CN113373470B - Bismuth vanadate photoanode, preparation method thereof and photoelectrochemical device - Google Patents
Bismuth vanadate photoanode, preparation method thereof and photoelectrochemical device Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 30
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 30
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 78
- 239000000758 substrate Substances 0.000 claims abstract description 60
- 239000011521 glass Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 21
- 238000002791 soaking Methods 0.000 claims abstract description 21
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 19
- 239000012266 salt solution Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000151 deposition Methods 0.000 claims abstract description 14
- 229910001868 water Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 10
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005137 deposition process Methods 0.000 claims description 5
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 48
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 26
- 230000007547 defect Effects 0.000 abstract description 26
- 239000001301 oxygen Substances 0.000 abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 abstract description 26
- 230000001678 irradiating effect Effects 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000010409 thin film Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
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- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 235000021354 omega 7 monounsaturated fatty acids Nutrition 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- FSJSYDFBTIVUFD-XHTSQIMGSA-N (e)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O FSJSYDFBTIVUFD-XHTSQIMGSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000007654 immersion Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 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
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- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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- 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
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- 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
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/087—Photocatalytic compound
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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Abstract
The invention provides a bismuth vanadate photo-anode, which comprises a transparent conductive glass substrate and BiVO formed on the transparent conductive glass substrate 4 A thin film, wherein, the BiVO 4 The film is subjected to a treatment process of soaking in an inorganic salt solution of metal ions and irradiating with ultraviolet rays to enrich the surface with oxygen defects. The preparation method comprises the following steps: s10, providing a transparent conductive glass substrate and pretreating the transparent conductive glass substrate; s20, depositing BiVO with a nano-porous structure on the pretreated transparent conductive glass substrate 4 A film; s30, mixing BiVO 4 Soaking the film in an inorganic salt solution of metal ions and irradiating by using ultraviolet rays to prepare the bismuth vanadate photo-anode. In the invention, oxygen defects are introduced to the surface of the bismuth vanadate photo-anode through the combined action of the metal ion solution and ultraviolet rays, the abundant oxygen defects promote the efficient separation of photo-generated carriers, and the bismuth vanadate photo-anode can be used as a photo-anode for catalyzing and decomposing water and shows excellent photoelectric conversion performance.
Description
Technical Field
The invention relates to the technical field of photoelectrochemical devices, in particular to a bismuth vanadate photo-anode and a preparation method thereof, and also relates to a photoelectrochemical device comprising the bismuth vanadate photo-anode.
Background
Photoelectrochemistry (PEC) is a promising method of converting solar energy into storable chemical fuels. The development of a low-cost, efficient and stable semiconductor-based photoelectrode is a key step in achieving cost-effective PEC energy conversion. For water splitting redox couples, p-type copper-based metal oxides have appropriate band gap values and favorable band edges, and a high-efficiency copper-based photocathode is combined with a high-performance photoanode, so that a high-efficiency laminated device can be constructed, water can be split without bias voltage, and the copper-based photocathode becomes a good candidate material for PEC solar energy conversion application.
Among the numerous photoanode materials, bismuth vanadate (BiVO) 4 ) The photo-anode has a narrow energy gap of about 2.4eV, a suitable energy band position, excellent photoelectrochemical stability of an aqueous solution, abundant reserves, and no toxicity, and thus has attracted attention. BiVO 4 Theoretical maximum photocurrent density (J) of photoanode max ) Is 7.5mA cm -2 However, the actual photoelectrocatalytic decomposition water current density (J) H2O ) Much less than its theoretical value. According to the previous report, J H2O ＝J max ×η abs ×η sep ×η trans Wherein eta abs Is the light absorption efficiency, η sep Is the charge separation efficiency, eta trans Is the surface carrier transfer efficiency. At present BiVO 4 Eta of photo-anode sep And η trans The method is poor, and the self instability further limits the improvement and practical application of the photoelectric conversion efficiency.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a bismuth vanadate photoanode and a preparation method thereof, so as to solve the problem that the charge separation efficiency and the surface carrier transfer efficiency of the existing bismuth vanadate photoanode are poor.
