CN112048746B - Alternating current electroplating method for nickel-based metal organic framework film - Google Patents
Alternating current electroplating method for nickel-based metal organic framework film Download PDFInfo
- Publication number
- CN112048746B CN112048746B CN202010831033.6A CN202010831033A CN112048746B CN 112048746 B CN112048746 B CN 112048746B CN 202010831033 A CN202010831033 A CN 202010831033A CN 112048746 B CN112048746 B CN 112048746B
- Authority
- CN
- China
- Prior art keywords
- nickel
- electroplating
- alternating current
- organic framework
- metal substrate
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention provides an alternating current electroplating method of a nickel-based metal organic framework film, which belongs to the field of new material synthesis, and particularly comprises the steps of firstly carrying out surface treatment on a nickel metal substrate, then using the nickel metal substrate as a negative electrode of an electrolytic cell, using a carbon rod electrode as a positive electrode, and carrying out alternating current electroplating in electroplating liquid to finally obtain a high-compactness Ni-MOF film with micron-sized grains, wherein Ni metal ions are derived from the Ni metal substrate and are finally electroplated back to the surface of the substrate, the pollution of an electroplating growth process to an electrolyte is extremely small, compared with the traditional method for preparing the MOF film, the prepared MOF film is more compact, the binding force between the film layer and the substrate is stronger, the film layer and the substrate are not easy to fall off, and the alternating current electroplating method has flexible and wide application prospects in the directions of.
Description
Technical Field
The invention belongs to the field of new material synthesis, and particularly relates to an alternating current electroplating method of a nickel-based metal organic framework film.
Background
A Metal Organic Framework (MOF) is used as a novel nano-pore crystalline material and is formed by connecting Metal ions or clusters with various organic ligands in a coordinate bond mode. The MOF material has the advantages of large aperture range, controllable aperture structure and size, high adsorption capacity and good thermal stability, and has wide application prospects in aspects of gas storage, catalysis, magnetism and the like. High quality thin film materials formed from MOF crystals have attracted considerable attention because they are the basis for electronic, optical, catalytic, etc. devices. Over the past few years, research into metal organic framework thin film (MOF) membranes has been frequently reported and has gained significant gains in many areas including small molecule separations, chemical sensors, optical sensors, membrane catalytic reactors, and the like.
The MOF film with good crystallinity and large grain size prepared on the rigid substrate has wide application prospect in the field of gas adsorption and purification, at present, two methods of hydrothermal deposition and direct current plating are mainly adopted for preparing the MOF film on the metal rigid substrate, wherein the hydrothermal method only forms physical adsorption between the MOF and the substrate, the adhesion is poor, and the MOF film can be peeled off and fall off in a severe application scene, although the direct current plating method can obtain the MOF film with high adhesion through an electrochemical method, the compactness and crystallinity of the MOF film are poor due to the limitation of the preparation process, so that the gas adsorption and filtration performance of the MOF film cannot meet the application requirements.
Disclosure of Invention
Aiming at the problems, the invention provides an alternating current electroplating method of a nickel-based metal organic framework film, which enables the deposited MOF film to have higher compactness and larger grain size by controlling the waveform, frequency, on-off ratio, average current and electroplating time of alternating current.
