CN113584552B - Preparation method and application of nano composite film - Google Patents
Preparation method and application of nano composite film Download PDFInfo
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- CN113584552B CN113584552B CN202110871397.1A CN202110871397A CN113584552B CN 113584552 B CN113584552 B CN 113584552B CN 202110871397 A CN202110871397 A CN 202110871397A CN 113584552 B CN113584552 B CN 113584552B
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 43
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 27
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004070 electrodeposition Methods 0.000 claims abstract description 22
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000010408 film Substances 0.000 claims description 64
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 239000010931 gold Substances 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 2
- 239000011540 sensing material Substances 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 20
- 229910052763 palladium Inorganic materials 0.000 abstract description 13
- 238000000151 deposition Methods 0.000 description 13
- 239000010409 thin film Substances 0.000 description 8
- 230000008021 deposition Effects 0.000 description 6
- 101150003085 Pdcl gene Proteins 0.000 description 5
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 244000137852 Petrea volubilis Species 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
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- 238000004146 energy storage Methods 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
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Abstract
The invention discloses a preparation method of a nano composite film, which comprises the following steps of putting a cleaned conductive substrate electrode into a prepared ammonium heptamolybdate solution for electrodeposition to obtain a molybdenum oxide film material. And carrying out electrodeposition on the prepared molybdenum oxide film material in a hydrochloric acid solution of palladium chloride by using the same method to obtain the palladium nanoparticle open-embedded molybdenum oxide film material. The method provided by the invention has the advantages of simple preparation process, extremely short preparation time, simple instrument and equipment, excellent performance of the nano composite film and obvious application value.
Description
Technical Field
The invention relates to the technical field of composite nano film materials, in particular to a preparation method and application of a nano composite film.
Background
The nano composite film material has more excellent performance than a single nano material, and is widely applied to the fields of electronics, sensors, energy storage, lubricants, electrochromism, photochromism, catalysts and the like. The preparation method of the conventional nano composite film material comprises the steps of preparing two nano materials respectively, then simply mixing the two or more nano materials, and preparing the nano composite film material by blade coating or spin coating. The preparation process of the nano composite film material is complex, time-consuming and high in cost, the components of the composite film material are easily embedded with each other, and the active components can not be fully exposed on the surface of the material, so that the loss of the active components is caused.
At present, the nano composite film material is generally prepared by respectively preparing each component of the composite film and then preparing the nano composite film through multi-component mixed blade coating or spin coating, the preparation process is complex, the cost is high, part of effective components are embedded, the utilization rate is low, and the performance of each component cannot be fully utilized.
Therefore, the problem to be solved by those skilled in the art is how to provide a method for developing and preparing a nanocomposite film material with simple preparation process, low cost, time saving and high efficiency.
Disclosure of Invention
In view of this, the present invention provides a method for preparing a nanocomposite film and applications thereof, and the present invention provides a method for preparing a molybdenum oxide film and open-embedded metal nanoparticles by wet electrodeposition. The preparation process is simple, the preparation time is extremely short, the instruments and equipment are simple, and the nano composite film has excellent performance and obvious application value.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nano composite film comprises the following steps:
(1) Polishing the conductive substrate with 3000-mesh sand paper, and cleaning;
(2) Preparing ammonium heptamolybdate solution and hydrochloric acid solution of palladium chloride;
(3) Carrying out electrodeposition by adopting a three-electrode system, placing an ammonium heptamolybdate solution in an electrolytic cell, and then placing a three-electrode in the ammonium heptamolybdate solution for electrodeposition to obtain a molybdenum oxide film;
(4) And (3) placing the molybdenum oxide film in a hydrochloric acid solution of palladium chloride, and then performing electrodeposition by using three electrodes to obtain the nano composite film.
Preferably, the conductive substrate in step (1) is a disk gold/carbon conductive substrate with a diameter of 3 mm.
Preferably, the cleaning in the step (1) is to sequentially put the polished smooth conductive substrate into sulfuric acid, acetone, alcohol and secondary water for ultrasonic treatment for 4-6min, wherein the ultrasonic frequency is 40kHZ.
The cleaning in the above step is to remove adsorbed substances such as dust on the surface, grease, and the like, and is intended to improve the degree of connection between the thin film and the conductive substrate and to prevent the thin film from falling off.
