CN104630821A - Photo-electrochemical hydrogen evolution electrode based on MoS2 and Ag modified silicon nanowire array and application thereof - Google Patents

Photo-electrochemical hydrogen evolution electrode based on MoS2 and Ag modified silicon nanowire array and application thereof Download PDF

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CN104630821A
CN104630821A CN201510075781.5A CN201510075781A CN104630821A CN 104630821 A CN104630821 A CN 104630821A CN 201510075781 A CN201510075781 A CN 201510075781A CN 104630821 A CN104630821 A CN 104630821A
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nanowire array
silicon nanowire
mos
electrode
hydrogen
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乔雷
李艳虹
周明
廖明佳
肖鹏
张云怀
张胜涛
陈刚才
张晟
周志恩
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Chongqing Academy Of Environmental Science
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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
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    • Y02P20/133—Renewable energy sources, e.g. sunlight

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Abstract

The invention discloses a photo-electrochemical hydrogen evolution electrode based on a MoS2 and Ag modified silicon nanowire array and a three-electrode system and an application thereof. The photo-electrochemical hydrogen evolution electrode based on the MoS2 and Ag modified silicon nanowire array comprises a silicon nanowire array, a Ag nano-granule layer and a MoS2 nano-granule layer with a charge transfer function, wherein the silicon nanowire array is prepared from a two-step metal-assisted catalysis electroless etching method; the MoS2 nano-granule layer is compounded on the surface of the silicon nanowire array modified by the Ag nano-granule layer by a thermal decomposition technology. By means of increasing the Ag in the MoS2 modified silicon nanowire array as a charge transfer medium, the charge transfer of the solid-solid interface is increased, so that more photo electrons for the hydrogen reduction reaction on the MoS2 can be provided, the participation probability of the photo electrons in the hydrogen reduction reaction is greatly increased and the energy conversion efficiency is increased, and the three-electrode system is constructed for industrial water decomposition to obtain the hydrogen energy.

Description

Based on MoS 2silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and application thereof is modified with Ag
Technical field
The invention belongs to electrochemical field, be specifically related to based on MoS 2other application of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, two electrodes using this electrode or three-electrode system system and this electrode are modified with Ag.
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 basis utilizing photoelectrochemistry to produce hydrogen.
Summary of the invention
In view of this, an object of the present invention is to provide based on MoS 2silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is modified with Ag; Two of object of the present invention is to provide the electrode system containing above-mentioned electrode; Three of object of the present invention is to provide MoS 2the application of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is modified with Ag; Four of object of the present invention is the application providing above-mentioned electrode system.
For achieving the above object, the invention provides following technical scheme:
1, based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag, comprise conductive substrates and be compounded in the silicon nanowire array in conductive substrates, described silicon nanowire array surface recombination has Ag nano particle cluster and MoS 2nano particle cluster, described Ag nano particle cluster is positioned at silicon nanowire array and MoS 2between nano particle cluster.
Especially, in described silicon nanowire array, 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 nanowire array surface-area is now large, gap is little, can form light trapping, improves light assimilated efficiency high, nanowire diameter suitable length of the present invention, shorten the delivery time of photogenerated charge, improve electricity conversion, and effective top load platform can be provided for modification.Especially, described MoS 2the particle diameter of nano particle cluster is 200-500 nanometer, and its total surface area is equivalent to the 40%-50% of silicon nanowire array surface-area.MoS now 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.Especially, the particle diameter of described Ag nano particle is 10-50nm, and its surface-area is the 5%-10% of silicon nanowire array surface-area.Now Ag nano particle can be dispersed in uniformly silicon nanowires top end surface, self ohm resistance suitably and can and MoS 2form good combination.Especially, described conductive substrates is copper sheet, and described nano-wire array is by conductive silver glue and copper base vertical glue joint, 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 the silicon nanowire array surface of Ag nano particle cluster modification.
2, use is described based on MoS 2two electrodes or the three-electrode system of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is modified with Ag.
Further, described based on MoS 2modifying silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag is working electrode, and platinized platinum is to electrode.
3, MoS 2the application of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode in photoelectrochemistry product hydrogen is modified with Ag.
4, use is described based on MoS 2two electrodes or the application of three-electrode system in photoelectrochemistry product hydrogen of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is modified with Ag.
