CN109569630A - A kind of pucherite composite material preparation loading nickel cobalt hydrotalcite nano particle and the application in photoelectricity water oxygen - Google Patents

A kind of pucherite composite material preparation loading nickel cobalt hydrotalcite nano particle and the application in photoelectricity water oxygen Download PDF

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CN109569630A
CN109569630A CN201910062016.8A CN201910062016A CN109569630A CN 109569630 A CN109569630 A CN 109569630A CN 201910062016 A CN201910062016 A CN 201910062016A CN 109569630 A CN109569630 A CN 109569630A
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electrode
bivo
composite material
film
nickel cobalt
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佘厚德
岳彭飞
赵子威
张靓
黄静伟
苏碧桃
王其召
王磊
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Northwest Normal University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • 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
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Abstract

The present invention provides a kind of pucherite composite material preparation for loading nickel cobalt hydrotalcite nano particle and the applications in photoelectricity water oxygen, and with the method for electrochemical deposition, deposition prepares precursor BiOI film on FTO electro-conductive glass, then passes through annealing synthesis BiVO4Film, and NiCo-LDH nanoparticle is successfully loaded BiVO again by electrochemical deposition4Membrane structure, the NiCo-LDH/BiVO of formation4Composite material has sponge structure, this structure restrained effectively the recombination of photo-generated carrier, accelerate the separation of electrons and holes, therefore with excellent PEC activity, it is used for liberation of hydrogen oxygen evolution reaction using it as photo cathode, shows excellent electrolysis aquatic products hydrogen and produces oxygen performance.

Description

It is a kind of load nickel cobalt hydrotalcite nano particle pucherite composite material preparation and in light Application in electric water oxygen
Technical field
The present invention relates to a kind of BiVO4Based composites more particularly to a kind of vanadium for loading nickel cobalt hydrotalcite nano particle The preparation of sour bismuth composite material is used for liberation of hydrogen oxygen evolution reaction mainly as photo cathode material.
Background technique
With the shortage of environmental pollution and resource, Hydrogen Energy is increasingly subject to widely pay close attention to as a kind of clean energy.Light Electrochemistry (PEC) battery has been lifted as the most effective approach for generating hydrogen.BiVO4As a kind of typical n-type semiconductor, Forbidden bandwidth Eg is about 2.4eV, has visible light activity, is used for evolving hydrogen reaction as photo cathode.However, BiVO4In illumination Under there are serious charge recombination and low water oxidation kinetics, will affect light-catalyzed reaction efficiency, thus people there is an urgent need into One step proposes to reduce BiVO4The effective ways of light induced electron and hole-recombination.
Summary of the invention
The object of the present invention is to provide a kind of preparation sides of pucherite composite material for loading nickel cobalt hydrotalcite nano particle BiVO is effectively reduced in method4Compound, the raising light-catalyzed reaction efficiency of light induced electron and hole.
It is a further object of the present invention to provide a kind of pucherite composite materials for loading nickel cobalt hydrotalcite nano particle in light Application in electric water oxygen liberation of hydrogen analysis oxygen.
