CN112619647A - Preparation method of Co-MOF derived cobaltosic oxide composite titanium dioxide heterojunction and application of electrolyzed water - Google Patents
Preparation method of Co-MOF derived cobaltosic oxide composite titanium dioxide heterojunction and application of electrolyzed water Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000012921 cobalt-based metal-organic framework Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title abstract description 32
- 239000004408 titanium dioxide Substances 0.000 title abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 38
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 38
- 239000011521 glass Substances 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 238000002791 soaking Methods 0.000 claims abstract description 17
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002073 nanorod Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 78
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012621 metal-organic framework Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000010335 hydrothermal treatment Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 239000011941 photocatalyst Substances 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 238000004502 linear sweep voltammetry Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/33—
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- B01J35/39—
-
- 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
-
- 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
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- 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
Abstract
The invention belongs to the technical field of composite materials, and relates to Co-MOF (metal organic framework) -derived cobaltosic oxide composite titanium dioxide (Co)3O4/TiO2) The preparation method of the heterojunction comprises the following steps: firstly, soaking a cleaned FTO glass sheet into HCl solution of tetrabutyl titanate, and preparing a loaded TiO after hydrothermal treatment2The FTO sheet of (a); 2-methylimidazole is then added to Co (NO)3)2·6H2Stirring the O in the deionized water solution uniformly to obtain a Co-MOF solution; will load TiO2Soaking the FTO sheet in a Co-MOF solution, taking out, washing with deionized water, calcining at 300-500 ℃ for 1-3 h, and naturally cooling to room temperature to obtain the FTO sheet.The invention also discloses the Co derived from the prepared Co-MOF3O4/TiO2The heterojunction is applied to photoelectrocatalysis in the aspect of hydrogen production by water electrolysis. Co-MOF derived Co3O4Is compounded in TiO2The surface of the nano rod effectively enhances Co3O4/TiO2The carrier migration rate of the heterojunction composite photoelectric catalyst improves the electron/hole separation efficiency, enhances the capture capability of the catalyst to light, and improves the photoelectric catalytic performance of the catalyst. Has good application prospect in the fields of environment, energy and the like.
Description
Technical Field
The invention belongs to the technical field of composite materials, relates to preparation of a photoelectric catalyst, and particularly relates to Co-MOF (metal organic framework) derived cobaltosic oxide composite titanium dioxide (Co3O4/TiO2) A preparation method of the heterojunction and the application of the electrolytic water.
Background
Water is an inexhaustible natural resource in the nature and can generate hydrogen and oxygen by decomposition, and hydrogen is a renewable, sustainable and pollution-free energy source and has great potential as a future energy source. The Photoelectrochemical (PEC) decomposition of water to produce hydrogen is considered one of the most desirable methods of hydrogen production, where the choice of semiconductor is key to improving the PEC performance. There are many types of semiconductors, and metal oxides have been widely studied.
Recently, due to TiO2The characteristics of good stability, high conductivity and the like in photoelectrode materials of photochemical batteries have attracted wide attention. However, the larger band gap (rutile, 3.0 eV) results in TiO2Is weak in light response performance. Therefore, the solar spectrum cannot be used to efficiently generate photocurrent, resulting in low solar conversion efficiency. To solve this problem, numerous efforts have been made to explore and improve TiO2Light absorption ability of (1). TiO 22The combination of photoelectrode and metal oxide is considered an effective strategy to improve photovoltaic efficiency and PEC performance. Such as found in Rui et al, TiO2The combination with ZnO can obviously improve TiO2The photoelectric properties of (1). Co3O4Is a typical transition metal oxide with a band gap of 2.07 eV, is rich in source, has unique optical and catalytic properties, and is used as a material for forming a film with TiO2Candidate materials for nanostructure composites.
Different metal oxides are designed by taking a Metal Organic Framework (MOF) as a precursor, and more reaction centers can be obtained after pyrolysis. As found by Sun et al, porous carbon polyhedra (Ni) doped with Co, N2P/CoN-PCP) nanoparticles immobilized on MOF-derived materialsThe above. The MOF-derived porous structure not only has larger specific surface area, but also exposes more active sites, and shows excellent catalytic performance in reactions of oxygen reduction, oxygen release and hydrogen release.
