CN110293231B - Preparation method of core-shell structure nanoparticle array with non-noble metal elements as cores and noble metal elements as shells - Google Patents
Preparation method of core-shell structure nanoparticle array with non-noble metal elements as cores and noble metal elements as shells Download PDFInfo
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Abstract
The invention discloses a preparation method of a non-noble metal @ noble metal core-shell structure nanoparticle array, which can greatly improve the utilization rate of noble metals and reduce the consumption of noble metals on the premise of ensuring high performance, thereby reducing the application cost of noble metal materials, prolonging the service life of core-shell structure nanoparticles, and solving the problems that the application cost of noble metal nanoparticles in various fields is limited due to the high application cost of noble metals in the prior art.
Description
The technical field is as follows:
the invention relates to the technical field of nano composite materials, in particular to a preparation method of an ordered core-shell structure nanoparticle array taking non-noble metal elements as cores and noble metal elements as shells.
Background art:
the noble metal nanoparticles have excellent characteristics such as oxidation-reduction catalytic performance, light-sensitive capacity and electric conductivity, so that the noble metal nanoparticles have important application value and wide application prospect in the fields of catalysis, optics, electrons, energy conversion and storage and the like. After the noble metal nano particles are uniformly and orderly arranged, the unique effect of the noble metal nano particles on the micro scale can be intensively embodied on the macro scale, and the probability of agglomeration of the noble metal nano particles in the application process can be remarkably reduced, so that high performance and high stability are realized. The block copolymer self-assembly template method (BC) can achieve the dispersability, order and uniformity required for the preparation of noble metal nanoparticles. The nano-particle array prepared by the BC method approaches to single distribution in the aspects of particle size, particle spacing, particle shape and the like, and has the advantage that other technologies cannot compare favorably in the aspect of controlling uniform order.
However, the application cost of the noble metal nanoparticles is always high due to adverse factors such as the reserves, the cost and the abnormal price of the noble metal, and thus the application cost of the noble metal nanoparticles to various fields is undoubtedly limited, which poses a great obstacle to the realization of large-scale commercial application of the noble metal nanoparticles. Therefore, how to further reduce the amount of the noble metal under the precondition of ensuring the performance needs to be considered, so as to realize the efficient utilization of the noble metal, thereby reducing the application cost of the noble metal nanoparticles.
The invention content is as follows:
the invention aims to provide a preparation method of a core-shell structure nanoparticle array taking a non-noble metal element as a core and a noble metal element as a shell (abbreviated as non-noble metal @ noble metal), the obtained non-noble metal @ noble metal core-shell structure nanoparticle array can greatly improve the utilization rate of noble metal and reduce the consumption of noble metal on the premise of ensuring high performance, thereby reducing the application cost of noble metal materials, having stability far higher than that of traditional core-shell structure dispersed particles, prolonging the service life of core-shell structure nanoparticles, and solving the problem that the application cost of noble metal nanoparticles in various fields is always high and the application of noble metal nanoparticles is limited in the prior art.
The invention is realized by the following technical scheme:
a preparation method of a core-shell structure nanoparticle array taking non-noble metal elements as cores and noble metal elements as shells (abbreviated as non-noble metals @ noble metals) comprises the following steps:
(1) the carrier is dipped, pulled or spin-coated with a uniform glue in a solution dispersed with non-noble metal precursor/diblock copolymer micelle, and a single-layer template array loaded with non-noble metal precursor/ordered spherical micelle is dip-coated or spin-coated on the carrier, and then the carrier is put into an air plasma cleaning machine for cleaning until the diblock copolymer template is completely removed, so as to obtain the initially implanted carrier of the ordered non-noble metal oxide nanoparticle array arranged according to a hexagonal lattice;
(2) dipping the carrier loaded with the non-noble metal oxide nanoparticle array obtained in the step (1) in a reducing solution or treating the carrier with hydrogen plasma, and then washing and airing the carrier with the non-noble metal oxide nanoparticle array by using deionized water without oxygen in an inert gas protective atmosphere to obtain the carrier loaded with the non-noble metal nanoparticle array;
(3) and (3) soaking the carrier loaded with the non-noble metal nanoparticle array obtained in the step (2) in a noble metal precursor solution with a certain concentration for a certain time, taking out, cleaning with deionized water, and airing to obtain the non-noble metal @ noble metal nanoparticle array.
