CN105040025A - Double metal hydroxide-composited porous bismuth vanadate photo-electrode and preparation method thereof - Google Patents
Double metal hydroxide-composited porous bismuth vanadate photo-electrode and preparation method thereof Download PDFInfo
- Publication number
- CN105040025A CN105040025A CN201510239020.9A CN201510239020A CN105040025A CN 105040025 A CN105040025 A CN 105040025A CN 201510239020 A CN201510239020 A CN 201510239020A CN 105040025 A CN105040025 A CN 105040025A
- Authority
- CN
- China
- Prior art keywords
- electrode
- bismuth
- bismuth vanadate
- bivo
- metal hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Hybrid Cells (AREA)
Abstract
The invention provides a double metal hydroxide-composited porous bismuth vanadate photo-electrode and a preparation method thereof, wherein a composite of Co-Al double metal hydroxide and bismuth vanadate is grown on the surface of an electric-conductive glass substrate. The pore size of the bismuth vanadate is 50-120 nm and the particle size of the bismuth vanadate is 200-300 nm. The Co-Al double metal hydroxide is grown on the bismuth vanadate particles with the thickness being 10-100 nm. The preparation method includes following steps: 1) preparing a porous bismuth vanadate electrode through an electro-deposition precursor method; and 2) growing the Co-Al double metal hydroxide on the porous bismuth vanadate electrode. The method is simple in operation and is mild in reaction conditions. With zinc ion as an electro-deposition additive for controlling the size and appearance of the bismuth vanadate electrode, the method is more green and environment-friendly compared with a method in the prior art with an organic template agent or organic additives, so that the method is suitable for large-scale production. The photo-electrode can be directly used in photo-electro-chemical water oxidizing catalytic reaction. Because of excellent catalytic performance and visible light absorption capability of the Co-Al double metal hydroxide, the photo-electrode is significantly improved in water oxidizing performance.
Description
Technical field
The invention belongs to optoelectronic pole field of material preparation, be specifically related to compound porous pucherite optoelectronic pole of double-metal hydroxide and preparation method thereof, and for sunlight drive photoelectrocatalysis water decomposition.
Background technology
Modern society, to the excessive exploitation of the traditional energy such as coal, oil and natural gas and use, has caused huge energy dilemma and problem of environmental pollution.In order to realize Sustainable development, development and utilization renewable energy source industry is own through becoming the grand strategy target of countries in the world.Wherein sun power is as a kind of clean renewable energy source, and its reserves are tens thousand of times of other renewable energy sources; Sun power in use discharges CO hardly simultaneously
2isothermal chamber gas, contribute to alleviating the environmental problems such as the Greenhouse effect that the environmental pollution that causes of crude oil leakage and fuel combustion cause, this allows sun power occupy critical role in renewable energy source industry.In various Solar use mode, photocatalytic water splitting is a kind of by the effective means of transform light energy chemical energy, and its degradation production is O
2and H
2, the former is extensively present in air, and for environmental diversity provides possibility, the latter is the novel secondary energy, and its energy density is high, use procedure is pollution-free, and products of combustion is only H
2o, has efficient, clean feature.Therefore greatly develop photo-electrocatalytic technology realize light-chemical energy for alleviating energy crisis, solve the aspects such as the environmental problem that goes from bad to worse and have active effect.Due to raw material be easy to get, Stability Analysis of Structures, efficiency is higher, inorganic semiconductor material causes extensive concern as optoelectronic pole, mainly contains titanium dioxide, zinc oxide, ferric oxide, pucherite etc.The band gap of pucherite is only 2.4eV, is a kind of optoelectronic pole material with good visible light-responded ability, reaches 29% [K.Sayama in the photoelectric transformation efficiency at 420nm place, A.Nomura, Z.Zou, R.Abe, Y.AbeandH.Arakawa.Chem.Comm., 2003,2908-2909.].
The bismuth resource reserve of China ranks first in the world, reserves are approximately 240,000 tons, account for world's total reserves 75% [Wang Shuling. Chinese bismuth resource situation and countermeasure. China Metal Bulletin, 2009,48:39-41], therefore developing bismuth oxycompound optoelectronic pole material has reliable resource base.The method preparing pucherite optoelectronic pole at present mainly contains organic metal salt decomposition method [P.M.Rao, L.Cai, C.Liu, I.S.Cho, C.H.Lee, J.M.Weisse, P.Yang, andX.Zheng.NanoLett., 2014,14,1099-1105], hydrothermal method [G.XiandJ.Ye, Chem.Commun., 2010,46,1893.], galvanic deposit precursor methods [D.Kang, Y.Park, J.C.Hill, andK.-S.Choi.J.Phys.Chem.Lett., 2014,5,2994-2999.] etc.Wherein, galvanic deposit precursor methods for precursor size, pattern easily regulates and controls, and is a kind of preparation method being conducive to morphology control.But the charge-conduction performance that pucherite is more weak and higher surface reaction energy barrier become the bottleneck that its performance of restriction improves.Some method of modifying are had for these problems, it is wherein the emphasis of research to the control of its pattern and size, this is because the pattern of optoelectronic pole affects the contact area of optoelectronic pole/electrolyte interface on the one hand, on the other hand, photohole has certain diffusion length, if optoelectronic pole size can be reduced, make photohole with electron recombination before diffuse to surface participate in oxidizing reaction, then can effectively promote photoelectric current [Z.-F.Huang, L.Pan, J.-J.Zou, X.Zhang, L.Wang.Nanoscale, 2014,6,14044-14063].In addition, be the important channel of improving optoelectronic pole surface water oxidation kinetics with eelctro-catalyst compound.Double-metal hydroxide (LDH) has unique laminate structure of two kinds of (or two or more) metallic element high dispersing, shows than monometallic oxyhydroxide or the higher catalytic performance of oxide compound in electrocatalysis, photochemical catalysis, photoelectrocatalysis reaction.Therefore, LDH eelctro-catalyst and optoelectronic pole compound can be improved optoelectronic pole performance; On the other hand, the LDH containing Co or Ni has visible light-responded character, therefore can promote optoelectronic pole absorbing sunlight after having visible light-responded LDH and optoelectronic pole compound.
