmol/L Silver Nitrate reacts 60 ~ 120 seconds, at silicon chip surface deposition Ag catalyzer;
C) etching reaction: by the silicon chip of Depositing Metal Catalyst silver etching reaction 10 ~ 60 minutes in the mixing solutions of 3 ~ 5mol/L hydrofluoric acid and 0.1 ~ 0.5mol/L hydrogen peroxide;
D) catalyzer is removed: remove cleaning-drying after the salpeter solution being 1:5 ~ 1:3 by the volume ratio that the silicon chip after etching puts into nitric acid and water reacts 2 ~ 5 hours and obtain silicon nanowires permutation;
2) at silicon nanowires permutation surface deposition MoS
2nano particle cluster: specifically comprise:
A) drip on silicon nanowires permutation surface appropriate with dimethyl formamide be solvent ammonium thiomolybdate solution and in 60-80 DEG C of oven dry;
B) in a nitrogen atmosphere 400-500 DEG C annealing 5 ~ 8 hours, obtain MoS
2modify silicon nanowire array;
3) by aforementioned MoS
2the silicon nanowire array modified and back contacts mode contact with conductive substrate and obtain MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode.
Preferred as preparation method of the present invention, step 3) conductive substrate is copper sheet, described MoS
2modification silicon nanowire array and copper sheet are bonded by conductive silver glue.
As preparation method of the present invention further preferably, also comprise step 4), utilize epoxy resin sealing to insulate outside copper sheet.
The present invention also provides use described based on MoS
2modify two electrodes or the three-electrode system of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode.
Beneficial effect of the present invention is: the invention discloses based on MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, silicon nanowire array high-sequential and perpendicular to substrate, there is compared with planar silicon larger specific surface area, for photoelectrochemistry reaction provides more avtive spot; Gap between silicon nanowires constitutes light trapping, can catch more photon, the high-specific surface area of silicon line self, and the more photon of Absorbable rod participates in optical excitation reaction, improves photoelectric transformation efficiency; Silicon line perpendicular to substrate can realize the radial migration of photogenerated minority carriers, improves effective separation rate that photogenerated charge is right; And the silicon nanowire array due to this electrode adopts two single metal auxiliary catalysis standby without electroetching legal system, its obtained silicon nanowires crystalline structure keeps better, few surface defects, and degree of oxidation is low, and photoelectrochemical behaviour performance is more excellent.Then the liberation of hydrogen catalyzer MoS of laminate structure will be had
2adopt pyrolysis technique to be compound in silicon nanowire array surface and make MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, obtained electrode not only has excellent anti-reflection and light absorption, also have good interfacial charge transfer ability and stability, with the silicon nanowire array for unmodified, electrochemistry is produced hydrogen density of photocurrent and is improve about 600%, open current potential and just move to 0.55V, carrier concentration adds nearly 100 times.And this electrode adopts and instead of precious metal, as Pt, greatly reduces the cost of photoelectrochemistry hydrogen-precipitating electrode, the commercialization for photoelectrochemistry liberation of hydrogen transforms lays a good foundation.
Accompanying drawing explanation
In order to make object of the present invention, technical scheme and beneficial effect clearly, the invention provides following accompanying drawing:
Fig. 1 is silicon nanowire array electrode and MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode X-ray diffraction 10 ° ~ 60 ° contrasts spectrogram (illustration is 10 ~ 80 degree of scopes).
Fig. 2 is MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode scanning electron microscope (SEM) photograph (A: silicon nanowire array electrode vertical view; B: silicon nanowire array electrode sectional view; C.MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode vertical view; Illustration is partial enlarged drawing (scale 400nm); D:EDX power spectrum test pattern).
Fig. 3 is MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and silicon nanowire array electrode pair ratio to diffuse spectrogram.
Fig. 4 is MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, silicon nanowire array electrode, MoS
2the LSV of silicon chip electrode and bare silicon wafer electrode sample tests J-E figure.
Fig. 5 is bare silicon wafer electrode, MoS
2silicon chip electrode, silicon nanowire array and MoS
2modify the dynamic potential scanning test result figure of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode.