Beneficial effect of the present invention is: the invention discloses MoS 2silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is modified with Ag, improve effciency of energy transfer, and do not need use expensive, the Pt element that reserves are low, reduce production cost, industrial water of decomposition can be widely used in after being built into three-electrode system and obtain Hydrogen Energy.
Beneficial effect of the present invention is: the invention discloses MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag, this electrode passes through at MoS 2modifying in silicon nanowire array and increase Ag as charge transfer layer, is MoS 2on hydrogen reduction reaction more light induced electron is provided, improve the Charger transfer of solid solid interface, improve the photoproduction carrier concentration of system, the probability making light induced electron participate in hydrogen reduction reaction improves greatly.And this electrode adopts two single metal auxiliary catalysis without electroetching legal system for silicon nanowire array, obtained silicon nanowires crystalline structure keeps better, few surface defects, and degree of oxidation is low, and makes silicon nanowire array high-sequential and perpendicular to substrate; Specific surface area is considerably increased, for photoelectrochemistry reaction provides more avtive spot compared with planar silicon; Gap between silicon nanowires constitutes light trapping, can catch more photon; The high-specific surface area of silicon line self, the more photon of Absorbable rod participates in optical excitation reaction, improves photoelectric transformation efficiency; And the radial migration of photogenerated minority carriers can be realized perpendicular to the silicon line of substrate, improve effective separation rate that photogenerated charge is right.In addition, MoS in preparation electrode of the present invention 2modify and adopt pyrolysis technique, directly high temperature roasting is carried out to forerunner's reactant ammonium thiomolybdate, make MoS 2high and the good stability of catalytic activity for hydrogen evolution, makes the MoS obtained 2good with Ag modification silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode photoelectrochemistry H2-producing capacity, find E through experimental verification oSjust move on to 0.62V, comparatively Ag/ silicon nanowires and MoS 2/ silicon nanowire array is 0.35V and 0.07V that shuffled respectively more; Under identical bias (vs.RHE-1.0V), MoS 2the liberation of hydrogen density of photocurrent of/Ag/ silicon nanowire array electrode is 12 times of silicon nanowire array electrode, and being 5 times of Ag/ silicon nanowires, is MoS 22 times of/silicon nanowire array, the H2-producing capacity synergy of modifying rear electrode is remarkable, MoS 2obviously strengthen with the co-modified effect than single modification of Ag, both have obvious synergy to the synergy of electrochemistry liberation of hydrogen.According to Faraday's law, the maximum electrochemistry hydrogen output (η=100%) of photic enhancing is about 325.9 μ L/min.And the metal preparing electrode use in the present invention is MoS 2and Ag, do not need use expensive and the few metal of reserves, as: Pt, can reduce the production cost of photoelectrochemistry hydrogen-precipitating electrode, be convenient to the conversion of industrial application.
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, Ag modifies silicon nanowire array and based on MoS 2collection of illustrative plates is contrasted at the XRD within the scope of 2 θ=10 ° ~ 80 ° with Ag silicon nanowire array.
Fig. 2 is based on MoS 2silicon nanowire array and silicon nanowire array scanning electron microscope (SEM) photograph (A. silicon nanowire array vertical view, B. silicon nanowire array sectional view is modified with Ag; C. based on MoS 2silicon nanowire array vertical view is modified with Ag; Illustration is partial enlarged drawing (scale 500nm); D.EDX power spectrum test pattern).
Fig. 3 is based on MoS 2silicon nanowire array, MoS is modified with Ag 2modify silicon nanowire array and the diffuse reflection spectrum curve comparison figure of silicon nanowire array within the scope of 300 ~ 1200nm ((projection at spectral line 800nm place is caused because changing lamp).
Fig. 4 is based on MoS 2silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, silicon nanowire array electrode, Ag modification silicon nanowire array electrode and MoS is modified with Ag 2the typical LSV modifying silicon nanowire array electrode tests J-E figure.
Fig. 5 is based on MoS 2silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, silicon nanowire array electrode, MoS is modified with Ag 2modification silicon nanowire array electrode and Ag modify silicon nanowire array electrode and carry out dynamic potential scanning test under simulated solar rayed.
Fig. 6 is silicon nanowire array electrode, MoS 2modify silicon nanowire array electrode, Ag modify silicon nanowire array electrode with based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode sample with Ag and carry out electrochemical impedance spectroscopy analysis chart.
