CN112410819A - Composite bismuth-based photoanode for photoelectrocatalytic decomposition of water and preparation method thereof - Google Patents
Composite bismuth-based photoanode for photoelectrocatalytic decomposition of water and preparation method thereof Download PDFInfo
- Publication number
- CN112410819A CN112410819A CN202011250239.6A CN202011250239A CN112410819A CN 112410819 A CN112410819 A CN 112410819A CN 202011250239 A CN202011250239 A CN 202011250239A CN 112410819 A CN112410819 A CN 112410819A
- Authority
- CN
- China
- Prior art keywords
- photoanode
- solution
- bivo
- photo
- water
- 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.)
- Pending
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 46
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- 239000007853 buffer solution Substances 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002659 electrodeposit Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002001 electrolyte material Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 5
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A composite bismuth-based photoanode for photoelectrocatalytic decomposition of water and a preparation method thereof belong to the field of preparation of photoelectrode materials. Pure BiVO4The photoanode was immersed in a borate solution (B-BiVO)4) Adsorption of tetrahedron on surface [ B (OH)4]‑The ligand is used as a passivating agent to inhibit surface charge recombination and promote the rapid transfer of surface holes; then, in B-BiVO4In-situ growth of bimetallic oxyhydroxides (e.g., Fe) on photoanodesxNi1‑xOOH、FexCo1‑xOOH、NixCo1‑xOOH) cocatalyst, increases the surface active sites of the photoanode, accelerates the transmission of holes on the interface of the photoanode and the electrolyte, and thus improves BiVO4Photoelectric water oxidation performance of (1). Based on photo-generated charges havingThe efficiency separation and the fast transmission of the cavity at the interface of the photo-anode and the electrolyte, and the prepared composite bismuth-based photo-anode can be efficiently applied to photoelectrochemical water decomposition.
Description
Technical Field
The invention belongs to the field of preparation of photoelectrode materials, and particularly relates to bismuth vanadate (BiVO)4) The photoanode is soaked in borate buffer solution for surface modification, and then a pH regulating solution impregnation method is used for loading a bimetallic oxyhydroxide cocatalyst on the surface of the photoanode to synthesize the compositeThe bismuth-based photoanode is used for the photoelectrocatalysis water decomposition reaction driven by sunlight.
Background
With the rapid development of industry and economy, the need for human to explore sustainable and clean energy to replace fossil fuels is forced to increase due to serious energy shortage and environmental pollution and other related problems. Green, clean, sustainable solar energy is currently considered to be the largest inexhaustible energy source on earth, and semiconductor materials can utilize solar energy to convert water into hydrogen and oxygen. Since Fujishima and Honda first reported the use of TiO2Since the Photoelectrochemical (PEC) decomposition of water has been carried out, PEC decomposition of water is considered as an ideal and effective technique for solving the current problems of energy shortage and environmental pollution.
The principle of photoelectrocatalysis water decomposition: that is, when the energy received by the semiconductor photo-anode is greater than or equal to the energy forbidden band width, electron-hole pairs are generated on the surface of the photo-anode, and the photo-generated electrons reach the counter electrode through the bias voltage of the external circuit to dissociate water+Reducing the hydrogen to hydrogen, and oxidizing water into oxygen by the photo-generated holes on the contact surface of the photo-anode and the electrolyte.
BiVO4As an n-type semiconductor material which is cheap, non-toxic, abundant in earth memory and good in stability, the N-type semiconductor material has a narrow band gap of 2.4eV and can easily absorb visible light. Can absorb 11 percent of spectrum under the irradiation of standard AM 1.5G sunlight, and the maximum theoretical photocurrent density can reach 7.5mA cm-2The solar hydrogen production conversion efficiency (STH) was 9.3%. However, to date, BiVO4The actual photocurrent density and STH of (a) is much lower than their theoretical values due to the weaker electron transport, slow water oxidation kinetics and lower carrier mobility resulting in BiVO4The internal charges are easy to recombine, thereby limiting BiVO4Large scale application of photoanodes. The photoelectrochemistry water oxidation performance is improved by constructing strategies such as heterojunction, element doping, cocatalyst loading, morphology regulation and the like.