Summary of the invention
The object of this invention is to provide optoelectronic pole that a kind of cobalt aluminum bimetal hydroxide and porous pucherite be compounded to form and preparation method thereof, it has visible absorption character and electrocatalytic properties simultaneously, can be used for photoelectrocatalysis Water oxidize reaction process.
The compound porous pucherite optoelectronic pole of cobalt aluminum bimetal hydroxide provided by the invention, be have cobalt aluminum bimetal hydroxide and pucherite mixture in the growth of conductive glass substrate surface, wherein pucherite chemical formula is BiVO
4, crystal formation is monocline, and its hole is 50 ~ 120nm, and size of particles is 200 ~ 300nm; The chemical formula of cobalt aluminum bimetal hydroxide is Co
xal
y(OH)
z(A) nH
2o, be abbreviated as CoAl-LDH, wherein x:y represents that cobalt ion and aluminum ions mol ratio are 1 ~ 4:1, n represents hydration number, n=5 ~ 15, A represents negatively charged ion, is one or both in sulfate radical, carbonate or nitrate radical, CoAl-LDH growth is on pucherite particle, and wherein the thickness of CoAl-LDH is 10 ~ 100nm.
This CoAl-LDH compound BiVO
4the preparation method of optoelectronic pole is: the mixing salt solution of preparation containing zinc and bismuth is electrolytic solution, and solvent is that water mixes mutually with ethylene glycol.Add in electrolyzer by this electrolytic solution, using conductive glass sheet as working electrode, apply constant potential to working electrode under room temperature and carry out galvanic deposit, bismuth ion is reduced to bismuth simple substance at working electrode surface, and the zine ion in solution plays additive.Electrode surface after deposit drips the dimethyl sulphoxide solution of vanadium acetylacetonate, and then calcine, in calcination process, bismuth simple substance is converted into pucherite, and sample removes excessive vanadium oxide in basic solution afterwards, obtains porous pucherite electrode; Preparation containing the solubility mixed-salt aqueous solution of cobalt, aluminium, and adds urea and Neutral ammonium fluoride, the pucherite electrode prepared is put into this mixing salt solution, obtains CoAl-LDH compound BiVO after hydro-thermal reaction
4optoelectronic pole.
Concrete preparation process is as follows:
A. bismuth salt and zinc salt are added preparation in mixed solvent and contain the mixing salt solution of zinc and bismuth, wherein the mol ratio of bismuth salt and zinc salt is Bi:Zn=1:1 ~ 4, bismuth ion volumetric molar concentration is 5 ~ 30mmol/L: described bismuth salt is the one in Bismuth trinitrate, bismuth chloride, bismuth sulfate, is preferably Bismuth trinitrate; Described zinc salt is the one in zinc nitrate, zinc chloride, zinc sulfate, is preferably zinc nitrate; Described mixed solvent is ethylene glycol and deionized water volume ratio is the mixing solutions of 1 ~ 6:1.
B. the mixing salt solution of steps A is added in three-electrode cell as electrolytic solution, be working electrode with conductive glass, take Ag/AgCl as reference electrode, platinum filament is to electrode, adopt electrochemical workstation to apply-0.6 ~ 0.4V constant potential to working electrode, deposition total charge dosage is-7 ~-15 × 10
-2ccm
-2, conductive glass electrode complete for deposition is taken out, with ethanol purge, at room temperature seasoning 0.5 ~ 3 hour;
Described conductive glass is the SnO of doped with fluorine
2conductive glass, is abbreviated as FTO conductive glass, and this conductive glass needs before using with acetone: Virahol: the solution ultrasonic cleaning of water=1:1:1 volume ratio, and naturally dries; The working area of conductive glass is 1 ~ 50cm
2.Described electrolyzer is single chamber or two rooms electrolyzer, and potential value is the electromotive force relative to reversible hydrogen electrode;
C. the dimethyl sulphoxide solution of the vanadium acetylacetonate of 0.05 ~ 0.2mol/L is prepared, in step B, post-depositional conductive glass electrode drips 100 ~ 400 μ L, then in retort furnace 400 ~ 550 DEG C calcining 2 ~ 4 hours, be down to after room temperature until temperature and take out, put into volumetric molar concentration be the NaOH aqueous solution of 0.2 ~ 2mol/L to the complete submergence of electrode slice, mild stirring 0.5 ~ 3 hour, takes out after electrode slice with deionized water rinsing, and at 60 ~ 80 DEG C dry 0.5 ~ 6 hour, obtain porous BiVO
4electrode;
D. Co (NO is used
3)
26H
2o, Al (NO
3)
39H
2o, urea, NH
4f is hybridly prepared into mixing salt solution, and wherein total concentration of metal ions is 15 ~ 50mmol/L, Co
2+with Al
3+mol ratio be 2 ~ 4:1, the concentration of urea is 30 ~ 80mmol/L, NH
4the concentration of F is 15 ~ 50mmol/L, after stirring, is transferred in water heating kettle inner bag, by the BiVO prepared in step D
4the conducting surface of electrode is swayed downwards in water heating kettle inner bag, and growth is had BiVO
4part be immersed in completely in solution, hydro-thermal reaction 2 ~ 8h at 100 ~ 200 DEG C, after naturally cooling, take out electrode, with after deionized water rinsing in 30 ~ 60 DEG C of baking ovens dry 20 ~ 60min, obtain CoAl-LDH compound BiVO
4optoelectronic pole.