So far, the preparation of Co by an electrostatic adsorption method by taking Co-MOF as a precursor is not disclosed3O4/TiO2A composite material.
Disclosure of Invention
To solve the problem of TiO2The invention discloses a Co-MOF derived Co, which solves the problems that an electron hole of a semiconductor material is easy to recombine, can only respond to ultraviolet light and has slow interface reaction kinetics3O4/TiO2A preparation method of a heterojunction photoelectric catalyst.
The technical scheme is as follows:
tetrabutyl titanate, concentrated hydrochloric acid and cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), 2-methylimidazole (C)4H6N2) Firstly, the FTO glass sheet is used as a raw material, and a simple and quick chemical reaction method is utilized to obtain the TiO loaded on the surface of the FTO glass sheet2Then the Co is synthesized by an adsorption method and a calcination treatment3O4/TiO2A composite photocatalyst.
Co-MOF derived Co3O4/TiO2The preparation method of the heterojunction comprises the following steps:
A、 TiO2preparing a nanorod array: adding tetrabutyl titanate into 3 mol/L HCl solution, uniformly mixing and stirring at a volume ratio of 60: 1-30: 1, preferably 50:1, transferring the mixed solution into a reaction kettle, soaking the reaction kettle in a cleaned FTO glass sheet, keeping the temperature at 180 ℃ for 6 hours, naturally cooling to room temperature, taking out, washing with deionized water, drying, and calcining at 450 ℃ in a muffle furnace for 2 hours to obtain the TiO-loaded glass2The FTO sheet of (a);
B. preparation of Co-MOF precursor solution: adding 2-methylimidazole to Co (NO)3)2·6H2Stirring the mixture evenly in deionized water solution of O to obtain Co-MOF solution, wherein the 2-methylimidazole and Co (NO) are3)2·6H2The mass-volume ratio of O to deionized water is 0.5-0.8 g:60 ml of 0.2-0.5 g, preferably 0.66 g, 0.29 g, 60 ml;
C、 Co3O4/TiO2the preparation of (1): will load TiO2Soaking the FTO sheet in a Co-MOF solution for 1-15 min, taking out, washing with deionized water, calcining at 300-500 ℃ for 1-3 h, preferably at 350 ℃ for 2h, taking out, naturally cooling to room temperature to obtain Co-MOF derived Co3O4/TiO2A heterojunction.
In the preferred embodiment of the invention, the cleaned FTO glass sheet in step a is prepared by cleaning the surface of the FTO glass sheet, ultrasonic cleaning the FTO glass sheet in acetone, isopropanol and ethylene glycol for 0.5h, taking out, and air drying.
According to the method disclosed by the invention, the prepared Co-MOF derived Co3O4/TiO2Heterojunction, TiO2The nano-rod is uniform and regular in shape, about 2-3 mu m in size and compounded with Co3O4Post TiO 22The surface was clearly rough.
It is another object of the invention to disclose the Co-MOF derived Co prepared3O4/TiO2The heterojunction is applied to photoelectrocatalysis in the aspect of hydrogen production by water electrolysis.
Experiment of photoelectrocatalysis water decomposition:
(1) 50 mL of the solution is prepared, and the concentration of the solution is 0.5-1.5 mol.L-1The NaOH solution of (2) is placed in the dark, preferably 1 mol. L-1And is introduced into N2Lasting for 30 min;
(2) taking Co with different soaking time3O4/TiO2And (3) placing the samples in a photoelectrocatalysis device respectively, adding the prepared NaOH solution, turning on a light source, and carrying out a experiment for preparing hydrogen by decomposing water through photoelectrocatalysis.
The invention has the characteristics that:
(1) introduction of Co3O4Formation of Co3O4/TiO2The heterojunction composite photocatalyst effectively promotes carrier migration and inhibits electron hole pair recombination;
(2) introduction of Co3O4Formation of Co3O4/TiO2Heterojunction composite lightThe electro-catalyst expands the photoresponse range of the photoelectrocatalysis hydrogen production reaction to a visible light region.
