CN114411173B - 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

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CN114411173B
CN114411173B CN202210211822.9A CN202210211822A CN114411173B CN 114411173 B CN114411173 B CN 114411173B CN 202210211822 A CN202210211822 A CN 202210211822A CN 114411173 B CN114411173 B CN 114411173B
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刘进轩
晋金鑫
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Dalian University of Technology
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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, due to their appropriate band gap (2.4 eV); long carrier lifetime (40 ns) and diffusion length (70 nm) and its theoretical photocurrent density can be distinguishedUp to 7.6 mA cm -2 The semiconductor material has development potential. However, the photoelectric properties of bismuth vanadate are limited by slow water oxidation kinetics, and to solve this problem, a proper promoter needs to be loaded to promote the photoelectric catalytic water oxidation performance. 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, the MOFs material is loaded on the surface of the 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 ·5H 2 O,2 mmol), stirring until dissolved. Another clean beaker is taken and p-benzoquinone (0.46 mmol) is dissolved in 20 mL anhydrous ethylAlcohol (99.7%), dissolved with stirring. Finally, the two cups of solution are mixed uniformly to be used as electroplating solution to dope tin dioxide (FTO, area 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 electrodepositing 300 s under the cathode voltage of-0.1V vs.
(3) 40 microliters of a solution containing 0.2M vanadyl acetylacetonate (VO (acac) 2 ) The ethylene glycol solution (2) was dropped on the BiOI electrode, and 2 h was calcined at 450 ℃ in a muffle furnace with a temperature rise rate of 2 ℃/min. The calcination process converts the BiOI into a crude product BiVO 4 The crude product BiVO is subsequently 4 Soaking in 1M NaOH solution for 30 min to remove excessive vanadium pentoxide (V) 2 O 5 ) And washing the mixture by using distilled water, and naturally drying the mixture in the air to obtain the BiVO 4 An electrode plate.
(4) Under nitrogen (N) 2 ) Under the conditions, to a 50 mL eggplant shaped Schlenk bottle was added ruthenium trichloride trihydrate (RuCl) 3 ·3H 2 O, 0.01 mol), dimethyl sulfoxide (DMSO, 15 mL), heating and refluxing at 150 ℃ for 5 minutes, stopping heating when the solution changes from dark red to yellow brown, then distilling at 100 ℃ under reduced pressure until yellow solid appears in the solution, cooling the solution to room temperature after stopping the distillation under reduced pressure, then adding acetone (20 mL) into the reaction solution, filtering, and washing the product with acetone (3X 10 mL) and newly distilled anhydrous ether (3X 10 mL) to obtain bright yellow solid powder, namely [ Ru (DMSO) 4 Cl 2 ]Drying the obtained product in a vacuum drying oven;
(5) Using a double-row tube operation system, an eggplant-shaped Schlenk bottle of 100mL was evacuated and filled with nitrogen, and after repeating the operation three times, the bottle was placed in a nitrogen-filled bottle 2 2,2 '-bipyridine-6,6' -dicarboxylic acid (732 mg, 3.0 mmol) and [ Ru (DMSO) were added under conditions 4 Cl 2 ](1.45 g, 3.0 mmol) and then dry methanol (30 mL) and triethylamine (1 mL) 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 was freshly evaporated with acetone (3X 15 mL) and acetone (3X 15 5363)Washed with anhydrous diethyl ether (3X 30 mL) to give a reddish brown powder, i.e., [ 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 N 2 Under these conditions, [ Ru (bda) (DMSO) was added 2 ](484 mg, 1 mmol) and isonicotinic acid (244 mg, 1 mmol), then anhydrous methanol (30 mL) and triethylamine (1 mL) were added, heated under reflux for 4 hours, a precipitate was generated, cooled to room temperature, distilled under reduced pressure to give a reddish brown solid, dried in vacuo. The crude product was dissolved in a small amount of methanol (CH) 3 OH) with methylene Chloride (CH) 2 Cl 2 ) Methanol (CH) 3 OH) =2:1 (V: V) as eluent, and obtaining a reddish brown solid [ Ru (bda) (isonicotinic acid) 2 ](yield 70%). 1 H NMR (500 MHz, DMSO-d 6 ): 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) Mixing [ Ru (bda) (isonicotinic acid) 2 ]Molecular catalyst (1.18 mg,0.002 mmol) was dissolved in 100mL ethanol, zinc acetate dihydrate (Zn (CH) 3 COO) 2 ·2H 2 O) (5.48 mg, 0.025 mmol) was dissolved in 100mL of ethanol and deposited sequentially to BiVO in a layer-by-layer spray 4 Or FTO substrate, circulating for 40 times, and preparing two-dimensional ruthenium-based metal organic framework (Ru-SURMOF).
