CN105040025B - Compound porous pucherite optoelectronic pole of double-metal hydroxide and preparation method thereof - Google Patents

Compound porous pucherite optoelectronic pole of double-metal hydroxide and preparation method thereof Download PDF

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CN105040025B
CN105040025B CN201510239020.9A CN201510239020A CN105040025B CN 105040025 B CN105040025 B CN 105040025B CN 201510239020 A CN201510239020 A CN 201510239020A CN 105040025 B CN105040025 B CN 105040025B
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pucherite
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bismuth
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CN105040025A (en
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项顼
何宛虹
周辰
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Beijing University of Chemical Technology
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Abstract

The invention provides compound porous pucherite optoelectronic pole of a kind of double-metal hydroxide and preparation method thereof, it is to have cobalt aluminum bimetal hydroxide and pucherite compound in the growth of electro-conductive glass substrate surface, wherein pucherite hole is 50~120nm, and particle size is 200~300nm；Cobalt aluminum bimetal hydroxide is grown on pucherite particle, and thickness is 10~100nm.Being prepared as of the optoelectronic pole first prepares porous vanadic acid bismuth pole using electro-deposition precursor methods; cobalt aluminum bimetal hydroxide is grown on porous vanadic acid bismuth pole again; this method is simple to operate; reaction condition is gentle; using size and pattern of the zinc ion as electro-deposition additive control vanadic acid bismuth pole; more traditional organic formwork agent or additive is more green, suitable for large-scale production.The optoelectronic pole can be directly used for optical electro-chemistry water oxygen catalytic reaction, because the good catalytic and visible absorption ability of cobalt aluminum bimetal hydroxide significantly improve the water oxidation susceptibility of the optoelectronic pole.

Description

Compound porous pucherite optoelectronic pole of double-metal hydroxide and preparation method thereof
Technical field
The invention belongs to optoelectronic pole field of material preparation, and in particular to the compound porous pucherite photoelectricity of double-metal hydroxide Pole and preparation method thereof, and for the photoelectrocatalysis water decomposition of sun optical drive.
Background technology
Excessive exploitation and use of the modern society to traditional energies such as coal, oil and natural gas, have had resulted in huge energy Source crisis and problem of environmental pollution.In order to realize sustainable development, it is own through turning into the world to develop and utilize regenerative resource industry The grand strategy target of various countries.For wherein solar energy as a kind of regenerative resource of cleaning, its reserves is other regenerative resources Tens thousand of times；Solar energy hardly discharges CO in use simultaneously2Isothermal chamber gas, alleviation crude oil leakage is contributed to cause Environmental pollution and fuel combustion caused by the environmental problem such as greenhouse effects, this allows solar energy to be occupied in regenerative resource industry Critical role.In the various Solar use modes, photocatalytic water splitting is a kind of luminous energy is changed into chemical energy to have efficacious prescriptions Formula, its catabolite are O2And H2, the former is widely present in air, provides possibility for environmental diversity, the latter is new Secondary energy sources, its energy density is high, pollution-free using process, and combustion product is only H2O, there is the feature of efficient cleaning.Therefore Greatly developing photo-electrocatalytic technology realizes light-chemical energy conversion for the worsening environmental problem of alleviating energy crisis, solution Etc. suffer from positive role.Because raw material is easy to get, Stability Analysis of Structures, efficiency are higher, inorganic semiconductor material is as optoelectronic pole Cause extensive concern, mainly there is titanium dioxide, zinc oxide, iron oxide, pucherite etc..The band gap of pucherite is only 2.4eV, is one Kind of the optoelectronic pole material with good visible light-responded ability, photoelectric transformation efficiency at 420nm up to 29% [K.Sayama, A.Nomura,Z.Zou,R.Abe,Y.Abe and H.Arakawa.Chem.Comm.,2003,2908-2909.]。