BiVO reported at present4The modification for improving the performance of the photo-anode material comprises the following steps:
TABLE 1 BiVO4Comparison of photoelectrochemical Water Oxidation Performance of photoanode
[1]SHE H,YUE P,HUANG J,et al.One-step hydrothermal deposition of F:FeOOH onto BiVO4photoanode for enhanced water oxidation[J].Chem.Eng.J.,392(2020)123703.
[2]ZHANG B,WANG L,ZHANG Y,et al.Ultrathin FeOOH Nanolayers with Abundant Oxygen Vacancies on BiVO4 Photoanodes for Efficient Water Oxidation[J].Angew.Chem.Int.Ed.,57(2018)2248-2252.
[3]MENG Q,ZHANG B,FAN L,et al.Efficient BiVO4 Photoanodes by Postsynthetic Treatment:Remarkable Improvements in Photoelectrochemical Performance from Facile Borate Modification[J].Angew.Chem.Int.Ed.,58(2019)19027-19033.
Disclosure of Invention
The invention aims at the BiVO in the prior art4The problem of the photoanode material is that the borate modified BiVO prepared by compounding the bimetallic oxyhydroxide with good PEC decomposition water property4Photo-anode (expressed as B-BiVO)4) The preparation method of (1). The method obviously enhances BiVO4PEC performance of the photoanode.
The preparation method comprises the following specific steps:
(1) preparation of the BiOI as Bi source on FTO using electrodeposition: in order to electrodeposit the BiOI, an electrolyte is prepared in advance, a three-electrode system is adopted in the electrodeposition process, FTO conductive glass is used as a working electrode, a Pt electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, the working electrode is immersed in the prepared electrolyte, a voltage of-0.5V vs. Ag/AgCl is applied for 1-10 min, the BiOI is uniformly deposited on the FTO, and the BiOI is sequentially washed by deionized water and ethanol and naturally dried at room temperature.
The electrolyte pre-configuration method comprises the following steps:
weighing 2.0-5.0 g KI and 0.5-1.5 g Bi (NO)3)2·5H2O is dissolved in10-50 mL of deionized water, and then adding HNO with a certain concentration3Adjusting the pH value to be acidic, and marking as a solution A; weighing 0.1-1.5 g of p-benzoquinone, dissolving into 5-20 mL of ethanol, and marking as a solution B; mixing the AB solution and the AB solution, and stirring for 10-60 min to obtain pre-configured electrolyte; the electrolyte material dosage relation can be simultaneously expanded or reduced by the same factor according to requirements;
the pH value of the solution A is 1.2-1.8.
(2) Dropwise adding VO (acac) containing 0.1-1M on the BiOI electrode2Heating the DMSO solution in a muffle furnace at a heating rate of 1-10 ℃/min to 200-600 ℃ for 1-5 h, and converting the DMSO solution into BiVO4A photo-anode;
(3) BiVO (bismuth oxide) is added4Placing the photoanode in 0.2-2M NaOH solution, magnetically stirring for 10-40 min, washing with deionized water, and naturally drying at room temperature to obtain pure BiVO4A photo-anode;
(4) pure BiVO4Dipping the photoanode in a borate buffer solution, washing with deionized water, and naturally drying at room temperature to obtain a photoanode modified by the borate solution;
the concentration of the borate buffer provided by the invention is as follows: 0.1 to 2.0M.
The pH value of the borate buffer solution provided by the invention is as follows: 7 to 12.
The soaking time provided by the invention is as follows: 1-24 h.
(5) And (4) dipping the photo-anode obtained in the step (4) in a bimetallic salt solution to load a bimetallic oxyhydroxide cocatalyst, washing with deionized water, and naturally drying at room temperature to obtain the cocatalyst-loaded photo-anode.
The invention provides a double metal salt solution corresponding to a cocatalyst: an aqueous solution of ferric chloride and cobalt chloride, or an aqueous solution of ferric chloride and nickel chloride, or an aqueous solution of cobalt chloride and nickel chloride.