Fig. 7 is that Ag modifies silicon nanowire array electrode, MoS 2modify silicon nanowire array electrode and based on MoS 2(A is that Ag modifies silicon nanowire array electrode to modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode illumination test Mott-S figure with Ag; B is MoS 2modify silicon nanowire array electrode; C is MoS 2silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is modified with Ag; Figure cathetus is linear fit curve).
Fig. 8 is based on MoS 2silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode photoelectrochemical liberation of hydrogen stability it test pattern is modified with Ag.
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, to prepare based on MoS 2silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is modified with Ag
The silicon nanowire array autoreduction utilizing Jia Wani effect (Galvanic Displacement) first to prepare in two single metal auxiliary catalysis etching methods is prepared Ag and is modified silicon nanowire array, show to modify Ag nano particle at silicon nanowire array, then modify silicon nanowire array as base material using Ag, utilize direct pyrolysis technique by MoS 2reducing loaded in this substrate, formed based on MoS 2modify silicon nanowire array with Ag, and be encapsulated as MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag, its concrete implementation step is as follows:
Method 1:
(1) two single metal auxiliary catalysis etching method prepares silicon nanowire array: silicon chip is used successively deionized water, dehydrated alcohol, acetone and SPM solution (V h2SO4: V h2O2=3:1) carry out supersound washing, remove the spot on 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) autoreduction prepares Ag modification silicon nanowire array: step (1) gained silicon nanowire array is placed in hydrofluoric acid acidifying silver nitrate solution reaction 120 seconds, takes out rinsing repeatedly, and nitrogen is dried and to be obtained Ag modification silicon nanowire array, for subsequent use; Wherein in hydrofluoric acid acidifying silver nitrate solution, the volume ratio of hydrofluoric acid and water is 1:200, Ag +concentration is 0.04 μM;
(3) on step (2) gained Ag modification 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 2silicon nanowire array is modified with Ag;
(4) by step (3) gained MoS 2modify silicon nanowire array with Ag 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 based on MoS 2silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is modified with Ag.
Method 2:
Method 2 is identical with method 1, and its difference is step (1) ~ (3), 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, remove the spot on 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): step (1) gained silicon nanowire array is placed in hydrofluoric acid acidifying silver nitrate solution reaction 120 seconds, takes out rinsing repeatedly, nitrogen is dried Ag modifies silicon nanowire array, for subsequent use; Wherein in hydrofluoric acid acidifying silver nitrate solution, the volume ratio of hydrofluoric acid and water is 1:200, Ag +concentration is 0.04 μM.
Step (3): 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 2silicon nanowire array is modified with Ag.
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, make the hydrogenation of surface silicon molecular end; 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): step (1) gained silicon nanowire array is placed in hydrofluoric acid acidifying silver nitrate solution reaction 120 seconds, takes out rinsing repeatedly, nitrogen is dried Ag modifies silicon nanowire array, for subsequent use; Wherein in hydrofluoric acid acidifying silver nitrate solution, the volume ratio of hydrofluoric acid and water is 1:200, Ag +concentration is 0.04 μM.
Step (3): 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 2silicon nanowire array is modified with Ag.
Embodiment 2, structure MoS 2the three-electrode system of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is modified with Ag
With MoS 2silicon nanowire array is modified with Ag; 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) characterizes MoS 2modify the essential property of silicon nanowire array electrode, and investigate prepared MoS in conjunction with the correlation technique of photoelectrochemistry test 2modify silicon nanowire array application of electrode produces hydrogen aspect performance in photoelectrochemistry.Investigate MoS 2modify silicon nanowire array 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 ScanningAnalysis, 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, Ag modifies silicon nanowire array and based on MoS 2modify silicon nanowire array with Ag and contrast collection of illustrative plates at the XRD within the scope of 2 θ=10 ° ~ 80 °, in illustration, dotted line frame enters the enlarged view of part.Result shows, and after Jia Wani (Galvanic Displacement) effect metal refining Ag, compared to the spectral line of silicon nanowire array, Ag modifies on silicon nanometer linear array XRD spectral line and occurred new diffraction peak.Reference standard card JCPDS 04-0783, Ag to modify on silicon nanowire array about 2 θ=38.25 ° and <111> and the <200> crystallographic plane diffraction peak of the 2 θ=44.48 ° diffraction peak that left and right occurs just in time corresponding A g, illustrates to deposit Ag by Jia Wani to be compound in silicon nanometer linear array surperficial.Reference standard card JCPDS 37-1492 analyzes collection of illustrative plates and can obtain, based on MoS 2about 2 θ=14.33 ° and 2 θ=58.34 °, MoS has been there is with Ag silicon nanowire array 2<002> and MoS 2<110> crystal face characteristic peak, and MoS 2overlapping of <100> crystallographic plane diffraction peak position and 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.Ag modify silicon nanowire array collection of illustrative plates in can be clear that Ag<111> and Ag<200>, but preparation based on MoS 2modifying silicon nanowire array with Ag but only has Ag<111> to occur, and the powerful width in peak weakens, and possible reason is MoS 2cover the Ag small-particle on silicon nanowire array, cause Ag to be detected.By MoS 2<002> and MoS 2the appearance of <110> diffraction peak, tentatively can judge MoS 2be compound in the surface that Ag modifies silicon nanowire array.