Preferably, the concentration of the ammonium heptamolybdate solution in the step (2) is 1-100mM; in the hydrochloric acid solution of palladium chloride, the concentration of the palladium chloride is 0.1-100mM, and the molar concentration ratio of the palladium chloride to the hydrochloric acid is (1.
In the above arrangement, the concentration of the ammonium heptamolybdate solution is such that a thin film can be obtained by electrodeposition, and the thin film can be obtained within the concentration range;
the concentration ratio is defined as the ratio that enables efficient electrodeposition of palladium, too low or too high being detrimental to the electrodeposition of palladium.
Preferably, the three electrodes comprise a working electrode, a reference electrode and a counter electrode, and the material of the working electrode is a conductive substrate; the reference electrode is made of silver/silver chloride; the counter electrode is made of carbon rods.
Preferably, the electrodeposition in the step (3) is carried out in a constant voltage or constant current mode, the deposition time is 0.001s-10s, the voltage is-0.5 to-1.0V, and the current is 1-500mA/cm 2 。
In the above steps, the thickness of the film can be controlled by controlling the deposition electric quantity or the deposition time.
Preferably, the electrodeposition in the step (4) is carried out in a constant voltage or constant current mode, the deposition time is 0.001s-10s, the voltage is 0-0.6V, and the current is 1-500mA/cm 2 。
The invention also aims to provide the application of the nano composite film prepared by the preparation method of the nano composite film in optical/electrochromic films, catalysts and sensing materials.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
because the molecular size of the molybdenum oxide precursor ammonium heptamolybdate is larger, a large amount of molybdenum oxide products can be generated by transferring unit charges during electrodeposition, a larger area of conductive substrate can be covered, and in addition, the molybdenum oxide is a semiconductor and has higher resistance, and the continuously deposited molybdenum oxide tends to be continuously deposited at the part with lower resistance which is not deposited or less deposited, so that the nanoscale ultrathin film can be efficiently generated. When the metal nano particles are further deposited, the crystals of the molybdenum oxide film and oxygen defect sites have higher surface energy and lower resistance, so that electrodeposited metal atoms grow preferentially at the defect sites, and finally a composite structure in which the nano particles are open and embedded in the molybdenum oxide film is formed. The size of nano particles involved in the structure is 1-100nm, and the thickness of a molybdenum oxide film is 1nm-10 mu m. The special structure combines the characteristics of the molybdenum oxide and the metal nano particles, and the nano particles are in the holes, so that the stability of long-term use is ensured.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an SEM image of a molybdenum oxide film;
FIG. 2 is an SEM image of a palladium-molybdenum oxide composite thin film material;
FIG. 3 is a comparison of Linear Sweep Voltammetry (LSV) plots of the catalytic hydrogen evolution reaction of palladium nanoparticles embedded in molybdenum oxide film in 1mol/L KOH solution;
FIG. 4 is a comparison of Linear Sweep Voltammetry (LSV) plots before and after palladium nanoparticles embedded in molybdenum oxide films were cycled in 1mol/L KOH solution for 500 cycles.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a nano composite film comprises the following steps:
(1) Polishing a disc gold conductive substrate with the diameter of 3mm smoothly, and sequentially putting the disc gold conductive substrate into sulfuric acid, acetone, alcohol and secondary water for ultrasonic treatment for 4min (ultrasonic treatment is required in the sulfuric acid, the acetone, the alcohol and the secondary water);
(2) Preparing an ammonium heptamolybdate solution with the concentration of 100mM; 10mM PdCl were added to 30mM HCl solution 2 Obtaining hydrochloric acid solution of palladium chloride;
(3) Carrying out electrodeposition by adopting a three-electrode system, taking a disc gold conductive substrate as a working electrode, silver/silver chloride as a reference electrode, a carbon rod as a counter electrode, placing an ammonium heptamolybdate solution in an electrolytic cell, and then placing the three-electrode in the ammonium heptamolybdate solution for deposition for 1s at-0.8V to obtain a molybdenum oxide film;
(4) And (3) placing the molybdenum oxide film in a hydrochloric acid solution of palladium chloride, and then depositing for 10s under-0.3V by using a three-electrode system to obtain the nano composite film, wherein the size of the prepared palladium nano particles is about 25nm, the molybdenum oxide film generates high-density holes, and the palladium nano particles are embedded into the molybdenum oxide film in an open manner.