The technical scheme of the invention is as follows:
an alternating current electroplating method of a nickel-based metal organic framework film is characterized by comprising the following steps:
step 1: surface treatment of a nickel metal substrate: firstly, placing a nickel metal substrate in a muffle furnace at 200-300 ℃ for heat treatment for 10min, heating at the speed of 10-20 ℃/min, then soaking the heat-treated nickel metal substrate in 0.5M hydrochloric acid solution for 30min, taking out the nickel metal substrate, then cleaning the residual hydrochloric acid solution on the surface by using ultrapure water and alcohol, and preserving the nickel metal substrate in an air-isolated manner;
step 2: preparing an electroplating solution: preparing the volume ratio of absolute ethyl alcohol to water as (3-7): 7, adding terephthalic acid and potassium pyrophosphate into the ethanol solution, dissolving to obtain a mixed solution, and titrating the mixed solution to pH 11 by using 0.01M sodium hydroxide solution to obtain an electroplating solution; wherein, the concentration of the terephthalic acid in the mixed solution is 3.32mg/mL, and the concentration of the potassium pyrophosphate is 1.4 mg/mL;
and step 3: alternating current electroplating: clamping the nickel metal substrate obtained in the step 1 in a negative electrode of an electrolytic cell, taking a carbon rod electrode as a positive electrode, immersing the negative electrode and the positive electrode into the electroplating solution obtained in the step 2 for alternating current electroplating, wherein the waveform of the alternating current electroplating is pulse square wave or pulse triangular wave, the average current is set to be 0.1-5 mA, the current amplitude is set to be 10-50% of the average current, the on-off ratio is set to be 0.5-1, the alternating current electroplating time is not more than 5h, the frequency F is set to be F-100 or less and F +100 or less, and F is the resonance peak frequency of the electrolytic cell measured by an electrochemical impedance spectroscopy test;
and 4, step 4: and (3) taking out the nickel metal substrate electroplated in the step (3), sequentially cleaning the residual electroplating solution on the surface by using ultrapure water and alcohol, and drying in vacuum to obtain the nickel-based metal organic framework film (Ni-MOF film).
Further, the nickel metal substrate in step 1 is foamed nickel or a nickel metal plate.
Further, the process of alternating current plating described in step 3 keeps the electrolytic cell sealed to reduce plating solution evaporation.
Further, the chemical component of the nickel-based metal organic framework film obtained in the step 4 is [ Ni ]3(OH)2(C8H4O4)2(H2O)4]·2H2O, the grain size of the film is 5-30 μm, and the specific surface area can be 1 e-4-20 m2/mm2And (4) adjusting within a range.
The invention has the beneficial effects that:
1. the invention provides an alternating current electroplating method of a nickel-based metal organic framework film, which enables the prepared Ni-MOF film to have highly controllable thickness, specific surface area and grain size which can reach micron order by controlling the waveform, frequency, on-off ratio, average current and electroplating time of alternating current, and has flexible and wide application prospect in the directions of gas adsorption and storage, tail gas purification, fine chemical catalysis and the like;
2. in the alternating current electroplating process, Ni metal ions of the nickel-based metal organic framework film come from the Ni metal substrate and are finally electroplated back to the surface of the substrate, and the pollution of the electroplating growth process to the electrolyte is extremely small, so that the electroplating solution can be repeatedly utilized after organic preparation raw materials are supplemented;
3. compared with the traditional method for preparing the MOF film, the method has the advantages that the prepared MOF film is more compact, the binding force between the film layer and the substrate is stronger, the film layer is not easy to fall off, the equipment is simple, the preparation efficiency is high, and the repeatability is good.
Drawings
FIG. 1 is an XRD pattern of a nickel-based metal organic framework thin film according to example 1 of the present invention;
FIG. 2 is an SEM image of a nickel-based metal organic framework thin film according to example 1 of the present invention;
FIG. 3 shows the BET test results of the Ni-based MOF thin film of example 1 according to the present invention;
FIG. 4 is a graph of pore size distribution data for a nickel-based metal organic framework thin film of example 1 of the present invention;
FIG. 5 is an SEM image of a Ni-based metal organic framework thin film of example 2 of the present invention.
Detailed Description
The technical scheme of the invention is detailed below by combining the accompanying drawings and the embodiment.