Fig. 2 is based on MoS 2silicon nanowire array scanning electron microscope (SEM) photograph is modified with Ag.From A ~ C in Fig. 2, there is a large amount of significantly particle to be stacked in the top of silicon nanowire array, analyze top particle enlarged view and find, MoS 2the particle diameter of nano particle is about 200 ~ 500nm, and its area coverage is about equivalent to 40% ~ 50% of silicon nanowire array surface-area.Show the MoS that Ag modification silicon nanowires is formed by thermolysis 2stacked in granulation mass, without obvious regular morphology.From D in Fig. 2, scanning spot is at MoS 2on particle, can clearly be seen that the feature excitation peak having occurred Si atom at 1.85keV, there is the feature excitation peak of Mo atom and S atom in 2.20keV overlap simultaneously, all there is feature excitation peak at about 2.80keV in Ag atom and Mo atom, this result is consistent with the detected result of XRD.
Fig. 3 is based on MoS 2silicon nanowire array, MoS is modified with Ag 2modify silicon nanowire array and silicon nanowire array typical diffuse reflection spectrum curve comparison figure within the scope of 300 ~ 1200nm.Three kinds of samples all show good anti-reflection as we can see from the figure, and especially within the scope of 300 ~ 1000nm, light reflectance is all less than 3%.The interpolation of Ag, on the not significantly impact of the anti-reflection performance of electrode, only makes anti-reflection rate slightly decline.Based on MoS 2the anti-reflection ability near infrared light is shown equally with Ag modification silicon nanowire array, but and MoS 2the otherness of modifying silicon nanowire array is little.From the character of semi-conductor, the introducing of metal conducting layer does not produce significantly impact to the energy band structure of silicon.
Fig. 4 is based on MoS 2silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode, silicon nanowire array electrode, Ag modification silicon nanowire array electrode and MoS is modified with Ag 2the typical LSV modifying silicon nanowire array electrode 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.Can clearly find out from figure, construct Ag electric charge carrier bed based on MoS 2the density of photocurrent comparatively MoS of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is modified with Ag 2modify silicon nanowire array electrode to have increased significantly.Under dark-state condition, when RHE-1.0V, the dark current density of silicon nanowire array electrode is only 0.06mA/cm 2, its E oSreach for-1.16V; Illumination is opened, and the current density of silicon nanowire array electrode promotes rapidly, E oSalso significantly-0.06V is moved to.Ag load, as the effect of Pt, can accelerate the transfer of electric charge between interface, thus promotes density of photocurrent, and E oSjust move to 0.27V.Under illumination, MoS 2the E of/silicon nanowire array oSfor 0.55V, be compounded with Ag based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag and show excellent photoelectrochemistry activity, E oSjust move on to 0.62V.
