CN117512689A - Preparation method of carbon cloth-loaded Ni-based MOF material Ni-PMDA electrode and application of carbon cloth-loaded Ni-based MOF material Ni-PMDA electrode in electrochemical synthesis of urea - Google Patents
Preparation method of carbon cloth-loaded Ni-based MOF material Ni-PMDA electrode and application of carbon cloth-loaded Ni-based MOF material Ni-PMDA electrode in electrochemical synthesis of urea Download PDFInfo
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—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
-
- 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
- C25B11/065—Carbon
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/09—Nitrogen containing compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a preparation method of a carbon cloth-loaded Ni-based MOF material Ni-PMDA electrode and application thereof in electrochemical synthesis of urea. Ni (NO) 3 ) 2 ·6H 2 O is dispersed in THF to form metal salt solution, PMDA is dispersed in THF to form ligand dispersion liquid, then PMDA dispersion liquid is added into Ni metal salt solution drop by drop, the mixed liquid is treated by ultrasonic and transferred into a Teflon high-pressure reactor, the temperature is heated to 120 ℃ and kept for 48 hours, after cooling to room temperature, the mixture is taken out, and Ni-PMDA catalyst powder is obtained through suction filtration, drying and grinding treatment, thus obtaining the Ni-based MOF catalytic material with simple raw material, convenient synthesis and stable performance. The catalytic material is prepared into ink, and the ink is smeared on carbon cloth to prepare a reduction electrode which is used for producing urea at-0.4V through electrocatalytic reactionFaraday efficiency of 29.31% at RHE and up to 2.703mmol h ‑1 mg ‑1 Urea yield of (2). The material has higher Faraday efficiency and yield, and has wide application prospect in the field of electrochemical C-N coupling synthesis of urea.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a preparation method of a carbon cloth loaded Ni-based MOF material Ni-PMDA electrode and application thereof in electrochemical synthesis of urea.
Background
In 1828, urea is artificially synthesized by Viiler, and the vital theory of organic compounds is broken. In the agricultural field, urea is used as a nitrogen-based fertilizer, so that the yield increase of grains is promoted, and the supply of human grains is ensured; in the industrial field, urea is a raw material for producing various chemicals such as urea formaldehyde resin, polyurethane, cosmetics and the like. The traditional urea synthesis method synthesizes ammonia through the traditional Haber-Bosch process, and then nitrogen-containing chemicals such as urea are further generated, and the synthesis method needs a high-temperature (350 ℃) high-pressure (10 MPa) environment, has large energy consumption and discharges CO 2 The harm is large, and the wastewater and waste gas treatment cost is high. The annual output of urea in the world exceeds 1.8 hundred million tons and accounts for 1% of the global energy consumption, and CO is discharged every year 2 More than two hundred million tons of waste gas are needed to find an energy-saving and efficient urea synthesis method.
Using nitrogen-containing waste (nitrates, nitriles, nitrogen oxides) and CO 2 The electrocatalytic C-N coupling production of urea is a new process for urea synthesis which has been recently attracting attention and is rich in NO 3 -1 CO is introduced into the liquid of (2) 2 And proper overpotential is applied, urea is synthesized by a one-step method under the action of an electrocatalyst, and compared with the traditional industrial method, the method has the advantages of low energy consumption, simplicity in operation, cleanness, environmental protection and the like. The key to realize the high-efficiency output of urea is to develop an electrocatalyst with high catalytic activity, good selectivity and long service life. Metal Organic Framework (MOF) is an emerging functional material with advantages in both metal catalytic properties and organic ligand framework configuration, and is of great interest in the field of electrosynthesis of urea, where Ni metal MOF catalysts are widely used for the electrocatalytic synthesis of urea with the advantage of low cost and high efficiency.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon cloth supported Ni-based MOF material Ni-PMDA electrode, which has the advantages of easily available raw materials, simple preparation method, high catalytic efficiency and good selectivity, and an application of the electrode in electrochemical synthesis of urea.
The technical scheme adopted by the invention is as follows:
a carbon cloth loaded Ni-based MOF material Ni-PMDA electrode, wherein the carbon cloth loaded Ni-based MOF material is prepared by using Ni (NO 3 ) 2 ·6H 2 The Ni metal in O is used as a central atom, and PMDA in the dispersion is used as a ligand.