Example 2
A preparation method of a nano composite film comprises the following steps:
(1) Polishing a disc gold conductive substrate with the diameter of 3mm by using sand paper, and sequentially putting the disc gold conductive substrate into sulfuric acid, acetone, alcohol and secondary water for ultrasonic treatment for 4min (ultrasonic treatment is required in the sulfuric acid, the acetone, the alcohol and the secondary water);
(2) 2mM PdCl were added to 10mM HCl solution 2 Obtaining hydrochloric acid solution of palladium chloride, and then preparing ammonium heptamolybdate solution with the concentration of 10 mM;
(3) Carrying out electrodeposition by adopting a three-electrode system, taking a disc gold conductive substrate as a working electrode, silver/silver chloride as a reference electrode and a carbon rod as a counter electrode, placing an ammonium heptamolybdate solution in an electrolytic cell, and then placing the three electrodes in the ammonium heptamolybdate solution for 0.1s at-0.7V to obtain a molybdenum oxide film;
(4) And (3) placing the molybdenum oxide film in a hydrochloric acid solution of palladium chloride, and then depositing for 5s under-0.4V by using a three-electrode system to obtain the nano composite film.
Example 3
A preparation method of a nano composite film comprises the following steps:
(1) Polishing a disc carbon conductive substrate with the diameter of 3mm smoothly, and sequentially putting the disc carbon conductive substrate into sulfuric acid, acetone, alcohol and secondary water for ultrasonic treatment for 4min (ultrasonic treatment is required in the sulfuric acid, the acetone, the alcohol and the secondary water);
(2) 0.5mM PdCl were added to a 2mM HCl solution 2 Obtaining hydrochloric acid solution of palladium chloride, and then preparing ammonium heptamolybdate solution with the concentration of 100mM;
(3) Carrying out electrodeposition by adopting a three-electrode system, taking a disc carbon conductive substrate as a working electrode, silver/silver chloride as a reference electrode and a carbon rod as a counter electrode, placing an ammonium heptamolybdate solution in an electrolytic cell, and then placing the three electrodes in the ammonium heptamolybdate solution for deposition for 10ms at-0.9V to obtain a molybdenum oxide film;
(4) And (3) placing the molybdenum oxide film in a hydrochloric acid solution of palladium chloride, and then depositing for 2s at-0.5V by using a three-electrode to obtain the nano composite film.
Example 4
A preparation method of a nano composite film comprises the following steps:
(1) Polishing a disc gold conductive substrate with the diameter of 3mm smoothly, and sequentially putting the disc gold conductive substrate into sulfuric acid, acetone, alcohol and secondary water for ultrasonic treatment for 4min (ultrasonic treatment is required in the sulfuric acid, the acetone, the alcohol and the secondary water);
(2) Preparing an ammonium heptamolybdate solution with the concentration of 100mM; 0.2mM PdCl are added to a 1mM HCl solution 2 Obtaining hydrochloric acid solution of palladium chloride;
(3) Adopting a three-electrode system to carry out electrodeposition, taking a disc gold conductive substrate as a working electrode, silver/silver chloride as a reference electrode and a carbon rod as a counter electrode, placing an ammonium heptamolybdate solution in an electrolytic cell, and thenThe three electrodes were placed in an ammonium heptamolybdate solution at 10mA/cm 2 Depositing for 3s to obtain a molybdenum oxide film;
(4) The molybdenum oxide film is placed in hydrochloric acid solution of palladium chloride, and then a three-electrode system is utilized to be 1mA/cm 2 And depositing for 1s to obtain the nano composite film.
Example 5
A preparation method of a nano composite film comprises the following steps:
(1) Polishing a disc carbon conductive substrate with the diameter of 3mm smoothly, and sequentially putting the disc carbon conductive substrate into sulfuric acid, acetone, alcohol and secondary water for ultrasonic treatment for 4min (ultrasonic treatment is required in the sulfuric acid, the acetone, the alcohol and the secondary water);
(2) Preparing an ammonium heptamolybdate solution with the concentration of 100mM; 1mM of PdCl were added to a 10mM HCl solution 2 Obtaining hydrochloric acid solution of palladium chloride;
(3) Performing electrodeposition by adopting a three-electrode system, taking a disc carbon conductive substrate as a working electrode, silver/silver chloride as a reference electrode, a carbon rod as a counter electrode, placing an ammonium heptamolybdate solution in an electrolytic cell, and then placing the three electrodes in the ammonium heptamolybdate solution at 1mA/cm 2 Depositing for 0.1s to obtain a molybdenum oxide film;
(4) The molybdenum oxide film was placed in a hydrochloric acid solution of palladium chloride and then at 20mA/cm using three electrodes 2 And depositing for 0.2s to obtain the nano composite film.