In order to compare based on MoS more intuitively 2silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and silicon nanowire array electrode, MoS is modified with Ag 2modification silicon nanowire array electrode, Ag modify the amplification size of the density of photocurrent of silicon nanowire array electrode, and under simulated solar rayed, carry out dynamic potential scanning test, result as shown in Figure 5.As shown in Figure 5, based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag and show excellent photoelectrochemistry catalysis product hydrogen activity.Relative to RHE-1.0V, its current density reaches nearly 50mA/cm 2, exceed about 12 times than silicon nanowire array electrode, compare MoS 2modifying silicon nanometer linear array electrode and exceed 2 times, is nearly 50 times of silicon nanowire array electrode.Its reason is based on MoS 2the dark current of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is modified because the load of metal A g improves the electro catalytic activity of silicon nanowires with Ag.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.In addition, the introducing due to Ag charge transport layer decreases the resistance reducing Charger transfer, makes MoS 2the current density ratio silicon nanowire array electrode modifying silicon chip electrode with Ag is higher.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 described below:
V H z = J ph V o t&eta; ( nF ) - 1
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 V omolecular volume (standard state) and the Avogadro constant of gas is represented respectively with F.Relative to RHE-1.00V, based on MoS 2the maximum electrochemistry hydrogen output (η=100%) of modifying the photic enhancing of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag is about 325.9 μ L/min.
In order to obtain based on MoS further 2the electronic structure of silicon nanowire array and the information of electronic transmission performance is modified, to silicon nanowire array electrode, MoS with Ag 2modify silicon nanowire array electrode, Ag modify silicon nanowire array electrode with based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode sample with Ag and carried out electrochemical impedance spectrum analysis, result as shown in Figure 6.In Fig. 6, A is silicon nanowire array electrode and MoS 2modify the electrochemical impedance spectrogram of silicon nanowire array electrode under illumination condition, figure B is based on MoS 2modify silicon nanowire array electrode under illumination condition with Ag modification silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode and Ag, the illustration in figure is respectively corresponding equivalent simulation circuit figure.Spherical line in figure represents test data of experiment, and star represents fitting result, and the equivalent electrical circuit corresponding to matching conforms to the equivalent electrical circuit of scheming to insert in B with figure A respectively.By composing to testing the EIS recorded the value that matching can draw each element in equivalent electrical circuit, the results are shown in Table 1 for these fitting data.
Table 1 is based on MoS 2silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode series of samples test EIS simulated data table is modified with Ag
Wherein R trepresent the total series resistance of circuit, comprise electrolyte solution, semiconductor base, the resistance of line structure array etc.; R ct, sreferring to the charge transfer resistance in semiconductor surface depletion layer, CPE selectric 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, reaction be the degree of being obstructed that electric charge passes that electrostatic double layer is transferred to electrode surface; W represents Warburg diffusion control impedor, and when there being low frequency to spread generation, this element will be introduced in simulating equivalent circuit.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.By model analysis, as shown in Table 1, based on MoS 2the R of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is modified with Ag ct.dlmatch value is 12.17 Ω/cm 2, than the R of silicon nanowire array electrode ct.dlbe worth 227.1 Ω/cm 2reduce nearly 94.5%, reduce about 90.2% compared with modifying silicon nanowire array electrode with Ag, compare MoS 2modify silicon nanowire array electrode and reduce 40.8%.And this electrode electricity structure mechanism aspect analyze result just in time with Fig. 5 in based on MoS 2the result producing maximum photoelectric current with Ag modification silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is consistent.The introducing of Ag electron transfer layer significantly reduces the charge transfer resistance of solid solid interface, can provide more free charge for the hydrogen reduction reaction of solid-liquid interface.The transfer of solid solid interface electric charge, accelerates the utilization of photo-generated carrier, decreases the compound of photohole-electron pair, improves electricity conversion.
For based on MoS 2the raising of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode photoelectrochemistry Hydrogen Evolution Performance is modified with Ag, in order to prove that silicon nanowire array structure falls into layer as anti-reflection layer and light and is responsible for catching more photon, and MoS 2photocatalyst is as liberation of hydrogen catalyzer, and Ag is as solid solid interface charge transfer medium, for the fast transfer of light induced electron provides passage, reduce the compound of photohole-electron pair, the synergistic effect of three improves the electricity conversion of whole optoelectronic pole system, and the principle that photo-generated carrier must increase.This just in time can verify this explanation mechanism to utilize not special Schottky to test (Mott-Schottky measurement).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)/(qN Aε 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, N afor acceptor density, ε sthe specific inductivity of electrode materials, ε 0be the specific inductivity of vacuum, A is the reaction area of sample, and typical Mott-S result measured under illumination condition is as shown in Figure 7, as shown in table 2 to pattern analysis results.