A preparation method of a carbon cloth loaded Ni-based MOF material Ni-PMDA electrode comprises the following steps:
1) Accurately weighing Ni (NO) 3 ) 2 ·6H 2 Dissolving O solid and PMDA solid in THF to obtain metal salt solution and PMDA solution, then dripping PMDA solution into the metal salt solution by using a rubber head dropper, continuously stirring, ultrasonically dispersing the mixed solution, transferring the solution into a Teflon high-pressure reactor, cooling to room temperature after hydrothermal reaction, taking out the liquid in the reaction kettle, and carrying out suction filtration, drying and grinding into powder to obtain Ni-based MOF material powder;
2) Mixing the obtained Ni-based MOF material powder with a film solution, 2-alkyne black, isopropanol and ultrapure water to prepare ink, and dripping the ink on carbon cloth by using an injector to obtain the Ni-PMDA electrode.
Further, in the above preparation method, in step 1), ni (NO 3 ) 2 ·6H 2 The amount of O was 0.16mmol, dissolved in 30mL THF; the amount of PMDA was 0.6mmol, dissolved in 10mL THF.
Further, in the above preparation method, in step 1), the ultrasonic dispersion time is 10min.
Further, in the preparation method, in the step 1), the hydrothermal reaction temperature is 120 ℃, and the reaction time is 48 hours.
Further, in the above preparation method, in step 2), the amounts of the Ni-based MOF material powder, the film solution, the 2-alkyne black, the isopropyl alcohol, and the ultrapure water are 3mg, 30. Mu.L, 3mg, 170. Mu.L, and 200. Mu.L, respectively.
In the above preparation method, in step 2), the carbon cloth has a rectangular shape with a size of 1cm×2 cm.
In the preparation method, in step 2), the carbon cloth is immersed in acetone, absolute ethyl alcohol, concentrated nitric acid, absolute ethyl alcohol and acetone respectively for 30min.
The application of the carbon cloth supported Ni-based MOF material Ni-PMDA electrode in the electrochemical synthesis of urea.
Further, the application method comprises the following steps: taking a carbon cloth loaded Ni-based MOF material Ni-PMDA electrode as a working electrode cathode, taking a platinum sheet electrode as an anode, using an Ag/AgCl reference electrode as a reference electrode, and using 0.1M KNO as a catholyte solution 3 Solution and 0.1M KHCO 3 35mL each of solution was used with 0.1M KHCO for the anolyte solution 3 70mL of the solution is electrolyzed for 2h under the potential of-0.3-0.7 V.s.RHE, and a catholyte product is collected.
The beneficial effects of the invention are as follows:
1. the invention synthesizes the catalyst powder by utilizing a solvothermal strategy and prepares the ink, and the carbon cloth supported catalyst is used, so that the raw materials are simple and easy to obtain, and the synthetic operation difficulty is low.
2. The catalytic electrode synthesized by the invention is used for electrochemically synthesizing urea, and reaches the maximum Faraday efficiency of 29.31% under-0.4 V.s.RHE and the maximum 2.703mmol h under-0.6 V.s.RHE -1 mg -1 Urea yield of (2).
3. The catalytic electrode synthesized by the invention is continuously electrolyzed for 15 hours under the condition of-0.4 V.s.RHE, and the current density is stabilized at 0.5mA cm -2 The MOF catalytic electrode has good electrocatalytic activity and stability, and has good application prospect in the field of electrocatalytic urea synthesis.
Drawings
FIG. 1 is a FT-IR chart of Ni-PMDA in a Ni-PMDA electrode of a carbon cloth-supported Ni-based MOF material prepared in example 1.
FIG. 2 is an XRD pattern of a Ni-PMDA electrode of the carbon cloth-supported Ni-based MOF material prepared in example 1.
FIG. 3 is a diagram of an experimental apparatus for electrochemical synthesis of urea by a Ni-PMDA electrode of a carbon cloth supported Ni-based MOF material in example 2.
FIG. 4 is a carbon cloth-supported Ni-based MOF material Ni-PMDA electrode in Ar atmosphere and CO in example 2 2 LSV curve versus graph in atmosphere.
FIG. 5 is a graph of UV-vis absorption spectra and urea standard curves of diacetyl monoxime assay of example 2 for urea yield and Faraday efficiency.