The bismuth resource reserve of China ranks first in the world, and reserves are about 240,000 tons, account for world's gross reserves 75% [king is refined Tinkling of pieces of jade China bismuth resource situation and countermeasure China Metal Bulletins, 2009,48:39-41], therefore develop bismuth oxo-compound photoelectricity Pole material has reliable resource base.The method for preparing pucherite optoelectronic pole at present mainly has organic metal salt decomposition method [P.M.Rao,L.Cai,C.Liu,I.S.Cho,C.H.Lee,J.M.Weisse,P.Yang,and X.Zheng.Nano Lett., 2014,14,1099-1105], hydro-thermal method [G.Xi and J.Ye, Chem.Commun., 2010,46,1893.], electricity Deposit precursor methods [D.Kang, Y.Park, J.C.Hill, and K.-S.Choi.J.Phys.Chem.Lett., 2014,5, 2994-2999.] etc..Wherein, electro-deposition precursor methods for precursor size, pattern easily regulates and controls, be that one kind is advantageous to pattern control The preparation method of system.But the weaker charge-conduction performance of pucherite and higher surface reaction energy barrier are as its performance of restriction The bottleneck of raising.There are some method of modifying for these problems, wherein the control to its pattern and size is the emphasis of research, this It is that on the other hand, photohole has because the pattern of one side optoelectronic pole influences the contact area of optoelectronic pole/electrolyte interface Certain diffusion length, if optoelectronic pole size can be reduced so that photohole with electronics it is compound before diffuse to surface participate in oxygen Change reaction, then can effectively be lifted photoelectric current [Z.-F.Huang, L.Pan, J.-J.Zou, X.Zhang, L.Wang.Nanoscale, 2014,6,14044-14063].In addition, compound with elctro-catalyst is to improve the optoelectronic pole surface dynamic (dynamical) important way of water oxygenization Footpath.Double-metal hydroxide (LDH) has unique layer structure of two kinds of (or two or more) metallic element high degree of dispersion, in electricity The catalytic performance higher than monometallic hydroxide or oxide is shown in catalysis, photocatalysis, photoelectrocatalysis reaction.Therefore, By LDH elctro-catalysts with optoelectronic pole is compound improves optoelectronic pole performance；On the other hand, the LDH containing Co or Ni has visible ray sound Answer property, thus by with visible light-responded LDH and optoelectronic pole it is compound after can lift optoelectronic pole sunshine is absorbed.
The content of the invention
It is an object of the invention to provide the optoelectronic pole that a kind of cobalt aluminum bimetal hydroxide and porous pucherite are compounded to form And preparation method thereof, it has visible absorption property and electrocatalytic properties simultaneously, available for photoelectrocatalysis water oxidation reaction mistake Journey.
The compound porous pucherite optoelectronic pole of cobalt aluminum bimetal hydroxide provided by the invention, is in electro-conductive glass substrate table Look unfamiliar with cobalt aluminum bimetal hydroxide and pucherite compound, wherein pucherite chemical formula is BiVO4, crystal formation is monocline knot Structure, its hole are 50~120nm, and particle size is 200~300nm；The chemical formula of cobalt aluminum bimetal hydroxide is CoxAly (OH)z(A)·nH2O, it is abbreviated as CoAl-LDH, wherein x:Y represents that cobalt ions and aluminum ions mol ratio are 1~4:1, n represents Hydration number, n=5~15, A represent anion, are one or both of sulfate radical, carbonate or nitrate anion, CoAl- LDH is grown on pucherite particle, and wherein CoAl-LDH thickness is 10~100nm.