To achieve the above object, the technical scheme adopted by the invention is that: a kind of load nickel cobalt hydrotalcite nano particle The preparation method of pucherite composite material, specifically sequentially includes the following steps:
1) 3~4 ︰ 1 in mass ratio take potassium iodide (KI) He Wushui bismuth nitrate (Bi (NO respectively3)3·5H2O), then 1,4-benzoquinone is taken (C6H4O2), the mass ratio of taken 1,4-benzoquinone and taken potassium iodide is 1 ︰ 6~7, potassium iodide is dissolved in deionized water, then plus Enter Bi (NO3)3·5H2O is vigorously stirred, until Bi (NO3)3·5H2O is completely dissolved；1M HNO is added3PH value is adjusted, obtaining pH value is 1.5~1.7 mixed liquor；
1,4-benzoquinone is added in 20mL dehydrated alcohol, stirring and dissolving obtains the 1,4-benzoquinone ethanol solution of brown；
2) 1,4-benzoquinone ethanol solution made from step 1) is slowly dropped in mixed liquor made from step 1), after being added dropwise again 30min is stirred, the electrolyte for electrochemical deposition preparation rufous BiOI nanometer sheet film is obtained；
3) it is deposited with the electrolytic cell of typical three electrode, in three electrodes, FTO(electro-conductive glass) it is used as working electrode (WE), Ag/AgCl(3M KCl) it is used as reference electrode (RE), platinum is used as to electrode (CE) electrode；Using it is preceding with isopropanol, acetone and Distilled water mixing ultrasonic cleaning carries out electro-deposition using cyclic voltammetry in the electrolyte heating electrolytic cell in step 2 (CV): in the potential areas of 0~-0.13V, 10 circle of scanning, sweep speed 5mV/s electro-deposition 250~270s seconds, is working Electrode deposition BiOI film, the working electrode for being deposited with BiOI film is rinsed with deionized water, 50 DEG C~80 DEG C at a temperature of it is dry It is dry, obtain BiOI film；
4) by addition 0.1667g vanadyl acetylacetonate (VO (acac) in 2.5mL dimethyl sulfoxide (DMSO)2) ratio, by diformazan Base sulfoxide is added in vanadyl acetylacetonate, and stirring obtains vanadyl acetylacetonate solution to dissolving；
5) 100 μ L vanadyl acetylacetonate solution are drawn with liquid-transfering gun uniformly to drip on the BiOI film made from step 3)；Then, it sets In Muffle furnace, 450 DEG C~500 DEG C are warming up to the heating rate of 2 DEG C/min, is calcined 2~2.5 hours, so that BiOI be made to turn It is changed to BiVO4；It cools to room temperature with the furnace, takes out, immerse stirring in 1M NaOH solution and impregnate at least 30 minutes, remove BiVO4On Extra Bi2O3、V2O5Equal impurity, distilled water flushing, and it is dry at a temperature of 60 DEG C, obtain BiVO4Film；
6) 1 ︰, 1 ︰ 1.5~2.5 in molar ratio, takes CoSO respectively4、Ni(NO3)2And NH4Cl, it is completely soluble in water, it is formed water-soluble Liquid；It is deposited with the electrolytic cell of typical three electrode, in three electrode, BiVO4Film is as working electrode (WE), Ag/ AgCl(3MKCl) electrode is used as to electrode (CE) as reference electrode (RE), platinum；Aqueous solution is added in electrolytic cell, nitrogen is blown After sweeping aqueous solution 0.3~0.6 hour, three electrodes are put into electrolytic cell, under the voltage of -0.4~-0.6V deposit 250~ Nickel cobalt hydrotalcite (NiCo-LDH, LDH therein indicate layered double hydroxide) is deposited on BiVO by 350s4On electrode； Then, by BiVO4The vanadic acid of load nickel cobalt hydrotalcite nano particle is made in 50~80 DEG C of at a temperature of drying 30min in electrode Bismuth (NiCo-LDH/BiVO4) composite material.
4The characterization of composite material
The SEM that Figure 1A, 1B are BiOI schemes.The BiOI that the present invention synthesizes it can be seen from Figure 1A, 1B is what sheet intersected to form BiOI film, the nanometer sheet of straight uniform are arranged on FTO electro-conductive glass, illustrate that BiOI has been loaded on electro-conductive glass.
Fig. 1 C, 1D BiVO4SEM figure.The BiVO of synthesis it can be seen from Fig. 1 C, 1D4For worm shape structure, with a thickness of The nanometer sheet of 2 ~ 2.5nm straight uniform is arranged on FTO electro-conductive glass, illustrates that BiOI is converted to BiVO4。
Fig. 1 E, 1F NiCo-LDH/BiVO4SEM figure.NiCo-LDH/ prepared by the present invention can be seen that by Fig. 1 E, 1F BiVO4Composite material is spongy little particle, illustrates NiCo-LDH/BiVO4It is successfully prepared.