Example 6
The catalytic performance of the molybdenum oxide film and the palladium nanoparticle open-embedded composite molybdenum oxide film prepared in example 1 was tested by electrochemical hydrogen evolution reaction, and the solution was 1mol/L KOH.
The SEM image of the obtained electrodeposited molybdenum oxide film is shown in figure 1, and the molybdenum oxide is seen to be in a two-dimensional film structure, and the surface is very smooth and flat. As shown in Table 1, the chemical composition is MoO x (2≤x≤3)。
TABLE 1 analysis of the X-ray energy spectrum components of molybdenum oxide
The SEM image of the obtained palladium nanoparticle open-embedded molybdenum oxide thin film is shown in fig. 2, and it can be seen from the figure that the material has high density of nanopores, and palladium nanoparticles are in the pores.
The linear cyclic voltammetry curve of the obtained palladium nanoparticle open-embedded molybdenum oxide thin film material in a 1mol/L KOH solution is shown in FIG. 3, and the graph shows that the initial potential is low (about-60 mV), and 10mA/cm 2 And 100mA/cm 2 The overpotential under the current density is 90mV and 200mV respectively, which shows that the material has higher catalytic hydrogen evolution performance which is obviously higher than that of a molybdenum oxide film and pure palladium nano particles.
The obtained palladium nanoparticle open-embedded molybdenum oxide thin film material has a Linear Sweep Voltammetry (LSV) graph before and after 500 cycles of circulation in a 1mol/L KOH solution, as shown in FIG. 4. It can be seen from the figure that the LSV graph of the material is changed less before and after scanning 500 CV cycles in 1mol/L KOH solution, which indicates that the material has higher stability.
In the present specification, the embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed in the embodiment corresponds to the method disclosed in the embodiment, so that the description is simple, and the relevant points can be referred to the description of the method part.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. A method for preparing a nano composite film is characterized by comprising the following steps:
(1) Polishing the conductive substrate with 3000-mesh abrasive paper, and cleaning;
the conductive substrate is a disk gold/carbon conductive substrate with the diameter of 3 mm;
(2) Preparing ammonium heptamolybdate solution and hydrochloric acid solution of palladium chloride;
(3) Carrying out electrodeposition by adopting a three-electrode system, placing an ammonium heptamolybdate solution in an electrolytic cell, and then placing a three-electrode in the ammonium heptamolybdate solution for electrodeposition to obtain a molybdenum oxide film;
(4) Placing the molybdenum oxide film in a hydrochloric acid solution of palladium chloride, and then performing electrodeposition by using a three-electrode system to finally form a composite structure in which the nano particles are open and embedded into the molybdenum oxide film;
the concentration of the ammonium heptamolybdate solution in the step (2) is 0.1-100mM; in the hydrochloric acid solution of palladium chloride, the concentration of the palladium chloride is 0.1-100mM, and the molar concentration ratio of the palladium chloride to the hydrochloric acid is (1;
in the step (3), the electrodeposition is carried out in a constant voltage or constant current mode for 0.001s-10s, the voltage is-0.5 to-1.0V, and the current is 1-500mA/cm 2 ；
In the step (4), the electrodeposition is carried out for 0.001s-10s in a constant voltage or constant current mode, the voltage is 0-minus 0.6V, and the current is 1-500mA/cm 2 。
2. The method for preparing a nano composite film according to claim 1, wherein the cleaning in step (1) is to sequentially put the polished smooth conductive substrate into sulfuric acid, acetone, alcohol and secondary water for ultrasonic treatment at 40kHz for 4-6 min.
3. The method of claim 1, wherein the three electrodes comprise a working electrode, a reference electrode and a counter electrode; the reference electrode is made of silver/silver chloride; the counter electrode is made of carbon rod.
4. The use of the composite structure of the nano-particle open-embedded molybdenum oxide film prepared by the method for preparing a nano-composite film according to any one of claims 1 to 3 in optical/electrochromic films, catalysts and sensing materials.
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