CN114411173A - Preparation method and application of two-dimensional ruthenium-based metal organic framework - Google Patents

Preparation method and application of two-dimensional ruthenium-based metal organic framework Download PDF

Info

Publication number
CN114411173A
CN114411173A CN202210211822.9A CN202210211822A CN114411173A CN 114411173 A CN114411173 A CN 114411173A CN 202210211822 A CN202210211822 A CN 202210211822A CN 114411173 A CN114411173 A CN 114411173A
Authority
CN
China
Prior art keywords
ruthenium
organic framework
electrode
dimensional
based metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210211822.9A
Other languages
Chinese (zh)
Other versions
CN114411173B (en
Inventor
刘进轩
晋金鑫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian University of Technology
Original Assignee
Dalian University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN202210211822.9A priority Critical patent/CN114411173B/en
Publication of CN114411173A publication Critical patent/CN114411173A/en
Application granted granted Critical
Publication of CN114411173B publication Critical patent/CN114411173B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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
    • 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
    • C25B11/042—Electrodes formed of a single material
    • C25B11/049—Photocatalysts
    • 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
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/067—Inorganic compound e.g. ITO, silica or titania
    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
    • 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

Abstract

A preparation method and application of a two-dimensional ruthenium-based metal organic framework belong to the technical field of photoelectrochemistry energy storage materials. The invention adopts a spraying method in a liquid phase epitaxial method to coordinate ruthenium-based molecular ligand and zinc ions, and prepares a two-dimensional ruthenium-based metal organic framework on the surfaces of an FTO substrate and a bismuth vanadate photoelectrode. And coordinating ruthenium-based molecular ligand and zinc ions to construct a two-dimensional ruthenium-based metal organic framework, and applying the synthesized two-dimensional ruthenium-based metal organic framework to photoelectrocatalytic water oxidation reaction. The method utilizes the characteristics of more active sites and adjustable structure of the metal-organic framework reaction, introduces the ruthenium-based molecular catalyst into the metal-organic framework structure to prepare the more efficient photoelectric water oxidation catalyst, and applies the catalyst to the photoelectric catalytic water oxidation reaction.