The invention can regulate the size of nano particles by regulating the concentration of the non-noble metal precursor, and can regulate the amount of the replaced noble metal by regulating the concentration of the noble metal precursor solution or the replacement time length.
The dipping and pulling mode in the step (1) is specifically as follows: and (3) putting the carrier into the solution dispersed with the non-noble metal precursor/diblock copolymer micelle, soaking for more than 30s, then uniformly pulling the carrier out of the solution at a speed of 2-5 mm/min, and standing to obtain the single-layer carrier loaded with the non-noble metal precursor/ordered spherical micelle template array.
The spin coating and glue homogenizing mode in the step (1) specifically comprises the following steps: placing a carrier at a suction piece of a table type spin coater, adjusting spin coating time and spin coating speed after pressing the suction piece, setting the spin coating time to be 10-60 s according to actual requirements generally, setting the spin coating speed to be 500-5000 rpm according to requirements generally, dropwise adding the solution dispersed with the non-noble metal precursor/diblock copolymer micelle on the carrier by using a glass dropper, starting spin coating, and standing and airing to obtain a single-layer carrier loaded with the non-noble metal precursor/ordered spherical micelle template array.
Preferably, the carrier includes but is not limited to one of a semiconductor, a conductive glass and the like.
Preferably, the diblock copolymer is polystyrene-polyvinylpyridine, the solution dispersed with the non-noble metal precursor/diblock copolymer micelle in the step (1) is prepared by adding the non-noble metal precursor and pyridine into a PS-b-P4VP spherical micelle solution, and stirring at a constant temperature of 50 ℃ for 8 hours at a constant speed, and the solution is prepared by taking an organic solvent with selective solubility as a solvent, so that the solubility of polystyrene PS is better than that of polyvinylpyridine PVP, and the spherical micelle structure can be formed by self-assembly.
Particularly, the molar ratio of acid radicals of the non-noble metal precursor to pyridine is 1: 8-2: 1.
The selectively soluble organic solvent includes but is not limited to one of PS selective solvents such as tetrahydrofuran, toluene and the like.
Preferably, the non-noble metal precursor includes, but is not limited to, one or more of non-noble metal salts such as iron nitrate, cobalt nitrate, nickel nitrate, chromium nitrate, copper nitrate, ferric chloride, and cobalt chloride.
Preferably, the noble metal precursor includes, but is not limited to, one or more of noble metal chloro-complex acids such as chloroauric acid, chloroplatinic acid, chloroiridic acid, chlororuthenic acid, chlororhodic acid, chloropalladic acid, chloroaosmic acid, sodium hexachloroplatinate, sodium tetrachloroplatinate, silver nitrate, and the like, and various salts.
When the diblock copolymer is polystyrene-polyvinylpyridine, the solution dispersed with the non-noble metal precursor/diblock copolymer micelle in the step (1) loads the non-noble metal precursor on the central part of the spherical micelle, the spherical micelle loaded with the non-noble metal precursor according to the molar ratio is uniformly coated on a carrier in a dipping, lifting or spin-coating glue homogenizing mode to obtain an ordered spherical micelle template array loaded with the non-noble metal precursor, and when the PS at the periphery of the micelle and the PVP inside the micelle are removed by plasma cleaning, the non-noble metal precursor loaded on the inside PVP is decomposed, and a decomposition product of the non-noble metal precursor, namely an ordered array of non-noble metal oxide is obtained. And then, reducing the obtained non-noble metal precursor decomposition product, namely the ordered array of non-noble metal oxide to obtain a non-noble metal ordered array, and then changing the type and concentration of the noble metal precursor and the time length of replacement to obtain the non-noble metal @ noble metal core-shell structure nanoparticle array substituted with different types of noble metals and different noble metal amounts.
Particularly, the reducing solution in the step (2) is sodium borohydride solution.
The invention has the following beneficial effects:
1) the non-noble metal @ noble metal core-shell structure nanoparticle array obtained by the method can greatly improve the utilization rate of noble metals and reduce the consumption of the noble metals on the premise of ensuring high performance, thereby reducing the application cost of noble metal materials.