Fig. 1 is BiVO
4x-ray powder diffraction (XRD) result of electrode, occurs in figure corresponding to BiVO
4(011), (121) diffraction peak, with the BiVO of monoclinic form sheelite phase
4diffraction peak (JCPDSNo.75-1866) is consistent;
Fig. 2 is CoAl-LDH compound BiVO
4x-ray powder diffraction (XRD) result of optoelectronic pole, except BiVO
4outside the diffraction peak of FTO conductive glass sheet, there is (003), (006), (009) of LDH, (018) characteristic peak;
Fig. 3 is porous BiVO
4the scanning electron microscope (SEM) photograph (SEM) of electrode, wherein pucherite even particle distribution, surface irregularity, median size is 240nm, and hole is 70 ~ 100nm.
By CoAl-LDH compound BiVO
4optoelectronic pole is used for the performance test of photoelectricity Water oxidize reaction, and result is the Water oxidize density of photocurrent of this optoelectronic pole under 1.23V electromotive force is 0.8 ~ 1.2mA/cm
2, this value is simple BiVO
4more than 2 times of electrode.
The present invention has following unusual effect:
(1) adopt simple inorganic zinc salt as the size of additive control pucherite electrode and pattern, more traditional organic formwork agent or additive is more green, environmental protection, nontoxicity, cost is lower.
(2) the porous pucherite electrode prepared using inorganic zinc salt as additive has abundant pore structure, is conducive to high-performance, low cost optical electrode as photochemical catalyzing, is applicable to mass-producing exploitation.
(3) double-metal hydroxide and pucherite complex light electrode, double-metal hydroxide can be utilized to strengthen optoelectronic pole to visible absorption character utilize sunlight, and CoAl-LDH has good electrocatalytic properties, can significantly reduce photoelectric current take-off potential, improve efficiency of energy utilization.
Accompanying drawing explanation
Fig. 1: the BiVO that embodiment 1 obtains
4the XRD figure of electrode.
Fig. 2: the CoAl-LDH compound BiVO that embodiment 1 obtains
4the XRD figure of optoelectronic pole.
Fig. 3: the porous BiVO that embodiment 1 obtains
4the SEM figure of electrode.
Embodiment
Embodiment 1
A. 0.4851gBi (NO is taken
3)
35H
2o, 0.8925gZn (NO
3)
26H
2o joins in the mixing solutions of 50mL deionized water and 100mL ethylene glycol, is mixed with mixing salt solution;
B. acetone is used: Virahol: the solution ultrasonic cleaning FTO (SnO of doped with fluorine of water=1:1:1 volume ratio
2conductive glass) conductive glass sheet, and naturally dry conductive glass sheet; Be transferred in three-electrode cell by the mixing salt solution of steps A, with conductive glass substrate for working electrode, wherein the working area of conductive glass sheet is 2cm
2.Take Ag/AgCl as reference electrode, platinum filament is to electrode, and electrolyzer is single compartment electrolytic cell, and adopt electrochemical workstation to apply the constant negative potential of 0.01V to working electrode, the total charge dosage of galvanic deposit is-8.35 × 10
-2ccm
-2.Electrode complete for deposition is taken out, with ethanol purge, at room temperature seasoning 0.5 hour;
C. take 0.1393g vanadium acetylacetonate and be dissolved in 2mL dimethyl sulfoxide (DMSO), the electrode slice obtained drips 200 these solution of μ L in step B, then calcine 2 hours with 450 DEG C in retort furnace, be down to after room temperature until temperature and take out; Take 4gNaOH, be dissolved in 100mL deionized water, the electrode slice after calcining in step C is put into NaOH solution, gentle agitation 0.5 hour, take out with deionized water rinsing after electrode slice, and at 70 DEG C dry 0.5 hour, obtain porous BiVO
4electrode, its median size is 240nm, and hole is 70 ~ 100nm;
D. 0.3056gCo (NO is taken
3)
26H
2o, 0.1313gAl (NO
3)
39H
2o, 0.2102g urea, 0.0519gNH
4f and deionized water preparation 70mL salts solution; Stir and be transferred in water heating kettle inner bag, by the BiVO prepared in step D
4optoelectronic pole faces down and sways in water heating kettle inner bag, and grown BiVO
4part be immersed in completely in solution, hydro-thermal reaction 4h at 100 DEG C, after naturally cooling, take out optoelectronic pole, in 40 DEG C of baking ovens, dry 30min with after deionized water rinsing, obtain CoAl-LDH compound BiVO
4optoelectronic pole.