In order to solve the above technical problems, an aspect of the present invention is to provide a bismuth vanadate photoanode comprising a transparent conductive glass substrate and BiVO having a nanoporous structure formed on the transparent conductive glass substrate 4 A thin film, wherein, the BiVO 4 The film is subjected to a treatment process of soaking in an inorganic salt solution of metal ions and irradiating with ultraviolet rays to enrich the surface with oxygen defects.
Specifically, the thickness of the conductive glass substrate is 2.0-2.2 mm, the light transmittance is more than 80%, and the thickness of the conductive material film layer with the square resistance of 6-7 omega is 300-350 nm; the BiVO 4 The thickness of the film is 500 nm-1500 nm.
Specifically, the inorganic salt solution of the metal ions is selected from any one of sulfate, nitrate or chloride solutions of copper ions, iron ions, nickel ions or cobalt ions.
In order to solve the above technical problems, another aspect of the present invention is to provide a method for preparing a bismuth vanadate photo-anode, including:
s10, providing a transparent conductive glass substrate and pretreating the transparent conductive glass substrate;
s20, depositing BiVO with a nano-porous structure on the pretreated transparent conductive glass substrate 4 A film;
s30, mixing the BiVO 4 Soaking the film in an inorganic salt solution of metal ions and irradiating the BiVO with ultraviolet rays 4 A film, preparing the bismuth vanadate photo-anode;
wherein the inorganic salt solution of the metal ions is selected from any one of sulfate, nitrate or chloride solution of copper ions, iron ions, nickel ions or cobalt ions.
Specifically, in step S30, the concentration of the inorganic salt solution of metal ions is 0.01M to 0.1M, and the illumination intensity of the ultraviolet light irradiation is 5mW cm -2 ～30mW cm -2 The time for soaking and irradiation is 5-30 h.
Specifically, the step S10 includes:
immersing the transparent conductive glass substrate cut to a preset size into a mixed solution of acetone and an alcohol solvent for ultrasonic treatment for 10-20 min; wherein the mass ratio of the acetone to the alcohol solvent is 1: 1-1: 2;
immersing the transparent conductive glass substrate into a mixed solution of hydrogen peroxide and concentrated sulfuric acid, standing and cleaning for 5-15 min; wherein the mass ratio of the hydrogen peroxide to the concentrated sulfuric acid is 3: 1-4: 1;
and soaking the transparent conductive glass substrate in water or alcohol solvent for 5-10 min, and drying.
Specifically, the step S20 includes:
preparing a precursor BiOI film by a three-electrode deposition process at room temperature by taking a transparent conductive glass substrate as a deposition electrode, a Pt electrode as a counter electrode and an Ag/AgCl electrode as a reference electrode;
cleaning and drying the prepared precursor BiOI film, dropwise adding a dimethyl sulfoxide solution containing 0.3-0.5M of acetylacetonatovanadium onto the precursor BiOI film, continuously heating in a muffle furnace at 400-500 ℃ for 1-3 h, and converting the precursor BiOI film into BiVO 4 A film;
the BiVO obtained is 4 Soaking the film in 0.1-2.0M NaOH solution, slowly stirring for 20-30 min, cleaning the surface with deionized water, and drying to obtain BiVO with a nano-porous structure 4 A film.
Specifically, the preparation method further comprises the step of preparing the electrodeposition solution, which comprises the following steps:
will be 1 × 10 -2 M～2.5×10 -2 Bi (NO) of M 3 ) 3 ·5H 2 Dissolving O and 0.3-0.5M NaI in HNO 3 Obtaining a solution A in the solution;
and mixing the solution A with absolute ethyl alcohol containing 2.0-3.0M p-benzoquinone, and stirring to obtain the electrodeposition solution.
Specifically, in the three-electrode deposition process, deposition is carried out at a constant potential of-0.01V for 1-10 min relative to an Ag/AgCl reference electrode.