FIG. 6 is a graph of urea yield and Faraday efficiency of a carbon cloth-supported Ni-based MOF material Ni-PMDA electrode of example 2.
FIG. 7 is a graph showing the catalytic stability of a Ni-PMDA electrode of a carbon cloth-supported Ni-based MOF material of example 2.
Detailed Description
Example 1 preparation of carbon cloth-supported Ni-based MOF Material Ni-PMDA electrode
The preparation method comprises the following steps:
1) Pretreatment of carbon cloth: cutting carbon cloth into rectangles with the size of 1cm multiplied by 2cm, sequentially soaking in acetone solution, absolute ethyl alcohol, concentrated nitric acid, absolute ethyl alcohol and acetone solution, carrying out ultrasonic vibration for 30min each time, repeatedly cleaning with ultrapure water, and vacuum drying the treated carbon cloth for later use.
2) Preparation of Ni-based MOF material: accurately weigh 0.16mmol Ni (NO) 3 ) 2 ·6H 2 O, dispersing in 30mL of Tetrahydrofuran (THF), accurately weighing 0.6mmol of pyromellitic dianhydride (PMDA), dispersing in 10mL of THF, dropwise adding the dispersed PMDA solution into a metal salt solution by using a rubber head dropper, continuously stirring in the dropping process, ultrasonically oscillating the mixed solution for 10min, transferring to a 100mL Teflon lining, assembling a hydrothermal reaction kettle, transferring to a blast drying oven, reacting at 120 ℃ for 48h, standing for 12h after the reaction, filtering the reaction solution by using a sand core filtering device, drying the obtained solid for 12h, grinding and collecting Ni-based MOF material powder.
3) Preparation of a carbon cloth-loaded Ni-based MOF material Ni-PMDA electrode: 3mg of Ni-based MOF material powder, 3mg of 2-alkyne black, 30 mu L of Du Bangmo solution, 170 mu L of isopropanol and 200 mu L of ultrapure water are mixed to prepare catalyst ink, the ink is uniformly dispersed for 60 minutes by ultrasound, the ink is dripped on carbon cloth by using a pipetting gun, the dripping amount is 10-12 drops, the weight is measured after drying, and the catalyst loading is calculated according to the mass of the carbon cloth before and after dripping.
(II) detection results
FIG. 1 is a FTIR spectrum of Ni-PMDA electrode powder of Ni-based MOF material prepared in example 1, as can be seen from FIG. 1, the Ni-PMDA powder was prepared in the following manner3400cm -1 The hydroxyl stretching vibration peak appears at the position of 1500cm -1 The asymmetric stretching vibration peak of carbonyl comes from ligand PMDA molecule, which proves that PMDA participates in the reaction, and the reaction is carried out according to experimental design. FIG. 2 is an XRD spectrum of Ni-PMDA electrode powder of the Ni-based MOF material prepared in example 1, compared with the PMDA spectrum of the raw material, the PMDA raw material peak disappears in the newly synthesized Ni-PMDA powder, and the generation of new substances is confirmed.
Example 2 application of carbon cloth-supported Ni-PMDA electrode in electrocatalytic urea synthesis
The testing method comprises the following steps: and taking the prepared carbon cloth loaded Ni-based MOF material Ni-PMDA electrode as a working electrode.
The experimental device is shown in FIG. 3, the experimental electrolytic tank is H-type electrolytic tank of Tianjin Aida, the proton exchange membrane is Nafion117 membrane, the electrode prepared in example 1 is placed on a cathode electrode clamp to be used as a working electrode, the reference electrode is Ag/AgCl electrode, the counter electrode is platinum sheet electrode, and the catholyte is 35mL 0.1M KNO 3 Solution and 35mL of 0.1M KHCO 3 Solution, anolyte 70ml 0.1M KHCO 3 A solution. The experimental potential is set to be-0.3-0.7V.s.RHE, the electrolysis time is 2h, and the diacetyl monoxime method is used for detecting the concentration of urea in the electrolyte.
Carbon cloth loaded Ni-based MOF material Ni-PMDA electrode in Ar atmosphere and CO 2 The LSV curve in the atmosphere is shown in FIG. 4, the current density in Ar atmosphere is higher than CO 2 The current density in the atmosphere, i.e. the strong hydrogen evolution side reaction takes place in the Ar atmosphere, CO 2 The hydrogen evolution reaction is weakened under the atmosphere, which is favorable for CO 2 And NO 3 -1 And (3) carrying out reduction reaction and further synthesizing urea by C-N coupling.