Co prepared by the invention3O4/TiO2The composite photocatalyst is used for analyzing the appearance structure and the composition of a product by utilizing instruments such as X-ray diffraction (XRD), a Scanning Electron Microscope (SEM), X-ray photoelectron spectroscopy (XPS) and the like, an ultraviolet-visible spectrophotometer is used for measuring absorbance, and a standard three-electrode electrochemical workstation is used for measuring transient photocurrent and stability so as to evaluate the photocatalytic activity of the composite photocatalyst.
The reagent used in the invention is commercially available.
The invention prepares Co by simple electrostatic adsorption process3O4/TiO2Heterojunction, Zeta potential test, TiO2The Zeta potential of the metal is-31.98 mV, while the Zeta potential of the Co-MOF (ZIF-67) is 26.7 mV, so the two can be firmly combined together through electrostatic adsorption, and then the Co-MOF can be converted into Co through pyrolysis treatment3O4Thereby obtaining Co3O4/TiO2A composite photocatalyst.
Advantageous effects
The invention synthesizes Co through a very simple hydrothermal method, a soaking method and a calcining treatment3O4/TiO2Heterojunction, Co-MOF derived Co3O4Is compounded in TiO2The surface of the nano rod effectively enhances Co3O4/TiO2The heterojunction carrier migration rate is increased, the electron hole separation efficiency is improved, the light capturing capability of the catalyst is enhanced, the photoelectrocatalysis performance of the heterojunction composite photoelectrocatalysis is improved, and the prepared Co3O4/TiO2The catalyst has good application prospect in the fields of environment, energy and the like.
Drawings
FIG. 1 Co prepared in example 13O4/TiO2XRD diffraction pattern of the composite photoelectric catalyst;
FIG. 2 Co prepared in example 13O4/TiO2XPS plot of composite photocatalyst;
FIG. 3 Co prepared in example 13O4/TiO2A Scanning Electron Microscope (SEM) image of the composite photocatalyst;
FIG. 4 Co prepared in example 13O4/TiO2UV-vis spectrogram of the composite photocatalyst;
FIG. 5 Co prepared in example 13O4/TiO2A Linear Sweep Voltammetry (LSV) profile of the composite photocatalyst;
FIG. 6 Co prepared in example 13O4/TiO2Stability (I-t) diagram of the composite photocatalyst.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Unless otherwise defined, terms (including technical and scientific terms) used herein should be construed to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
Co-MOF derived Co3O4/TiO2The preparation method of the heterojunction comprises the following steps:
A、 TiO2preparing a nanorod array: the FTO glass pieces were cleaned and ultrasonically cleaned in acetone, isopropanol, and ethylene glycol for 0.5 hours, respectively. Preparing HCl solution with the molar concentration of 3 mol/L, adding 1.2 mL of tetrabutyl titanate into the solution, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, immersing into a cleaned FTO glass sheet, keeping the temperature at 180 ℃ for 6 hours, naturally cooling to room temperature, taking out, washing with deionized water, drying, and calcining in a muffle furnace at 450 ℃ for 2 hours;
B. preparation of Co-MOF precursor: 0.66 g of 2-methylimidazole was added to 30 mL of the solutionPreparing ionic water into solution, and collecting 0.29 g Co (NO)3)2·6H2Adding 30 mL of deionized water into the O to prepare a solution, and mixing and stirring the solution for 10 minutes to obtain a mixed solution;
C、 Co3O4/TiO2the preparation of (1): will load TiO2Soaking the FTO sheet in a Co-MOF solution for 6 minutes, 9 minutes and 12 minutes respectively, taking out, washing with deionized water, and calcining in a muffle furnace at 350 ℃ for 2 hours to obtain the FTO sheet.