The invention also provides a photoelectrochemical device comprising a bismuth vanadate photoanode as described above.
BiVO, a bismuth vanadate photo-anode provided by the embodiment of the invention 4 The film layer is soaked in an inorganic salt solution of metal ions and is irradiated by ultraviolet rays, so that the surface of the film layer is rich in oxygen defects, the introduction of the surface oxygen defects can remarkably promote the migration of holes, reduce the recombination of surface charges and increase the number of surface active sites, and the oxygen defects can induce the driving force of the outward capture of the holes, drive the migration of high-oxidizing holes at the interface of the photoanode/electrolyte and improve the photoelectric conversion efficiency. The preparation method of the bismuth vanadate photo-anode has the advantages of simple equipment and process, low cost, uniform appearance and wide application prospect in the field of photoelectrocatalysis.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention or in the description of the prior art will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flowchart illustrating steps of a method for preparing a bismuth vanadate photo-anode according to the present invention;
FIG. 2 shows that BiVO with a nano-porous structure is prepared in example 1 of the present invention 4 SEM images of photoanodes;
FIG. 3 shows that CuSO with different concentrations is obtained by the preparation method in example 2 of the present invention 4 BiVO under solution treatment 4 A photo-response current J-V curve chart of the photo-anode;
FIG. 4 shows BiVO obtained by the preparation of example 3 of the present invention under irradiation of ultraviolet light at different times 4 A photo-response current J-V curve chart of the photo-anode;
FIG. 5 shows a BiVO of a comparative group prepared in example 4 of the present invention 4 A photo-response current J-V curve chart of the photo-anode;
FIG. 6 shows the optimum conditions in example 4 of the present inventionPreparing to obtain BiVO 4 SEM image of photo-anode;
FIGS. 7a-7d are BiVO prepared under the optimal conditions in example 4 of the present invention 4 XPS profile of photoanode.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "horizontal", "inner", "outer", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed in a specific orientation, and operate, and thus, should not be construed as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In order to solve the problem of the charge separation efficiency (eta) of the existing bismuth vanadate photoanode sep ) And surface carrier transfer efficiency (η) trans ) In order to solve the problem of poor performance, the embodiment of the invention provides a bismuth vanadate photo-anode and a preparation method thereof.
The embodiment of the invention firstly provides a bismuth vanadate photo-anode, and the bismuth vanadate (BiVO) 4 ) The photoanode comprises a transparent conductive glass substrate and BiVO with a nano-porous structure formed on the transparent conductive glass substrate 4 A thin film, wherein, the BiVO 4 Soaking the filmIn an inorganic salt solution of metal ions and using a treatment process of ultraviolet ray irradiation to make the surface rich in oxygen defects.
The inorganic salt solution of the metal ions is selected from any one of sulfate, nitrate or chloride solution of copper ions, iron ions, nickel ions or cobalt ions. For example CuSO 4 Solution, Cu (NO) 3 ) 2 Solution, CuCl 2 Solution, Fe 2 (SO 4 ) 3 Solution, Fe (NO) 3 ) 3 Solution, FeCl 3 Solution, NiSO 4 Solution, Ni (NO) 3 ) 2 Solution, NiCl 2 Solution, CoSO 4 Solution, Co (NO) 3 ) 2 Solution, CoCl 2 And (3) solution. CuSO is preferably used 4 And (3) solution.
Oxygen defects are introduced to the surface of the bismuth vanadate photo-anode under the combined action of the metal ion solution and ultraviolet light, the introduction of the surface oxygen defects can remarkably promote the migration of holes, reduce the recombination of surface charges and increase the number of surface active sites, and the oxygen defects can induce the driving force of the holes for capturing outwards, so that the high-oxidizing hole migration at the interface of the photo-anode/electrolyte is driven, and the photoelectric conversion efficiency is improved.