Further, area of FTO: 1X 2 cm 2 (ii) a Thickness: 0.2 And (5) ultrasonically cleaning the FTO substrate for 20 to 30 minutes by using acetone, absolute ethyl alcohol and deionized water.
Further, mixing [ Ru (bda) (isonicotinic acid) 2 ]Molecular catalyst (1.18 mg,0.002 mmol) and Zinc acetate dihydrate (Zn (CH) 3 COO) 2 ·2H 2 O) (5.48 mg, 0.025 mmol) were placed in 100mL of ethanol and sonicated for 20 to 30 minutes.
Further, during spraying, the time for each spraying of both solutions was 35s.
Further, the method can be used for preparing a novel liquid crystal displayEach cycle, first, a zinc acetate solution was sprayed, 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 to 12 hours.
Further, the ultrasonic frequency of the used ultrasonic equipment is 50 to 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, which comprises the following steps: in a standard three-electrode system (Ag/AgCl is used as a reference electrode, a platinum wire is used as a counter electrode, and a prepared electrode is used as a working electrode), the light source is an LED light source which can provide simulated sunlight (AM 100G standard spectrum), and when the light source directly irradiates on the working electrode from the back, the light intensity of the light source at a sample in the test process can be ensured to be 100 mW cm -2 And 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 system 2 ]Ru-SURMOF has more excellent catalytic performance, which indicates that Ru-SURMOF has more reactive active sites. In addition, with respect to moleculesThe catalyst needs to be adhered to the surface of the photoelectrode by using a Nafion solution, and Ru-SURMOF can be easily loaded on the surface of the photoelectrode by a liquid phase epitaxy method.
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 solution of the embodiment of the present invention, the drawings required in the embodiment 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 an LSV curve of a two-dimensional ruthenium-based metal organic framework-supported 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 ·5H 2 O,2 mmol), stirring until dissolved. Another clean beaker is taken, p-benzoquinone (0.46 mmol) is dissolved in 20 mL absolute ethyl alcohol (99.7%), and stirring is carried out for dissolution. Finally, the two cups of solution are mixed uniformly to be used as electroplating solution to dope tin dioxide (FTO, area 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 electrodepositing 300 s under the cathode voltage of-0.1V vs.
(3) 40 microliters of a solution containing 0.2M vanadyl acetylacetonate (VO (acac) 2 ) The ethylene glycol solution was dropped on the BiOI electrode and calcined in a muffle furnace at 450 ℃ for 2 h with a heating rate of 2 ℃/min. The calcination process converts the BiOI into a crude product BiVO 4 Then the crude product BiVO 4 Soaking in 1M NaOH solution for 30 min to remove excessive vanadium pentoxide (V) 2 O 5 ) And is washed by distilled water and is naturally dried in the air to obtain BiVO 4 An electrode sheet.