Fig. 6 is bare silicon wafer electrode, MoS
2silicon chip electrode, silicon nanowire array electrode and MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and carry out electrochemical impedance spectrum analysis.
Fig. 7 is MoS
2(A is silicon nanowire array electrode to the illumination test Mott-S figure of modification silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and silicon nanowire array electrode; B is MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode; Straight line in figure is linear fit curve).
Fig. 8 is under illumination condition and additional constant bias-0.5V (vs.RHE), MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, silicon nanowire array electrode, MoS
2silicon chip electrode and bare silicon wafer electrode are containing 0.1M H
2sO
4with 0.5M K
2sO
4mixed electrolytic solution in carry out photoelectrochemistry and produce the it stability correlation curve figure of hydrogen.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.The experimental technique of unreceipted actual conditions in embodiment, the usually conveniently conditioned disjunction condition of advising according to manufacturer.
Embodiment 1, preparation MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode
MoS
2modify the preparation method of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, comprise the steps:
Method 1:
1, silicon chip is used successively deionized water, dehydrated alcohol, acetone and SPM solution (V
h2SO4: V
h2O2=3:1) carry out supersound washing, the spot on removing surface; Then silicon chip is immersed in the mixing solutions containing 3mol/L hydrofluoric acid and 1mmol/L Silver Nitrate and react 120 seconds, make metal catalyst Ag be deposited on silicon chip surface, the silicon chip of Ag must be deposited; Again the silicon chip of deposition Ag is put into the mixing solutions etching reaction 10 minutes containing 3mol/L hydrofluoric acid and 0.1mol/L hydrogen peroxide; Then the silicon chip of etching reaction is put into dilute nitric acid solution (V
hNO3: V
h2O=1:5) in reaction 5 hours, remove the catalyzer that remains between silicon nanowire array, obtain silicon nanowire array; 2, on step (1) gained silicon nanowire array, the ammonium thiomolybdate ((NH that concentration is 10mg/mL is dripped
4)
2moS
4) solution, the solvent of ammonium thiomolybdate solution is dimethyl formamide, then dries under 60 DEG C of conditions in atmosphere, then anneals 5 hours 450 DEG C of nitrogen atmosphere conditions, obtains MoS
2modify silicon nanowire array; 3, by MoS obtained for step (2)
2modify silicon nanowire array to bond with back contacts mode conductive silver glue and copper sheet, and with epoxy resin, insulation is closed at whole for the electrode back side, obtain MoS2 and modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode.
Method 2:
Method 2 is identical with method 1, and its difference is step (1) and step (2), and step (1) is: deionized water, dehydrated alcohol, acetone and SPM solution (V
h2SO4: V
h2O2=3:1) carry out supersound washing, the spot on removing surface; Then silicon chip is immersed in the mixing solutions containing 5mol/L hydrofluoric acid and 10mmol/L Silver Nitrate and react 60 seconds, make metal catalyst Ag be deposited on silicon chip surface, the silicon chip of Ag must be deposited; Again the silicon chip of deposition Ag is put into the mixing solutions etching reaction 60 minutes containing 5mol/L hydrofluoric acid and 0.5mol/L hydrogen peroxide; Then the silicon chip of etching reaction is put into dilute nitric acid solution (V
hNO3: V
h2O=1:4) in reaction 2 hours, remove the catalyzer that remains between silicon nanowire array, obtain silicon nanowire array.
Step (2): being dripped on step (1) gained silicon nano-array surface take dimethyl formamide as the ammonium thiomolybdate solution of solvent, then dries at 80 DEG C, then 400 DEG C of annealing 8 hours in a nitrogen atmosphere, obtain MoS
2modify silicon nanowire array.