The concentration of the bimetallic salt solution provided by the invention is as follows: 1 to 100 mM.
The dipping time provided by the invention is as follows: 1-48 h.
The invention converts pure BiVO4The photoanode is soaked in borate solution to adsorb tetrahedron B on its surface(OH)4]-The ligand is used as a passivating agent to inhibit surface charge recombination and promote the rapid transfer of surface holes; then, in B-BiVO4In situ growth of bimetallic oxyhydroxide promoters (e.g., Fe) on photoanodesxNi1-xOOH、FexCo1-xOOH、NixCo1-xOOH, etc.), and increases the surface active sites of the photoanode, accelerates the transmission of holes at the interface of the photoanode and the electrolyte, thereby improving BiVO4The PEC water oxidation performance of (a). Based on effective separation of photo-generated charges and rapid transmission of holes at the interface of a photo-anode and an electrolyte, the prepared bimetallic oxyhydroxide composite B-BiVO4The photoanode can be efficiently used for PEC water splitting.
The invention has the following remarkable effects:
(1) dipping in B-BiVO by pH regulating solution4The bimetallic oxyhydroxide cocatalyst grows on the surface of the photo-anode in situ, the preparation process is simple and convenient, the raw material source is rich, the economy is high, and the method is a green, environment-friendly, nontoxic and economical photo-anode preparation method.
(2) Composite B-BiVO4/FexCo1-xThe photocurrent density of the OOH photoanode was pure BiVO4The PEC performance is greatly enhanced by more than 4.5 times that of the photoanode.
(3) Composite B-BiVO4/FexCo1-xThe surface charge transfer efficiency of the OOH photoanode is pure BiVO43.9 times of the light anode, effectively inhibits the serious recombination of electron-hole pairs, thereby enhancing the BiVO4Water oxidation kinetics of the photoanode.
(4) Composite B-BiVO4/FexCo1-xThe OOH photoanode is realized by a two-step dipping method, BiVO4The area of the photo-anode is flexible and adjustable, and the method is suitable for large-scale preparation of the photo-anode with high performance and low cost, and has clear commercialization prospect.
Drawings
FIG. 1 shows B-BiVO in example 14/FexCo1-xOOH photo-anode plane scanning electron microscope image.
FIG. 2 shows B-BiVO in example 14/FexCo1-xLinear sweep voltammogram of OOH photoanode.
FIG. 3 shows B-BiVO in example 14/FexCo1-xOOH photo-anode surface charge transfer efficiency plot.
Detailed description of the invention
In order to describe the invention in more detail, the following examples are given to further illustrate the invention, but not to limit it, in connection with the figures and examples.
Example 1
BiVO4Preparing a photo-anode:
(1) preparation of the BiOI as Bi source on FTO using electrodeposition: in order to electrodeposit the BiOI, an electrolyte is prepared in advance, a three-electrode system is adopted in the electrodeposition process, FTO conductive glass is used as a working electrode, a Pt electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, the working electrode is immersed in the prepared electrolyte, a voltage of-0.1V vs. Ag/AgCl is applied for 3min, the BiOI is uniformly deposited on the FTO, and the BiOI is sequentially washed by deionized water and ethanol and naturally dried at room temperature.
The electrolyte pre-configuration method comprises the following steps:
3.32g KI and 0.975g Bi (NO) were weighed3)2·5H2O was dissolved in 50mL deionized water and then treated with HNO3Adjusting the pH value to be acidic, and marking as a solution A; weighing 0.497g of p-benzoquinone and dissolving into 20mL of ethanol, and marking as solution B; and mixing the AB two solutions, and stirring for 30min to obtain the pre-configured electrolyte.
(2) Dropwise adding a solution containing 0.2M VO (acac) on the BiOI electrode2Heating the DMSO solution in a muffle furnace to 500 ℃ at the heating rate of 2 ℃/min for 2h, and converting the DMSO solution into BiVO4And a photo-anode.
(3) BiVO (bismuth oxide) is added4The photoanode is placed in 1M NaOH solution to be magnetically stirred for 30min, washed by deionized water and naturally dried at room temperature to obtain pure BiVO4And a photo-anode.