The compound BiVO of the CoAl-LDH4The preparation method of optoelectronic pole is：The mixing salt solution containing zinc and bismuth is prepared as electricity Liquid is solved, solvent is that water and ethylene glycol mix.The electrolyte is added in electrolytic cell, using electro-conductive glass piece as working electrode, Constant potential is applied to working electrode at room temperature and carries out electro-deposition, bismuth ion is reduced to bismuth simple substance in working electrode surface, molten Zinc ion in liquid plays additive.The dimethyl sulphoxide solution of vanadium acetylacetonate is added dropwise in electrode surface after deposit, Then calcined, bismuth simple substance is converted into pucherite in calcination process, and sample removes the oxidation of excess in alkaline solution afterwards Vanadium, obtain porous vanadic acid bismuth pole；The soluble mixed-salt aqueous solution containing cobalt, aluminium is prepared, and adds urea and ammonium fluoride, will be prepared Good vanadic acid bismuth pole is put into the mixing salt solution, and the compound BiVO of CoAl-LDH are obtained after hydro-thermal reaction4Optoelectronic pole.
Specific preparation process is as follows：
A. bismuth salt and zinc salt are added into the mixed solvent and prepares the mixing salt solution containing zinc and bismuth, wherein bismuth salt and zinc salt Mol ratio be Bi:Zn=1:1~4, bismuth ion molar concentration is 5~30mmol/L：The bismuth salt be bismuth nitrate, bismuth chloride, One kind in bismuth sulfate, preferably it is bismuth nitrate；Described zinc salt is one kind in zinc nitrate, zinc chloride, zinc sulfate, preferably It is zinc nitrate；Described mixed solvent is ethylene glycol and deionized water volume ratio is 1~6:1 mixed solution.
B. step A mixing salt solution is added as electrolyte in three-electrode cell, using electro-conductive glass as work electricity Pole, using Ag/AgCl as reference electrode, platinum filament is to electrode, applies -0.6~0.4V to working electrode using electrochemical workstation Constant potential, deposition total charge dosage are -7~-15 × 10-2C·cm-2, the conductive glass electrode that finishes will be deposited and taken out, use second Alcohol cleans, and spontaneously dries 0.5~3 hour at room temperature；
Described electro-conductive glass is the SnO for adulterating fluorine2Electro-conductive glass, FTO electro-conductive glass is abbreviated as, the electro-conductive glass uses Before need to use acetone：Isopropanol：Water=1:1:The solution of 1 volume ratio is cleaned by ultrasonic, and naturally dry；The working face of electro-conductive glass Product is 1~50cm2.Described electrolytic cell is single chamber or dual chamber electrolytic cell, and potential value is the potential relative to reversible hydrogen electrode；
C. the dimethyl sulphoxide solution of 0.05~0.2mol/L vanadium acetylacetonate is prepared, it is post-depositional into step B to lead In electric glass electrode be added dropwise 100~400 μ L, then in Muffle furnace 400~550 DEG C calcine 2~4 hours, treat that temperature is down to room Taken out after temperature, be put into the NaOH aqueous solution that molar concentration is 0.2~2mol/L and be totally submerged to electrode slice, gentle agitation 0.5 ~3 hours, deionized water rinsing is used after taking out electrode slice, and is dried 0.5~6 hour at 60~80 DEG C, obtains porous BiVO4 Electrode；
D. Co (NO are used3)2·6H2O、Al(NO3)3·9H2O, urea, NH4F is hybridly prepared into mixing salt solution, wherein total gold Category ion concentration is 15~50mmol/L, Co2+With Al3+Mol ratio be 2~4:1, the concentration of urea is 30~80mmol/L, NH4F Concentration be 15~50mmol/L, after stirring, be transferred in water heating kettle inner bag, the BiVO that will be prepared in step D4Electrode Conduction is swayed in water heating kettle inner bag downwards, and growth is had into BiVO4Part be totally submerged in solution, at 100~200 DEG C 2~8h of lower hydro-thermal reaction, after natural cooling, electrode is taken out, with drying 20 in 30~60 DEG C of baking ovens after deionized water rinsing ~60min, obtain the compound BiVO of CoAl-LDH4Optoelectronic pole.