2) Compared with the traditional core-shell structure dispersed particles, the non-noble metal @ noble metal core-shell structure nanoparticle array obtained by the invention has the advantage of difficult agglomeration, so the stability is far higher than that of the traditional core-shell structure dispersed particles, the high-stability nanoparticle array also has the advantage of high stability on the premise of keeping high performance, the service life of the core-shell structure nanoparticles can be prolonged, and the cost is further reduced.
3) According to the invention, by changing the types, concentrations and replacement time lengths of the non-noble metal precursor and the noble metal precursor, core-shell structure nanoparticle arrays with different core element types, different shell element types, different particle sizes and different shell thicknesses can be obtained, so that the method has wide applicability and can provide a new design idea for material development and research in the fields of catalysis, optics, electronics, energy conversion and storage and the like.
Description of the drawings:
FIG. 1a is a morphology chart of the ITO conductive glass Ni-loaded oxide nanoparticle array obtained in step (1) of example 1;
FIG. 1b is a schematic representation of the Ni @ Pt nanoparticle array obtained in step (2) of example 1;
FIG. 1c is a cyclic voltammogram of the Ni @ Pt nanoparticle array obtained in step (2) of example 1, as tested by cyclic voltammogram scanning under a three-electrode system;
FIG. 2 is a topographical view of the ITO conductive glass Ni @ Pt nanoparticle array prepared in example 2;
FIG. 3a is a topographical view of an ITO conductive glass Co-loaded @ Pt nanoparticle array prepared in example 3;
FIG. 3b is a cyclic voltammogram of the Co @ Pt nanoparticle array prepared in example 3 tested by cyclic voltammogram scanning under a three-electrode system;
FIG. 4a is a topographical view of an ITO conductive glass Cr @ Pt nanoparticle array prepared in example 4;
FIG. 4b is a cyclic voltammogram of the Cr @ Pt nanoparticle array prepared in example 4 tested by cyclic voltammogram scanning under a three-electrode system;
FIG. 5 is a topographical map of a Si-supported Ni @ Pt nanoparticle array prepared in example 5;
FIG. 6 is a topographical view of a Si-supported Ni @ Pt nanoparticle array prepared in example 6;
FIG. 7 is a topographical view of a Si substrate Co @ Au nanoparticle array prepared in example 7;
FIG. 8 is a graphical representation of an FTO conductive glass Cr-loaded @ Pt nanoparticle array prepared in example 8.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1:
a preparation method of a non-noble metal @ noble metal core-shell structure nanoparticle array comprises the following steps:
1) preparation of Ni oxide nano-particle ordered array by diblock copolymer template method
Preparing a 4m/mL PS-b-P4VP spherical micelle/tetrahydrofuran solution by taking tetrahydrofuran as a solvent, adding non-noble metal precursor solid nickel nitrate hexahydrate and pyridine into the micelle solution according to a molar ratio of 1:4, and magnetically stirring for 6 hours at room temperature at a rotor speed of 400rpm to obtain the tetrahydrofuran solution dispersed with the nickel nitrate/diblock copolymer micelle.
Selecting ITO conductive glass as a carrier, carrying out pretreatment of ultrasonic cleaning of the carrier for 10min by using absolute ethyl alcohol and deionized water respectively, and then airing for later use. Soaking dried ITO conductive glass in tetrahydrofuran solution of prepared nickel nitrate/diblock copolymer micelle as soaking solution, standing for 30s, then pulling out the ITO conductive glass at a constant speed at a pulling speed of 2mm/min, horizontally standing in air for 24h, then putting the ITO conductive glass into an air plasma cleaning machine to clean for 5min, and obtaining the carrier carrying the Ni oxide nanoparticle array after cleaning, wherein the shape picture is shown in figure 1 a.