Table 2 is based on MoS 2the electrical properties of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode series of samples is modified with Ag
Wherein Ag modifies the flat-band potential of silicon nanowire array electrode is 0.491V (vs.Ag/AgCl), MoS 2modifying silicon nanowire array electrode is 0.601V (vs.Ag/AgCl), based on MoS 2modifying silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag is 0.425V (vs.Ag/AgCl).As can be seen from analytical data, at Ag or MoS 2after electrode face finish, the flat-band potential of sample all decreases before comparatively modifying.Based semiconductor electrode electrolyte interface and energy bandgaps model analysis, catalyzer MoS 2with metal A g, positive effect is all played for electrode photoelectric improved performance.All enable photogenerated charge move rapidly to the quickening of hydrogen reduction reaction speed and the Charger transfer of acceleration solid solid interface, decrease the probability with hole-recombination, comparatively Ag modifies silicon nanowire array electrode carrier concentration 1.07 × 10 22and MoS 2modify silicon nanowire array electrode carrier concentration 6.83 × 10 23, based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode photoproduction carrier concentration with Ag and bring up to 1.96 × 10 24.The raising of photoproduction carrier concentration concentration has directly been reflected in MoS 2modify the increase of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode density of photocurrent with Ag, the experimental result of this and LSV, DPS matches.
Fig. 8 is based on MoS 2with Ag modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode under illumination and additional constant bias-0.5V (vs.RHE) electrochemistry liberation of hydrogen stability it test pattern (electrolytic solution is 0.1M H 2sO 4with 0.5M K 2sO 4mixed solution).Result shows, when illumination is opened, and MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode photoelectric current with Ag significantly to improve, and be stabilized in 27mA/cm very soon 2left and right.When experiment is carried out, can actually observe based on MoS 2modify on the surface of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag, have a large amount of bubble hydrogens produce and promptly depart from electrode surface, move up to solution surface effusion.Curve obviously up and down fluctuation be define temporary transient gas-barrier layer because reaction that electrode surface is violent creates a large amount of bubble at electrode surface, make the ion in solution cannot reach interface continuously and the fluctuation of current that causes.This shows, based on MoS 2modify with Ag the performance that silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode structure strengthens self photoelectrochemistry liberation of hydrogen greatly, facilitate hydrionic reduction.After constant light is shone and reacted 1.5 hours under bias voltage, based on MoS 2the photoelectric current modifying silicon nanowire array with Ag does not almost have anything to decay, and which illustrates based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag and there is satisfactory stability.
Above-mentioned analysis can be found out, at MoS 2modify in silicon nanowire array and increase Ag as charge transfer layer, build MoS 2modify silicon nanowire array structure with Ag, analyzed by XRD, EDX, Ag is compound in electrode structure, and DRS shows MoS 2modify silicon nanowire array with Ag and there is good anti-reflection and light absorption.Therefore obtain based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag and there is good photoelectrochemistry Hydrogen Evolution Performance.This electrode not only has excellent anti-reflection and light absorption, and charge transport layer Ag adds the Charger transfer that improve solid solid interface, and the probability making light induced electron participate in hydrogen reduction reaction improves greatly.MoS 2high and the good stability of catalytic activity for hydrogen evolution, Ag is MoS as charge transport layer 2on hydrogen reduction reaction more light induced electron is provided, strengthen the degree of reaction, improve effciency of energy transfer.The silicon nanowire array of contrast unmodified, electrochemistry is produced hydrogen density of photocurrent and is improve about 12 times, and open current potential and just move to 0.62V, carrier concentration adds 300 times.
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 (10)

1. based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag, 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 Ag nano particle cluster and MoS 2nano particle cluster, described Ag nano particle cluster is positioned at silicon nanowire array and MoS 2between nano particle cluster.
2. according to claim 1 based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag, 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. according to claim 1 based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag, 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 the 40%-50% of silicon nanowire array surface-area.
4. according to claim 1 based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag, it is characterized in that: the particle diameter of described Ag nano particle is 10-50nm, and its surface-area is the 5%-10% of silicon nanowire array surface-area.
5. according to claim 1 based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag, it is characterized in that: described conductive substrates is copper sheet, described nano-wire array is by conductive silver glue and copper base vertical glue joint, and described copper base is also coated with epoxy resin sealing insulation layer outward.
6. according to claim 1-5 any one based on MoS 2modify silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag, 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 the silicon nanowire array surface of Ag nano particle cluster modification.
7. use described in claim 1-6 any one based on MoS 2two electrodes or the three-electrode system of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode is modified with Ag.