Fig. 2 is BiVO4、NiCo-LDH/BiVO4XRD diagram.It can be seen from the figure that coming from BiVO4Diffraction maximum can return Belong to monocline scheelite crystallographic system column (JCPDS No.14-0688), there are also conductive substrates SnO for diffraction maximum2Diffraction maximum (JCPDS No.41-1445).Continuation deposits NiCo-LDH, XRD spectrum and BiVO on BiVO4 electrode4Electrode map is compared not to be had substantially It changes, illustrates because the content of load NiCo-LDH is below the detection limit of XRD spectrum.
Fig. 3 is BiVO4、NiCo-LDH/BiVO4The high-resolution transmission electron microscopy electron microscope of electrode, is clear that BiVO4And NiCo-LDH/BiVO4The microscopic appearance of electrode, while finding out corresponding BiVO4And NiCo-LDH/BiVO4The crystalline substance of electrode Lattice fringe spacing, 3.0938nm, 2.9211nm and 2.745nm are respectively belonging to BiVO4(- 121), (040) crystal face and NiCo-LDH/BiVO4(100) crystal face.
4The photochemical properties of composite material are tested
BiVO is assessed by test UV-Vis diffusing reflection spectrum4And NiCo-LDH/BiVO4Optical property.Fig. 4 is respectively BiVO4、NiCo-LDH/BiVO4UV-Vis diffuse spectrogram A and forbidden bandwidth figure B.BiVO4In the wavelength of 350~500nm Strong absorption, BiVO are shown in range4The ABSORPTION EDGE of film makes composite material in 500nm or so, the deposition of NiCo-LDH Absorption intensity increase and red shift occur.Axis is extended to by the greatest gradient (α hv is to h ν) from Tauc curve to calculate band gap, The intersection point of tangent line and abscissa is the forbidden band broadband value of composite sample.As seen from the figure, after NiCo-LDH deposition, composite material Forbidden bandwidth value becomes smaller, this illustrates NiCo-LDH/BiVO4More visible lights can preferably be utilized.
Fig. 5 is BiVO4The density of photocurrent figure of series of samples.It can be seen that the photoelectric current of NiCo-LDH is under 0.6V bias Reach 2.82mA/cm2, it is BiVO4Photoelectric current (1.14mA/cm2) 2.47 times.Illustrate NiCo-LDH/BiVO4Composite material tool There is good water oxidisability.
Fig. 6 records BiVO4, NiCo-LDH/BiVO4LSV, impedance curve.Fig. 6 A shows under light conditions, NiCo- LDH/BiVO42.89mA/cm is reached in 1.23 V vs.RHE2, with BiVO4(1.19mA/cm2) film is compared to increasing 2.42 Times.NiCo-LDH is deposited into BiVO4Surface on to form NiCo-LDH/BiVO4Hetero-junctions, this can expand BiVO4It can Light-exposed range absorbability, and be conducive to the transfer and separation of electrons and holes.Fig. 6 B shows LSV curve under no illumination, With BiVO4Film is compared, NiCo-LDH/BiVO4The take-off potential of film is 2.06V(relative to RHE).Load NiCo-LDH receives Rice corpuscles may reduce BiVO4The partial size of nanoparticle on surface, therefore the Percentage bound of carrier significant subtracts during water oxygen It is few, promote the efficiency of electrolysis water.
The chronoamperometry of chopping the light is measured to compare the response of the transient photocurrents due to caused by water oxidation kinetics, such as Fig. 6 C It is shown, for each application current potential, from 0.05V to 1.81V(relative to RHE) record photoelectric current 10 seconds.NiCo-LDH/BiVO4 Electrode, which is shown, compares BiVO4Higher transient photocurrents density, especially in the low bias voltage regions of 0.2~0.6V.All sound It should all show the positive current transition of the difference amplitude when opening lamp.Transient state indicates the hole accummulation at electrode/electrolyte interface And it is not injected into electrolyte.BiVO4Electrode shows high current spike, especially in low potential, shows that there are high injection barriers. By reducing potential barrier, the photoelectric current transition is in NiCo-LDH/BiVO4It is reduced on heterojunction photovoltaic anode, relative to surface charge Accumulation, NiCo-LDH/BiVO4Hetero-junctions can promote the separation of charge in light induced electron and hole.