B-BiVO4Preparing a photo-anode:
(1) 5.0g of boric acid was weighed and dissolved in 100mL of deionized water, and NaOH solid was added to adjust the pH to be alkaline, to obtain a borate buffer.
(2) Pure BiVO4Dipping the photoanode in a borate solution, washing with deionized water, and naturally drying at room temperature to obtain B-BiVO4And a photo-anode.
B-BiVO4/FexCo1-xOOH photo-anode preparation:
(1) 120mg of FeCl was weighed3Solids and 100mg CoCl2The solid is dissolved in 100mL of deionized water in sequence to obtain FeCl3And CoCl2The aqueous solution was mixed.
(2) Dipping method is adopted to prepare B-BiVO4Loading cocatalyst on the photo-anode, soaking for 10h, washing with deionized water, and naturally drying at room temperature to obtain B-BiVO4/FexCo1-xOOH photo-anode.
Example 2
B-BiVO used in this example4The photoanode was the same as in example 1, except that the cocatalyst was supported on the surface thereof.
(1) 120mg of FeCl was weighed3Solid and 100mg NiCl2The solid is dissolved in 100mL of deionized water in sequence to obtain FeCl3And NiCl2The aqueous solution was mixed.
(2) Dipping method is adopted to prepare B-BiVO4Loading cocatalyst on the photoelectric anode, soaking for 10h, washing with deionized water, and naturally drying at room temperature to obtain B-BiVO4/FexNi1-xOOH photo-anode.
Example 3
B-BiVO used in this example4The photoanode was the same as in example 1, except that the cocatalyst was supported on the surface thereof.
(1) Weighing 100mg NiCl2Solids and 100mg CoCl2The solid is dissolved in 100mL of deionized water in sequence to obtain NiCl2And CoCl2The aqueous solution was mixed.
(2) Dipping method is adopted to prepare B-BiVO4Loading cocatalyst on the photo-anode, soaking for 10h, washing with deionized water, and naturally drying at room temperature to obtain B-BiVO4/NixCo1-xOOH photo-anode.
In the examples, the PEC performance test method for the prepared high-activity photoanode is as follows:
B-BiVO was characterized by Scanning Electron Microscope (SEM) (JEOL JSM-6701F)4/FexCo1-xMorphology of OOH photoanode.
Photoelectrochemical properties were measured by an electrochemical analyzer (CHI660C) in a standard three-electrode system using a 300W xenon lamp with an AM 1.5G filter as the Light source and the photoelectric intensity calibrated to 100mW cm by a photometer (International Light ILT 1400A)-2Ag/AgCl, Pt and a photoanode are used as a reference electrode, a counter electrode and a working electrode, respectively, wherein the electrolyte is borate buffer.
Results of the experiment
(1)B-BiVO4/FexCo1-xThe OOH photoanode is shown in figure 1 by a planar scanning electron microscope, and has the appearance of interconnected double-hole worm-shaped monoclinic crystals, rough surface and attached small grains.
(2)B-BiVO4/FexCo1-xThe OOH photoanode linear sweep voltammogram is shown in FIG. 2, and the photocurrent density is 5.11mA cm at 1.23V vs. RHE-2。
(3)B-BiVO4/FexCo1-xThe OOH photoanode surface charge transfer efficiency is 86.3% at 1.23V vs. rhe, as shown in fig. 3.
Replacing the kind of the bimetal element gives similar effects to those of example 1.