Description

Preparation method and application of two-dimensional ruthenium-based metal organic framework
Technical Field
The invention belongs to the technical field of photoelectrochemistry energy storage materials, and relates to preparation and application of two-dimensional Metal Organic Frameworks (MOFs), wherein the two-dimensional ruthenium-based metal organic framework with high catalytic performance is prepared based on ruthenium-based molecules and is used for photoelectric water oxidation.
Background
Because the fossil energy is not renewable, the energy crisis and the environmental problem can be caused by the massive use of the fossil energy, and hydrogen is known as clean energy, is easy to store and has high combustion heat value, so that how to utilize solar energy to produce hydrogen is widely concerned. The semiconductor photoelectrocatalysis technology can utilize solar energy and a small amount of applied bias voltage to decompose water into hydrogen and oxygen, and a feasible path is provided for solving the energy problem.
Among the various types of semiconductor materials, bismuth vanadate semiconductor materials have a suitable band gap (2.4 eV); long carrier lifetime (40 ns) and diffusion length (70 nm), and theoretical photocurrent density can reach 7.6 mA-cm-2The semiconductor material has development potential. However, the photoelectric property of bismuth vanadate is limited by slow water oxidation kinetics, and to solve the problem, a proper promoter is required to be loaded to promote the photoelectric catalytic water oxidation property. Compared with a material catalyst, the molecular catalyst has clear structure, active sites, a catalytic mechanism and adjustability, and is a catalyst with great prospect. However, the molecular catalyst has a single loading mode, low catalytic efficiency and limited catalytic active sites, so the catalytic effect is limited.
Disclosure of Invention
According to the technical problems, the invention provides a preparation method and application of a two-dimensional ruthenium-based metal-organic framework, aiming at introducing a molecular catalyst into the metal-organic framework structure by utilizing the adjustable characteristic of the metal-organic framework structure and preparing the metal-organic framework with high-efficiency catalytic performance for photoelectrocatalytic water oxidation. Metal-organic frameworks (MOFs) are porous materials formed of metal ion (or cluster) centers and organic linkers, which are constructed in such a way that the MOFs have porosity and large specific surface area, thereby providing more reactive sites. The molecular catalyst is introduced into the MOFs structure by utilizing the characteristic of many reaction active sites of the MOFs, so that the catalytic performance of the molecular catalyst is improved. Meanwhile, MOFs materials are loaded on the surface of a semiconductor substrate by using a liquid phase epitaxy method, which is an effective catalyst loading mode.
The technical scheme adopted by the invention is as follows: a preparation method of a two-dimensional ruthenium-based metal organic framework comprises the following steps:
(1) ultrasonically cleaning the FTO substrate by using acetone, absolute ethyl alcohol and deionized water in sequence and drying;
(2) dissolving potassium iodide (KI, 20 mmol) in deionized water, magnetically stirring, slowly adding concentrated nitric acid dropwise into the solution after it is dissolved sufficiently to adjust pH to about 1.7, stirring continuously, and adding bismuth nitrate (Bi (NO)3)3·5H2O, 2 mmol), stirring until dissolved. Another clean beaker was used to dissolve p-benzoquinone (0.46 mmol) in 20 mL of absolute ethanol (99.7%) and stirred for dissolution. Finally, the two cups of solution are mixed uniformly to be used as electroplating solution to dope tin dioxide (FTO, the area is 1 multiplied by 2.0 cm)2) The electrode is a working electrode, the Ag/AgCl electrode is a reference electrode, the Pt electrode is a counter electrode, and the bismuth oxyiodide (BiOI) electrode is obtained by electrodeposition for 300 s under the cathode voltage of-0.1V vs. Ag/AgCl.
(3) 40 microliters of a solution containing 0.2M vanadyl acetylacetonate (VO (acac)2) The ethylene glycol solution is dripped on the BiOI electrode and is roasted for 2 hours at 450 ℃ in a muffle furnace, and the heating rate is set to be 2 ℃/min. The calcination process converts the BiOI into a crude product BiVO4Then the crude product BiVO4Soaking in 1M NaOH solution for 30 min to remove excessive vanadium pentoxide (V)2O5) And washing the mixture by using distilled water, and naturally drying the mixture in the air to obtain the BiVO4An electrode sheet.