Fig. 6 D is impedance diagram, and each sample only observes that a semicircle, lesser semicircle radius indicate that better charge turns Shifting ability (that is, faster Surface reaction kinetics).Radius is smaller, and the carrier transport of material is faster, light induced electron and hole It is compound smaller, electric charge transfer is faster.BiVO4The semicircle radius of electrode is greater than NiCo-LDH/BiVO4Electrode, meanwhile, BiVO4 It shows to compare NiCo-LDH/BiVO4Worse charge transport capability.
4Production hydrogen for liberation of hydrogen oxygen evolution reaction produces oxygen performance
NiCo-LDH/BiVO4With excellent PEC activity.As shown in fig. 7, determining the H2-producing capacity figure of 3h, as seen from the figure As photoelectric decomposition water 3h, BiVO4Hydrogen output be 39.11 μm of ol, oxygen-producing amount is 23.09 μm of ol, see Fig. 7 A；NiCo-LDH/ BiVO4Hydrogen output be 134 μm of ol, oxygen-producing amount is 37.37 μm of ol, see Fig. 7 B.It can be proved that NiCo-LDH/BiVO4Composite wood The photoelectric decomposition aquatic products hydrogen of material produces oxygen performance ratio BiVO4It is high.
The present invention is with BiVO4For research material, body before preparation is deposited on FTO electro-conductive glass with the method for electrochemical deposition Body thin film, then pass through calcining synthesis BiVO4Film, and pass through chemical deposition for NiCo-LDH/BiVO4It is successfully loaded BiVO4Film Structure forms the NiCo-LDH/BiVO with spongelike structure then by building hetero-junctions4Composite material, this structure have The recombination for inhibiting to effect photo-generated carrier, accelerates the separation of electrons and holes, this is because NiCo-LDH and BiVO4Between Level-density parameter be conducive to transmission of the transmission and hole of light induced electron to electro-conductive glass (FTO) to surface, BiVO4 can be Incident light irradiation is lower to generate electron-hole pair, the interaction induction between NiCo-LDH and BiVO4 film position of energy band The electronics transfer of NiCo-LDH to BiVO4 and the hole capture of NiCo-LDH.Then, electronics reaches cathode through external circuit and occurs also It is primary at hydrogen, the valence band of hole migration to NiCo-LDH nanoparticle occurs oxidation reaction and generates oxygen., therefore have excellent Different PEC activity, liberation of hydrogen oxygen evolution reaction is used for using it as photo cathode, is shown excellent electrolysis aquatic products hydrogen and is produced oxygen performance.
Detailed description of the invention
The SEM that Figure 1A, 1B are pure BiOI schemes.Fig. 1 C, 1D are pure BiVO4SEM figure.Fig. 1 E, 1F NiCo-LDH/BiVO4 SEM figure.
Fig. 2 is BiVO4、NiCo-LDH/BiVO4XRD diagram.
Fig. 3 is respectively BiVO4、NiCo-LDH/BiVO4The TEM of electrode schemes
Fig. 4 is respectively BiVO4、NiCo-LDH/BiVO4The UV-Vis diffusing reflection spectrum (A) and forbidden bandwidth figure (B) of electrode.
Fig. 5 is BiVO4、NiCo-LDH/BiVO4The photoelectric current time plot of electrode.
Fig. 6 A, 6B BiVO4、NiCo-LDH/BiVO4The linear scan figure of light reaction and the dark reaction of electrode.Fig. 6 C, 6D AC impedance EIS figure respectively under the transient photocurrents density and illumination condition of electrode under light illumination.
Fig. 7 A, 7B are respectively BiVO4、NiCo-LDH/BiVO4The production hydrogen of electrode produces oxygen performance map.
Specific embodiment
Below by specific embodiment to NiCo-LDH/BiVO of the present invention4Composite material and performance are described further.