Claims (10)
1. A preparation method of a composite bismuth-based photoanode for photoelectrocatalytic decomposition of water is characterized by comprising the following specific preparation steps:
(1) preparation of the BiOI as Bi source on FTO using electrodeposition: in order to electrodeposit the BiOI, an electrolyte is prepared in advance, a three-electrode system is adopted in the electrodeposition process, FTO conductive glass is used as a working electrode, a Pt electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, the working electrode is immersed in the prepared electrolyte, the voltage of-0.5V vs. Ag/AgCl is applied for 1-10 min, the BiOI is uniformly deposited on the FTO, and the BiOI is sequentially washed by deionized water and ethanol and naturally dried at room temperature;
the electrolyte pre-configuration method comprises the following steps:
weighing 2.0-5.0 g KI and 0.5-1.5 g Bi (NO)3)2·5H2Dissolving O in 10-50 mL of deionized water, and then using HNO with a certain concentration3Adjusting the pH value to be acidic, and marking as a solution A; weighing 0.1-1.5 g of p-benzoquinone, dissolving into 5-20 mL of ethanol, and marking as a solution B; mixing the AB solution and the AB solution, and stirring for 20-60 min to obtain pre-configured electrolyte; the electrolyte material dosage relation can be simultaneously expanded or reduced by the same factor according to requirements;
(2) dropwise adding VO (acac) containing 0.1-1M on the BiOI electrode2Heating the DMSO solution in a muffle furnace at a heating rate of 1-10 ℃/min to 200-600 ℃ for 1-5 h, and converting the DMSO solution into BiVO4A photo-anode;
(3) BiVO (bismuth oxide) is added4The photoanode is placed in 0.2-2M NaOH solution to be magnetically stirred for 10-40 min, washed by deionized water and naturally dried at room temperature to obtain pure BiVO4A photo-anode;
(4) pure BiVO4Dipping the photoanode in a borate buffer solution, washing with deionized water, and naturally drying at room temperature to obtain a photoanode modified by the borate solution;
(5) and (4) dipping the photo-anode obtained in the step (4) in a bimetallic salt solution to load a bimetallic oxyhydroxide cocatalyst, washing with deionized water, and naturally drying at room temperature to obtain the cocatalyst-loaded photo-anode.
2. The preparation method of the composite bismuth-based photoanode for photoelectrocatalytic decomposition of water according to claim 1, wherein the pH value of the solution A is 1.2-1.8.
3. The method for preparing the composite bismuth-based photoanode for photoelectrocatalytic decomposition of water according to claim 1, wherein the concentration of the borate solution is 0.1-2.0M.
4. The preparation method of the composite bismuth-based photoanode for photoelectrocatalytic decomposition of water according to claim 1, wherein the pH value of the borate solution is 7-12.
5. The method for preparing the composite bismuth-based photoanode for photoelectrocatalytic decomposition of water according to claim 1, wherein the boric acid-modified BiVO4The dipping time of (a) is 1 to 24 hours.
6. The method for preparing the composite bismuth-based photoanode for photoelectrocatalytic decomposition of water according to claim 1, wherein the double metal salt solution: an aqueous solution of ferric chloride and cobalt chloride, or an aqueous solution of ferric chloride and nickel chloride, or an aqueous solution of cobalt chloride and nickel chloride.
7. The method for preparing the composite bismuth-based photoanode for photoelectrocatalytic decomposition of water according to claim 1, wherein the concentration of the double metal salt solution is 1-100 mM.
8. The preparation method of the composite bismuth-based photoanode for photoelectrocatalytic decomposition of water according to claim 1, wherein the soaking time in the step (5) is 1-20 h.