Method 3:
Method 2 is identical with method 1, and its difference is step (1) and step (2), and step (1) is: silicon chip is used successively deionized water, dehydrated alcohol, acetone and SPM solution (V
h2SO4: V
h2O2=3:1) carry out supersound washing, the spot on removing surface; Then silicon chip is immersed in the mixing solutions containing 4mol/L hydrofluoric acid and 5mmol/L Silver Nitrate and react 90 seconds, make metal catalyst Ag be deposited on silicon chip surface, the silicon chip of Ag must be deposited; Again the silicon chip of deposition Ag is put into the mixing solutions etching reaction 30 minutes containing 4mol/L hydrofluoric acid and 0.3mol/L hydrogen peroxide; Then the silicon chip of etching reaction is put into dilute nitric acid solution (V
hNO3: V
h2O=1:3) in reaction 3 hours, remove the catalyzer that remains between silicon nanowire array, obtain silicon nanowire array.
Step (2): being dripped on step (1) gained silicon nano-array surface take dimethyl formamide as the ammonium thiomolybdate solution of solvent, then dries at 70 DEG C, then 500 DEG C of annealing 6 hours in a nitrogen atmosphere, obtain MoS
2modify silicon nanowire array.
Embodiment 2, structure MoS
2modify the three-electrode system of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode
With MoS
2modifying silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is working electrode, and Ag/AgCl (saturated KCl) electrode is reference electrode, and platinum plate electrode is to electrode, according to three-electrode system design junction circuit.The apparent area controlling working electrode is 1cm
2, electrolyte solution is for containing 0.5M K
2sO
4with 0.1M H
2sO
4mixed aqueous solution.Experiment test condition is atmospheric environment, and temperature is room temperature, and during simulated solar irradiation illumination test, light source input electric power is 250W, and wavelength region is 400 ~ 1200nm.
Then x-ray diffractometer (X-Ray Diffraction is adopted, XRD), field emission scanning electron microscope (Field Emission Scanning Electron microscope, FESEM), X-ray energy spectrum analyser (Energy Dispersive X-ray Spectrometer, EDX), UV, visible light infrared spectra diffuse-reflectance instrument (UV-Vis-IR Diffusion Reflectance Spectroscopy, DRS) essential property that MoS2 modifies silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is characterized, and investigate prepared MoS in conjunction with the correlation technique of photoelectrochemistry test
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and be applied to the performance that photoelectrochemistry produces hydrogen aspect.Investigate MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode mainly based on the photoelectrochemistry test macro of CHI electrochemical workstation, major equipment comprises CHI660C electrochemical workstation, PLS-SXE300 type xenon source, main testing method adopts linear voltammetric scan method (Linear Sweep Voltammetry, LSV), dynamic potential scanning test (Potentiodynamic Scanning Analysis, PSA), electrochemical impedance spectroscopy (Electrochemical Impedance Spectroscopy, EIS), not special Schottky test (Mott-Schottkymeasurement, and time current stability test (i-t measurement Mott-S), it).Concrete outcome is as follows:
Fig. 1 is silicon nanowire array electrode and MoS
2modify the X-ray diffraction of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode at 10 ° ~ 60 ° contrast spectrograms.Result shows, MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and occurred obvious MoS about 2 θ=14.33 °
2<002> crystal face characteristic peak, this peak is MoS
2, simultaneously about 2 θ=58.34 °, there is MoS in the strongest characteristic diffraction peak
2<110> crystallographic plane diffraction peak, and MoS
2<100> crystallographic plane diffraction peak position and the overlapping of Si<200> crystal face, and Si<200> crystallographic plane diffraction peak intensity is far longer than MoS
2<100> crystal face peak, makes it be difficult to differentiate.Although MoS
2<100> crystal face peak is difficult to identification, but MoS because of overlap
2<002> and MoS
2the appearance of <110> crystallographic plane diffraction peak, the high-temperature roasting described under nitrogen protection can make precursor (NH4)
2moS
4siNWs array decomposes in order to MoS
2.In addition, also MoS prepared by the present invention is judged according to diffraction peak position
2belong to the 2H-MoS of triangular prism coordination configuration
2.