Test above-mentioned CoAl-LDH compound BiVO
4performance as optoelectronic pole: in the electrolyzer of three electrode configurations, with CoAl-LDH compound BiVO
4photoelectricity is working electrode very, and Ag/AgCl is reference electrode, and platinum filament is to electrode, and electrolyzer is single chamber or double-chamber structure; Irradiate optoelectronic pole front with the xenon source (simulated solar irradiation) of assembling AM1.5G spectral filter, light intensity is 100mW/cm
2; Utilize electrochemical workstation (CHI660C) to apply voltage, electrolytic solution is the phosphate buffer soln (potassium primary phosphate-dipotassium hydrogen phosphate) of pH=7, and concentration is 0.1mol/L; Use cyclic voltammetry (CV) to test, wherein the scanning speed of cyclic voltammetry is 0.01V/s.Test the electromotive force (E obtained
ag/AgCl) be converted into electromotive force (E to reversible hydrogen electrode
rHE): E
rHE=E
ag/AgCl+ 0.197+0.059 × pH.Result: its photoelectric current take-off potential is 0.24V, under electromotive force is 1.23V, Water oxidize generates the density of photocurrent of oxygen is 0.95mA/cm
2.
Embodiment 2
A. 0.4851gBi (NO is taken
3)
35H
2o, 0.595gZn (NO
3)
26H
2o joins in the mixing solutions of 50mL deionized water and 100mL ethylene glycol, is mixed with mixing salt solution;
B is with embodiment 1, and difference is the working area of conductive glass is 1.5cm
2, total deposited charge of galvanic deposit is-10 × 10
-2ccm
-2
C. take 0.1393g vanadium acetylacetonate and be dissolved in 2mL dimethyl sulfoxide (DMSO), the electrode slice obtained drips 150 these solution of μ L in step B, then calcine 2 hours with 450 DEG C in retort furnace, be down to after room temperature until temperature and take out; Take 4gNaOH, be dissolved in 100mL deionized water, to add in step C the electrode slice after calcining, gentle agitation 1 hour, take out with deionized water rinsing after electrode slice, and at 70 DEG C dry 0.5 hour, obtain porous BiVO
4electrode, its median size is 260nm, and hole is 60 ~ 95nm;
D. 0.4365gCo (NO is taken
3)
26H
2o, 0.1875gAl (NO
3)
39H
2o, 0.2102g urea, 0.0519gNH
4f is formulated as the 50mL aqueous solution; After salts solution is stirred, be transferred in water heating kettle inner bag, by the BiVO prepared in step D
4optoelectronic pole faces down and sways in water heating kettle inner bag, and grown BiVO
4part be immersed in completely in solution, hydro-thermal reaction 4h at 100 DEG C, after naturally cooling, take out optoelectronic pole, in 40 DEG C of baking ovens, dry 30min with after deionized water rinsing, obtain CoAl-LDH compound BiVO
4optoelectronic pole.
Adopt with embodiment 1 evaluation method, evaluation result: photoelectric current take-off potential is 0.26V, under electromotive force is 1.23V, Water oxidize generates the density of photocurrent of oxygen is 0.90mA/cm
2.
Embodiment 3
A. 0.4851gBi (NO is taken
3)
35H
2o, 0.2975gZn (NO
3)
26H
2o joins in the mixing solutions of 50mL deionized water and 100mL ethylene glycol, is mixed with mixing salt solution;
B is with embodiment 1, and difference is the constant negative potential that galvanic deposit uses is-0.18V, and total deposited charge of galvanic deposit is-9 × 10
-2ccm
-2
C. take 0.1393g vanadium acetylacetonate and be dissolved in 2mL dimethyl sulfoxide (DMSO), the electrode slice obtained drips 200 these solution of μ L in step B, then calcine 3 hours with 450 DEG C in retort furnace, be down to after room temperature until temperature and take out; Take 4gNaOH, be dissolved in 100mL deionized water, to add in step C the electrode slice after calcining, gentle agitation 1 hour, take out with deionized water rinsing after electrode slice, and at 70 DEG C dry 0.5 hour, obtain porous BiVO
4electrode, its median size is 236nm, and hole is 85 ~ 100nm;
D. 0.4365gCo (NO is taken
3)
26H
2o, 0.1875gAl (NO
3)
39H
2o, 0.1050g urea, 0.0370gNH
4f is formulated as the 50mL aqueous solution; After salts solution is stirred, be transferred in water heating kettle inner bag, by the BiVO prepared in step D
4optoelectronic pole faces down and sways in water heating kettle inner bag, and grown BiVO
4part be immersed in completely in solution, hydro-thermal reaction 6h at 100 DEG C, after naturally cooling, take out optoelectronic pole, in 40 DEG C of baking ovens, dry 30min with after deionized water rinsing, obtain CoAl-LDH compound BiVO
4optoelectronic pole.
Adopt with embodiment 1 evaluation method, evaluation result: photoelectric current take-off potential is 0.23V, under electromotive force is 1.23V, Water oxidize generates the density of photocurrent of oxygen is 0.93mA/cm
2.
Embodiment 4
A. 0.7276gBi (NO is taken
3)
35H
2o, 0.4462gZn (NO
3)
26H
2o joins in the mixing solutions of 50mL deionized water and 100mL ethylene glycol, is mixed with mixing salt solution;
B is with embodiment 1, and difference is the working area of conductive glass is 1.8cm
2, the constant negative potential that galvanic deposit uses is-0.08V, and total deposited charge of galvanic deposit is-12 × 10
-2ccm
-2
C. take 0.1393g vanadium acetylacetonate and be dissolved in 2mL dimethyl sulfoxide (DMSO), the electrode slice obtained drips 120 these solution of μ L in step B, then calcine 2 hours with 450 DEG C in retort furnace, be down to after room temperature until temperature and take out; Take 4gNaOH, be dissolved in 100mL deionized water, to add in step C the electrode slice after calcining, gentle agitation 0.5 hour, take out with deionized water rinsing after electrode slice, and at 70 DEG C dry 0.5 hour, obtain porous BiVO
4electrode, its median size is 252nm, and hole is 77 ~ 110nm.