9. A composite bismuth-based photoanode prepared according to the method of any one of claims 1 to 8.
10. Use of a composite bismuth based photoanode prepared according to the method of any one of claims 1 to 8 for Photoelectrochemical (PEC) water splitting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011250239.6A CN112410819A (en) | 2020-11-10 | 2020-11-10 | Composite bismuth-based photoanode for photoelectrocatalytic decomposition of water and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011250239.6A CN112410819A (en) | 2020-11-10 | 2020-11-10 | Composite bismuth-based photoanode for photoelectrocatalytic decomposition of water and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112410819A true CN112410819A (en) | 2021-02-26 |
Family
ID=74781589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011250239.6A Pending CN112410819A (en) | 2020-11-10 | 2020-11-10 | Composite bismuth-based photoanode for photoelectrocatalytic decomposition of water and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112410819A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113136602A (en) * | 2021-04-19 | 2021-07-20 | 西北师范大学 | Preparation and application of bismuth vanadate/Vo-FeNiOOH composite photo-anode |
| CN113235124A (en) * | 2021-05-18 | 2021-08-10 | 西北师范大学 | S-FeOOH/bismuth vanadate composite photo-anode and preparation method thereof |
| CN113267549A (en) * | 2021-07-01 | 2021-08-17 | 萍乡学院 | BiVO4/CdS photo-anode, preparation method and Cu thereof2+Applications on detection |
| CN114016082A (en) * | 2021-11-10 | 2022-02-08 | 辽宁大学 | Method for directly depositing and recovering metal bismuth on conductive substrate by utilizing solar energy |
| CN114196985A (en) * | 2022-01-19 | 2022-03-18 | 辽宁大学 | BiVO4/NiF2Application of photo-anode in aspect of photocatalytic water splitting |
| CN114261956A (en) * | 2021-12-09 | 2022-04-01 | 陕西师范大学 | Photo-anode water-splitting electrolyte solution based on amino acid carbon dots |
| CN114411194A (en) * | 2022-01-20 | 2022-04-29 | 辽宁大学 | BiVO based on LSV photoelectrochemistry method4Surface state passivation method for generating oxygen vacancy on electrode surface and application thereof |
| CN114452970A (en) * | 2022-02-08 | 2022-05-10 | 权冉(银川)科技有限公司 | Material suitable for hydrogen energy and preparation process thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20150101664A1 (en) * | 2013-10-10 | 2015-04-16 | The California Institute Of Technology | Protecting the surface of a light absorber in a photoanode |
| CN107099818A (en) * | 2017-04-27 | 2017-08-29 | 西北师范大学 | The preparation and application of Ferrite/pucherite composite |
| 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 |
| CN109913896A (en) * | 2019-03-01 | 2019-06-21 | 西北师范大学 | A kind of preparation and application of the pucherite composite material of supported bi-metallic oxide nano-particles |
| CN111146004A (en) * | 2020-01-10 | 2020-05-12 | 北京化工大学 | Metal oxyhydroxide composite B-BiVO4Photoelectric anode and preparation method thereof |
-
2020
- 2020-11-10 CN CN202011250239.6A patent/CN112410819A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20150101664A1 (en) * | 2013-10-10 | 2015-04-16 | The California Institute Of Technology | Protecting the surface of a light absorber in a photoanode |
| CN107099818A (en) * | 2017-04-27 | 2017-08-29 | 西北师范大学 | The preparation and application of Ferrite/pucherite composite |
| 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 |
| CN109913896A (en) * | 2019-03-01 | 2019-06-21 | 西北师范大学 | A kind of preparation and application of the pucherite composite material of supported bi-metallic oxide nano-particles |
| CN111146004A (en) * | 2020-01-10 | 2020-05-12 | 北京化工大学 | Metal oxyhydroxide composite B-BiVO4Photoelectric anode and preparation method thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113136602A (en) * | 2021-04-19 | 2021-07-20 | 西北师范大学 | Preparation and application of bismuth vanadate/Vo-FeNiOOH composite photo-anode |
| CN113235124A (en) * | 2021-05-18 | 2021-08-10 | 西北师范大学 | S-FeOOH/bismuth vanadate composite photo-anode and preparation method thereof |
| CN113267549B (en) * | 2021-07-01 | 2023-05-30 | 萍乡学院 | BiVO 4 CdS photo-anode, preparation method and Cu thereof 2+ Application to detection |
| CN113267549A (en) * | 2021-07-01 | 2021-08-17 | 萍乡学院 | BiVO4/CdS photo-anode, preparation method and Cu thereof2+Applications on detection |