Fig. 1 is BiVO4X-ray powder diffraction (XRD) result of electrode, occur in figure corresponding to BiVO4(011), (121) diffraction maximum, the BiVO with monoclinic form scheelite phase4Diffraction maximum (JCPDS No.75-1866) is consistent；
Fig. 2 is the compound BiVO of CoAl-LDH4X-ray powder diffraction (XRD) result of optoelectronic pole, except BiVO4It is conductive with FTO Outside the diffraction maximum of sheet glass, there is LDH (003), (006), (009), (018) characteristic peak；
Fig. 3 is porous BiVO4The scanning electron microscope (SEM) photograph (SEM) of electrode, wherein pucherite even particle distribution, rough surface, Average grain diameter is 240nm, and hole is 70~100nm.
By the compound BiVO of CoAl-LDH4Optoelectronic pole is used for the performance test of photoelectricity water oxidation reaction, and result is in 1.23V electricity The water oxygen density of photocurrent of the optoelectronic pole under gesture is 0.8~1.2mA/cm2, the value is simple BiVO4More than 2 times of electrode.
The present invention has following remarkable result：
(1) using size and pattern of the simple inorganic zinc salt as additive control vanadic acid bismuth pole, more traditional has Machine template or additive are more green, environmentally friendly, non-toxic, and cost is lower.
(2) the porous vanadic acid bismuth pole prepared using inorganic zinc salt as additive has abundant pore structure, is advantageous to make For the high-performance of photochemical catalyzing, low cost optical electrode, it is adapted to scale exploitation.
(3) double-metal hydroxide and pucherite complex light electrode, using double-metal hydroxide to visible absorption Property strengthens optoelectronic pole and sunshine is utilized, and CoAl-LDH has good electrocatalytic properties, can significantly reduce photoelectric current Take-off potential, improve efficiency of energy utilization.
Brief description of the drawings
Fig. 1：The BiVO that embodiment 1 obtains4The XRD of electrode.
Fig. 2：The compound BiVO of CoAl-LDH that embodiment 1 obtains4The XRD of optoelectronic pole.
Fig. 3：The porous BiVO that embodiment 1 obtains4The SEM figures of electrode.
Embodiment
Embodiment 1
A. 0.4851g Bi (NO are weighed3)3·5H2O, 0.8925g Zn (NO3)2·6H2O be added to 50mL deionized waters and In the mixed solution of 100mL ethylene glycol, mixing salt solution is configured to；
B. acetone is used：Isopropanol：Water=1:1:The solution of 1 volume ratio is cleaned by ultrasonic the FTO (SnO of doping fluorine2Conductive glass Glass) electro-conductive glass piece, and naturally dry electro-conductive glass piece；Step A mixing salt solution is transferred in three-electrode cell, with Electro-conductive glass substrate is working electrode, and wherein the work area of electro-conductive glass piece is 2cm2.Using Ag/AgCl as reference electrode, platinum Silk is that electrolytic cell is single compartment electrolytic cell to electrode, applies the constant negative potentials of 0.01V to working electrode using electrochemical workstation, The total charge dosage of electro-deposition is -8.35 × 10-2C·cm-2.The electrode taking-up finished will be deposited, cleaned with ethanol, at room temperature Spontaneously dry 0.5 hour；
C. 0.1393g vanadium acetylacetonates are weighed and are dissolved in 2mL dimethyl sulfoxide (DMSO)s, are added dropwise on the electrode slice obtained into step B The 200 μ L solution, then calcined 2 hours with 450 DEG C in Muffle furnace, taken out after temperature is down to room temperature；4g NaOH are weighed, It is dissolved in 100mL deionized waters, the electrode slice after being calcined in step C is put into NaOH solution, gentle agitation 0.5 hour, taken Deionized water rinsing is used after going out electrode slice, and is dried 0.5 hour at 70 DEG C, obtains porous BiVO4Electrode, its average grain diameter are 240nm, hole are 70~100nm；
D. 0.3056g Co (NO are weighed3)2·6H2O、0.1313gAl(NO3)3·9H2O, 0.2102g ureas, 0.0519gNH4F and deionized water prepare 70mL salting liquids；Stir and be transferred in water heating kettle inner bag, will be prepared in step D BiVO4Optoelectronic pole, which faces down, sways in water heating kettle inner bag, and grown BiVO4Part be totally submerged in solution, The hydro-thermal reaction 4h at 100 DEG C, after natural cooling, optoelectronic pole is taken out, with being dried after deionized water rinsing in 40 DEG C of baking ovens 30min, obtain the compound BiVO of CoAl-LDH4Optoelectronic pole.