D. 0.6984gCo (NO is taken
3)
26H
2o, 0.2250gAl (NO
3)
39H
2o, 0.1050g urea, 0.0370gNH
4f is formulated as the 60mL aqueous solution; After salts solution is stirred, be transferred in water heating kettle inner bag, by the BiVO prepared in step D
4optoelectronic pole faces down and sways in water heating kettle inner bag, and grown BiVO
4part be immersed in completely in solution, hydro-thermal reaction 3h at 100 DEG C, after naturally cooling, take out optoelectronic pole, in 40 DEG C of baking ovens, dry 30min with after deionized water rinsing, obtain CoAl-LDH compound BiVO
4optoelectronic pole.
Adopt with embodiment 1 evaluation method, evaluation result: photoelectric current take-off potential is 0.25V, under electromotive force is 1.23V, Water oxidize generates the density of photocurrent of oxygen is 0.94mA/cm
2.
Claims (2)
1. the preparation method of the compound porous pucherite optoelectronic pole of double-metal hydroxide: concrete steps are as follows:
A. bismuth salt and zinc salt are added preparation in mixed solvent and contain the mixing salt solution of zinc and bismuth, wherein the mol ratio of bismuth salt and zinc salt is Bi:Zn=1:1 ~ 4, bismuth ion volumetric molar concentration is 5 ~ 30mmol/L: described bismuth salt is the one in Bismuth trinitrate, bismuth chloride, bismuth sulfate, is preferably Bismuth trinitrate; Described zinc salt is the one in zinc nitrate, zinc chloride, zinc sulfate, is preferably zinc nitrate; Described mixed solvent is ethylene glycol and deionized water volume ratio is the mixing solutions of 1 ~ 6:1;
B. the mixing salt solution of steps A is added in three-electrode cell as electrolytic solution, be working electrode with conductive glass, take Ag/AgCl as reference electrode, platinum filament is to electrode, adopt electrochemical workstation to apply-0.6 ~ 0.4V constant potential to working electrode, deposition total charge dosage is-7 ~-15 × 10
-2ccm
-2, conductive glass electrode complete for deposition is taken out, with ethanol purge, at room temperature seasoning 0.5 ~ 3 hour;
Described conductive glass is the SnO of doped with fluorine
2conductive glass, the working area of conductive glass is 1 ~ 50cm
2; Described electrolyzer is single chamber or two rooms electrolyzer, and potential value is the electromotive force relative to reversible hydrogen electrode;
C. the dimethyl sulphoxide solution of the vanadium acetylacetonate of 0.05 ~ 0.2mol/L is prepared, in step B, post-depositional conductive glass electrode drips 100 ~ 400 μ L, then in retort furnace 400 ~ 550 DEG C calcining 2 ~ 4 hours, be down to after room temperature until temperature and take out, put into volumetric molar concentration be the NaOH aqueous solution of 0.2 ~ 2mol/L to the complete submergence of electrode slice, mild stirring 0.5 ~ 3 hour, takes out after electrode slice with deionized water rinsing, and at 60 ~ 80 DEG C dry 0.5 ~ 6 hour, obtain porous BiVO
4electrode;
D. Co (NO is used
3)
26H
2o, Al (NO
3)
39H
2o, urea, NH
4f is hybridly prepared into mixing salt solution, and wherein total concentration of metal ions is 15 ~ 50mmol/L, Co
2+with Al
3+mol ratio be 2 ~ 4:1, the concentration of urea is 30 ~ 80mmol/L, NH
4the concentration of F is 15 ~ 50mmol/L, after stirring, is transferred in water heating kettle inner bag, by the BiVO prepared in step D
4the conducting surface of electrode is swayed downwards in water heating kettle inner bag, and growth is had BiVO
4part be immersed in completely in solution, hydro-thermal reaction 2 ~ 8h at 100 ~ 200 DEG C, after naturally cooling, take out electrode, with after deionized water rinsing in 30 ~ 60 DEG C of baking ovens dry 20 ~ 60min, obtain cobalt aluminum bimetal hydroxide compound BiVO
4optoelectronic pole.