| CN114016082A (en) * | 2021-11-10 | 2022-02-08 | 辽宁大学 | Method for directly depositing and recovering metal bismuth on conductive substrate by utilizing solar energy |
| CN114016082B (en) * | 2021-11-10 | 2023-11-10 | 辽宁大学 | Method for directly depositing and recovering metal bismuth on conductive substrate by utilizing solar energy |
| CN114261956A (en) * | 2021-12-09 | 2022-04-01 | 陕西师范大学 | Photo-anode water-splitting electrolyte solution based on amino acid carbon dots |
| CN114261956B (en) * | 2021-12-09 | 2022-12-27 | 陕西师范大学 | Photoanode water-splitting electrolyte solution based on amino acid carbon dots |
| CN114196985A (en) * | 2022-01-19 | 2022-03-18 | 辽宁大学 | BiVO4/NiF2Application of photo-anode in aspect of photocatalytic water splitting |
| CN114196985B (en) * | 2022-01-19 | 2023-11-10 | 辽宁大学 | BiVO (binary organic acid) 4 /NiF 2 Application of photo-anode in photocatalytic water splitting |
| CN114411194A (en) * | 2022-01-20 | 2022-04-29 | 辽宁大学 | BiVO based on LSV photoelectrochemistry method4Surface state passivation method for generating oxygen vacancy on electrode surface and application thereof |
| CN114452970A (en) * | 2022-02-08 | 2022-05-10 | 权冉(银川)科技有限公司 | Material suitable for hydrogen energy and preparation process thereof |
| CN114452970B (en) * | 2022-02-08 | 2024-06-04 | 中鼎新材料科技(河北)有限公司 | Material suitable for hydrogen energy and preparation process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112410819A (en) | Composite bismuth-based photoanode for photoelectrocatalytic decomposition of water and preparation method thereof | |
| Ding et al. | ZIF-8 derived ZnO/TiO2 heterostructure with rich oxygen vacancies for promoting photoelectrochemical water splitting | |
| CN109913898B (en) | WO (WO)3/CuWO4Preparation method of/NiFe LDH ternary composite photoelectrode film | |
| CN111774057B (en) | High-performance heterojunction material Fe2O3/CuO photoelectrode film and preparation method and application thereof | |
| CN110344029B (en) | Preparation method of surface hydroxylated iron oxide film photo-anode material | |
| 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 | |
| CN111261413B (en) | Ti-doped alpha-Fe2O3Nanorod composite MOFs heterojunction photo-anode and preparation method and application thereof | |
| CN110655656A (en) | Cobalt metal organic framework material and preparation method and application thereof | |
| WO2022144043A1 (en) | Preparation method for heterojunction of mof-derived zinc oxide and titanium dioxide composite, and use in photoelectric water splitting | |
| CN111146004A (en) | Metal oxyhydroxide composite B-BiVO4Photoelectric anode and preparation method thereof | |
| Li et al. | Development of iron-based heterogeneous cocatalysts for photoelectrochemical water oxidation | |
| CN111569896A (en) | BiVO4-Ni/Co3O4Synthesis method of heterojunction and application of heterojunction to photoelectrolysis water | |
| CN107761127B (en) | Preparation method of polyacid and phthalocyanine jointly modified nano porous bismuth vanadate oxygen evolution electrode | |
| CN108364792B (en) | Preparation method and application of nickel-cobalt-selenium hollow spherical multilevel structure material | |
| CN111359609A (en) | Visible light response iron oxide/cuprous oxide photocatalytic film and preparation method thereof | |
| CN109308982B (en) | Preparation method of co-modified copper bismuthate nanorod photocathode | |
| CN108511198B (en) | Ni-doped BiVO4Thin-film photoelectric anode, preparation method and application thereof | |
| CN107829108B (en) | FeOOH/CdS/Ti: Fe2O3Composite photoelectrode and preparation method thereof | |
| Wang et al. | Dual-doping in the bulk and the surface to ameliorate the hematite anode for photoelectrochemical water oxidation | |
| CN111889117A (en) | Core-shell copper selenide @ nickel iron hydrotalcite electrocatalyst, preparation method thereof and application of electrocatalyst in water electrolysis | |
| CN110965073B (en) | WO containing defects3Preparation method of photoelectrode | |
| CN109402661B (en) | MIL-100(Fe)/TiO2Preparation method and application of composite photoelectrode | |
| CN111705333A (en) | Ag-Pi/BiVO4Heterogeneous combination method and application thereof in photoelectrolysis water | |
| CN109518213B (en) | NiB auxiliary agent modified bismuth vanadate nano porous film electrode and preparation method and application thereof | |
| CN115287696A (en) | Preparation method of high-efficiency indium zinc sulfide photo-anode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210226 |