The standard curve and urea faraday efficiency and yield for the urea test are shown in fig. 5 and 6: the concentrations of five standard curves are 0, 0.5, 1.0, 1.5 and 2.0 mug ml in sequence -1 R of the standard curve is measured by experiment 2 Up to 0.99954, the reliability is higher, and the method can be used as an external standard curve. FIG. 6 shows the result of measurement, where the Ni-PMDA electrode reached 29.31% maximum Faraday efficiency at-0.4 V.s.RHE and a maximum 2.703mmol h at-0.6 V.s.RHE -1 mg -1 Is a yield of (2).
The catalytic stability test is shown in fig. 7: under the highest Faraday potential, continuous electrolysis is carried out for 15h by using a chronoamperometric method, and the current density is stabilized at 0.5mA cm -1 The prepared Ni-PMDA electrode has higher catalytic stability.
In conclusion, the carbon cloth-loaded Ni-based MOF material Ni-PMDA electrode has higher Faraday efficiency and urea yield and better electrocatalytic stability, so that the carbon cloth-loaded Ni-based MOF material Ni-PMDA electrode has ideal development prospect in the field of electrocatalytic synthesis of urea.
Claims (10)
1. A carbon cloth loaded Ni-based MOF material Ni-PMDA electrode is characterized in that the carbon cloth loaded Ni-based MOF material is prepared from Ni (NO 3 ) 2 ·6H 2 The Ni metal in O is used as a central atom, and PMDA in the dispersion is used as a ligand.
2. The preparation method of the carbon cloth supported Ni-based MOF material Ni-PMDA electrode is characterized by comprising the following steps of:
1) Accurately weighing Ni (NO) 3 ) 2 ·6H 2 Dissolving O solid and PMDA solid in THF to obtain metal salt solution and PMDA solution, then dripping PMDA solution into the metal salt solution by using a rubber head dropper, continuously stirring, ultrasonically dispersing the mixed solution, transferring the solution into a Teflon high-pressure reactor, cooling to room temperature after hydrothermal reaction, taking out the liquid in the reaction kettle, and carrying out suction filtration, drying and grinding into powder to obtain Ni-based MOF material powder;
2) Mixing the obtained Ni-based MOF material powder with a film solution, 2-alkyne black, isopropanol and ultrapure water to prepare ink, and dripping the ink on carbon cloth by using an injector to obtain the Ni-PMDA electrode.
3. The method according to claim 2, wherein in step 1), ni (NO 3 ) 2 ·6H 2 The amount of O was 0.16mmol, dissolved in 30mL THF; the amount of PMDA was 0.6mmol, dissolved in 10mL THF.
4. The method according to claim 2, wherein in step 1), the ultrasonic dispersion time is 10min.
5. The method according to claim 2, wherein in step 1), the hydrothermal reaction temperature is 120 ℃ and the reaction time is 48 hours.
6. The method according to claim 2, wherein in step 2), the Ni-based MOF material powder, the film solution, 2-acetylenic black, isopropyl alcohol, and ultrapure water are used in an amount of 3mg, 30 μl, 3mg, 170 μl, and 200 μl, respectively.
7. The method according to claim 2, wherein in step 2), the carbon cloth has a rectangular shape with a size of 1cm x 2 cm.
8. The method according to claim 2, wherein in step 2), the carbon cloth is immersed in acetone, absolute ethanol, concentrated nitric acid, absolute ethanol, and acetone for 30min, respectively, in this order before use.
9. The use of a carbon cloth supported Ni-based MOF material Ni-PMDA electrode as defined in claim 1 in electrochemical synthesis of urea.
10. The use according to claim 9, characterized in that the method is as follows: taking a carbon cloth loaded Ni-based MOF material Ni-PMDA electrode as a working electrode cathode, taking a platinum sheet electrode as an anode, using an Ag/AgCl reference electrode as a reference electrode, and using 0.1M KNO as a catholyte solution 3 Solution and 0.1M KHCO 3 35mL each of solution was used with 0.1M KHCO for the anolyte solution 3 70mL of the solution is electrolyzed for 2h under the potential of-0.3-0.7 V.s.RHE, and a catholyte product is collected.
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