Experiment for photoelectrocatalysis water decomposition
(1) 50 mL of the solution was prepared at a concentration of 1 mol. L-1The NaOH solution is placed in the dark and N is introduced2Lasting for 30 min;
(2) taking Co with different soaking time3O4/TiO2And (3) placing the samples in a photoelectrocatalysis device respectively, adding the prepared NaOH solution, turning on a light source, and carrying out a experiment for preparing hydrogen by decomposing water through photoelectrocatalysis.
Co3O4/TiO2Characterization of heterojunction composite photocatalysts
As shown in FIG. 1, different Co contents3O4/TiO2The XRD pattern of the heterojunction composite photocatalyst shows that Co is not found3O4Is due to Co3O4The content is low;
as shown in FIG. 2, the XPS chart containing the existence of Ti, O and Co elements and corresponding valence states proves that Co is effectively prepared3O4；
As shown in FIG. 3, TiO2Morphology of nanorods and Co3O4Uniformly adhered to the TiO2A surface;
as shown in FIG. 4, pure TiO2Exhibits a narrow absorbance at 410 nm, Co3O4/TiO2The light absorbing edge of the heterojunction photocatalyst shows obvious red shift;
as shown in FIG. 5, Co3O4/TiO2Linear Sweep Voltammetry (LSV) testing of heterojunction composite photocatalysts with a maximum photocurrent of 1.04 mA/cm treated at different soaking times2（1.23 V vs RHE）；
As shown in FIG. 6, Co3O4/TiO2The heterojunction composite photoelectric catalyst has good stability.
Example 2
Co-MOF derived Co3O4/TiO2The preparation method of the heterojunction comprises the following steps:
A、 TiO2preparing a nanorod array: the FTO glass pieces were cleaned and ultrasonically cleaned in acetone, isopropanol, and ethylene glycol for 0.5 hours, respectively. Preparing an HCl solution with the molar concentration of 3 mol/L, adding 1 mL of tetrabutyl titanate into the solution, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, immersing the FTO glass sheet into the cleaned FTO glass sheet, keeping the temperature at 180 ℃ for 6 hours, naturally cooling to room temperature, taking out, washing with deionized water, drying, and calcining for 2 hours at 450 ℃ in a muffle furnace;
B. preparation of Co-MOF precursor: 0.5 g of 2-methylimidazole is added into 30 mL of deionized water to prepare a solution, and 0.2 g of Co (NO) is taken3)2·6H2Adding 30 mL of deionized water into the O to prepare a solution, and mixing and stirring the solution for 10 minutes to obtain a mixed solution;
C、 Co3O4/TiO2the preparation of (1): will load TiO2Soaking the FTO sheet in a Co-MOF solution for 1, 3 and 5 minutes, taking out, washing with deionized water, and calcining in a muffle furnace at 300 ℃ for 1 hour to obtain the FTO sheet.
Experiment for photoelectrocatalysis water decomposition
(1) 50 mL of the solution was prepared at a concentration of 0.5 mol. L-1The NaOH solution is placed in the dark and N is introduced2Lasting for 30 minutes;
(2) taking Co3O4/TiO2And (3) placing the samples in a photoelectrocatalysis device respectively, adding the prepared NaOH solution, turning on a light source, and carrying out a experiment for preparing hydrogen by decomposing water through photoelectrocatalysis.
Co3O4/TiO2Maximum photocurrent of 0.69 mA/cm of Linear Sweep Voltammetry (LSV) test of heterojunction composite photocatalyst2（1.23 V vs RHE）。
Example 3
Co-MOF derived Co3O4/TiO2The preparation method of the heterojunction comprises the following steps:
A、 TiO2preparing a nanorod array: the FTO glass pieces were cleaned and ultrasonically cleaned in acetone, isopropanol, and ethylene glycol for 0.5 hours, respectively. Preparing HCl solution with the molar concentration of 3 mol/L, adding 1.5 mL of tetrabutyl titanate into the solution, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, immersing into a cleaned FTO glass sheet, keeping the temperature at 180 ℃ for 6 hours, naturally cooling to room temperature, taking out, washing with deionized water, drying, and calcining in a muffle furnace at 450 ℃ for 2 hours;
B. preparation of Co-MOF precursor: 0.55 g of 2-methylimidazole is added into 30 mL of deionized water to prepare a solution, and 0.25 g of Co (NO) is taken3)2·6H2Adding 30 mL of deionized water into the O to prepare a solution, and mixing and stirring the solution for 10 minutes to obtain a mixed solution;
C、 Co3O4/TiO2the preparation of (1): will load TiO2Soaking the FTO sheet in a Co-MOF solution for 2, 4 and 6 minutes, taking out, washing with deionized water, and calcining in a muffle furnace at 450 ℃ for 2 hours to obtain the FTO sheet.