Fig. 2 is MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode scanning electron microscope (SEM) photograph, wherein A is silicon nanowire array vertical view, and B is silicon nanowire array sectional view; C is MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode vertical view.Result shows, and the diameter of silicon nanowires is 200-600 micron, MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and have obvious MoS
2clustered particles is distributed in the top of silicon nanowire array equably, and the MoS that thermolysis is formed
2nano particle, the MoS of formation
2the particle diameter of nano particle is 200-500 nanometer, covers the surface-area (area of described silicon nano-array is the area summation on silicon nanowires top) of silicon nanowire array 40 ~ 50%.D is EDX power spectrum test pattern, and scanning spot is at MoS
2on nano particle, the feature excitation peak having occurred Si atom at 1.85keV can be found out by D in Fig. 2, occurred the feature excitation peak of Mo atom and S atom in 2.2keV overlap, and both atomic ratios be about Mo:S=1:2, and MoS is described simultaneously
2really be present in silicon nanowire array surface, this result is consistent with the detected result of XRD.
Fig. 3 is MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and silicon nanowire array electrode pair ratio to diffuse spectrogram.Result shows, MoS
2modification silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and silicon nanowire array electrode all show good anti-reflection (projection at spectral line 800nm place is caused because changing lamp) within the scope of 300 ~ 1100nm.To the minimizing of luminous reflectance, will inevitably increase the absorbed dose of photon, a large amount of photons can excite more photohole-electron pair, and the concentration of photo-generated carrier increases, and adds the amount of charge participating in hydrogen reduction, will certainly improve effciency of energy transfer like this.Preparation MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode not because MoS
2load and make anti-reflection degradation, within the scope of 300 ~ 1000nm, it is the same with the silicon nanowire array of unmodified, all has good anti-reflection ability, to light reflectance all below 3%.And MoS
2modify the silicon nanowire array that the anti-reflection of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode in infrared light district is obviously better than unmodified, MoS is described
2load semi-conducting electrode is increased the utilization ratio of infrared light.MoS
2the spectrum band edge modifying silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode comparatively silicon nanowire array has obvious red shift, shows MoS
2have impact on the energy band structure of silicon after modifying silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode to a certain extent, its energy gap is reduced to some extent, and such change is conducive to MoS
2modification silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is applied to photoelectrocatalysis (PEC) and produces hydrogen.
Fig. 4 is MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, silicon nanowire array electrode, MoS
2the LSV of silicon chip electrode and bare silicon wafer electrode sample tests J-E figure.In figure, potential value is by V
rHE=V
m, Ag/AgCl+ V
0, Ag/AgClvs.NHE+ 0.059pH formula is by the V being benchmark with Ag/AgCl electrode of test gained
m, Ag/AgClpotential value has carried out stdn conversion, wherein V
0, Ag/AgClvs.NHEbe 0.199V when room temperature 25 DEG C.As shown in Figure 4, MoS
2it is the strongest for responding with the photoelectrochemistry of silicon nanowire array.Under dark-state condition, because do not have the input of photon, the transfer of bare silicon wafer to electric charge of semiconductor property creates very high inhibition.Relative to RHE-1.0V, the dark current density of bare silicon wafer is very low, only has 0.04mA/cm
2, its E
oSfor-1.87V.By contrast, when light source is opened, when photon injects in a large number, the photoelectric current of bare silicon wafer obviously increases, simultaneously E
oSalso just-0.71V is moved to; And under same illumination condition, the photoelectric current of silicon nanowire array electrode improves further, E
oSthen just move to-0.06 further.But, in bare silicon wafer electrode and silicon nanowire array electrode, only there is a small amount of light induced electron can be sent to solid/liquid interfaces and participate in reduction H
+, and most of photo-generated carrier there occurs compound again because not realizing solid-liquid interface transfer rapidly.And MoS
2the introducing of catalyzer is just in time silicon electrode surface and H in solution
+between Charger transfer set up the passage of a high rate data transmission.Photo-generated carrier before compound again, by Si and MoS
2solid solid interface be transferred to MoS
2, electronics is at MoS
2laminated structure on fast transfer to active edge and with the H in solution
+react.So MoS
2the introducing of catalyzer improves MoS
2silicon chip electrode and MoS
2modify the photoelectric current of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, simultaneously MoS
2the E of silicon chip electrode
oSjust move to 0.18V, and MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode E
oSjust transfer to 0.55V.The above results indicates, MoS
2more reactive behavior site can be provided for reaction, add the degree of reaction.