Example 1
The embodiment provides an alternating current electroplating method of a nickel-based metal organic framework film, which specifically comprises the following steps:
step 1: surface treatment of foamed nickel: carrying out surface heat treatment on 2 cm-4 cm-sized 1 mm-thick foamed nickel in a muffle furnace, setting the heat preservation temperature at 300 ℃ for 10min, raising the temperature at 10 ℃/min, naturally cooling to room temperature after heat treatment, soaking the foamed nickel in 0.5M dilute hydrochloric acid solution for 30min, taking out the foamed nickel, cleaning residual hydrochloric acid solution on the surface by using ultrapure water and alcohol in sequence, and preserving the foamed nickel in an air-isolated manner;
step 2: preparing an electroplating solution: firstly, preparing a mixture of absolute ethyl alcohol and water according to a volume ratio of 1: 1 in 50mL of an ethanol solution, 0.166g of terephthalic acid and 0.07g of potassium pyrophosphate were added thereto in this order, and after sufficient dissolution, a mixed solution was obtained, and then the mixed solution was titrated with a 0.01M sodium hydroxide solution to pH 11, to obtain an electroplating solution;
and step 3: alternating current electroplating: clamping the processed foamed nickel obtained in the step 1 on a negative electrode of an electrolytic cell, taking a carbon rod electrode as a positive electrode, immersing the negative electrode and the positive electrode into the electroplating solution obtained in the step 2 for alternating current electroplating, wherein the waveform of the alternating current electroplating is a pulse square wave, the average current of the square wave is set to be 1mA, the current amplitude is set to be 500 muA, and the resonance peak frequency of the system is 3270Hz through an electrochemical impedance spectrum test, so that the frequency is set to be 3300Hz, the on-off ratio is set to be 0.75, the alternating current electroplating is continued for 3h, and the sealing of the electrolytic cell is kept in the electroplating process to reduce the volatilization of;
and 4, taking out the foamed nickel after the electroplating is finished, sequentially cleaning residual electroplating solution on the surface by using ultrapure water and alcohol, and drying in vacuum to obtain the nickel-based metal organic framework film (Ni-MOF film).
XRD and SEM characterization of the Ni-based metal organic framework thin film prepared in the example are carried out, and the XRD pattern shown in figure 1 shows that the Ni-MOF film has purer components [ Ni ]3(OH)2(C8H4O4)2(H2O)4]·2H2O, almost no co-deposition phenomenon of impurities and byproducts exists in the electroplating process; as can be seen from the SEM image shown in FIG. 2, the quality of the Ni-MOF film is good, and the grain size distribution is 10-30 μm.
In order to characterize the density of the Ni-MOF film, the Ni-MOF film obtained in this example was subjected to isothermal nitrogen desorption and adsorption tests, and the results are shown in fig. 3, according to the formula for calculating the specific surface area of Brunauer-Emmett-Teller:
the specific surface area per unit mass of the Ni-MOF membrane is 232.75m by introducing the linear segment slope of the desorption curve2Per g, converted to a specific surface area per unit area of 17.39m2/mm2(75mg/mm2) The method has great application potential in the aspects of gas adsorption, storage and the like;
from the pore size distribution shown in FIG. 4, it can be seen that the pore size of the Ni-MOF membrane is mainly distributed below 10nm, and a large number of large-scale mesopores are not present, which indicates that the Ni-MOF membrane obtained by AC electroplating has good compactness.
Example 2
The embodiment provides an alternating current electroplating method of a nickel-based metal organic framework film, which specifically comprises the following steps:
step 1: surface treatment of a nickel metal substrate: carrying out surface heat treatment on a high-purity nickel metal plate (99.99%) with the size of 2cm x 4cm and the thickness of 300 microns in a muffle furnace, setting the heat preservation temperature at 200 ℃ for 10min, raising the temperature at 10 ℃/min, naturally cooling to room temperature after heat treatment, soaking the high-purity nickel metal plate in 0.5M dilute hydrochloric acid solution for 30min, taking out the high-purity nickel metal plate, cleaning residual hydrochloric acid solution on the surface by using ultrapure water and alcohol in sequence, and preserving the high-purity nickel metal plate in an air-isolated manner;
step 2: preparing an electroplating solution: firstly, preparing a mixture of absolute ethyl alcohol and water according to a volume ratio of 3: 7 in 50mL of an ethanol solution, 0.166g of terephthalic acid and 0.07g of potassium pyrophosphate were added thereto in this order, and after sufficiently dissolving them, a mixed solution was obtained, and then the mixed solution was titrated with a 0.01M sodium hydroxide solution to pH 11, thereby obtaining a plating solution;
and step 3: alternating current electroplating: clamping the treated high-purity nickel metal plate obtained in the step 1 on a negative electrode of an electrolytic cell, taking a carbon rod electrode as a positive electrode, immersing the negative electrode and the positive electrode into the electroplating solution obtained in the step 2 for alternating current electroplating, wherein the waveform of the alternating current electroplating is a pulse triangular wave, the average current of the pulse triangular wave is set to be 500 muA, the current amplitude is set to be 100 muA, and the resonance peak frequency of the system obtained through an impedance-frequency test is 5279Hz, so that the frequency is set to be 5300Hz, the on-off ratio is set to be 0.5, the alternating current electroplating is continued for 0.5h, and the electrolytic cell is kept sealed in the electroplating process to reduce the volatilization of the;
and 4, taking out the high-purity nickel metal plate after electroplating, sequentially cleaning residual electroplating solution on the surface by using ultrapure water and alcohol, and drying in vacuum to obtain the nickel-based metal organic framework film (Ni-MOF film).