In a preferred scheme, the thickness of the conductive glass substrate is 2.0 mm-2.2 mm, the light transmittance is more than 80%, the sheet resistance is 6 omega-7 omega, and the thickness of the conductive material film layer is 300 nm-350 nm. For example, in some specific schemes, the conductive glass substrate is an FTO glass substrate or an ITO glass substrate, and the thickness of the FTO film layer or the ITO film layer is 300nm to 350 nm; the BiVO 4 The thickness of the film is 500 nm-1500 nm.
The embodiment of the present invention further provides a preparation method of the bismuth vanadate photo-anode, referring to fig. 1, the preparation method includes the following steps:
step S10: providing a transparent conductive glass substrate and pretreating the transparent conductive glass substrate.
In a preferred scheme, the thickness of the conductive glass substrate is 2.0 mm-2.2 mm, the light transmittance is more than 80%, the sheet resistance is 6 omega-7 omega, and the thickness of the conductive material film layer is 300 nm-350 nm. For example, in some specific schemes, the conductive glass substrate is an FTO glass substrate or an ITO glass substrate, and the thickness of the FTO film layer or the ITO film layer is 300nm to 350 nm.
In a preferred embodiment, the pretreatment of the transparent conductive glass substrate specifically comprises the following steps:
s101, cutting the transparent conductive glass substrate into a preset size, such as 2 x 4cm 2 。
S102, immersing the transparent conductive glass substrate cut to the preset size into a mixed solution of acetone and an alcohol solvent for ultrasonic treatment for 10-20 min; wherein the mass ratio of the acetone to the alcohol solvent is preferably 1: 1-1: 2; the alcohol solvent is, for example, absolute ethanol, methanol or isopropanol.
S103, immersing the transparent conductive glass substrate cleaned in the step S102 into a mixed solution of hydrogen peroxide and concentrated sulfuric acid, standing and cleaning for 5-15 min; the mass ratio of the hydrogen peroxide to the concentrated sulfuric acid is preferably 3: 1-4: 1.
And S104, soaking the transparent conductive glass substrate cleaned in the step S103 in water or an alcohol solvent for 5-10 min, and then drying the transparent conductive glass substrate, wherein the alcohol solvent is absolute ethyl alcohol, methanol or isopropanol.
Specifically, the transparent conductive glass substrate was subjected to a drying treatment with nitrogen gas, which was high-purity nitrogen gas having a purity of 99.999%.
It can be understood that the invention can remove the pollutants attached to the surface of the substrate by pretreating the transparent conductive glass substrate, ensure the surface of the substrate to be flat and clean, and improve the hydrophilicity of the conductive side of the substrate, thereby being beneficial to the subsequent nanoporous BiVO 4 The film is uniformly grown on the surface of the substrate.
Step S20: depositing BiVO with a nano porous structure on the pretreated transparent conductive glass substrate 4 A film.
In a preferred scheme, BiVO with a nano porous structure is deposited on a pretreated transparent conductive glass substrate 4 The film comprises the following steps:
s201: and immersing the pretreated transparent conductive glass substrate serving as a deposition electrode, a Pt electrode serving as a counter electrode and an Ag/AgCl (saturated KCl solution) electrode serving as a reference electrode into the electrodeposition solution, and preparing the precursor BiOI film by a three-electrode deposition method at room temperature.
In a preferred embodiment, the method further comprises the step of preparing the electrodeposition solution, comprising: will be 1 × 10 -2 M～2.5×10 -2 Bi (NO) of M 3 ) 3 ·5H 2 O and 0.3M to 0.5M NaI are dissolved in HNO 3 Obtaining a solution A in the solution; and mixing the solution A with absolute ethyl alcohol containing 2.0-3.0M p-benzoquinone, and stirring for 5-10 min to obtain the electrodeposition solution.
Specifically, in the three-electrode deposition process, deposition is carried out at a constant potential of-0.01V for 1min to 10min, preferably 6min, relative to an Ag/AgCl reference electrode.
S202: and washing off redundant residual liquid on the surface of the BiOI film obtained after deposition by using absolute ethyl alcohol, transferring the BiOI film to a drying box, and drying for 10-20 min at 40-60 ℃.