(4) Under nitrogen (N)2) Under the conditions, to a 50 mL eggplant-shaped Schlenk flask was added ruthenium trichloride trihydrate (RuCl)3·3H2O, 0.01 mol), dimethyl sulfoxide (DMSO, 15 mL), heated at 150 ℃ under reflux for 5 minutes, heating stopped when the solution changes from dark red to yellowish brown, then distillation under reduced pressure at 100 ℃ until a yellow solid appears in the solution, cooling the solution to room temperature after stopping distillation under reduced pressure, then adding acetone (20 mL) to the reaction solution, filtering, and using acetone (3X 10 mL), freshly distilled anhydrous ethyl acetateWashing the product with ether (3X 10 mL) to obtain bright yellow solid powder, namely [ Ru (DMSO)4Cl2]Drying the obtained product in a vacuum drying oven;
(5) using a double row tube system, a 100mL eggplant-shaped Schlenk bottle was evacuated and filled with nitrogen gas for three times, and then subjected to N 22,2 '-bipyridine-6, 6' -dicarboxylic acid (732 mg, 3.0 mmol) and [ Ru (DMSO) were added under the conditions4Cl2](1.45 g, 3.0 mmol) and then anhydrous methanol (30 mL) and triethylamine (1mL) were added. Heating and refluxing for 4 hours, a reddish brown solid was produced. The solution was cooled to room temperature, filtered, and the solid washed with acetone (3X 15 mL) and freshly distilled dry diethyl ether (3X 30 mL) to give a reddish brown powder, [ Ru (bda) (DMSO)2]Drying the obtained product in a vacuum drying oven;
(6) using a double-row tube operation system, vacuumizing an eggplant-shaped Schlenk bottle, filling nitrogen, and repeatedly operating for three times in N2Under the condition, add [ Ru (bda) (DMSO)2](484 mg, 1 mmol) and isonicotinic acid (244 mg, 1 mmol), then anhydrous methanol (30 mL) and triethylamine (1mL) were added, which was heated under reflux for 4 hours, whereupon a precipitate was generated, cooled to room temperature, distilled under reduced pressure to give a reddish brown solid, which was dried in vacuo. The crude product was dissolved in a small amount of methanol (CH)3OH) with methylene Chloride (CH)2Cl2) Methanol (CH)3OH) = 2:1 (V: V) as eluent, and obtaining a reddish brown solid [ Ru (bda) (isonicotinic acid)2](yield 70%).1H NMR (500 MHz, DMSO-d6): δ= 8.69 (d, 2H), 7.93-7.83 (m, 4H), 7.71 (d, 4H), 7.47 (d, 4H)，HR-MS (ESI): m/z = 591.1[M+Na]+(calcd: 591.2) the resulting product was dried in a vacuum oven.
(7) Reacting [ Ru (bda) (isonicotinic acid)2]Molecular catalyst (1.18 mg, 0.002 mmol) was dissolved in 100mL ethanol, zinc acetate dihydrate (Zn (CH)3COO)2·2H2O) (5.48 mg, 0.025 mmol) was dissolved in 100mL ethanol and deposited sequentially in a layer-by-layer spray to BiVO4Or on FTO substrate, circulating for 40 times, and preparing two-dimensional rutheniumA metal-organic framework (Ru-SURMOF).
Further, area of FTO: 1 x 2 cm2(ii) a Thickness: and (3) ultrasonically cleaning the FTO substrate for 20-30 minutes by using acetone, absolute ethyl alcohol and deionized water with the thickness of 0.2 mm.
Further, mixing [ Ru (bda) (isonicotinic acid)2]Molecular catalyst (1.18 mg, 0.002 mmol) and Zinc acetate dihydrate (Zn (CH)3COO)2·2H2O) (5.48 mg, 0.025 mmol) were placed in 100mL of ethanol, respectively, and sonicated for 20-30 minutes.
Further, during spraying, the time for each spraying of both solutions was 35 s.
Further, for each cycle, a zinc acetate solution was sprayed first, followed by [ Ru (bda) (isonicotinic acid)2]A solution of the molecule.
And further, putting the prepared Ru-SURMOF loaded photoelectrode into a vacuum drying oven for drying for 6-12 hours.
Furthermore, the ultrasonic frequency of the used ultrasonic equipment is 50-53 KHz.
The invention also provides an application of the two-dimensional ruthenium-based metal organic framework prepared by the preparation method in the field of photoelectrocatalysis water oxidation: in a standard three-electrode system (Ag/AgCl as a reference electrode, a platinum wire as a counter electrode and a prepared electrode as a working electrode), the light source is an LED light source which can provide simulated sunlight (AM 100G standard spectrum), and when the simulated sunlight is directly irradiated on the working electrode from the back, the illumination intensity of the simulated sunlight at a sample in the test process can be ensured to be 100 mW cm-2And carrying out photoelectrocatalysis water oxidation reaction.
Further, the electrolyte adopts a prepared 0.1M phosphoric acid buffer solution.
The invention adopts a liquid phase epitaxy method to coordinate ruthenium-based molecular ligand and zinc ions to construct a two-dimensional ruthenium-based metal organic framework, and the synthesized two-dimensional ruthenium-based metal organic framework is used for photoelectrocatalytic water oxidation reaction.