As shown in the SEM image of the Ni-MOF film obtained in the embodiment shown in FIG. 5, the quality of the Ni-MOF film is good, and the grain size distribution is 5-10 μm; from the BET test results, it can be seen thatThe specific surface area is 4.267e-4m because the Ni-MOF film is thinner2/mm2。
Claims (4)
1. An alternating current electroplating method of a nickel-based metal organic framework film is characterized by comprising the following steps:
step 1: surface treatment of a nickel metal substrate: firstly, placing a nickel metal substrate in a muffle furnace at 200-300 ℃ for heat treatment for 10min, wherein the heating rate is 10-20 ℃/min, then soaking the heat-treated nickel metal substrate in 0.5M hydrochloric acid solution for 30min, taking out the nickel metal substrate, and cleaning to obtain the treated nickel metal substrate;
step 2: preparing an electroplating solution: preparing the volume ratio of absolute ethyl alcohol to water as (3-7): 7, adding terephthalic acid and potassium pyrophosphate into the ethanol solution, dissolving to obtain a mixed solution, and titrating the mixed solution to pH 11 by using 0.01M sodium hydroxide solution to obtain an electroplating solution; wherein, the concentration of the terephthalic acid in the mixed solution is 3.32mg/mL, and the concentration of the potassium pyrophosphate is 1.4 mg/mL;
and step 3: alternating current electroplating: taking the nickel metal substrate treated in the step 1 as a negative electrode, taking a carbon rod electrode as a positive electrode, and carrying out alternating current electroplating in the electroplating solution obtained in the step 2, wherein the waveform of the alternating current electroplating is pulse square wave or pulse triangular wave, the average current is set to be 0.1-5 mA, the current amplitude is set to be 10-50% of the average current, the on-off ratio is set to be 0.5-1, the alternating current electroplating time is not more than 5h, the frequency F is set to be F-100 or more and F +100 or less, and F is the electrolytic cell resonance peak frequency measured by an electrochemical impedance spectroscopy test;
and 4, step 4: and (4) taking out the nickel metal substrate electroplated in the step (3), and cleaning and vacuum drying to obtain the nickel-based metal organic framework film.
2. The alternating current electroplating method for the nickel-based metal organic framework film according to claim 1, wherein the nickel metal substrate in step 1 is foamed nickel or a nickel metal plate.
3. The AC plating method for nickel-based metal organic framework thin film according to claim 1, wherein the AC plating process of step 3 keeps the electrolytic cell sealed to reduce plating solution volatilization.