S203: containing 0.3-0.5M vanadium acetylacetonate (VO (acac)) 2 ) Dropwise adding dimethyl sulfoxide (DMSO) solution on the precursor BiOI film, continuously heating for 1-3 h in a muffle furnace at 400-500 ℃, and converting the precursor BiOI film into BiVO 4 A film. In the preferred scheme, the temperature rise rate of the muffle furnace is 3 ℃/min.
S204: the obtained BiVO 4 Soaking the film in 0.1-2.0M NaOH solution, stirring for 20-30 min, cleaning the surface with deionized water, and drying to obtain BiVO with a nano-porous structure 4 A film.
Step S30: subjecting the BiVO to 4 Soaking the film in an inorganic salt solution of metal ions and irradiating the BiVO with ultraviolet rays 4 And preparing the bismuth vanadate photo-anode.
Wherein the inorganic salt solution of the metal ions is selected from any one of sulfate, nitrate or chloride solution of copper ions, iron ions, nickel ions or cobalt ions. For example CuSO 4 Solution, Cu (NO) 3 ) 2 Solution, CuCl 2 Solution, Fe 2 (SO 4 ) 3 Solution, Fe (NO) 3 ) 3 Solution, FeCl 3 Solution, NiSO 4 Solution, Ni (NO) 3 ) 2 Solution, NiCl 2 Solution, CoSO 4 Solution, Co (NO) 3 ) 2 Solution, CoCl 2 And (3) solution. CuSO is preferably used 4 And (3) solution.
Specifically, in step S30, the concentration of the inorganic salt solution of metal ions is 0.01M to 0.1M, and the illumination intensity of the ultraviolet light irradiation is 5mW cm -2 ～30mW cm -2 The time for soaking and irradiation is 5-30 h.
In the most preferred scheme, the inorganic salt solution of the metal ions is selected as CuSO 4 The solution, the concentration of which is 0.05M, is soaked for 20h of irradiation time.
Further, in step S30, after the immersion irradiation is completed, the BiVO is taken out 4 Photo-anode, and then to said BiVO 4 Cleaning and drying the surface of the photo-anode to finally obtain the BiVO with the surface rich in oxygen defects 4 And a photo-anode.
The BiVO provided by the above embodiment of the invention 4 The preparation method of the photo-anode is characterized in that oxygen defects are introduced into BiVO by soaking in an inorganic salt solution of metal ions and combining with a method of ultraviolet ray radiation 4 The surface of the photoanode is not introduced with other miscellaneous elements, and rich oxygen defects promote the efficient separation of photon-generated carriers, thereby effectively improving BiVO 4 Photoelectric conversion efficiency. The preparation method has the advantages of simple equipment and process, low cost, good economic benefit and good practical application prospect.
The embodiment of the invention also provides a photoelectrochemical device, for example, a photoelectrochemical device which uses light irradiation to decompose water to generate hydrogen, and comprises a photocathode and a photoanode, wherein the photoanode adopts the BiVO provided by the embodiment of the invention 4 And a photo-anode.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It is composed ofIn the following examples, the inorganic salt solution of metal ions is selected to be CuSO 4 The solution is specifically described.
It should be noted that the following examples relate to photoelectrochemical tests:
1. all photoelectrochemical measurements were performed using a CHI660e potentiostat in a typical three electrode cell at room temperature with a photoanode (BiVO in the examples of the invention) 4 Photoanode) as the working electrode, Pt as the counter electrode, and Ag/AgCl as the reference electrode.
2. The electrolyte is 0.5M Na 2 SO 4 Buffered to pH 7.
3. The test area is 1 x 1cm 2 。
4. Photoelectrochemical measurements were performed using a peccell PEC-L01 solar simulator integrating a 300W xenon arc lamp and an AM 1.5G filter under 1 simulated sunlight exposure.
5. For photocurrent measurements, Linear Sweep Voltammetry (LSV) was used, with the sweep rate being maintained at 0.05V/s.