Embodiment 1
It weighs 3.3g potassium iodide to be dissolved in 50mL deionized water, 0.9gBi (NO is added3)3·5H2O is vigorously stirred, until Bi (NO3)3·5H2O is completely dissolved；1M HNO is added3PH value is adjusted, the mixed liquor that pH value is 1.5 is obtained；0.4980g is weighed to benzene Quinone is added in 20mL dehydrated alcohol, and stirring and dissolving obtains the 1,4-benzoquinone ethanol solution of brown；1,4-benzoquinone ethanol solution is slow It is added drop-wise in mixed liquor, is stirred for 30min after being added dropwise, obtain and prepare rufous BiOI nanometer sheet film for electrochemical deposition Electrolyte；It is deposited with the electrolytic cell of typical three electrode, in three electrodes, FTO is as working electrode, Ag/AgCl(3M KCl it) is used as reference electrode, platinum is used as to electrode electrode；It is cleaned by ultrasonic using preceding with isopropanol, acetone and distilled water mixing, Electro-deposition is carried out using cyclic voltammetry: in the potential areas of 0V, 10 circle of scanning, sweep speed 5mV/s, electro-deposition 250s Second, working electrode deposit BiOI film, the working electrode for being deposited with BiOI film is rinsed with deionized water, 60 DEG C at a temperature of It is dry, obtain BiOI film；0.1667g vanadyl acetylacetonate is weighed, is added in 2.5mL dimethyl sulfoxide, stirring is obtained to dissolving Vanadyl acetylacetonate solution；100 μ L vanadyl acetylacetonate solution are drawn with liquid-transfering gun uniformly to drip on BiOI film obtained；So Afterwards, it is placed in Muffle furnace, is warming up to 450 DEG C with the heating rate of 2 DEG C/min, calcines 2.5 hours, so that BiOI be made to be converted to BiVO4；It cools to room temperature with the furnace, takes out, immerse stirring in 1M NaOH solution and impregnate at least 30 minutes, remove BiVO4It is upper extra Bi2O3、V2O5Equal impurity, distilled water flushing, and it is dry at a temperature of 60 DEG C, obtain BiVO4Film；With the electricity of typical three electrode Xie Chi is deposited, in three electrode, BiVO4Film is as working electrode, Ag/AgCl(3MKCl) it is used as reference electrode, platinum pair Electrode is used as to electrode；Aqueous solution is added in electrolytic cell, the CoSO of 0.84g is contained in the aqueous solution4, 0.87g Ni (NO3)2 With the NH of 0.30g4Three electrodes are put into electrolytic cell by Cl after nitrogen purges aqueous solution 0.3 hour, are sunk in the voltage of -0.5V Product 250s, is deposited on BiVO for nickel cobalt hydrotalcite4On electrode；Then, by BiVO4At a temperature of drying of the electrode at 50~80 DEG C The pucherite composite material of load nickel cobalt hydrotalcite nano particle is made in 30min.
Embodiment 2
It weighs 3.4g potassium iodide to be dissolved in 50mL deionized water, 1.0gBi (NO is added3)3·5H2O is vigorously stirred, until Bi (NO3)3·5H2O is completely dissolved；1M HNO is added3PH value is adjusted, the mixed liquor that pH value is 1.7 is obtained；0.50g 1,4-benzoquinone is weighed, It is added in 20mL dehydrated alcohol, stirring and dissolving obtains the 1,4-benzoquinone ethanol solution of brown；1,4-benzoquinone ethanol solution is slowly added dropwise Into mixed liquor, it is stirred for 30min after being added dropwise, obtains the electricity for electrochemical deposition preparation rufous BiOI nanometer sheet film Solve liquid；It is deposited with the electrolytic cell of typical three electrode, in three electrodes, FTO is as working electrode, Ag/AgCl(3M KCl) As reference electrode, platinum is used as to electrode electrode；Using preceding with isopropanol, acetone and distilled water mixing ultrasonic cleaning, use Cyclic voltammetry carries out electro-deposition: in the potential areas of -0.13V, 10 circle of scanning, and sweep speed 5mV/s, electro-deposition 270s Second, working electrode deposit BiOI film, the working electrode for being deposited with BiOI film is rinsed with deionized water, 60 DEG C at a temperature of It is dry, obtain BiOI film；0.1667g vanadyl acetylacetonate is weighed, is added in 2.5mL dimethyl