Experiment for photoelectrocatalysis water decomposition
(1) 50 mL of the solution was prepared at a concentration of 0.8 mol. L-1The NaOH solution is placed in the dark and N is introduced2Lasting for 30 minutes;
(2) taking Co3O4/TiO2And (3) placing the samples in a photoelectrocatalysis device respectively, adding the prepared NaOH solution, turning on a light source, and carrying out a experiment for preparing hydrogen by decomposing water through photoelectrocatalysis.
Co3O4/TiO2Maximum photocurrent of 0.89 mA/cm of Linear Sweep Voltammetry (LSV) test of heterojunction composite photocatalyst2（1.23 V vs RHE）。
Example 4
Co-MOF derived Co3O4/TiO2The preparation method of the heterojunction comprises the following steps:
A、 TiO2preparing a nanorod array: cleaning the FTO glass sheet and subjecting it to separate treatments in acetone, isopropanol and ethylene glycolUltrasonic cleaning was performed for 0.5 hour. Preparing an HCl solution with the molar concentration of 3 mol/L, adding 2 mL of tetrabutyl titanate into the solution, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, immersing the FTO glass sheet into the cleaned FTO glass sheet, keeping the temperature at 180 ℃ for 6 hours, naturally cooling to room temperature, taking out, washing with deionized water, drying, and calcining for 2 hours at 450 ℃ in a muffle furnace;
B. preparation of Co-MOF precursor: 0.7 g of 2-methylimidazole is added into 30 mL of deionized water to prepare a solution, and 0.3 g of Co (NO) is taken3)2·6H2Adding 30 mL of deionized water into the O to prepare a solution, and mixing and stirring the solution for 10 minutes to obtain a mixed solution;
C、 Co3O4/TiO2the preparation of (1): will load TiO2Soaking the FTO sheet in a Co-MOF solution for 5, 10 and 15 minutes, taking out, washing with deionized water, and calcining in a muffle furnace at 400 ℃ for 2 hours to obtain the FTO sheet.
Experiment for photoelectrocatalysis water decomposition
(1) 50 mL of the solution was prepared at a concentration of 1.5 mol. L-1The NaOH solution is placed in the dark and N is introduced2Lasting for 30 minutes;
(2) taking Co3O4/TiO2And (3) placing the samples in a photoelectrocatalysis device respectively, adding the prepared NaOH solution, turning on a light source, and carrying out a experiment for preparing hydrogen by decomposing water through photoelectrocatalysis.
Co3O4/TiO2Maximum photocurrent of 0.83 mA/cm of Linear Sweep Voltammetry (LSV) test of heterojunction composite photocatalyst2（1.23 V vs RHE）。
Example 5
Co-MOF derived Co3O4/TiO2The preparation method of the heterojunction comprises the following steps:
A、 TiO2preparing a nanorod array: the FTO glass pieces were cleaned and ultrasonically cleaned in acetone, isopropanol, and ethylene glycol for 0.5 hours, respectively. Preparing HCl solution with the molar concentration of 3 mol/L, adding 1.5 mL of tetrabutyl titanate into the HCl solution, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, immersing into a clean FTO glass sheet, and keeping the temperature at 180 DEG CNaturally cooling to room temperature, taking out, washing with deionized water, drying, and calcining in a muffle furnace at 450 ℃ for 2 h;
B. preparation of Co-MOF precursor: 0.6 g of 2-methylimidazole is added into 30 mL of deionized water to prepare a solution, and 0.4 g of Co (NO) is taken3)2·6H2Adding 30 mL of deionized water into the O to prepare a solution, and mixing and stirring the solution for 10 minutes to obtain a mixed solution;
C、 Co3O4/TiO2the preparation of (1): will load TiO2Soaking the FTO sheet in a Co-MOF solution for 5, 6 and 7 minutes, taking out, washing with deionized water, and calcining in a muffle furnace at 380 ℃ for 3 hours to obtain the FTO sheet.