6. According to Nernst equation (E) RHE ＝E Ag/AgCl +0.0591pH+E 0 Ag/Cl ) Converting the measured potential of the Ag/AgCl electrode (saturated KCl solution) into a reversible hydrogen electrode (V) RHE ) An electrical potential.
Example 1: preparation of BiVO with nano-porous structure on conductive glass substrate 4 Film(s)
(1) Selecting an FTO glass substrate, and pretreating the FTO glass substrate, wherein the method specifically comprises the following steps:
a. cutting FTO glass substrate into 2 × 4cm by using glass cutter 2 Size;
b. immersing the cut FTO glass substrate into a 1:1 mixed solution of acetone and absolute ethyl alcohol, and ultrasonically cleaning for 15 min;
c. soaking the FTO glass substrate in a mixed solution of hydrogen peroxide and concentrated sulfuric acid at a ratio of 3:1, and standing for 10 min;
d. then soaking the FTO glass substrate in absolute ethyl alcohol, and standing for 15 min;
e. finally using high-purity nitrogen (N) 2 99.999%) of the FTO glass substrate is dried。
(2) The preparation method of the electrodeposition liquid comprises the following steps:
A. mixing 2.25X 10 -2 M Bi(NO3) 3 ·5H 2 O and 0.4M NaI in 50ml HNO 3 Obtaining a solution A in an aqueous solution (PH is approximately equal to 1.2);
B. the solution A was mixed with 22.5mL of anhydrous ethanol containing 2.5M p-benzoquinone, and vigorously stirred for 5min to obtain an electrodeposition solution.
(3) And (2) taking the FTO glass substrate pretreated in the step (1) as a deposition electrode, taking Pt as a counter electrode and an Ag/AgCl (saturated KCl solution) electrode as a reference electrode, immersing the FTO glass substrate into an electrodeposition solution, and preparing a precursor BiOI film by a three-electrode deposition method at a constant potential of-0.01V at room temperature for 6 min.
(4) And (3) washing the deposited BiOI film by using absolute ethyl alcohol to remove excessive residual liquid on the surface, transferring the BiOI film to a drying box, and drying the BiOI film for 15min at the temperature of 60 ℃.
(5) 0.1ml of a solution containing 0.4M vanadium acetylacetonate VO (acac) 2 The dimethyl sulfoxide DMSO solution is dripped on the prepared BiOI film and is continuously heated in a muffle furnace at the temperature of 450 ℃ for 2h, the heating rate is 3 ℃/min, and the BiOI film is converted into BiVO 4 A material.
(6) The obtained BiVO 4 Soaking the material in 1M NaOH solution, slowly stirring for 30min, cleaning the surface with deionized water and drying, thereby preparing the BiVO with the nano-porous structure on the conductive glass substrate 4 Film forming of preliminary BiVO 4 And (3) a photo-anode structure.
BiVO was measured by SEM as shown in FIG. 2 4 From the top view of the microstructure of the photoanode, it can be observed that BiVO 4 The surface of the film is formed into a nano porous structure formed by connecting the sintered micro particles.
Example 2: different CuSO 4 BiVO with oxygen-rich defect on surface obtained under solution concentration 4 Photo-anode
(1) The nanoporous BiVO is prepared by the same method as the method in the above example 1 4 And a photo-anode.
(2) BiVO obtained in the step (1) 4 The photo-anode is soaked in 0.01M,0.02M, 0.05M and 0.1M CuSO 4 Placing in dark room, and irradiating with ultraviolet light at intensity of 10Wm cm for 10 hr -2 。
(3) Taking out the BiVO 4 Photo-anode, and then to said BiVO 4 The surface of the photo-anode is cleaned by deionized water and dried to obtain BiVO with oxygen-rich defects on the surface 4 And (6) a photo-anode.
As shown in FIG. 3, it can be seen from the J-V curve that 0.05M CuSO is applied under the same UV irradiation time 4 The solution co-processing effect is optimal, and the photoresponse current density is maximum.