2) Reduction, replacement process
And (3) dipping the ITO conductive glass carrier loaded with the Ni oxide nanoparticle array into a large amount of excessive sodium borohydride solution for 5min, reducing the Ni oxide to a simple substance state by using the large amount of excessive sodium borohydride, then using nitrogen as an inert gas protective atmosphere, flushing with deionized water subjected to high-purity nitrogen purging for 15min to remove oxygen, and airing to obtain the carrier loaded with the Ni nanoparticle array. And (3) soaking the carrier loaded with the Ni nanoparticle array in 1mg/mL chloroplatinic acid aqueous solution for 6min, taking out, cleaning with deionized water, and airing to obtain the Ni @ Pt nanoparticle array. The morphology photo of the obtained Ni @ Pt nanoparticle array is shown in FIG. 1b, the Ni @ Pt nanoparticle array is arranged in a hexagonal lattice form, and the diameter of the Ni @ Pt nanoparticles is not obviously changed compared with the particle size before replacement. The electrochemical activity of the Ni @ Pt nano-particles is tested, the electrochemical activity is analyzed by cyclic voltammetry scanning under a three-electrode system, the scanning speed is 100mV/s, and the electrolyte used in the test is 0.5M H2SO4Aqueous solution of saturated mercury/mercury sulfate (Hg/HgSO)4RHE) as reference electrode. Introducing high-purity nitrogen into the electrolyte for 15min before electrochemical test to remove dissolved oxygen, converting all electrode potentials into electrode potential V (vs. RHE) relative to a reversible hydrogen electrode in an analysis discussion, and calculating the electrochemical active surface of the prepared Ni @ Pt nano particles as shown in FIG. 1c according to a cyclic voltammetry curve obtained by the testThe product is: ECSANi@Pt＝85.1m2Per g, it is known from a review of the literature that the electrochemical active area of commercial Pt/C is about 55m2About/g, therefore, the electrochemical activity of the prepared Ni @ Pt nano particles is obviously higher than that of commercial Pt/C. The use amount of the noble metal is reduced under the condition of ensuring and even improving the electrochemical activity, and the aim of reducing the consumption cost of the noble metal is fulfilled.
Example 2:
the specific implementation steps of this example are substantially the same as those of example 1, except that: in the first step of example 1, in the preparation of the Ni oxide nanoparticle ordered array by the diblock copolymer template method, the dip-draw method is replaced by a spin-coating method, and the specific implementation steps are as follows:
1) preparation of Ni oxide nano-particle ordered array by diblock copolymer template method
Preparing a 4m/mL PS-b-P4VP spherical micelle/tetrahydrofuran solution by taking tetrahydrofuran as a solvent, adding solid nickel nitrate hexahydrate and pyridine into the micelle solution according to a molar ratio of 1:8, magnetically stirring for 6 hours at room temperature at a rotor speed of 400rpm, and loading non-noble metal element nickel into a precursor/copolymer tetrahydrofuran solution in the spherical micelle according to a molar ratio of 1:8 to obtain the tetrahydrofuran solution dispersed with nickel nitrate/diblock copolymer micelles.
Selecting ITO conductive glass as a carrier, carrying out pretreatment of ultrasonic cleaning of the carrier for 10min by using absolute ethyl alcohol and deionized water respectively, and then airing for later use. Placing the treated and dried ITO conductive glass at a suction piece of a table type spin coater, setting the spin coating time length to be 60s after pressing the suction piece, setting the spin coating speed to be 2000rpm, dropwise adding a prepared nickel nitrate/block copolymer tetrahydrofuran solution on a carrier by using a glass dropper, starting spin coating, and then standing for 24h and drying. The subsequent operation is the same as that of example 1, and finally, the Ni @ Pt nanoparticle array can be obtained. The morphology photo of the obtained Ni @ Pt nanoparticle array is shown in FIG. 2, and the Ni @ Pt nanoparticle array is arranged in a hexagonal lattice form.
Example 3:
the detailed implementation steps and implementation of the embodimentExample 1 is essentially the same except that: the non-noble metal precursor is changed from nickel nitrate hexahydrate to cobalt nitrate hexahydrate, and chloroplatinic acid is still selected as the noble metal precursor. The Co @ Pt nanoparticle array can be obtained through the same processing steps as in example 1. The morphology of the obtained Co @ Pt nanoparticle array is shown in FIG. 3a, and the Co @ Pt nanoparticle array is arranged in a hexagonal lattice form. The Co @ Pt nanoparticles were tested for electrochemical activity, which was analyzed by cyclic voltammetric scanning under a three-electrode system with a scan rate of 100mV/s, with 0.5M aqueous H2SO4 solution as the electrolyte, and saturated mercury/mercury sulfate (Hg/HgSO4, -0.7V vs. RHE) as the reference electrode. Before electrochemical test, high-purity nitrogen is introduced into the electrolyte for 15min to remove dissolved oxygen, all electrode potentials can be converted into electrode potential V (vs. RHE) relative to a reversible hydrogen electrode in an analysis discussion, a cyclic voltammetry curve obtained by the test is shown in FIG. 3b, and the electrochemical active area of the prepared Co @ Pt nano-particles is calculated as follows: ECSACo@Pt＝154.2m2The electrochemical activity of the Pt/g is still higher than that of common commercial Pt/C.