In order to compare MoS more intuitively
2modify the amplification size of the density of photocurrent of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and unmodified electrode, to bare silicon wafer electrode, MoS under simulated solar rayed
2silicon chip electrode, silicon nanowire array electrode and MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and carried out a series of dynamic potential scanning test, result as shown in Figure 5.Result shows, relative to RHE-1.0V, MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and show excellent photoelectrochemistry catalysis product hydrogen activity.Its current density reaches nearly 25mA/cm
2, exceed 6 times than silicon nanowire array electrode, compare MoS
2silicon chip electrode exceeds 12 times, is 25 times of bare silicon wafer electrode.Be it can also be seen that by figure, MoS
2the dark current modifying silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode promotes to some extent compared with other samples, and this is just because of MoS
2good electro catalytic activity.The high density of photocurrent activity of silicon nanowire array electrode has benefited from large specific surface sum that linear array gives to the high anti-reflection of light.According to Faraday's law, based on testing the photogenerated current numerical value recorded, can be used for calculating the hydrogen volume produced.Specific formula for calculation is as follows:
Wherein J
phphotogenerated current numerical value (J
ph=J
illumination-J
darkness), t is the time of reaction under simulated solar is irradiated, and with minute for time unit, η is current efficiency, and n is the quantity of transfer charge in each hydrogen molecule, and Vo and F represents molecular volume (standard state) and the Faraday's number of gas respectively.Relative to RHE-1.00V, MoS
2the maximum electrochemistry hydrogen output (η=100%) of modifying the photic enhancing of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is about 168.3 μ L/min.
In order to obtain MoS further
2modify the electronic structure of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and the information of electronic transmission performance, bare silicon wafer electrode, MoS
2silicon chip electrode, silicon nanowire array electrode and MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and carry out electrochemical impedance spectrum analysis, result as shown in Figure 6.Spherical line in figure represents test data of experiment, and star represents fitting result, the equivalent electrical circuit corresponding to matching.Drawn the value of each element in equivalent electrical circuit by the electrochemical impedance spectroscopy matching recorded experiment, result is as shown in table 1.
Table 1, MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode test electrochemical impedance spectroscopy model analysis data
Wherein R
trepresent the total series resistance of circuit, comprise the resistance of electrolyte solution, semiconductor base, line structure array etc.; R
ct, sreferring to the charge transfer resistance in semiconductor surface depletion layer, CPEs electric capacity phase element by with the electric capacity representing semiconductor surface depletion layer, CPE
dlfor representing the electric capacity of semi-conducting electrode-electrolyte interface electrostatic double layer, R
ct.dlbe charge transfer resistance, the dynamical phase that its value is reacted with faraday associates, reflection be the degree of being obstructed that electric charge passes that electrostatic double layer is transferred to electrode surface; Relative to the high pass speed of electric charge at semiconductor surface depletion layer, R
ct.dlit is the deciding factor of whole electric charge solid-liquid transmittance process.Formation due to silicon nanowire array electrode considerably increases the specific surface area of electrode, makes MoS
2modify the CPE of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and silicon nanowire array electrode
dlwith the numerical value of CPEs comparatively silicon chip electrode had remarkable increase.By model analysis, as known in table 1 data, MoS
2modify the R of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode
ct.dlmatch value is 20.55 Ω/cm
2, than the R of silicon nanowire array electrode
ct.dlmatch value 227.1 Ω/cm
2, MoS
2759.4 Ω/cm of silicon chip electrode
2and 1100 Ω/cm of bare silicon wafer electrode
2all little.And this electrode electricity structure mechanism aspect analyze result just in time with MoS in Fig. 4 and Fig. 5
2the result of modifying the maximum photoelectric current of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode gained is consistent.The above results shows MoS
2there is after modifying silicon nanowire array as catalyzer anti-reflection and the sunken effect of light, effectively can reduce the charge transfer resistance of solid-liquid interface, enhance the charge transport capability of solid-liquid interface.And utilize MoS
2self also enhances MoS to hydrionic adsorption catalysis effect
2modify the effciency of energy transfer of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode system in PEC.