(4) Under nitrogen (N) 2 ) Under the conditions, to a eggplant-shaped Schlenk bottle of 50 mL was added ruthenium trichloride trihydrate (RuCl) 3 ·3H 2 O, 0.01 mol), dimethyl sulfoxide (DMSO, 15 mL), heating and refluxing at 150 ℃ for 5 minutes, stopping heating when the solution changes from dark red to yellow brown, then distilling at 100 ℃ under reduced pressure until yellow solid appears in the solution, cooling the solution to room temperature after stopping the distillation under reduced pressure, then adding acetone (20 mL) into the reaction solution, filtering, and washing the product with acetone (3X 10 mL) and newly distilled anhydrous ether (3X 10 mL) to obtain bright yellow solid powder, namely [ Ru (DMSO) 4 Cl 2 ]Drying the obtained product in a vacuum drying oven;
(5) Using a double-row tube operation system, an eggplant-shaped Schlenk bottle of 100mL was evacuated and filled with nitrogen, and after repeating the operation three times, the bottle was placed in a nitrogen-filled bottle 2 2,2 '-bipyridine-6,6' -dicarboxylic acid (732 mg, 3.0 mmol) and [ Ru (DMSO) were added under conditions 4 Cl 2 ](1.45 g, 3.0 mmol) and then anhydrous methanol (30 mL) and triethylamine (1 m)L). Heating and refluxing for 4 hours, a reddish brown solid was produced. Cooling the solution to room temperature, filtering, washing the solid with acetone (3 × 15 mL) and freshly distilled anhydrous ether (3 × 30 mL) to obtain 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 N 2 Under conditions, [ Ru (bda) (DMSO) was added 2 ](484 mg, 1 mmol) and isonicotinic acid (244 mg, 1 mmol), then anhydrous methanol (30 mL) and triethylamine (1 mL) were added, heated under reflux for 4 hours, a precipitate was generated, cooled to room temperature, distilled under reduced pressure to give a reddish brown solid, dried in vacuo. The crude product was dissolved in a small amount of methanol (CH) 3 OH) with dichloromethane (CH) 2 Cl 2 ) Methanol (CH) 3 OH) =2:1 (V: V) as an 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, 1 H NMR (500 MHz, DMSO-d 6 ): 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) Mixing [ Ru (bda) (isonicotinic acid) 2 ]Molecular catalyst (1.18 mg,0.002 mmol) was dissolved in 100mL ethanol, zinc acetate dihydrate (Zn (CH) 3 COO) 2 ·2H 2 O) (5.48 mg, 0.025 mmol) was dissolved in 100mL ethanol and [ Ru (bda) (isonicotinic acid) was added at a concentration of 20. Mu.M 2 ]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) sequentially in a layer-by-layer manner to BiVO 4 Or 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 at room temperature in a conventional three electrode systemIn a standard three-electrode system (Ag/AgCl is used as a reference electrode, a platinum wire is used as a counter electrode, and a prepared electrode is used as a working electrode), a light source is an LED light source, the LED light source can provide simulated sunlight (AM 100G standard spectrum), and when the light source directly irradiates on the working electrode from the back, the illumination intensity of the light source at a sample in the test process can be ensured to be 100 mW cm -2 Carrying out photoelectrocatalysis water oxidation reaction, wherein the scanning range is 0.2V to 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 is C=O At 1542 cm -1 The 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, 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 calcining; after calcination, the electrode is soaked in NaOH solution, washed by distilled water and naturally dried to obtain BiVO 4 An electrode sheet;
(4) Heating ruthenium trichloride trihydrate and dimethyl sulfoxide under reflux under nitrogen, stopping heating when the solution turns 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) 4 Cl 2 ]；
(5) 2,2 '-bipyridine-6,6' -dicarboxylic acid and [ Ru (DMSO) under nitrogen 4 Cl 2 ]Adding anhydrous methanol and triethylamine, heating and refluxing; cooled, filtered, and washed with acetone, dry ether to give a reddish brown powder [ Ru (bda) (DMSO) 2 ]；
The 2,2 '-bipyridine-6,6' -dicarboxylic acid and [ Ru (DMSO) 4 Cl 2 ]Is 1:1;
(6) Under 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; the crude product was subjected to silica gel column separation to obtain a reddish brown solid [ Ru (bda) (isonicotinic acid) 2 ]；
The [ Ru (bda) (DMSO) 2 ]And isonicotinic acid in a molar ratio of 1:1;
(7) Mixing [ Ru (bda) (isonicotinic acid) 2 ]The molecular catalyst and the zinc acetate dihydrate are respectively dissolved by ethanol and are sequentially deposited to the BiVO in a layer-by-layer spraying manner 4 Preparing a two-dimensional ruthenium-based metal organic framework Ru-SURMOF on the electrode sheet;
the zinc acetate dihydrate is reacted with [ Ru (bda) (isonicotinic acid) 2 ]The molar ratio of the molecular catalyst is 10-15.
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.
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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
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