Example 4:
the specific implementation steps of this example are substantially the same as those of example 1, except that: the non-noble metal precursor is changed from nickel nitrate hexahydrate to chromium nitrate nonahydrate, the molar ratio of solid chromium nitrate nonahydrate to pyridine is changed to 1:8, the solid chromium nitrate nonahydrate and the pyridine are added into the micelle solution, and the noble metal precursor is still selected from chloroplatinic acid. The Cr @ Pt nanoparticle array was obtained through the same processing steps as in example 1. The morphology photograph of the obtained Cr @ Pt nanoparticle array is shown in FIG. 4a, and the Cr @ Pt nanoparticle array is arranged in a hexagonal lattice form. The Cr @ Pt nanoparticles were tested for electrochemical activity, which was analyzed by cyclic voltammetric scanning under a three-electrode system with a scan rate of 100mV/s, with 0.5M aqueous H2SO4 solution as the electrolyte, and saturated mercury/mercury sulfate (Hg/HgSO4, -0.7V vs. RHE) as the reference electrode. High purity nitrogen was bubbled into the electrolyte for 15min to remove dissolved oxygen before electrochemical testing, and all electrode potentials in the analytical discussion were converted to electrodes relative to reversible hydrogen electrodesRhe, and the cyclic voltammogram obtained by the test is shown in fig. 4b, and the electrochemical active area of the prepared Cr @ Pt nanoparticles is calculated as follows: ECSACr@Pt＝164.3m2The electrochemical activity of the catalyst is still higher than that of the commercial Pt/C.
Example 5:
the specific implementation steps of this example are substantially the same as those of example 1, except that: changing the molar ratio of solid nickel nitrate hexahydrate to pyridine to be 1:8, adding the mixture into the micelle solution, and replacing the carrier with an ITO conductive glass to be a Si sheet, wherein the Si sheet is processed by the following steps:
mixing 20% hydrogen peroxide aqueous solution and concentrated sulfuric acid according to the weight ratio of 3: 7, then immersing the cut Si wafer in the mixture, heating to 200 ℃ and keeping the temperature constant, continuously stirring the silicon wafer in the treatment process to ensure that the surface of the silicon wafer is fully contacted with the mixed solution to be activated so as to increase the affinity of the Si wafer and the solvent, cooling to room temperature after three hours, taking out the silicon wafer, washing with the ionized water, and airing for later use. Other operations are the same as in example 1, and finally, an array of Ni @ Pt nanoparticles supported on a Si sheet can be obtained. The morphology photograph of the obtained Ni @ Pt nanoparticle array is shown in FIG. 5, and the obtained Ni @ Pt nanoparticle array is arranged in a hexagonal lattice form.
Example 6:
the specific implementation steps of this example are substantially the same as those of example 2, except that: the molar ratio of the solid nickel nitrate hexahydrate to the pyridine was changed to 1:8, the solid nickel nitrate hexahydrate and the pyridine were added to the micelle solution, the used organic solvent with selective solubility was toluene, the used carrier was a Si sheet, and the other operations were the same as in example 2, and finally, an array of Ni @ Pt nanoparticles supported on the Si sheet was obtained. The morphology photograph of the obtained Ni @ Pt nanoparticle array is shown in FIG. 6, and the obtained Ni @ Pt nanoparticle array is arranged in a hexagonal lattice form.
Example 7:
the specific implementation steps of this example are substantially the same as those of example 3, except that: the noble metal precursor is changed from chloroplatinic acid to chloroauric acid, and the carrier is a Si sheet. The Co @ Au nanoparticle array was obtained through the same processing steps as in example 2. The morphology photo of the obtained Co @ Au nanoparticle array is shown in FIG. 7, and the Co @ Au nanoparticle array is arranged in a hexagonal lattice form.