In order to verify MoS
2modify the raising of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode photoelectrochemistry Hydrogen Evolution Performance, whether fall into layer by silicon nanowire array structure as anti-reflection layer and light and be responsible for catching more photon, and MoS
2catalyzer, as interfacial charge Transfer Medium, is responsible for fast transfer light induced electron, reduces the compound of photohole-electron pair, and is H
+reduction reactive behavior site is provided, both synergistic effect increases that the carrier concentration of whole optoelectronic pole causes.Utilize not special Schottky (Mott-Schottky measurement, Mott-S) test, Mott-S test is flat-band potential and the carrier concentration of being determined electrode by the relation between analyzing electrode space surface electric capacity and the electromotive force applied, and concrete analysis is that Mott-Schottky relation equation realizes as described below:
1/C
2＝-2(V
a-V
fb-kT/q)/(qNAε
sε
0A
2)
Wherein C is space charge capacitance, V
afor applied electropotential, k is Boltzmann constant, and T is thermodynamic temperature, and q is elemental charge electricity, and NA is acceptor density, ε
sthe specific inductivity of electrode materials, ε
0be the specific inductivity of vacuum, A is the reaction area of sample, and Mott-S result measured under illumination condition as shown in Figure 7, analyzes to obtain result shown in table 2 to experimental patterns.
Table 2, MoS2 modify the electrical properties data of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode series of samples
Result can find out MoS
2the flat-band potential modifying silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is 0.601V (vs.Ag/AgCl), and silicon nanowire array electrode is 0.732V (vs.Ag/AgCl).Show at load MoS
2after catalyzer, MoS
2the flat-band potential modifying silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode comparatively silicon nanowire array electrode decreases.Based semiconductor electrode electrolyte interface and energy bandgaps model analysis, MoS
2load effect make silicon nanowire array valence band (E
vB) and conduction band (E
cB) energy level sinuousness reduce, reduce flat-band potential.In addition, MoS
2stratiform cluster catalyzer act as the effect of electric charge collection transmission medium at semi-conductor/electrolyte interface, and the marginal position avtive spot of exposure accelerates H
+reduction.The electric charge of solid-liquid interface consumes fast, accelerates photo-generated carrier by semi-conductor to MoS
2transfer, decrease the compound in semiconductor bulk phase and surface, effective photo-generated carrier ratio significantly improves.Therefore, MoS
2the carrier concentration of modifying silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode rises to 6.83 × 10
20, the density of photocurrent macroscopically adding electrode and produce, the experimental result of this and LSV, DPS matches.
Fig. 8 represents under illumination condition and additional constant bias-0.5V (vs.RHE), MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, silicon nanowire array electrode, MoS
2silicon chip electrode and bare silicon wafer electrode are containing 0.1M H
2sO
4with 0.5M K
2sO
4mixed electrolytic solution in carry out photoelectrochemistry and produce the it stability correlation curve figure of hydrogen.As can be seen from the figure, in the whole time range that illumination is opened, MoS
2modifying silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode can keep stable photoelectric current to export for a long time, and photoelectric current is obviously greater than other control groups.In an experiment, can actually observe at MoS
2modify on the surface of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, have obvious small bubbles promptly depart from from electrode surface and upwards overflow from solution surface.And silicon nanowire array electrode, MoS
2although silicon chip electrode and bare silicon wafer electrode have also seen that bubble is formed at electrode surface, generally only has dozens of, the minimum number of silicon chip electrode; After about one second, bubble is from MoS
2silicon chip electrode and silicon nanowire array electrode surface depart from, and speed is considerably slower than MoS
2modify the bubble effusion speed of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, on silicon chip, produce the interval of bubble in addition about ten several seconds.This shows, MoS
2load and the lifting of formation to photoelectrochemistry H2-producing capacity of silicon nanowires serve keying action.MoS simultaneously
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and provide a large amount of hydrogen evolution activity reaction site, especially at MoS
2laminate structure marginal position, which promote hydrionic reduction, simultaneously photo-generated carrier utilization ratio increases, and compound reduces, and ensure that the supply of the light induced electron needed for evolving hydrogen reaction, adds the speed of liberation of hydrogen; And the line gap between array is overflowed provide enough gas passages to hydrogen, makes bubble hydrogen can release rapidly from electrode surface, and reduce the obstruction to follow-up evolving hydrogen reaction.After constant light is shone and is reacted 1.5 hours under bias voltage, MoS
2the photoelectric current decay of modifying silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode almost can be ignored, and this demonstrate that MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and there is satisfactory stability.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.