Experiment for photoelectrocatalysis water decomposition
(1) 50 mL of the solution was prepared at a concentration of 0.6 mol. L-1The NaOH solution is placed in the dark and N is introduced2Lasting for 30 minutes;
(2) taking Co3O4/TiO2And (3) placing the samples in a photoelectrocatalysis device respectively, adding the prepared NaOH solution, turning on a light source, and carrying out a experiment for preparing hydrogen by decomposing water through photoelectrocatalysis.
Co3O4/TiO2Maximum photocurrent of 0.73 mA/cm of Linear Sweep Voltammetry (LSV) test of heterojunction composite photocatalyst2（1.23 V vs RHE）。
Example 6
Co-MOF derived Co3O4/TiO2The preparation method of the heterojunction comprises the following steps:
A、 TiO2preparing a nanorod array: the FTO glass pieces were cleaned and ultrasonically cleaned in acetone, isopropanol, and ethylene glycol for 0.5 hours, respectively. Preparing an HCl solution with the molar concentration of 3 mol/L, adding 3 mL of tetrabutyl titanate into the solution, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, immersing the FTO glass sheet into the cleaned FTO glass sheet, keeping the temperature at 180 ℃ for 6 hours, naturally cooling to room temperature, taking out, washing with deionized water, drying, and calcining for 2 hours at 450 ℃ in a muffle furnace;
B. preparation of Co-MOF precursor: adding 0.8g of 2-methylimidazole into 30 mL of deionized water to prepare solution, and taking0.5 g Co(NO3)2·6H2Adding 30 mL of deionized water into the O to prepare a solution, and mixing and stirring the solution for 10 minutes to obtain a mixed solution;
C、 Co3O4/TiO2the preparation of (1): will load TiO2Soaking the FTO sheet in a Co-MOF solution for 7, 10 and 15 minutes, taking out, washing with deionized water, and calcining in a muffle furnace at 410 ℃ for 2 hours to obtain the FTO sheet.
Experiment for photoelectrocatalysis water decomposition
(1) 50 mL of the solution was prepared at a concentration of 0.8 mol. L-1The NaOH solution is placed in the dark and N is introduced2Lasting for 30 minutes;
(2) taking Co3O4/TiO2And (3) placing the samples in a photoelectrocatalysis device respectively, adding the prepared NaOH solution, turning on a light source, and carrying out a experiment for preparing hydrogen by decomposing water through photoelectrocatalysis.
Co3O4/TiO2Maximum photocurrent of 0.77 mA/cm of Linear Sweep Voltammetry (LSV) test of heterojunction composite photocatalyst2（1.23 V vs RHE）。
Example 7
Co-MOF derived Co3O4/TiO2The preparation method of the heterojunction comprises the following steps:
A、 TiO2preparing a nanorod array: the FTO glass pieces were cleaned and ultrasonically cleaned in acetone, isopropanol, and ethylene glycol for 0.5 hours, respectively. Preparing an HCl solution with the molar concentration of 3 mol/L, adding 3 mL of tetrabutyl titanate into the solution, mixing and stirring uniformly, transferring the mixed solution into a reaction kettle, immersing the FTO glass sheet into the cleaned FTO glass sheet, keeping the temperature at 180 ℃ for 6 hours, naturally cooling to room temperature, taking out, washing with deionized water, drying, and calcining for 2 hours at 450 ℃ in a muffle furnace;
B. preparation of Co-MOF precursor: 0.69 g of 2-methylimidazole is added into 30 mL of deionized water to prepare a solution, and 0.28 g of Co (NO) is taken3)2·6H2Adding 30 mL of deionized water into the O to prepare a solution, and mixing and stirring the solution for 10 minutes to obtain a mixed solution;
C、 Co3O4/TiO2the preparation of (1): will be negativeLoaded with TiO2Soaking the FTO sheet in a Co-MOF solution for 6, 8 and 10 minutes, taking out, washing with deionized water, and calcining in a muffle furnace at 430 ℃ for 1 hour to obtain the FTO sheet.