2. the compound porous pucherite optoelectronic pole of double-metal hydroxide prepared of method according to claim 1, it is for having cobalt aluminum bimetal hydroxide and pucherite mixture in the growth of conductive glass substrate surface, and wherein pucherite particle chemical formula is BiVO
4, crystal formation is monocline, and its hole is 50 ~ 120nm, and size of particles is 200 ~ 300nm; The chemical formula of cobalt aluminum bimetal hydroxide is Co
xal
y(OH)
z(A) nH
2o, wherein x:y represents that cobalt ion and aluminum ions mol ratio are that 1 ~ 4:1, n represent hydration number, n=5 ~ 15, A represents negatively charged ion, is one or both in sulfate radical, carbonate or nitrate radical, the growth of cobalt aluminum bimetal hydroxide is on pucherite particle, and its thickness is 10 ~ 100nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510239020.9A CN105040025B (en) | 2015-05-12 | 2015-05-12 | Compound porous pucherite optoelectronic pole of double-metal hydroxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510239020.9A CN105040025B (en) | 2015-05-12 | 2015-05-12 | Compound porous pucherite optoelectronic pole of double-metal hydroxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105040025A true CN105040025A (en) | 2015-11-11 |
| CN105040025B CN105040025B (en) | 2018-01-23 |
Family
ID=54446987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510239020.9A Active CN105040025B (en) | 2015-05-12 | 2015-05-12 | Compound porous pucherite optoelectronic pole of double-metal hydroxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105040025B (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186206A (en) * | 2016-07-19 | 2016-12-07 | 北京化工大学 | A kind of G@LDHs is combined BiVO4optoelectronic pole and preparation method thereof |
| CN106222685A (en) * | 2016-08-22 | 2016-12-14 | 南京航空航天大学 | A kind of WO of photoelectrocatalysis water decomposition3the preparation method of LDH laminated film |
| CN106975509A (en) * | 2017-04-20 | 2017-07-25 | 江西科技学院 | A kind of preparation method and application of nitrogen, iron codope pucherite visible light catalyst |
| CN107099818A (en) * | 2017-04-27 | 2017-08-29 | 西北师范大学 | The preparation and application of Ferrite/pucherite composite |
| CN107268021A (en) * | 2017-06-26 | 2017-10-20 | 河南大学 | A kind of NiCoAl LDH modifications di-iron trioxide complex light anode material and its preparation method and application |
| CN107324441A (en) * | 2017-07-07 | 2017-11-07 | 黄河科技学院 | Ferronickel oxyhydroxide modification pucherite optoelectronic pole and preparation method thereof, application |
| CN107354476A (en) * | 2017-06-27 | 2017-11-17 | 青岛鲁润中科环境工程技术开发有限公司 | The preparation method and applications of iron-based double-metal hydroxide/pucherite light anode |
| WO2018133197A1 (en) * | 2017-01-22 | 2018-07-26 | 天津大学 | Electrode having multiple layers of bivo4, manufacturing method for same, and uses thereof in photoelectrocatalysis |
| CN108842169A (en) * | 2018-07-02 | 2018-11-20 | 西北师范大学 | A kind of metal oxide-loaded pucherite composite material and its preparation and application |
| CN108842168A (en) * | 2018-06-29 | 2018-11-20 | 太原理工大学 | A kind of two-step electrochemical method preparation g-C3N4/ MMO compound film optoelectronic pole |
| CN109440130A (en) * | 2018-11-29 | 2019-03-08 | 山东大学 | A kind of large-sized nanoporous BiVO4 light anode and the preparation method and application thereof |
| CN109569630A (en) * | 2019-01-23 | 2019-04-05 | 西北师范大学 | A kind of pucherite composite material preparation loading nickel cobalt hydrotalcite nano particle and the application in photoelectricity water oxygen |
| CN109794232A (en) * | 2019-01-24 | 2019-05-24 | 重庆大学 | A kind of preparation method of the spherical visible light catalyst of zinc doping pucherite |
| CN109913892A (en) * | 2019-03-20 | 2019-06-21 | 齐鲁工业大学 | A method of utilizing indium sulfide/ferronickel houghite composite membrane photoelectrocatalysioxidization oxidization xylose |
| CN110308187A (en) * | 2019-07-09 | 2019-10-08 | 济南大学 | A kind of preparation method and application of porous nano pucherite/bismuth sulfide optical electro-chemistry aptamer sensor based on zinc and cobalt doped |
| CN110357223A (en) * | 2019-08-06 | 2019-10-22 | 郑州航空工业管理学院 | A kind of synergistically modified cerium oxide combination electrode of zinc bismuth and its preparation method and application |
| CN110368968A (en) * | 2019-07-15 | 2019-10-25 | 中国石油大学(北京) | NiFe-LDH/Ti3C2/Bi2WO6Nano-chip arrays and preparation method and application |
| CN111172559A (en) * | 2020-03-17 | 2020-05-19 | 北京化工大学 | Ultrathin hydrotalcite-based composite photoelectrode and application thereof in photoelectric decomposition water coupling organic matter oxidation reaction |
| CN112408556A (en) * | 2020-11-25 | 2021-02-26 | 南京工程学院 | Dispersed built-in electric field tungsten-bismuth-based array for water oxidation and preparation method thereof |
| CN112461904A (en) * | 2020-10-07 | 2021-03-09 | 江苏大学 | Preparation method and application of photoelectrochemical aptamer sensor for detecting enrofloxacin |
| CN113293393A (en) * | 2020-11-02 | 2021-08-24 | 台州学院 | Bismuth vanadate/sodium phytate/iron oxyhydroxide composite photoelectrode and preparation method and application thereof |
| CN113571717A (en) * | 2021-07-23 | 2021-10-29 | 中国人民解放军军事科学院军事医学研究院 | High-efficiency photoelectrode and preparation method and application thereof |