Claims (9)
1.MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, it is characterized in that: comprise conductive substrates and be compounded in the silicon nanowire array in conductive substrates, described silicon nanowire array surface recombination has MoS
2nano particle cluster.
2. MoS according to claim 1
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, it is characterized in that: in described silicon nanowire array, the diameter of single silicon nanowires is 200-600 nanometer, length is 5-10 micron, and the distance between centers of tracks of each nano wire is 0.8-1.2 micron.
3. MoS according to claim 1
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, it is characterized in that: described MoS
2the particle diameter of nano particle cluster is 200-500 nanometer, and its total surface area is equivalent to 40 ~ 50% of silicon nanowire array surface-area.
4. MoS according to claim 1
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, it is characterized in that: described conductive substrates is copper sheet, described nano-wire array is bonded by conductive silver glue and copper base, and described copper base is also coated with epoxy resin sealing insulation layer outward.
5. MoS according to claim 1-4 any one
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, it is characterized in that: described silicon nanowire array adopts two single metal auxiliary catalysis standby without electroetching legal system, described MoS
2nano particle cluster adopts pyrolysis technique to be compound in silicon nanowire array surface.
6. preparation MoS as described in claim 1-5 any one
2modify the preparation method of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, it is characterized in that, comprise the steps:
1) silicon nanowire array is prepared: specifically comprise:
A) Wafer Cleaning: get silicon chip and carry out supersound washing with deionized water, dehydrated alcohol, acetone and SPM solution according to this; B) deposited catalyst: the mixing solutions silicon chip after cleaning being placed in 3 ~ 5mol/L hydrofluoric acid and 1 ~ 10mmol/L Silver Nitrate reacts 60 ~ 120 seconds, at silicon chip surface deposition Ag catalyzer;
C) etching reaction: by the silicon chip of Depositing Metal Catalyst silver etching reaction 10 ~ 60 minutes in the mixing solutions of 3 ~ 5mol/L hydrofluoric acid and 0.1 ~ 0.5mol/L hydrogen peroxide;
D) catalyzer is removed: remove cleaning-drying after the salpeter solution being 1:5 ~ 1:3 by the volume ratio that the silicon chip after etching puts into nitric acid and water reacts 2 ~ 5 hours and obtain silicon nanowire array;
2) at silicon nanowire array surface deposition MoS
2nano particle cluster: specifically comprise:
A) drip on silicon nanowire array surface appropriate with dimethyl formamide be solvent ammonium thiomolybdate solution and in 60-80 DEG C of oven dry;
B) in a nitrogen atmosphere 400-500 DEG C annealing 5 ~ 8 hours, obtain MoS
2modify silicon nanowire array;
3) by aforementioned MoS
2the silicon nanowire array modified and back contacts mode contact with conductive substrate and obtain MoS
2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode.
7. prepare MoS according to claim 6
2modify the preparation method of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, it is characterized in that: step 3) conductive substrate is copper sheet, described MoS
2modification silicon nanowire array and copper sheet are bonded by conductive silver glue.
8. prepare MoS according to claim 6
2modify the preparation method of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, it is characterized in that: also comprise step 4), utilize outside epoxy resin sealing insulation copper sheet.
9. use MoS described in claim 1-5 any one
2modify two electrodes or the three-electrode system of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode.
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