Compared with the prior art, the invention has the following advantages:
1. the invention coordinates ruthenium-based molecular ligand and zinc ions by using a spraying method in a liquid phase epitaxy method, and prepares a two-dimensional ruthenium-based metal organic framework on the surfaces of an FTO substrate and a bismuth vanadate photoelectrode.
2. The invention utilizes the characteristics of more reactive active sites and adjustable structure of the metal organic framework to introduce the ruthenium-based molecular catalyst into the metal organic framework structure to prepare the more efficient photoelectric water oxidation catalyst.
3. Relative to ruthenium-based molecular catalyst [ Ru (bda) (isonicotinic acid) in a 0.1M phosphoric acid buffer system2]Ru-SURMOF has more excellent catalytic performance, which indicates that Ru-SURMOF has more reactive active sites. In addition, Ru-surfof can be easily loaded on the surface of the photoelectrode by a liquid phase epitaxy method, as opposed to a molecular catalyst that needs to be adhered to the surface of the photoelectrode using Nafion solution.
In summary, the invention provides a method for constructing a two-dimensional ruthenium-based metal-organic framework by coordinating ruthenium-based molecular ligands and zinc ions by adopting a liquid phase epitaxy method, and the synthesized two-dimensional ruthenium-based metal-organic framework is used for photoelectrocatalytic water oxidation reaction.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments will be briefly described below.
FIG. 1 shows the prepared ruthenium-based molecular catalyst [ Ru (bda) (isonicotinic acid)2]Nuclear magnetic map of (a).
FIG. 2 is a Fourier infrared spectrum of a two-dimensional ruthenium-based metal-organic framework prepared by liquid phase epitaxy.
FIG. 3 is an X-ray diffraction spectrum of a two-dimensional ruthenium-based metal organic framework prepared by liquid phase epitaxy.
FIG. 4 is a scanning electron microscope image of a two-dimensional ruthenium-based metal organic framework prepared by liquid phase epitaxy.
FIG. 5 is an energy spectrum of a two-dimensional ruthenium-based metal organic framework prepared by liquid phase epitaxy.
FIG. 6 is LSV curves of a two-dimensional ruthenium-based metal-organic framework loaded bismuth vanadate electrode and a comparative sample thereof.
Detailed Description
In order that the invention may be more readily understood, the following examples are preferred and are to be considered in connection with the accompanying drawings. The starting materials are available from open commercial sources unless otherwise specified.
Example 1 preparation of a two-dimensional ruthenium-based Metal-organic framework
(1) Ultrasonically cleaning the FTO substrate by using acetone, absolute ethyl alcohol and deionized water in sequence and drying;
(2) dissolving potassium iodide (KI, 20 mmol) in deionized water, magnetically stirring, slowly adding concentrated nitric acid dropwise into the solution after it is dissolved sufficiently to adjust pH to about 1.7, stirring continuously, and adding bismuth nitrate (Bi (NO)3)3·5H2O, 2 mmol), stirring until dissolved. Another clean beaker was used to dissolve p-benzoquinone (0.46 mmol) in 20 mL of absolute ethanol (99.7%) and stirred for dissolution. Finally, the two cups of solution are mixed uniformly to be used as electroplating solution to dope tin dioxide (FTO, the area is 1 multiplied by 2.0 cm)2) The electrode is a working electrode, the Ag/AgCl electrode is a reference electrode, the Pt electrode is a counter electrode, and the bismuth oxyiodide (BiOI) electrode is obtained by electrodeposition for 300 s under the cathode voltage of-0.1V vs. Ag/AgCl.
(3) 40 microliters of a solution containing 0.2M vanadyl acetylacetonate (VO (acac)2) The ethylene glycol solution is dripped on the BiOI electrode and is roasted for 2 hours at 450 ℃ in a muffle furnace, and the heating rate is set to be 2 ℃/min. The calcination process converts the BiOI into a crude product BiVO4Then the crude product BiVO4Soaking in 1M NaOH solution for 30 min to remove excessive vanadium pentoxide (V)2O5) And washing the mixture by using distilled water, and naturally drying the mixture in the air to obtain the BiVO4An electrode sheet.