sulfoxide, stirring is obtained to dissolving Vanadyl acetylacetonate solution；100 μ L vanadyl acetylacetonate solution are drawn with liquid-transfering gun uniformly to drip on BiOI film；Then, it sets In Muffle furnace, 500 DEG C are warming up to the heating rate of 2 DEG C/min, is calcined 2 hours, so that BiOI be made to be converted to BiVO4；With Furnace is cooled to room temperature, and is taken out, and is immersed stirring in 1M NaOH solution and is impregnated at least 30 minutes, removes BiVO4Upper extra Bi2O3、 V2O5Equal impurity, distilled water flushing, and it is dry at a temperature of 60 DEG C, obtain BiVO4Film；With the electrolytic cell of typical three electrode into Row deposits, in three electrode, BiVO4Film is as working electrode, Ag/AgCl(3MKCl) electrode is made as reference electrode, platinum For to electrode；Aqueous solution is added in electrolytic cell, the CoSO of 0.90g is contained in the aqueous solution4, 0.92g Ni (NO3)2With The NH of 0.35g4Three electrodes are put into electrolytic cell, deposit under the voltage of -0.5V after nitrogen purges aqueous solution 0.6 hour by Cl Nickel cobalt hydrotalcite is deposited on BiVO by 350s4On electrode；Then, by BiVO4At a temperature of drying 30min of the electrode at 80 DEG C, system The pucherite composite material of nickel cobalt hydrotalcite nano particle must be loaded.
Embodiment 3
It weighs 3.35g potassium iodide to be dissolved in 50mL deionized water, 0.95gBi (NO is added3)3·5H2O is vigorously stirred, until Bi (NO3)3·5H2O is completely dissolved；1M HNO is added3PH value is adjusted, the mixed liquor that pH value is 1.6 is obtained；0.4990g is weighed to benzene Quinone is added in 20mL dehydrated alcohol, and stirring and dissolving obtains the 1,4-benzoquinone ethanol solution of brown；1,4-benzoquinone ethanol solution is slow It is added drop-wise in mixed liquor, is stirred for 30min after being added dropwise, obtain and prepare rufous BiOI nanometer sheet film for electrochemical deposition Electrolyte；It is deposited with the electrolytic cell of typical three electrode, in three electrodes, FTO is as working electrode, Ag/AgCl(3M KCl it) is used as reference electrode, platinum is used as to electrode electrode；It is cleaned by ultrasonic using preceding with isopropanol, acetone and distilled water mixing, Electro-deposition is carried out using cyclic voltammetry: in the potential areas of -0.065V, 10 circle of scanning, sweep speed 5mV/s, electro-deposition 260s seconds, BiOI film is deposited in working electrode, the working electrode for being deposited with BiOI film is rinsed with deionized water, in 60 DEG C of temperature Lower drying is spent, BiOI film is obtained；0.1667g vanadyl acetylacetonate is weighed, is added in 2.5mL dimethyl sulfoxide, is stirred to molten Solution, obtains vanadyl acetylacetonate solution；100 μ L vanadyl acetylacetonate solution are drawn with liquid-transfering gun uniformly to drip on BiOI film；So Afterwards, it is placed in Muffle furnace, is warming up to 475 DEG C with the heating rate of 2 DEG C/min, calcines 2.3 hours, so that BiOI be made to be converted to BiVO4；It cools to room temperature with the furnace, takes out, immerse stirring in 1M NaOH solution and impregnate at least 30 minutes, remove BiVO4It is upper extra Bi2O3、V2O5Equal impurity, distilled water flushing, and it is dry at a temperature of 60 DEG C, obtain BiVO4Film；With the electricity of typical three electrode Xie Chi is deposited, in three electrode, BiVO4Film is as working electrode, Ag/AgCl(3MKCl) it is used as reference electrode, platinum pair Electrode is used as to electrode；Aqueous solution is added in electrolytic cell, the CoSO of 0.87g is contained in the aqueous solution4, 0.895g Ni (NO3)2With the NH of 0.325g4Three electrodes are put into electrolytic cell, after nitrogen purges aqueous solution 0.45 hour -0.5V's by Cl 300s is deposited under voltage, nickel cobalt hydrotalcite is deposited on BiVO4On electrode；Then, by BiVO4Electrode 65 DEG C at a temperature of it is dry The pucherite composite material of load nickel cobalt hydrotalcite nano particle is made in dry 30min.