Example 3: BiVO with oxygen-rich defect on surface obtained under different ultraviolet irradiation time 4 Photo-anode
(1) The nanoporous BiVO is prepared by the same method as the method in the above example 1 4 And a photo-anode.
(2) BiVO obtained in the step (1) 4 The photo-anode is soaked in 0.05M CuSO 4 Placing in dark room, and irradiating with ultraviolet light at intensity of 10Wm cm for 5 hr, 10 hr, 20 hr and 30 hr -2 。
(3) Taking out the BiVO 4 Photo-anode, and then to said BiVO 4 The surface of the photo-anode is cleaned by deionized water and dried to obtain BiVO with oxygen-rich defects on the surface 4 And a photo-anode.
As shown in FIG. 4, it can be seen from the J-V curve that under the same CuSO 4 Under the soaking of the solution concentration, the performance is best when the ultraviolet light is irradiated for 20 hours, and the photoresponse current density is maximum.
Example 4: comparative experiment
(1) The nanoporous BiVO is prepared by the same method as the method in the above example 1 4 And a photo-anode.
(2) BiVO obtained in the step (1) 4 The photo-anode is soaked in 0.05M CuSO 4 Standing for 20h in the solution, taking out, washing with deionized water, and drying to obtain CuSO 4 -BiVO 4 And a photo-anode.
(3) BiVO obtained in the step (1) 4 Placing the photo-anode in a dark room and irradiating with ultraviolet light with intensity of 10 Wmc for 20hm -2 To obtain UV-BiVO 4 And a photo-anode.
(4) BiVO obtained in the step (1) 4 The photo-anode is soaked in 0.05M CuSO 4 Placing in a dark room, irradiating with ultraviolet light at intensity of 10Wm cm for 20 hr -2 Taking out, washing with deionized water and drying to obtain CuSO 4 -UV-BiVO 4 And a photo-anode.
As shown in FIG. 5, it can be seen from the J-V curve that CuSO is used in comparison to CuSO alone 4 Solution treatment or ultraviolet irradiation, and BiVO (BiVO) is improved by using metal solution to assist ultraviolet irradiation co-treatment 4 The catalytic effect is better. Soaking in 0.05M CuSO under optimal conditions 4 In solution, and irradiated with ultraviolet light for 20h, and the photoresponse current is about 2.0mA/cm at 1.23V 2 RHE, pure BiVO 4 The photo-anode is more than 3 times of the photo-anode, and has excellent water decomposition performance by photoelectrocatalysis.
As shown in FIG. 6, BiVO was processed under optimum conditions 4 SEM test of the photo-anode can observe pure phase BiVO 4 The comparative structure was not significantly changed. Meanwhile, the EDS spectrum analysis obtained the element distribution as shown in Table 1. BiVO after treatment as shown in Table 1 4 The photoanode had no Cu heteroatom incorporated.
Table 1:
BiVO under optimal condition treatment 4 The photoanode was subjected to XPS testing: as shown in FIG. 7a, it can also be found that BiVO is treated 4 The photo-anode did not detect the Cu element signal. As shown in FIG. 7b, the peaks for 529.6eV and 531.2eV are attributed to the O1s peak, which is defined as lattice oxygen (O) L ) And defect oxygen (O) V ) Typical value of the method, the oxygen defects on the surface of the material treated by the method are obviously increased, and BiVO is greatly improved 4 The photoelectric activity of (3); in FIG. 7b, the curve corresponding to the circle mark is O L Curve and O V The curves are superposed to form a curve. As shown in fig. 7c and 7d show that the signal intensity of Bi element and V element of the material treated by the method is relatively improved, so that the relative reduction of O element and the increase of surface oxygen defects can also be shown. Due to the formation of surface oxygen defects, with pure phase BiVO 4 Compared with Bi element and V element, the bonding energy is reduced slightly, and the bonding of the surface and the reactant is facilitated.