(4) Under nitrogen (N)2) Under the conditions, to a 50 mL eggplant-shaped Schlenk flask was added ruthenium trichloride trihydrate (RuCl)3·3H2O, 0.01 mol), dimethyl sulfoxide (DMSO, 15 mL), heated at 150 deg.C under reflux for 5 minutes, stopping heating until the solution turns from dark red to yellow brown, distilling at 100 deg.C under reduced pressure until yellow solid appears in the solution, stopping distilling under reduced pressure, cooling the solution toAt room temperature, acetone (20 mL) was then added to the reaction solution, filtered, and the product was washed with acetone (3X 10 mL), freshly distilled anhydrous ether (3X 10 mL) to give a bright yellow solid powder, i.e., [ Ru (DMSO)4Cl2]Drying the obtained product in a vacuum drying oven;
(5) using a double row tube system, a 100mL eggplant-shaped Schlenk bottle was evacuated and filled with nitrogen gas for three times, and then subjected to N 22,2 '-bipyridine-6, 6' -dicarboxylic acid (732 mg, 3.0 mmol) and [ Ru (DMSO) were added under the conditions4Cl2](1.45 g, 3.0 mmol) and then anhydrous methanol (30 mL) and triethylamine (1mL) were added. Heating and refluxing for 4 hours, a reddish brown solid was produced. The solution was cooled to room temperature, filtered, and the solid washed with acetone (3X 15 mL) and freshly distilled dry diethyl ether (3X 30 mL) to give a reddish brown powder, [ Ru (bda) (DMSO)2]Drying the obtained product in a vacuum drying oven;
(6) using a double-row tube operation system, vacuumizing an eggplant-shaped Schlenk bottle, filling nitrogen, and repeatedly operating for three times in N2Under the condition, add [ Ru (bda) (DMSO)2](484 mg, 1 mmol) and isonicotinic acid (244 mg, 1 mmol), then anhydrous methanol (30 mL) and triethylamine (1mL) were added, which was heated under reflux for 4 hours, whereupon a precipitate was generated, cooled to room temperature, distilled under reduced pressure to give a reddish brown solid, which was dried in vacuo. The crude product was dissolved in a small amount of methanol (CH)3OH) with methylene Chloride (CH)2Cl2) Methanol (CH)3OH) = 2:1 (V: V) as eluent, and obtaining a reddish brown solid [ Ru (bda) (isonicotinic acid)2](yield 70%) the product obtained was dried in a vacuum oven.
The nuclear magnetic spectrum of the product is shown in figure 1,1H NMR (500 MHz, DMSO-d6): δ= 8.69 (d, 2H), 7.93-7.83 (m, 4H), 7.71 (d, 4H), 7.47 (d, 4H)。HR-MS (ESI): m/z = 591.1[M+Na]+(calcd: 591.2)。
(7) reacting [ Ru (bda) (isonicotinic acid)2]Molecular catalyst (1.18 mg, 0.002 mmol) was dissolved in 100mL ethanol, zinc acetate dihydrate (Zn: (Zn) (R))CH3COO)2·2H2O) (5.48 mg, 0.025 mmol) was dissolved in 100mL of ethanol and [ Ru (bda)) (isonicotinic acid) was added at a concentration of 20. mu.M2]The molecular catalyst was deposited in ethanol (spray time: 35s, wait time: 15 s) and zinc acetate at a concentration of 0.25 mM in ethanol (spray time: 35s, wait time: 15 s) in a layer-by-layer manner sequentially to BiVO4Or FTO substrate, circulating for 40 times, and preparing two-dimensional ruthenium-based metal organic framework (Ru-SURMOF).
Example 2 application of two-dimensional ruthenium-based Metal-organic frameworks
All photoelectrochemical tests were performed in a conventional three-electrode system at room temperature, in a standard three-electrode system (Ag/AgCl as reference electrode, platinum wire as counter electrode, prepared electrode as working electrode), the light source was an LED light source capable of providing simulated sunlight (AM 100G standard spectrum), which when directly irradiated on the working electrode from the back ensured an illumination intensity of 100 mW cm at the sample during the test process of 100 mW cm-2Carrying out photoelectrocatalysis water oxidation reaction, wherein the scanning range is 0.2V-1.23V vs RHE, and the scanning speed is 50 mV.s-1。
Data analysis
(1) Characterization before catalytic reaction
As can be seen from the XRD pattern of FIG. 2, Ru-SURMOF shows the same XRD pattern as the simulated Ru-SURMOF, indicating that the prepared ruthenium-based MOFs grow along a single orientation. In FIG. 3, Ru-SURMOF was characterized by Fourier transform infrared (FT-IR) spectroscopy. [ Ru (bda) (isonicotinic acid)2]V isC=OAt 1542 cm-1The peak at (A) completely disappeared in Ru-SURMOF, indicating that the carboxyl group is coordinated with Zn. The above results demonstrate the successful synthesis of Ru-SURMOF. In FIG. 4, the Ru-SURMOF is in a lamellar structure under a Scanning Electron Microscope (SEM). The elemental analysis of FIG. 5 reveals that C, O, N, Zn and the Ru element are uniformly distributed in the Ru-SURMOF.
(2) Photoelectrochemical testing
It can be seen from the LSV in fig. 6 that at a bias of 1.23V, Ru-surfof as a promoter, more excellent photo-catalytic water oxidation performance was obtained compared to ruthenium-based molecules, which fully indicates that MOFs exert their characteristic of having many active sites.