8. require two electrodes or three-electrode system described in 7 according to right, to it is characterized in that: described based on MoS 2modifying silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode with Ag is working electrode, and platinized platinum is to electrode.
9. MoS described in any one of claim 1 ~ 7 2the application of silicon nanowire array photoelectrochemistry hydrogen-precipitating electrode in photoelectrochemistry product hydrogen is modified with Ag.
10. two electrodes described in claim 7 or 8 or three-electrode system produce the application in hydrogen in photoelectrochemistry.
CN201510075781.5A 2015-02-12 2015-02-12 Photo-electrochemical hydrogen evolution electrode based on MoS2 and Ag modified silicon nanowire array and application thereof Pending CN104630821A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109136984A (en) * 2018-09-30 2019-01-04 东南大学 A kind of three-dimensional composite catalyst Au NPs/MoS for efficient liberation of hydrogen2/ CFP and preparation method thereof
CN109628952A (en) * 2018-12-31 2019-04-16 武汉工程大学 A kind of Ni-based double-metal hydroxide electrocatalytic hydrogen evolution catalyst of foamed nickel supported Ag doping and preparation method thereof
CN110203876A (en) * 2019-06-28 2019-09-06 浙江大学 A kind of silicon nanowires chip and the Mass Spectrometry detection method based on silicon nanowires chip
CN116328803A (en) * 2023-03-11 2023-06-27 中南民族大学 Preparation method and application of CdS@Ti3C2MXene-MoS 2 ternary composite catalyst

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2377971A1 (en) * 2010-04-16 2011-10-19 EPFL Ecole Polytechnique Fédérale de Lausanne Amorphous transition metal sulphide films or solids as efficient electrocatalysts for hydrogen production from water or aqueous solutions
CN104071846A (en) * 2014-07-11 2014-10-01 中国科学技术大学 Transitional metal chalcogenide nanowire and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2377971A1 (en) * 2010-04-16 2011-10-19 EPFL Ecole Polytechnique Fédérale de Lausanne Amorphous transition metal sulphide films or solids as efficient electrocatalysts for hydrogen production from water or aqueous solutions
CN104071846A (en) * 2014-07-11 2014-10-01 中国科学技术大学 Transitional metal chalcogenide nanowire and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PHONG D. TRAN ET AL.,: "Novel Assembly of an MoS2 Electrocatalyst onto a Silicon Nanowire Array Electrode to Construct a Photocathode Composed of Elements Abundant on the Earth for Hydrogen Generation", 《CHEM. EUR. J》 *
QIYUAN HE ET AL.,: "Fabrication of Flexible MoS 2 Thin-Film Transistor Arrays for Practical Gas-Sensing Applications", 《SMALL》 *
SHANNON W. BOETTCHER ET AL.,: "Photoelectrochemical Hydrogen Evolution Using Si Microwire Arrays", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 *
乔雷: "硅纳米线阵列复合电极的制备及其光电化学分解水性能的研究", 《重庆大学博士学位论文》 *

Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN109136984A (en) * 2018-09-30 2019-01-04 东南大学 A kind of three-dimensional composite catalyst Au NPs/MoS for efficient liberation of hydrogen2/ CFP and preparation method thereof
CN109628952A (en) * 2018-12-31 2019-04-16 武汉工程大学 A kind of Ni-based double-metal hydroxide electrocatalytic hydrogen evolution catalyst of foamed nickel supported Ag doping and preparation method thereof
CN110203876A (en) * 2019-06-28 2019-09-06 浙江大学 A kind of silicon nanowires chip and the Mass Spectrometry detection method based on silicon nanowires chip
WO2020259186A1 (en) * 2019-06-28 2020-12-30 杭州汇健科技有限公司 Silicon nanowire chip and silicon nanowire chip-based mass spectrum detection method
CN110203876B (en) * 2019-06-28 2022-02-18 杭州汇健科技有限公司 Silicon nanowire chip and mass spectrum detection method based on silicon nanowire chip
CN116328803A (en) * 2023-03-11 2023-06-27 中南民族大学 Preparation method and application of CdS@Ti3C2MXene-MoS 2 ternary composite catalyst
CN116328803B (en) * 2023-03-11 2024-05-10 中南民族大学 Preparation method and application of CdS@Ti3C2MXene-MoS 2 ternary composite catalyst

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