Example 8:
the specific implementation steps of this example are substantially the same as those of example 3, except that: the non-noble metal precursor is chromium nitrate, and the molar ratio of acid radical to pyridine of the non-noble metal precursor is 2: 1. The noble metal precursor is chloroiridic acid, and the carrier is FTO glass. The morphology of the obtained Cr @ Ir nanoparticle array is shown in FIG. 8.
Claims (6)
1. A preparation method of a core-shell structure nanoparticle array taking non-noble metal elements as cores and noble metal elements as shells is characterized by comprising the following steps:
(1) the carrier is dipped, pulled or spin-coated with a uniform glue in a solution dispersed with non-noble metal precursor/diblock copolymer micelle, and a single-layer template array loaded with non-noble metal precursor/ordered spherical micelle is dip-coated or spin-coated on the carrier, and then the carrier is put into an air plasma cleaning machine for cleaning until the diblock copolymer template is completely removed, so as to obtain the initially implanted carrier of the ordered non-noble metal oxide nanoparticle array arranged according to a hexagonal lattice; the carrier comprises one of a semiconductor and conductive glass; the diblock copolymer is polystyrene-polyvinyl pyridine; the solution dispersed with the non-noble metal precursor/diblock copolymer micelle is prepared by adding the non-noble metal precursor and pyridine into a PS-b-P4VP spherical micelle solution, and stirring at constant temperature of 50 ℃ for 8 hours at constant speed, wherein an organic solvent with selective solubility is used as a solvent; the molar ratio of acid radicals of the non-noble metal precursor to pyridine is 1: 8-2: 1; the selective solubility organic solvent comprises one of tetrahydrofuran and toluene;
(2) dipping the carrier loaded with the non-noble metal oxide nanoparticle array obtained in the step (1) in a reducing solution or treating the carrier with hydrogen plasma, and then washing and airing the carrier with deionized water for removing oxygen in an inert gas protective atmosphere to obtain the carrier loaded with the non-noble metal oxide nanoparticle array;
(3) and (3) soaking the carrier loaded with the non-noble metal nanoparticle array obtained in the step (2) in a noble metal precursor solution with a certain concentration for a certain time, taking out, cleaning with deionized water, and airing to obtain the non-noble metal @ noble metal nanoparticle array.
2. The preparation method according to claim 1, wherein the size of the nanoparticles is controlled by controlling the concentration of the non-noble metal precursor, and the amount of the noble metal to be replaced is controlled by controlling the concentration of the noble metal precursor solution or the replacement time.
3. The preparation method according to claim 1, wherein the dipping and pulling manner in the step (1) is specifically: and (3) putting the carrier into the solution dispersed with the non-noble metal precursor/diblock copolymer micelle, soaking for more than 30s, then uniformly pulling the carrier out of the solution at a speed of 2-5 mm/min, and standing to obtain the single-layer carrier loaded with the non-noble metal precursor/ordered spherical micelle template array.
4. The preparation method according to claim 1, wherein the spin coating and spin coating in step (1) is specifically performed by: placing a carrier at a suction piece of a table type spin coater, adjusting spin coating time and spin coating speed after pressing the suction piece, setting the spin coating time at 10-60 s according to actual requirements, setting the spin coating speed at 500-5000 rpm according to requirements, dropwise adding the solution dispersed with the non-noble metal precursor/diblock copolymer micelle on the carrier by using a glass dropper, starting spin coating, and then standing and airing to obtain a single-layer carrier loaded with the non-noble metal precursor/ordered spherical micelle template array.
5. The preparation method according to claim 1, wherein the non-noble metal precursor comprises one or more of ferric nitrate, cobalt nitrate, nickel nitrate, chromium nitrate, cupric nitrate, ferric chloride and cobalt chloride; the noble metal precursor comprises one or more of chloroauric acid, chloroplatinic acid, chloroiridic acid, chlororuthenic acid, chlororhodic acid, chloropalladic acid, chloroosmic acid, sodium hexachloroplatinate, sodium tetrachloroplatinate and silver nitrate.
6. The method according to claim 1, wherein the reducing solution of step (2) is a sodium borohydride solution.
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