Claims (2)

1. A preparation method of a two-dimensional ruthenium-based metal organic framework is characterized by comprising the following steps:
(1) ultrasonically cleaning the FTO substrate by using acetone, absolute ethyl alcohol and deionized water in sequence and drying;
(2) dissolving potassium iodide in deionized water, and adding concentrated nitric acid to adjust the pH value to 1.7; continuously stirring and adding bismuth nitrate, and stirring until the bismuth nitrate is dissolved; then adding an ethanol solution of p-benzoquinone to obtain a mixed solution as an electroplating solution; performing electrodeposition to obtain a bismuth oxyiodide electrode by using fluorine-doped tin dioxide as a working electrode, an Ag/AgCl electrode as a reference electrode and a Pt electrode as a counter electrode;
the molar ratio of the potassium iodide to the bismuth nitrate is 8-12:1, and the molar ratio of the bismuth nitrate to the p-benzoquinone is 1: 2-4;
(3) dripping glycol solution containing vanadyl acetylacetonate on a bismuth oxyiodide electrode, and roasting and calcining the bismuth oxyiodide electrode; after calcination, the electrode is soaked in NaOH solution, washed by distilled water and naturally dried to obtain BiVO4An electrode sheet;
(4) heating and refluxing ruthenium trichloride trihydrate and dimethyl sulfoxide under nitrogen condition, stopping heating when the solution changes from dark red to yellow brown, distilling under reduced pressure, filtering, and washing with acetone and anhydrous ether to obtain bright yellow solid powder [ Ru (DMSO)4Cl2]；
(5) Under nitrogen, 2,2 '-bipyridine-6, 6' -dicarboxylic acid and [ Ru (DMSO)4Cl2]Adding anhydrous methanol and triethylamine, heating and refluxing; cooling, filtering and washing with acetone and anhydrous ether to obtain a reddish brown powder [ Ru (bda) (DMSO)2]；
The 2,2 '-bipyridine-6, 6' -dicarboxylic acid and [ Ru (DMSO)4Cl2]In a molar ratio of 1: 1;
(6) under the condition of nitrogen, [ Ru (bda) (DMSO)2]Adding anhydrous methanol and triethylamine into the isonicotinic acid, and heating and refluxing; cooling and distilling under reduced pressure to obtain a reddish brown crude product; mixing the crude productSeparating with silica gel column to obtain reddish brown solid [ Ru (bda) (isonicotinic acid)2]；
Said [ Ru (bda) (DMSO)2]And isonicotinic acid in a molar ratio of 1: 1;
(7) reacting [ Ru (bda) (isonicotinic acid)2]The molecular catalyst and zinc acetate dihydrate are dissolved by ethanol and are sequentially deposited to BiVO in a layer-by-layer spraying manner4Or preparing a two-dimensional ruthenium-based metal organic framework Ru-SURMOF on an FTO substrate;
said zinc acetate dihydrate with [ Ru (bda) (isonicotinic acid)2]The molar ratio of the molecular catalyst is 10-15: 1.
2. The preparation method of the two-dimensional ruthenium-based metal-organic framework according to claim 1, wherein the two-dimensional ruthenium-based metal-organic framework Ru-SURMOF is prepared and applied to a cocatalyst for photoelectrocatalytic water oxidation.
CN202210211822.9A 2022-03-04 2022-03-04 Preparation method and application of two-dimensional ruthenium-based metal organic framework Active CN114411173B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210211822.9A CN114411173B (en) 2022-03-04 2022-03-04 Preparation method and application of two-dimensional ruthenium-based metal organic framework