Claims (5)

1. a kind of preparation method for the pucherite composite material for loading nickel cobalt hydrotalcite nano particle, which is characterized in that the preparation Method specifically sequentially includes the following steps:
1) 3~4 ︰ 1 in mass ratio, take potassium iodide and five water bismuth nitrates, then take 1,4-benzoquinone respectively, taken 1,4-benzoquinone and taken iodate The mass ratio of potassium is 1 ︰ 6~7, and potassium iodide is dissolved in deionized water, five water bismuth nitrates is added, is vigorously stirred, until five water Bismuth nitrate is completely dissolved；PH value is adjusted, the mixed liquor that pH value is 1.5~1.7 is obtained；
1,4-benzoquinone is added to absolute ethanol, stirring and dissolving, obtains 1,4-benzoquinone ethanol solution；
2) 1,4-benzoquinone ethanol solution made from step 1) is added drop-wise in mixed liquor made from step 1), is stirred for after being added dropwise 30min obtains electrolyte；
3) it is deposited with the electrolytic cell of typical three electrode, in three electrodes, FTO is as working electrode, and Ag/AgCl is as reference Electrode, platinum are used as to electrode electrode；By in the electrolyte heating electrolytic cell in step 2, BiOI film is deposited in working electrode, The working electrode for being deposited with BiOI film is rinsed, in 50 DEG C~80 DEG C of at a temperature of drying, obtains BiOI film；
4) in 0.1667g vanadyl acetylacetonate ratio is added in 2.5mL dimethyl sulfoxide, acetylacetone,2,4-pentanedione is added in dimethyl sulfoxide In vanadyl, stirring obtains vanadyl acetylacetonate solution to dissolving；
5) 100 μ L vanadyl acetylacetonate solution are drawn uniformly to drip on the BiOI film made from step 3)；Then, it is placed in Muffle furnace In, 450 DEG C~500 DEG C are warming up to the heating rate of 2 DEG C/min, is calcined 2~2.5 hours；It cools to room temperature with the furnace, takes out, It immerses stirring in 1M NaOH solution to impregnate at least 30 minutes, rinse, it is dry, obtain BiVO4Film；
6) 1 ︰, 1 ︰ 1.5~2.5 in molar ratio, takes CoSO respectively4、Ni(NO3)2And NH4Cl, it is completely soluble in water, form aqueous solution； It is deposited with the electrolytic cell of typical three electrode, in three electrode, BiVO4Film is as working electrode, Ag/AgCl as ginseng Electrode is used as to electrode than electrode, platinum；Aqueous solution is added in electrolytic cell, and after nitrogen purges aqueous solution, three electrodes are put into electricity Xie Chizhong deposits 250~350s, dry BiVO under the voltage of -0.4~-0.6V4Electrode is made load nickel cobalt hydrotalcite and receives The pucherite composite material of rice corpuscles.
2. the preparation method of the pucherite composite material of load nickel cobalt hydrotalcite nano particle as described in claim 1, special Sign is, in the step 3), three electrodes are using preceding with isopropanol, acetone and distilled water mixing ultrasonic cleaning.
3. the preparation method of the pucherite composite material of load nickel cobalt hydrotalcite nano particle as described in claim 1, special Sign is, in the step 3), carries out electro-deposition using cyclic voltammetry: in the potential areas of 0~-0.13V, 10 circle of scanning, Sweep speed is 5mV/s, electro-deposition 250~270s seconds.
4. the preparation method of the pucherite composite material of load nickel cobalt hydrotalcite nano particle as described in claim 1, special Sign is, in the step 6), by BiVO4At a temperature of dry 30min of the electrode at 50~80 DEG C.
5. a kind of pucherite composite material of preparation method described in claim 1 load nickel cobalt hydrotalcite nano particle obtained It is applied to liberation of hydrogen oxygen evolution reaction as photo cathode material.
CN201910062016.8A 2019-01-23 2019-01-23 A kind of pucherite composite material preparation loading nickel cobalt hydrotalcite nano particle and the application in photoelectricity water oxygen Pending CN109569630A (en)

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