Experiment for photoelectrocatalysis water decomposition
(1) 50 mL of the solution was prepared at a concentration of 1.2 mol. L-1The NaOH solution is placed in the dark and N is introduced2Lasting for 30 minutes;
(2) taking Co3O4/TiO2And (3) placing the samples in a photoelectrocatalysis device respectively, adding the prepared NaOH solution, turning on a light source, and carrying out a experiment for preparing hydrogen by decomposing water through photoelectrocatalysis.
Co3O4/TiO2Maximum photocurrent of 0.91 mA/cm of Linear Sweep Voltammetry (LSV) test of heterojunction composite photocatalyst2（1.23 V vs RHE）。
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (8)
1. Co-MOF derived Co3O4/TiO2The preparation method of the heterojunction is characterized by comprising the following steps:
A. adding tetrabutyl titanate into 3 mol/L HCl solution, uniformly mixing and stirring according to the volume ratio of 60: 1-30: 1, transferring the mixed solution into a reaction kettle, soaking the mixed solution into a cleaned FTO glass sheet, keeping the temperature at 180 ℃ for 6 hours, naturally cooling to room temperature, taking out, washing with deionized water, drying, and calcining at 450 ℃ in a muffle furnace for 2 hours to obtain the TiO-loaded glass2The FTO sheet of (a);
B. adding 2-methylimidazole to Co (NO)3)2·6H2Stirring the mixture evenly in deionized water solution of O to obtain Co-MOF solution, wherein the 2-methylimidazole and Co (NO) are3)2·6H2The mass volume ratio of the O to the deionized water is 0.5-0.8 g: 0.2-0.5 g:60 ml;
C. to load a loadWith TiO2Soaking the FTO sheet in a Co-MOF solution for 1-15 min, taking out, washing with deionized water, calcining at 300-500 ℃ for 1-3 h, taking out, and naturally cooling to room temperature to obtain the FTO sheet.
2. Co-MOF derived Co according to claim 13O4/TiO2A method for preparing a heterojunction, characterized in that: and B, adding tetrabutyl titanate into 3 mol/L HCl solution in the step A, and uniformly mixing and stirring the tetrabutyl titanate and the HCl solution according to the volume ratio of 50: 1.
3. Co-MOF derived Co according to claim 13O4/TiO2A method for preparing a heterojunction, characterized in that: and B, cleaning the surface of the cleaned FTO glass sheet in the step A, then respectively ultrasonically cleaning the FTO glass sheet in acetone, isopropanol and ethylene glycol for 0.5h, taking out and airing.
4. Co-MOF derived Co according to claim 13O4/TiO2A method for preparing a heterojunction, characterized in that: 2-methylimidazole, Co (NO) in step B3)2·6H2The mass volume ratio of O to deionized water is 0.66 g:0.29 g:60 ml.
5. Co-MOF derived Co according to claim 13O4/TiO2A method for preparing a heterojunction, characterized in that: calcination at 350 ℃ for 2h is described in step C.
6. Co-MOF derived Co prepared according to the method of any one of claims 1 to 53O4/TiO2A heterojunction.
7. Co-MOF derived Co according to claim 63O4/TiO2A heterojunction, characterized in that: TiO 22The nano-rod is uniform and regular in shape, about 2-3 mu m in size and compounded with Co3O4Post TiO 22The surface is obviously roughIs rough.
8. Co-MOF derived Co of claim 6 or 73O4/TiO2Use of a heterojunction, characterized in that: the catalyst is used as a photoelectric catalyst to be applied to hydrogen production by water electrolysis.
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