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210211822.9A CN114411173B (en) 2022-03-04 2022-03-04 Preparation method and application of two-dimensional ruthenium-based metal organic framework

Publications (2)

Publication Number Publication Date
CN114411173A true CN114411173A (en) 2022-04-29
CN114411173B CN114411173B (en) 2023-02-03

Family

ID=81263513

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210211822.9A Active CN114411173B (en) 2022-03-04 2022-03-04 Preparation method and application of two-dimensional ruthenium-based metal organic framework

Country Status (1)

Country Link
CN (1) CN114411173B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111545250A (en) * 2020-05-21 2020-08-18 浙江工业大学 Ruthenium catalyst with efficient electrocatalytic full-hydrolytic performance and application thereof
CN112920416A (en) * 2021-01-22 2021-06-08 大连理工大学 Preparation method of transition metal-based SURMAOFs based on liquid phase epitaxy method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111545250A (en) * 2020-05-21 2020-08-18 浙江工业大学 Ruthenium catalyst with efficient electrocatalytic full-hydrolytic performance and application thereof
CN112920416A (en) * 2021-01-22 2021-06-08 大连理工大学 Preparation method of transition metal-based SURMAOFs based on liquid phase epitaxy method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JAVIER J. CONCEPCION等: ""Mechanism of water oxidation by [Ru(bda)(L)2]: the return of the "blue dimer""", 《CHEMICAL COMMUNICATIONS : CHEM COMM》 *
TAE WOO KIM等: ""Nanoporous BiVO4 Photoanodes with Dual-Layer Oxygen Evolution Catalysts for Solar Water Splitting"", 《SCIENCE》 *

Also Published As

Publication number Publication date
CN114411173B (en) 2023-02-03

Similar Documents

Publication Publication Date Title
Yuan et al. Metal-complex chromophores for solar hydrogen generation
Liu et al. Molecular cobalt salophen catalyst-integrated BiVO 4 as stable and robust photoanodes for photoelectrochemical water splitting
Muresan et al. Immobilization of a molecular cobaloxime catalyst for hydrogen evolution on a mesoporous metal oxide electrode
Kamata et al. Durable photoelectrochemical CO 2 reduction with water oxidation using a visible-light driven molecular photocathode
Zhang et al. Type II cuprous oxide/graphitic carbon nitride pn heterojunctions for enhanced photocatalytic nitrogen fixation
US20130220825A1 (en) Metal complex and use as multi-electron catalyst
Yüzer et al. Imidazole substituted Zinc (ii) phthalocyanines for co-catalyst-free photoelectrochemical and photocatalytic hydrogen evolution: influence of the anchoring group
Ding et al. Single Ru atoms confined into MOF/C3N4 for dual improved photocatalytic carbon dioxide reduction and nitrogen fixation
CN112210787B (en) Preparation method of metal organic framework material coating on surface of nano-structure substrate
CN114411173B (en) Preparation method and application of two-dimensional ruthenium-based metal organic framework
Said et al. A butterfly-like lead-doped titanium-oxide compound with high performance in photocatalytic cycloaddition of CO 2 to epoxide
CN115536860B (en) Biological MOF material for electrocatalysis and photocatalysis, and preparation method and application thereof
CN108842158B (en) BiVO for photoelectrocatalytic oxygen evolution4-Al2O3-Ni4O4Composite film and preparation method thereof
CN108855193B (en) TaN/BiVO4Heterojunction composite material and preparation method and application thereof
CN111302650B (en) Method for preparing bismuth vanadate photoelectric anode by spin coating of nanoparticle solution
Xin et al. Abundant manganese complex-anchored BiOI hybrid photocatalyst for visible light-driven CO2 reduction
CN112371120B (en) High-dispersion platinum modified metal ion doped semiconductor photocatalyst, preparation method and application thereof
CN111530502B (en) Preparation method of ZnTe-Mo/Mg-MOF photocathode material
Ding et al. The cocatalyst roles of three anionic Cd (II) porphyrinic metal-organic frameworks in the photocatalytic CO2 reduction to CO process carried out in Ru (bpy) 3Cl2/CH3CN/H2O/Triethylamine or triethanolamine system
CN114243031A (en) Simple MOF-derived Fe single-site oxygen reduction electrocatalyst and preparation method and application thereof
Wang et al. Highly Efficient and Selective Visible‐light Photocatalytic CO2 Reduction to CO Using a 2D Co (II)‐Imidazole MOF as Cocatalyst and Ru (bpy) 3Cl2 as Photosensitizer
CN110359058A (en) A kind of preparation method of the bloodstone nanometer stick array light anode of lead zirconate titanate modification
CN106801231B (en) The WO of molecular level iridium catalyst modification3Complex light anode and its application
CN116425996B (en) Metal organic framework material and ligand thereof and application of metal organic framework material in photocatalytic hydrogen production
CN111171083B (en) Nickel-sulfur complex containing PCNCP diphosphine ligand and preparation method and application thereof

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
GR01 Patent grant
GR01 Patent grant