In summary, the bismuth vanadate photo-anode, BiVO, provided in the embodiments of the present invention 4 The film layer is soaked in an inorganic salt solution of metal ions and is irradiated by ultraviolet rays, so that the surface of the film layer is rich in oxygen defects, the introduction of the surface oxygen defects can remarkably promote the migration of holes, reduce the recombination of surface charges and increase the number of surface active sites, and the oxygen defects can induce the driving force of the outward capture of the holes, drive the migration of high-oxidizing holes at the interface of the photoanode/electrolyte and improve the photoelectric conversion efficiency. The preparation method of the bismuth vanadate photo-anode has the advantages of simple equipment and process, low cost, uniform appearance and wide application prospect in the field of photoelectrocatalysis.
The foregoing is considered as illustrative only of the preferred embodiments of the invention, and is presented merely for purposes of illustration and description of the principles of the invention and is not intended to limit the scope of the invention in any way. Any modifications, equivalents and improvements made within the spirit and principles of the invention and other embodiments of the invention without the creative effort of those skilled in the art are included in the protection scope of the invention based on the explanation here.
Claims (5)
1. A method for preparing a bismuth vanadate photo-anode is characterized by comprising the following steps:
s10, providing a transparent conductive glass substrate and pretreating the transparent conductive glass substrate;
s20, depositing BiVO with a nano-porous structure on the pretreated transparent conductive glass substrate 4 A film;
s30, mixing the BiVO 4 Immersing the film in an inorganic salt solution of metal ions and using violetExternal light irradiates the BiVO 4 A film, preparing the bismuth vanadate photo-anode;
wherein the inorganic salt solution of metal ions is CuSO 4 Solution of said CuSO 4 The concentration of the solution is 0.01-0.1M, and the illumination intensity of the ultraviolet ray irradiation is 5mW cm -2 ~30 mW cm -2 And the soaking and irradiation time is 5-30 h.
2. The method according to claim 1, wherein the step S10 comprises:
immersing the transparent conductive glass substrate cut to a preset size into a mixed solution of acetone and an alcohol solvent for ultrasonic treatment for 10-20 min; wherein the mass ratio of the acetone to the alcohol solvent is 1: 1-1: 2;
immersing the transparent conductive glass substrate into a mixed solution of hydrogen peroxide and concentrated sulfuric acid, standing and cleaning for 5-15 min; wherein the mass ratio of the hydrogen peroxide to the concentrated sulfuric acid is 3: 1-4: 1;
and soaking the transparent conductive glass substrate in water or an alcohol solvent for 5 min-10 min, and then drying.
3. The method according to claim 1, wherein the step S20 comprises:
preparing a precursor BiOI film by a three-electrode deposition process at room temperature by taking a transparent conductive glass substrate as a deposition electrode, a Pt electrode as a counter electrode and an Ag/AgCl electrode as a reference electrode;
cleaning and drying the prepared precursor BiOI film, dropwise adding a dimethyl sulfoxide solution containing 0.3-0.5M of acetylacetonatovanadium onto the precursor BiOI film, continuously heating for 1-3 h in a muffle furnace at 400-500 ℃, and converting the precursor BiOI film into BiVO 4 A film;
the BiVO obtained is 4 Soaking the film in 0.1-2.0M NaOH solution, slowly stirring for 20-30 min, cleaning the surface with deionized water, and drying to obtain BiVO with a nano porous structure 4 A film.
4. The method of claim 3, wherein the method further comprises a step of preparing an electrodeposition solution comprising:
will be 1 × 10 -2 M ~2.5×10 -2 Bi (NO) of M 3 ) 3 ·5H 2 Dissolving O and 0.3-0.5M NaI in HNO 3 Obtaining a solution A in the solution;
and mixing the solution A with absolute ethyl alcohol containing 2.0-3.0M p-benzoquinone, and stirring to obtain the electrodeposition solution.
5. The method for preparing the bismuth vanadate photoanode according to claim 3 or 4, wherein in the three-electrode deposition process, deposition is performed at a constant potential of-0.01V for 1min to 10min relative to an Ag/AgCl reference electrode.
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