Test the compound BiVO of above-mentioned CoAl-LDH4Performance as optoelectronic pole：In the electrolytic cell of three electrode configurations, with The compound BiVO of CoAl-LDH4Photoelectricity extremely working electrode, Ag/AgCl are reference electrode, and platinum filament is that electrolytic cell is single chamber to electrode Or double-chamber structure；With xenon source (simulated solar irradiation) the irradiation optoelectronic pole front of assembling AM 1.5G optical filters, luminous intensity is 100mW/cm2；Apply voltage using electrochemical workstation (CHI 660C), electrolyte is pH=7 phosphate buffer solution (phosphorus Acid dihydride potassium-dipotassium hydrogen phosphate), concentration 0.1mol/L；Tested using cyclic voltammetry (CV), wherein cyclic voltammetry Sweep speed be 0.01V/s.Test obtained potential (EAg/AgCl) it is converted into potential (E to reversible hydrogen electrodeRHE)：ERHE= EAg/AgCl+0.197+0.059×pH.As a result：Its photoelectric current take-off potential is 0.24V, potential be 1.23V under water oxygen metaplasia into The density of photocurrent of oxygen is 0.95mA/cm2。
Embodiment 2
A. 0.4851gBi (NO are weighed3)3·5H2O, 0.595g Zn (NO3)2·6H2O be added to 50mL deionized waters and In the mixed solution of 100mL ethylene glycol, mixing salt solution is configured to；
B is with embodiment 1, except that the work area of electro-conductive glass is 1.5cm2, total deposited charge of electro-deposition for- 10×10-2C·cm-2
C. 0.1393g vanadium acetylacetonates are weighed and are dissolved in 2mL dimethyl sulfoxide (DMSO)s, are added dropwise on the electrode slice obtained into step B The 150 μ L solution, then calcined 2 hours with 450 DEG C in Muffle furnace, taken out after temperature is down to room temperature；4g NaOH are weighed, It is dissolved in 100mL deionized waters, the electrode slice added in step C after calcining, gentle agitation 1 hour, is spent after taking out electrode slice Ionized water rinses, and is dried 0.5 hour at 70 DEG C, obtains porous BiVO4Electrode, its average grain diameter are 260nm, hole 60 ~95nm；
D. 0.4365gCo (NO are weighed3)2·6H2O、0.1875gAl(NO3)3·9H2O, 0.2102g ureas, 0.0519gNH4F It is formulated as the 50mL aqueous solution；After salting liquid is stirred, it is transferred in water heating kettle inner bag, the BiVO that will be prepared in step D4Light Electrode, which faces down, sways in water heating kettle inner bag, and grown BiVO4Part be totally submerged in solution, at 100 DEG C Lower hydro-thermal reaction 4h, after natural cooling, optoelectronic pole is taken out, with 30min is dried in 40 DEG C of baking ovens after deionized water rinsing, is obtained To the compound BiVO of CoAl-LDH4Optoelectronic pole.
Using the same evaluation method of embodiment 1, evaluation result：Photoelectric current take-off potential is 0.26V, in the case where potential is 1.23V Water oxygen metaplasia into the density of photocurrent of oxygen be 0.90mA/cm2。
Embodiment 3
A. 0.4851gBi (NO are weighed3)3·5H2O, 0.2975g Zn (NO3)2·6H2O be added to 50mL deionized waters and In the mixed solution of 100mL ethylene glycol, mixing salt solution is configured to；
B is with embodiment 1, except that the constant negative potential that electro-deposition uses is -0.18V, total deposition electricity of electro-deposition Lotus is -9 × 10-2C·cm-2
C. 0.1393g vanadium acetylacetonates are weighed and are dissolved in 2mL dimethyl sulfoxide (DMSO)s, are added dropwise on the electrode slice obtained into step B The 200 μ L solution, then calcined 3 hours with 450 DEG C in Muffle furnace, taken out after temperature is down to room temperature；4g NaOH are weighed, It is dissolved in 100mL deionized waters, the electrode slice added in step C after calcining, gentle agitation 1 hour, is spent after taking out electrode slice Ionized water rinses, and is dried 0.5 hour at 70 DEG C, obtains porous BiVO4Electrode, its average grain diameter are 236nm, hole 85 ~100nm；
D. 0.4365gCo (NO are weighed3)2·6H2O、0.1875gAl(NO3)3·9H2O, 0.1050g ureas, 0.0370gNH4F It is formulated as the 50mL aqueous solution；After salting liquid is stirred, it is transferred in water heating kettle inner bag, the BiVO that will be prepared in step D4Light Electrode, which faces down, sways in water heating kettle inner bag, and grown BiVO4Part be totally submerged in solution, at 100 DEG C Lower hydro-thermal reaction 6h, after natural cooling, optoelectronic pole is taken out, with 30min is dried in 40 DEG C of baking ovens after deionized water rinsing, is obtained To the compound BiVO of CoAl-LDH4Optoelectronic pole.
Using the same evaluation method of embodiment 1, evaluation result：Photoelectric current take-off potential is 0.23V, in the case where potential is 1.23V Water oxygen metaplasia into the density of photocurrent of oxygen be 0.93mA/cm2。
Embodiment 4
A. 0.7276g Bi (NO are weighed3)3·5H2O, 0.4462g Zn (NO3)2·6H2O be added to 50mL deionized waters and In the mixed solution of 100mL ethylene glycol, mixing salt solution is configured to；
B is with embodiment 1, except that the work area of electro-conductive glass is 1.8cm2, constant negative electricity that electro-deposition uses Gesture is -0.08V, and total deposited charge of electro-deposition is -12 × 10-2C·cm-2
C. 0.1393g vanadium acetylacetonates are weighed and are dissolved in 2mL dimethyl sulfoxide (DMSO)s, are added dropwise on the electrode slice obtained into step B The 120 μ L solution, then calcined 2 hours with 450 DEG C in Muffle furnace, taken out after temperature is down to room temperature；4g NaOH are weighed, It is dissolved in 100mL deionized waters, the electrode slice added in step C after calcining, gentle agitation 0.5 hour, is used after taking out electrode slice Deionized water rinsing, and dried 0.5 hour at 70 DEG C, obtain porous BiVO4Electrode, its average grain diameter are 252nm, and hole is 77~110nm.
D. 0.6984gCo (NO are weighed3)2·6H2O、0.2250gAl(NO3)3·9H2O, 0.1050g ureas, 0.0370gNH4F It is formulated as the 60mL aqueous solution；After salting liquid is stirred, it is transferred in water heating kettle inner bag, the BiVO that will be prepared in step D4Light Electrode, which faces down, sways in water heating kettle inner bag, and grown BiVO4Part be totally submerged in solution, at 100 DEG C Lower hydro-thermal reaction 3h, after natural cooling, optoelectronic pole is taken out, with 30min is dried in 40 DEG C of baking ovens after deionized water rinsing, is obtained To the compound BiVO of CoAl-LDH4Optoelectronic pole.
Using the same evaluation method of embodiment 1, evaluation result：Photoelectric current take-off potential is 0.25V, in the case where potential is 1.23V Water oxygen metaplasia into the density of photocurrent of oxygen be 0.94mA/cm2。

Claims (2)

  1. A kind of 1. preparation method of the compound porous pucherite optoelectronic pole of double-metal hydroxide：Comprise the following steps that：
    A. the mixing salt solution containing zinc and bismuth by bismuth salt and zinc salt addition in the mixed solvent preparation, wherein bismuth salt and zinc salt rub Your ratio is Bi:Zn=1:1~4, bismuth ion molar concentration is 5~30mmol/L：The bismuth salt is bismuth nitrate, bismuth chloride, sulfuric acid One kind in bismuth；Described zinc salt is one kind in zinc nitrate, zinc chloride, zinc sulfate；Described mixed solvent be ethylene glycol and Deionized water volume ratio is 1~6:1 mixed solution；
    B. step A mixing salt solution is added in three-electrode cell as electrolyte, using electro-conductive glass as working electrode, with Ag/AgCl is reference electrode, and platinum filament is to electrode, applies the constant electricity of -0.6~0.4V to working electrode using electrochemical workstation Gesture, deposition total charge dosage are -7~-15 × 10-2C·cm-2, the conductive glass electrode that finishes will be deposited and taken out, cleaned with ethanol, Spontaneously dry 0.5~3 hour at room temperature；
    Described electro-conductive glass is the SnO for adulterating fluorine2Electro-conductive glass, the work area of electro-conductive glass is 1~50cm2；Described electricity Xie Chi is single chamber or dual chamber electrolytic cell, and potential value is the potential relative to reversible hydrogen electrode；
    C. the dimethyl sulphoxide solution of 0.05~0.2mol/L vanadium acetylacetonate, the post-depositional conductive glass into step B are prepared On glass electrode be added dropwise 100~400 μ L, then in Muffle furnace 400~550 DEG C calcine 2~4 hours, after temperature is down to room temperature Take out, be put into the NaOH aqueous solution that molar concentration is 0.2~2mol/L and be totally submerged to electrode slice, gentle agitation 0.5~3 is small When, deionized water rinsing is used after taking out electrode slice, and dried 0.5~6 hour at 60~80 DEG C, obtain porous BiVO4Electrode；
    D. Co (NO are used3)2·6H2O、Al(NO3)3·9H2O, urea, NH4F is hybridly prepared into mixing salt solution, wherein total metal ion Concentration is 15~50mmol/L, Co2+With Al3+Mol ratio be 2~4:1, the concentration of urea is 30~80mmol/L, NH4F concentration For 15~50mmol/L, after stirring, it is transferred in water heating kettle inner bag, the BiVO that will be prepared in step D4The conducting surface of electrode Sway in water heating kettle inner bag downwards, growth is had into BiVO4Part be totally submerged in solution, the hydro-thermal at 100~200 DEG C React 2~8h, after natural cooling, take out electrode, with after deionized water rinsing in 30~60 DEG C of baking ovens drying 20~ 60min, obtain the compound BiVO of cobalt aluminum bimetal hydroxide4Optoelectronic pole.
  2. 2. the compound porous pucherite optoelectronic pole of double-metal hydroxide prepared by a kind of method according to claim 11, its To have cobalt aluminum bimetal hydroxide and pucherite compound, wherein pucherite particle chemistry in the growth of electro-conductive glass substrate surface Formula is BiVO4, crystal formation is monocline, and its hole is 50~120nm, and particle size is 200~300nm；Cobalt Al bimetal hydrogen The chemical formula of oxide is CoxAly(OH)z(A)·nH2O, wherein x:Y represents that cobalt ions and aluminum ions mol ratio are 1~4: 1, n represents hydration number, and n=5~15, A represent anion, are one or both of sulfate radical, carbonate or nitrate anion, Cobalt aluminum bimetal hydroxide is grown on pucherite particle, and its thickness is 10~100nm.
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CN116889875B (en) * 2023-07-28 2024-08-20 中国科学院地理科学与资源研究所 BiVO (binary organic acid)4CoAlLa-LDH composite photocatalyst, and preparation method and application thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1683074A (en) * 2005-03-11 2005-10-19 南京大学 Process for preparing visible light responding photo catalytic film layer
CN101775615A (en) * 2010-01-20 2010-07-14 南京大学 BiVO4 nano photoelectrode and application thereof in hydrogen production from water splitting
CN101811051A (en) * 2009-11-24 2010-08-25 昆明理工大学 Carbonyl sulfide hydrolysis catalyst prepared by using cobalt(Co)-nickel(Ni)-aluminum(Al) hydrotalcites as precursor and preparation method thereof
CN102151577A (en) * 2011-01-28 2011-08-17 东华大学 Ag3PO4/Mg-Al LDO (Layered Double Oxide) visible light composite photo catalyst, preparation and application thereof
KR20120083989A (en) * 2011-01-19 2012-07-27 서강대학교산학협력단 Manganese-chromium layered double hydroxide, preparing method of the same, and photocatalyst containing the same
CN103097284A (en) * 2010-07-16 2013-05-08 特温特大学 Photocatalytic water splitting
CN103240073A (en) * 2013-04-26 2013-08-14 南京信息工程大学 Zn<2+>-doped BiVO4 visible-light-driven photocatalyst and preparation method thereof
EP2647430A1 (en) * 2012-04-05 2013-10-09 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Method for preparing a catalyst mediating H2 evolution, said catalyst and uses thereof
WO2014136783A1 (en) * 2013-03-07 2014-09-12 学校法人東京理科大学 Bismuth-vanadate-laminate manufacturing method and bismuth-vanadate laminate

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1683074A (en) * 2005-03-11 2005-10-19 南京大学 Process for preparing visible light responding photo catalytic film layer
CN101811051A (en) * 2009-11-24 2010-08-25 昆明理工大学 Carbonyl sulfide hydrolysis catalyst prepared by using cobalt(Co)-nickel(Ni)-aluminum(Al) hydrotalcites as precursor and preparation method thereof
CN101775615A (en) * 2010-01-20 2010-07-14 南京大学 BiVO4 nano photoelectrode and application thereof in hydrogen production from water splitting
CN103097284A (en) * 2010-07-16 2013-05-08 特温特大学 Photocatalytic water splitting
KR20120083989A (en) * 2011-01-19 2012-07-27 서강대학교산학협력단 Manganese-chromium layered double hydroxide, preparing method of the same, and photocatalyst containing the same
CN102151577A (en) * 2011-01-28 2011-08-17 东华大学 Ag3PO4/Mg-Al LDO (Layered Double Oxide) visible light composite photo catalyst, preparation and application thereof
EP2647430A1 (en) * 2012-04-05 2013-10-09 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Method for preparing a catalyst mediating H2 evolution, said catalyst and uses thereof
WO2014136783A1 (en) * 2013-03-07 2014-09-12 学校法人東京理科大学 Bismuth-vanadate-laminate manufacturing method and bismuth-vanadate laminate
CN103240073A (en) * 2013-04-26 2013-08-14 南京信息工程大学 Zn<2+>-doped BiVO4 visible-light-driven photocatalyst and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Preparation of Bi-Based Ternary Oxide Photoanodes BiVO4, Bi2WO6,and Bi2Mo3O12 Using Dendritic Bi Metal Electrodes;Donghyeon Kang et al.;《J. Phys. Chem. Lett.》;20140821;第5卷;382-389 *
PREPARATION OF LARGE PLATY PARTICLES OF Co-Al LAYERED DOUBLE HYDROXIDES;MIHOKO KAYANO et al.;《Clays and Clay Minerals》;20061231;第54卷(第3期);2994?2999 *
Synthesis, characterization and enhanced visible light photocatalytic activity of Bi2MoO6/Zn–Al layered double hydroxide hierarchical heterostructures;Haiping Li et al.;《Catal. Sci. Technol.》;20141231;第4卷;1028-1037 *

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