4. The AC electroplating method for nickel-based metal organic framework film according to claim 1, wherein the obtained nickel-based metal organic framework film has a grain size of 5-30 μm and a specific surface area of 1 e-4-20 m2/mm2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010831033.6A CN112048746B (en) | 2020-08-18 | 2020-08-18 | Alternating current electroplating method for nickel-based metal organic framework film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010831033.6A CN112048746B (en) | 2020-08-18 | 2020-08-18 | Alternating current electroplating method for nickel-based metal organic framework film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112048746A CN112048746A (en) | 2020-12-08 |
| CN112048746B true CN112048746B (en) | 2021-07-06 |
Family
ID=73600583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010831033.6A Active CN112048746B (en) | 2020-08-18 | 2020-08-18 | Alternating current electroplating method for nickel-based metal organic framework film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112048746B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116516433B (en) * | 2022-01-24 | 2024-04-26 | 中国科学院深圳先进技术研究院 | Green rapid preparation method of metal organic framework compound film coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101473069A (en) * | 2006-05-16 | 2009-07-01 | 巴斯夫欧洲公司 | Process for preparing porous metal organic frameworks |
| CN107185787A (en) * | 2017-05-12 | 2017-09-22 | 云南云铝涌鑫铝业有限公司 | Application of the nano ceramics base coating in prevention aluminium cell anode steel pawl oxidation |
| CN110484932A (en) * | 2019-09-04 | 2019-11-22 | 哈尔滨理工大学 | A kind of method of electrochemically synthesizing metal organic framework materials Ni-BTC |
-
2020
- 2020-08-18 CN CN202010831033.6A patent/CN112048746B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101473069A (en) * | 2006-05-16 | 2009-07-01 | 巴斯夫欧洲公司 | Process for preparing porous metal organic frameworks |
| CN107185787A (en) * | 2017-05-12 | 2017-09-22 | 云南云铝涌鑫铝业有限公司 | Application of the nano ceramics base coating in prevention aluminium cell anode steel pawl oxidation |
| CN110484932A (en) * | 2019-09-04 | 2019-11-22 | 哈尔滨理工大学 | A kind of method of electrochemically synthesizing metal organic framework materials Ni-BTC |
Non-Patent Citations (2)
| Title |
|---|
| Metal–organic framework thin films:electrochemical fabrication techniques andcorresponding applications & perspectives;Wei-Jin Li;《J. Mater. Chem. A》;20160621;全文 * |
| Patterned Growth of Metal-Organic FrameworkCoatings by Electrochemical Synthesis;Rob Ameloot;《Chem. Mater.》;20091231;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112048746A (en) | 2020-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111575729B (en) | Nickel phosphide compound with multi-level hole structure and preparation method and application thereof | |
| CN111282582A (en) | Preparation method of foam nickel-based catalyst for hydrogen production by water electrolysis | |
| CN110512228B (en) | Preparation method of nickel phosphide/nickel foam electrochemical functional hydrogen evolution material | |
| CN113373476B (en) | Phosphorus-doped bimetallic selenide electrocatalyst material with single metal element and adjustable electronic structure as well as preparation method and application thereof | |
| CN108588751B (en) | Oxygen-group cobalt-based catalyst, preparation method and application of electrocatalytic oxygen evolution | |
| CN107673332B (en) | Method for preparing large-area 3D graphene by using composite metal template | |
| CN112080759B (en) | Preparation method of bismuth-doped bimetallic sulfide electrode for electrocatalytic oxidation of urea | |
| CN112076791A (en) | Ni-MOF film photocatalyst growing on surface of foamed nickel in situ, and preparation method and application thereof | |
| CN110635141B (en) | Non-noble metal hydrazine oxidation catalyst based on synergistic modification and preparation method thereof | |
| CN110983361B (en) | Tantalum nitride carbon nano film integrated electrode for limited-area growth of cobalt nanoparticles and preparation method and application thereof | |
| CN114016077B (en) | Cadmium sulfide-indium zinc sulfide heterojunction nanorod array composite material and preparation method thereof | |
| CN110787806A (en) | Preparation method of full-hydrolysis catalyst with heterojunction structure | |
| CN114289043B (en) | Preparation method and application of self-supporting porous nano-plate cobalt-nickel phosphide catalyst | |
| CN112048746B (en) | Alternating current electroplating method for nickel-based metal organic framework film | |
| CN114875442A (en) | Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof | |
| CN114164451B (en) | Phosphide heterogeneous nanosheet and preparation method thereof | |
| CN114892206A (en) | Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof | |
| CN110306199A (en) | A kind of carbon dioxide electro-catalysis reduction film and the preparation method and application thereof | |
| CN112827500B (en) | Tungsten carbide film catalytic material and preparation method thereof | |
| CN110548527B (en) | Preparation of load type Ni-Fe-P-MnFeO by chemical plating 3 Method of electrocatalyst | |
| CN114477144A (en) | Preparation method of carbon nanotube array | |
| CN110042391B (en) | Nickel array method for coating bismuth vanadate nano particles based on anodic aluminum oxide template | |
| CN110735152B (en) | Ni-Cu-C electrocatalyst and preparation method and application thereof | |
| CN110872742A (en) | Preparation method of C fiber/WO 3 three-dimensional network composite structure | |
| CN115636480B (en) | Carbon-coated tungsten oxide composite electrode material 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 |