| CN114054018A (en) * | 2021-10-22 | 2022-02-18 | 浙江华源颜料股份有限公司 | Heterojunction material BiVO for photocatalytic degradation of norfloxacin4@LDHs |
| CN116889875A (en) * | 2023-07-28 | 2023-10-17 | 中国科学院地理科学与资源研究所 | BiVO (binary organic acid) 4 CoAlLa-LDH composite photocatalyst, and preparation method and application thereof |
Citations (9)
| 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 |
-
2015
- 2015-05-12 CN CN201510239020.9A patent/CN105040025B/en active Active
Patent Citations (9)
| 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)
| Title |
|---|
| DONGHYEON KANG ET AL.: "Preparation of Bi-Based Ternary Oxide Photoanodes BiVO4, Bi2WO6,and Bi2Mo3O12 Using Dendritic Bi Metal Electrodes", 《J. PHYS. CHEM. LETT.》 * |
| HAIPING LI ET AL.: "Synthesis, characterization and enhanced visible light photocatalytic activity of Bi2MoO6/Zn–Al layered double hydroxide hierarchical heterostructures", 《CATAL. SCI. TECHNOL.》 * |
| MIHOKO KAYANO ET AL.: "PREPARATION OF LARGE PLATY PARTICLES OF Co-Al LAYERED DOUBLE HYDROXIDES", 《CLAYS AND CLAY MINERALS》 * |
Cited By (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186206A (en) * | 2016-07-19 | 2016-12-07 | 北京化工大学 | A kind of G@LDHs is combined BiVO4optoelectronic pole and preparation method thereof |
| CN106222685A (en) * | 2016-08-22 | 2016-12-14 | 南京航空航天大学 | A kind of WO of photoelectrocatalysis water decomposition3the preparation method of LDH laminated film |
| CN106222685B (en) * | 2016-08-22 | 2018-08-07 | 南京航空航天大学 | A kind of WO of photoelectrocatalysis water decomposition3The preparation method of-LDH laminated films |
| WO2018133197A1 (en) * | 2017-01-22 | 2018-07-26 | 天津大学 | Electrode having multiple layers of bivo4, manufacturing method for same, and uses thereof in photoelectrocatalysis |
| CN106975509A (en) * | 2017-04-20 | 2017-07-25 | 江西科技学院 | A kind of preparation method and application of nitrogen, iron codope pucherite visible light catalyst |
| CN106975509B (en) * | 2017-04-20 | 2020-04-07 | 江西科技学院 | Preparation method and application of nitrogen and iron co-doped bismuth vanadate visible-light-driven photocatalyst |
| CN107099818A (en) * | 2017-04-27 | 2017-08-29 | 西北师范大学 | The preparation and application of Ferrite/pucherite composite |
| CN107268021B (en) * | 2017-06-26 | 2019-08-09 | 河南大学 | A kind of NiCoAl-LDH modification di-iron trioxide complex light anode material and its preparation method and application |
| CN107268021A (en) * | 2017-06-26 | 2017-10-20 | 河南大学 | A kind of NiCoAl LDH modifications di-iron trioxide complex light anode material and its preparation method and application |
| CN107354476A (en) * | 2017-06-27 | 2017-11-17 | 青岛鲁润中科环境工程技术开发有限公司 | The preparation method and applications of iron-based double-metal hydroxide/pucherite light anode |
| CN107324441A (en) * | 2017-07-07 | 2017-11-07 | 黄河科技学院 | Ferronickel oxyhydroxide modification pucherite optoelectronic pole and preparation method thereof, application |
| CN107324441B (en) * | 2017-07-07 | 2019-08-20 | 黄河科技学院 | Ferronickel oxyhydroxide modifies pucherite optoelectronic pole and preparation method thereof, application |
| CN108842168A (en) * | 2018-06-29 | 2018-11-20 | 太原理工大学 | A kind of two-step electrochemical method preparation g-C3N4/ MMO compound film optoelectronic pole |
| CN108842168B (en) * | 2018-06-29 | 2020-06-02 | 太原理工大学 | Two-step electrochemical method for preparing g-C3N4/MMO composite film photoelectrode |
| CN108842169A (en) * | 2018-07-02 | 2018-11-20 | 西北师范大学 | A kind of metal oxide-loaded pucherite composite material and its preparation and application |
| CN109440130A (en) * | 2018-11-29 | 2019-03-08 | 山东大学 | A kind of large-sized nanoporous BiVO4 light anode and the preparation method and application thereof |
| CN109569630A (en) * | 2019-01-23 | 2019-04-05 | 西北师范大学 | A kind of pucherite composite material preparation loading nickel cobalt hydrotalcite nano particle and the application in photoelectricity water oxygen |
| CN109794232A (en) * | 2019-01-24 | 2019-05-24 | 重庆大学 | A kind of preparation method of the spherical visible light catalyst of zinc doping pucherite |
| CN109913892A (en) * | 2019-03-20 | 2019-06-21 | 齐鲁工业大学 | A method of utilizing indium sulfide/ferronickel houghite composite membrane photoelectrocatalysioxidization oxidization xylose |
| CN109913892B (en) * | 2019-03-20 | 2021-02-02 | 齐鲁工业大学 | Method for photoelectrocatalytic oxidation of xylose by indium sulfide/nickel iron hydrotalcite composite membrane |
| CN110308187B (en) * | 2019-07-09 | 2021-05-28 | 济南大学 | Preparation method and application of photoelectrochemical aptamer sensor based on zinc and cobalt doped porous nano bismuth vanadate/bismuth sulfide |
| CN110308187A (en) * | 2019-07-09 | 2019-10-08 | 济南大学 | A kind of preparation method and application of porous nano pucherite/bismuth sulfide optical electro-chemistry aptamer sensor based on zinc and cobalt doped |
| CN110368968A (en) * | 2019-07-15 | 2019-10-25 | 中国石油大学(北京) | NiFe-LDH/Ti3C2/Bi2WO6Nano-chip arrays and preparation method and application |
| CN110357223A (en) * | 2019-08-06 | 2019-10-22 | 郑州航空工业管理学院 | A kind of synergistically modified cerium oxide combination electrode of zinc bismuth and its preparation method and application |
| CN110357223B (en) * | 2019-08-06 | 2021-07-20 | 郑州航空工业管理学院 | Zinc-bismuth cooperatively modified cerium oxide composite electrode and preparation method and application thereof |
| CN111172559A (en) * | 2020-03-17 | 2020-05-19 | 北京化工大学 | Ultrathin hydrotalcite-based composite photoelectrode and application thereof in photoelectric decomposition water coupling organic matter oxidation reaction |
| CN111172559B (en) * | 2020-03-17 | 2021-05-04 | 北京化工大学 | Ultrathin hydrotalcite-based composite photoelectrode and application thereof in photoelectric decomposition water coupling organic matter oxidation reaction |
| CN112461904B (en) * | 2020-10-07 | 2023-01-17 | 江苏大学 | Preparation method and application of photoelectrochemical aptamer sensor for detecting enrofloxacin |
| CN112461904A (en) * | 2020-10-07 | 2021-03-09 | 江苏大学 | Preparation method and application of photoelectrochemical aptamer sensor for detecting enrofloxacin |
| CN113293393A (en) * | 2020-11-02 | 2021-08-24 | 台州学院 | Bismuth vanadate/sodium phytate/iron oxyhydroxide composite photoelectrode and preparation method and application thereof |
| CN113293393B (en) * | 2020-11-02 | 2022-03-18 | 台州学院 | Bismuth vanadate/sodium phytate/iron oxyhydroxide composite photoelectrode and preparation method and application thereof |
| CN112408556A (en) * | 2020-11-25 | 2021-02-26 | 南京工程学院 | Dispersed built-in electric field tungsten-bismuth-based array for water oxidation and preparation method thereof |
| CN113571717A (en) * | 2021-07-23 | 2021-10-29 | 中国人民解放军军事科学院军事医学研究院 | High-efficiency photoelectrode and preparation method and application thereof |
| CN113571717B (en) * | 2021-07-23 | 2024-03-19 | 中国人民解放军军事科学院军事医学研究院 | Efficient photoelectrode and preparation method and application thereof |
| CN114054018A (en) * | 2021-10-22 | 2022-02-18 | 浙江华源颜料股份有限公司 | Heterojunction material BiVO for photocatalytic degradation of norfloxacin4@LDHs |
| CN114054018B (en) * | 2021-10-22 | 2024-03-08 | 浙江华源颜料股份有限公司 | Heterojunction material BiVO for photocatalytic degradation of norfloxacin 4 @LDHs |
| CN116889875A (en) * | 2023-07-28 | 2023-10-17 | 中国科学院地理科学与资源研究所 | BiVO (binary organic acid) 4 CoAlLa-LDH composite photocatalyst, and preparation method and application thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105040025B (en) | 2018-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105040025A (en) | Double metal hydroxide-composited porous bismuth vanadate photo-electrode and preparation method thereof | |
| CN107268021B (en) | A kind of NiCoAl-LDH modification di-iron trioxide complex light anode material and its preparation method and application | |
| CN109402656B (en) | Preparation method of cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode | |
| CN103708559B (en) | Tungsten trioxide nano-film with photocatalytic performance, and preparation method thereof | |
| CN108579765B (en) | Preparation of copper sulfide/bismuth vanadate double-layer film composite material and application of copper sulfide/bismuth vanadate double-layer film composite material as photoelectric anode | |
| CN108597886B (en) | A kind of organic solution and its application for modified oxidized iron light anode | |
| CN106222685A (en) | A kind of WO of photoelectrocatalysis water decomposition3the preparation method of LDH laminated film | |
| CN108193219B (en) | Phosphorized copper modified titanic oxide optoelectronic pole and preparation method thereof and the application in photoelectrocatalysis decomposition water | |
| CN111569896A (en) | BiVO4-Ni/Co3O4Synthesis method of heterojunction and application of heterojunction to photoelectrolysis water | |
| CN104525209B (en) | Iron oxide zinc ferrite hetero-junction thin-film and preparation method thereof and the application in photocatalysis | |
| CN108842168B (en) | Two-step electrochemical method for preparing g-C3N4/MMO composite film photoelectrode | |
| CN106186206B (en) | A kind of compound BiVO of G@LDHs4Optoelectronic pole and preparation method thereof | |
| CN102815748A (en) | Titanium dioxide material, preparation method thereof, and dye sensitization solar cell | |
| CN113089020B (en) | Co(OH) 2 /FePO 4 Photoelectrode thin film and application thereof in photoelectrochemical water decomposition | |
| CN108565469A (en) | A kind of cobalt-nitrogen-doped carbon composite material and preparation method | |
| CN105568309B (en) | A kind of preparation method of the optoelectronic pole of photoelectrochemical cell | |
| CN109957814A (en) | A kind of Bi-BiOI/TNA composite material and its application | |
| CN103579595A (en) | Application of zinc-based binary layered composite oxide to zinc-nickel battery electrode material | |
| CN110911170B (en) | Photo-anode material with molybdenum sulfide modified bismuth oxybromide in two-dimensional structure and preparation method thereof | |
| CN107265401A (en) | A kind of PDA/Bi AgIn5S8/TiO2Heterojunction photovoltaic pole and preparation method and purposes | |
| CN114849689B (en) | Heterojunction type composite photocatalytic material and preparation method thereof | |
| CN102553626A (en) | Preparation method of carbon-nitrogen-codoped TiO2 nano catalysis material | |
| CN109487291A (en) | A kind of photocathode preparation method, photocathode and its photoelectrochemical cell | |
| CN109402661A (en) | MIL-100(Fe)/TiO2The preparation method and applications of complex light electrode | |
| CN105225839B (en) | The preparation method of a kind of high efficiency zno-based dye-sensitized solar cell anode and prepared light anode thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |