CN109647381B - Method for controllably preparing highly-dispersed mesoporous carbon-based composite material of platinum particles as efficient hydrogen production electrocatalyst - Google Patents
Method for controllably preparing highly-dispersed mesoporous carbon-based composite material of platinum particles as efficient hydrogen production electrocatalyst Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 88
- 239000002245 particle Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000001257 hydrogen Substances 0.000 title abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 title abstract description 16
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- 239000010411 electrocatalyst Substances 0.000 title description 3
- 239000002243 precursor Substances 0.000 claims abstract description 54
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 18
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 9
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 9
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- -1 platinum ions Chemical class 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
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- 239000006228 supernatant Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 238000011065 in-situ storage Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/33—
-
- B01J35/393—
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- 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
- C25B11/093—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 noble metal or noble metal oxide and at least one non-noble metal oxide
Abstract
The invention relates to a preparation method of a highly dispersed mesoporous carbon-based composite material of platinum particles, which comprises the following steps: 1) mixing tetracarboxyl porphyrin, zirconium tetrachloride, benzoic acid and N, N-diethylformamide to obtain a platinum-loaded carrier; 2) dissolving the platinum-loaded carrier obtained in the step 1) and a certain amount of platinum source in N, N-dimethylformamide, water or a mixed solution of the N, N-dimethylformamide and the water, heating to a certain temperature, and keeping for a certain time to obtain a platinum-loaded roasting precursor; 3) roasting and carbonizing the platinum-loaded roasting precursor obtained in the step 2) in inert gas; 4) treating the roasted product obtained in the step 3) with acid (preferably hydrofluoric acid) to obtain the composite material. The highly dispersed mesoporous carbon-based composite material of the platinum particles can be used as a high-efficiency electrochemical hydrogen production catalyst, and the nano-size effect and the surface effect of the highly dispersed platinum particles are utilized, so that the platinum particles are fully utilized, and the utilization rate of resources is greatly improved.
Description
Technical Field
The invention mainly relates to the technical field of nano materials, in particular to a method for preparing noble metal nano particles loaded on a carbon-based material in a controllable manner to produce hydrogen by high-efficiency electrocatalysis.
Background
With the increasingly prominent global energy and environmental problems, hydrogen is expected to become a substitute of fossil fuels as a clean and pollution-free energy with high heat release. Electrochemical decomposition of water to produce hydrogen is an effective method for producing hydrogen in large quantities, however, this process relies on highly active and highly stable electrocatalysts.
Platinum-based catalysts have been considered as the most efficient electrochemical hydrogen production catalysts, but their high price is far from meeting the needs of industrial development due to insufficient storage and uneven distribution on earth. In the electrocatalysis hydrogen production process, the known catalytic active sites are only positioned at the edges of the noble metal platinum particles, the catalytic activity in the particles is small, and the noble metal platinum particles are easy to agglomerate in the electrochemical hydrogen production process. Therefore, how to control the size of platinum particles is reduced as much as possible so as to expose more surface atoms and effectively improve the utilization rate of noble metals. Meanwhile, the platinum particles and the carbon material uniformly doped with heterogeneous atoms are compounded in situ, so that the electrocatalytic performance of the platinum is greatly improved.
Therefore, the size of the platinum particles is effectively controlled to be reduced as much as possible, so that the platinum can be efficiently utilized, the waste of noble metal can be avoided, and the method has important significance for social development.
Disclosure of Invention
In order to overcome the phenomenon that noble metals are easy to agglomerate and realize the full utilization of resources, the invention provides a method for controllably preparing a carbon nano rod-shaped material uniformly doped with nitrogen atoms loaded on noble metal platinum nano particles.
The technical scheme adopted by the invention is as follows:
a method for preparing a mesoporous carbon-based composite material with highly dispersed platinum particles is characterized by comprising the following steps:
1) mixing tetracarboxyl porphyrin, zirconium tetrachloride, benzoic acid and N, N-diethylformamide to obtain a platinum-loaded carrier;
2) dissolving the platinum-loaded carrier obtained in the step 1) and a certain amount of platinum source in N, N-dimethylformamide, water or a mixed solution of the N, N-dimethylformamide and the water, heating to a certain temperature, and keeping for a certain time to obtain a platinum-loaded roasting precursor;
3) roasting and carbonizing the platinum-loaded roasting precursor obtained in the step 2) in inert gas;
4) treating the roasted product obtained in the step 3) with acid (preferably hydrofluoric acid) to obtain the composite material.
The method of the invention prepares the controllable platinum particle loaded nitrogen uniformly doped composite material.
According to the present invention, in step 1), the platinum carrier can be mass-produced by enlarging the raw material ratio as necessary. For example, it can be produced by a 2-to 10-fold scale-up method.
In the step (1), the platinum-loaded carrier is obtained by adopting a solvothermal mode.
According to the present invention, the platinum-carrying support (also referred to as "carrying precursor") of step 1) is prepared by the following method: certain amounts of zirconium tetrachloride, porphyrin and benzoic acid are dissolved in a high-pressure reaction kettle by N, N-diethylformamide, and the solution is placed in an oven and kept at the temperature of 110-125 ℃ for 24-48 hours, and then kept at the temperature of 130-140 ℃ for 12-36 hours. And centrifuging and drying to obtain the load precursor.
Preferably, amounts of zirconium tetrachloride, tetracarboxylporphyrin and benzoic acid are dissolved in N, N-diethylformamide in an autoclave, placed in an oven at 120 ℃ for 48 hours, and then at 130 ℃ for 24 hours. And centrifuging and drying to obtain the load precursor.
According to the invention, in step 2), the source of platinum is selected from chloroplatinic acid, ammonium chloroplatinate, preferably chloroplatinic acid.
According to the invention, in the step 2), the mass ratio of the platinum source to the load precursor can be controlled to be 1: 1 to 3: 2, preferably between 1: 1 to 2: 1.
According to the invention, in the step 2), the solvent used in the loading is selected from N, N-dimethylformamide, water or a mixed solution of any of the two.
According to the invention, in step 2), the heating temperature range and the holding temperature range of the platinum source and the load precursor are selected from 60 to 90 ℃, preferably 80 to 90 ℃; the holding temperature is selected from the range of 12 to 48 hours, preferably 20 to 36 hours.
According to the invention, in step 3), the calcination temperature is 800-. The preferred calcination temperature is 800-850 ℃. The calcination time is preferably 60 to 180 minutes, more preferably 100-150 minutes.
According to the present invention, in step 3), the inert gas may be nitrogen, argon, etc., preferably argon.
According to the invention, in step 3), the calcination is preferably carried out in a tube furnace. The specific method comprises the following steps: putting the platinum-loaded roasting precursor into a tube furnace, vacuumizing the tube furnace by using a pump, blowing nitrogen or argon, and roasting at the temperature of 800-. After that, natural cooling and programmed cooling can be adopted.
According to the invention, in step 4) the concentration of hydrofluoric acid is chosen in the range of 0.5-3 mol/l, preferably 1-2 mol/l. The treatment time with hydrofluoric acid is selected from 12 to 48 hours, preferably 20 to 30 hours.
In the method, a material with porphyrin macromolecules is used as a load precursor, and the material generally has larger pore passages and unsaturated coordination sites. Under a certain solvent, platinum ions diffuse into the pore canal of the loaded precursor and interact with unsaturated coordination sites in the porphyrin ring. And roasting and carbonizing the roasting precursor loaded with the highly dispersed platinum in inert gas to obtain the mesoporous carbon-based material with the highly dispersed platinum particles. Finally, the carbon material is preferably treated in dilute acid to etch away the resulting impurities, which increase the porosity of the material surface.
The invention also provides a mesoporous carbon-based composite material with highly dispersed platinum particles, which is prepared by the method.
According to the invention, the composite material has periodic channels.
The mesoporous carbon-based composite material with highly dispersed platinum particles, which is prepared by the preparation method, keeps the framework of the loaded precursor and still has a certain periodic pore channel. Preferably, the particle size distribution is in the range of 2-3 nm.
The mesoporous carbon-based composite material with the highly dispersed platinum particles has a nano-size effect, high porosity and high dispersibility of heterogeneous atoms, so that the composite material has good catalytic property in the electrocatalytic hydrogen production process. The full utilization of resources is realized.
The invention also provides application of the mesoporous carbon-based composite material with the highly dispersed platinum particles, which is used for an electro-catalytic hydrogen production material. Has high activity and stability.
Compared with the prior art, the invention has the following characteristics:
1. the method has simple preparation process, highly disperses the limited noble metal platinum in nature and controls the platinum to be in a nanometer level.
2. The platinum particle highly-dispersed mesoporous carbon-based composite material prepared by the preparation method still keeps the periodicity of the original framework and pore canal of the loaded precursor after high-temperature carbonization.
3. The highly-dispersed mesoporous carbon-based composite material of the platinum particles obtained by the preparation method of the invention obtains smaller platinum particles and can stably exist for a long time, so that more platinum atoms are exposed on the surface, and the full utilization of resources is realized. And the nitrogen source in the precursor framework is loaded, the in-situ doping is in the carbon framework and the carbon framework is uniformly dispersed, so that the electrocatalytic activity sites are increased, and the electrocatalytic activity is further improved.
Drawings
FIG. 1: scanning electron micrographs of the supported precursor prepared in example 1.
FIG. 2: transmission electron micrograph of the supported precursor prepared in example 1.
FIG. 3: powder diffraction patterns before and after loading of platinum on the supported precursor prepared in example 1.
FIG. 4: scanning electron microscope image of highly dispersed mesoporous carbon-based composite material of platinum particles prepared in example 1.
FIG. 5: a transmission electron microscope image of the highly dispersed mesoporous carbon-based composite material of platinum particles prepared in example 1.
FIG. 6: a distribution graph of the particle size of the platinum nanoparticles in the platinum particle highly dispersed mesoporous carbon-based composite material prepared in example 1.
FIG. 7: a powder diffraction pattern of the highly dispersed mesoporous carbon-based composite material of platinum particles prepared in example 1.
FIG. 8: the isothermal adsorption curve of nitrogen and the pore size distribution diagram of the highly dispersed mesoporous carbon-based composite material of platinum particles prepared in example 1.
FIG. 9: a picture of electrocatalytic hydrogen production of the platinum particle highly dispersed mesoporous carbon-based composite material prepared in example 1.
Detailed Description
The technical solutions of the present invention are described in detail by the following exemplary specific examples, but these examples should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The starting materials and reagents used in the examples are all commercially available materials.
Example 1:
50mg of zirconium chloride, 50mg of tetracarboxylporphyrin and 2700mg of benzoic acid were dissolved in 8mL of N, N-diethylformamide and sonicated until dissolved uniformly. The mixed solution was poured into a 25mL reaction vessel of polytetrafluoroethylene. Placed in an oven and held at 120 degrees celsius for 48 hours, then the oven temperature was set to 130 degrees celsius and held for 24 hours. And naturally cooling the reaction kettle to room temperature, separating out a reddish brown precipitate at the bottom of the reaction kettle, centrifugally washing the precipitate with ethanol for multiple times until the supernatant becomes colorless and transparent, and drying the reddish brown precipitate to obtain the load precursor. According to the mass ratio of the load precursor to the argon chloroplatinic acid amine of 2: 1 and put into a 25mL glass reaction bottle, 10 mL of N, N-dimethylformamide is added, and ultrasonic treatment is carried out until the mixture is uniformly dispersed. And (4) placing the precursor into an oven, keeping the temperature at 85 ℃ for 48 hours, and then naturally cooling the precursor to room temperature to obtain the platinum-loaded roasting precursor. Washing the roasted precursor with ethanol for several times until the supernatant becomes colorless and transparent, and drying. And (3) putting the dried precursor into a roasting crucible, putting the crucible into a tube furnace, introducing high-purity argon, controlling the temperature by adopting a program, heating to 850 ℃ per minute at 5 ℃, and keeping for two hours. And then naturally cooling. And taking out the carbonized black precursor, treating the carbonized black precursor by using 0.5 mol of hydrofluoric acid aqueous solution, soaking for 12 hours, washing the carbonized black precursor to be neutral by using secondary water, removing impurities generated in the carbonization process, and placing the carbonized black precursor in an oven to be dried at 60 ℃ to obtain the platinum particle highly-dispersed mesoporous carbon-based composite material.
Example 2
550mg of zirconium chloride, 550mg of tetracarboxylporphyrin and 29.7g of benzoic acid were dissolved in 88mL of N, N-diethylformamide, and the solution was sonicated until homogeneous. The mixed solution was poured into a 200mL reaction vessel of polytetrafluoroethylene. The mixture was placed in an oven at 125 ℃ for 36 hours and 135 for 30 hours. And naturally cooling the reaction kettle to room temperature, separating out a reddish brown precipitate at the bottom of the reaction kettle, centrifugally washing the precipitate with ethanol for multiple times until the supernatant becomes colorless and transparent, and drying the reddish brown precipitate to obtain the load precursor. According to the mass ratio of the load precursor to the chloroplatinic acid amine of 3: 1 and put into a 25ml glass reaction bottle, 10 ml of water is added, and ultrasonic treatment is carried out until the mixture is uniformly dispersed. And (4) putting the precursor into an oven, keeping the temperature at 80 ℃ for 24 hours, and then naturally cooling the precursor to room temperature to obtain the precursor loaded with platinum. And (2) placing the dried precursor loaded with platinum in a crucible and placing in a tube furnace, introducing high-purity nitrogen, raising the temperature to 800 ℃ by adopting a program, keeping for 150 minutes, then carrying out program cooling according to 10 ℃ per minute, taking out a sample when the temperature of the tube furnace is reduced to room temperature, treating the sample by using a hydrofluoric acid aqueous solution with the concentration of 1.0 mol, soaking for 6 hours, washing to be neutral by using deionized water, and placing in an oven for drying at 100 ℃ to obtain the platinum particle highly-dispersed mesoporous carbon-based composite material.
Example 3
The composite material prepared in example 1 was examined.
The scanning electron microscope picture of the mesoporous carbon-based composite material with the highly dispersed precursor and platinum particles is characterized by a JSM-6700 type scanning electron microscope;
the powder diffraction patterns before and after loading the precursor with platinum are characterized by a MiniFlex II type powder diffractometer;
the transmission electron microscope picture of the loaded precursor and the highly dispersed platinum particle mesoporous carbon-based composite material is characterized by a TecnaiG2F20 type transmission electron microscope;
the electrocatalytic hydrogen production experiment of the platinum particle highly-dispersed mesoporous carbon-based composite material is completed by the test of an electrochemical workstation CHI 760E.
Fig. 1 is a scanning electron micrograph of the supported precursor prepared in example 1. a represents a scanning electron microscope picture of the load precursor prepared in the example 1, wherein the magnification of the scan electron microscope picture is 5000 times; b represents a 30000-fold scanning electron micrograph of the supported precursor prepared in example 1. It can be seen from the sem images that the loaded precursor was rod-shaped and its surface was smooth.
Fig. 2 is a transmission electron micrograph of the supported precursor prepared in example 1. The periodic arrangement of the surface of the loaded precursor can be seen from the figure, and the loaded precursor has certain hierarchy.
Fig. 3 is a powder diffraction pattern before and after loading platinum on the supported precursor prepared in example 1. The powder diffraction peak of the precursor after platinum loading is consistent with that before platinum loading, which shows that the precursor can not be damaged in the loading process and still maintains the original framework.
Fig. 4 is a scanning electron microscope image of the highly dispersed mesoporous carbon-based composite material of platinum particles prepared in example 1. From the figure, it can be confirmed that the composite material still maintains the rod-like structure of the supported precursor, but cracks occur on the surface of the composite material, so that the surface area of the composite material is more favorably increased.
Fig. 5 is a transmission electron microscope image of the highly dispersed mesoporous carbon-based composite material of platinum particles prepared in example 1. The black particles are platinum, and the highly dispersed distribution of platinum particles can be seen from the figure.
Fig. 6 is a distribution diagram of the particle size of platinum nanoparticles in the highly dispersed mesoporous carbon-based composite material of platinum particles prepared in example 1. Wherein the histogram is the percentage content of different particle sizes; a total of 81 points were measured, with a maximum particle size of 15.69 nm, a minimum particle size of 4.16 nm and an average particle size of 9.11 nm.
Fig. 7 is a powder diffraction pattern of the highly dispersed mesoporous carbon-based composite material of platinum particles prepared in example 1. It can be seen from the figure that the composite contains only peaks of elemental platinum and carbon. The material was determined to be a platinum-supported carbon-based material.
Fig. 8 is a nitrogen adsorption drawing of the highly dispersed mesoporous carbon-based composite material of platinum particles prepared in example 1. In the drawing, it can be seen that the nitrogen adsorption curve has an obvious hysteresis loop indicating the existence of mesopores, which is beneficial to the electrocatalysis effect.
Example 4
The composite material prepared in example 1 is used for electrocatalytic hydrogen production for detection.
Ethanol 940 microliter and nafion solution with the mass fraction of 5% 60 microliter are mixed to obtain mixed solution of 1.0 milliliter, 10 milligrams of catalyst prepared in example 1 is weighed and mixed with the mixed solution, and the mixture is subjected to ultrasonic treatment to obtain black suspension. 3 microliter of the black suspension is transferred by a liquid transfer gun and rotationally coated on a rotating disk electrode to serve as a working electrode, a carbon rod serves as a counter electrode, a silver/silver chloride electrode serves as a reference electrode, and 0.5 mol of sulfuric acid serves as an electrolyte.
The test results are shown in FIG. 9. Fig. 9 is a comparison of the linear sweep voltammogram of the composite with a mass fraction of 20% of commercial platinum carbon. It can be seen from fig. 9 that the composite material requires less potential than commercial platinum carbon. Therefore, the composite material is suitable for serving as an electrocatalytic hydrogen production material.
Claims (20)
1. A preparation method of a mesoporous carbon-based composite material with highly dispersed platinum particles is characterized by comprising the following steps:
1) mixing tetracarboxyl porphyrin, zirconium tetrachloride, benzoic acid and N, N-diethylformamide to obtain a platinum-loaded carrier;
2) dissolving the platinum-loaded carrier obtained in the step 1) and a certain amount of platinum source in N, N-dimethylformamide, water or a mixed solution of the N, N-dimethylformamide and the water, heating to a certain temperature, and keeping for a certain time to obtain a platinum-loaded roasting precursor;
3) roasting and carbonizing the platinum-loaded roasting precursor obtained in the step 2) in inert gas;
4) and (3) treating the roasted product obtained in the step 3) with acid to obtain the composite material.
2. The method of claim 1, wherein in step 4), the acid is hydrofluoric acid.
3. The method according to claim 1, wherein the platinum-carrying carrier is mass-produced in step 1) by enlarging a raw material ratio as necessary.
4. The method according to claim 1, wherein the platinum-carrying support is obtained in step 1) solvothermally.
5. The method according to any one of claims 1 to 4, wherein the platinum-supporting carrier of step 1) is prepared by: certain amounts of zirconium tetrachloride, tetracarboxylporphyrin and benzoic acid are dissolved in a high-pressure reaction kettle by using N, N-diethylformamide, and the solution is placed in an oven and kept at the temperature of 110-125 ℃ for 24-48 hours, and then kept at the temperature of 130-140 ℃ for 12-36 hours.
6. The method according to claim 5, wherein in the step 1), the carrier loaded with platinum is obtained by further centrifuging and drying.
7. The method according to claim 5, wherein the platinum-supporting carrier of step 1) is prepared by: dissolving a certain amount of zirconium tetrachloride, tetracarboxylporphyrin and benzoic acid in a high-pressure reaction kettle by using N, N-diethylformamide, placing the reaction kettle in an oven, keeping the reaction kettle at 120 ℃ for 48 hours, then keeping the reaction kettle at 130 ℃ for 24 hours, centrifuging and drying to obtain the platinum-loaded carrier.
8. The method according to any one of claims 1 to 4, wherein in step 2), the mass ratio of the platinum source to the carrier is controlled to be 1: 1 to 3: 2.
9. The method according to any one of claims 1 to 4, wherein in step 2) the source of platinum is selected from the group consisting of chloroplatinic acid, ammonium chloroplatinate.
10. The method as claimed in claim 1, wherein, in the step 2), the heating temperature range and the holding temperature range are selected from 60-90 degrees celsius and the holding temperature time range is selected from 12-48 hours when the platinum source is mixed with the carrier.
11. The method as claimed in claim 10, wherein, in the step 2), the heating temperature range and the holding temperature range are selected from 80-90 degrees celsius and the holding temperature time range is selected from 20-36 hours when the platinum source is mixed with the carrier.
12. The method as claimed in any one of claims 1 to 4, wherein, in step 3), the calcination temperature is 800-900 ℃; the roasting time is 60-180 minutes.
13. The method as claimed in claim 12, wherein, in the step 3), the roasting temperature is 800-850 ℃; the calcination time is 100-150 minutes.
14. The method according to any one of claims 1 to 4, wherein in step 3), the inert gas is nitrogen, argon.
15. The process according to any one of claims 1 to 4, wherein, in step 3), the roasting is carried out in a tube furnace;
optionally, a natural or programmed cooling is then employed.
16. The method as claimed in claim 15, wherein in step 3), the precursor loaded with platinum is placed in a tube furnace, the tube furnace is evacuated by a pump, nitrogen or argon is blown in, and the precursor is baked at a temperature of 800 ℃ and 900 ℃ for a certain time.
17. A process according to any one of claims 1 to 4, wherein in step 4) the calcined product of step 3) is mixed with an acid, the acid being 0.5 to 3 moles of dilute acid and the treatment time with acid being 12 to 48 hours.
18. The process of claim 17, wherein in step 4), the calcined product of step 3) is mixed with an acid, the acid being 1-2 moles of dilute acid, and the time of treatment with the acid is 20-30 hours.
19. The method of any one of claims 1-4, wherein the platinum particle highly dispersed mesoporous carbon-based composite material has periodic channels.
20. The method of claim 19, wherein the particle size distribution of the composite material is uniform, the particle size distribution being between 2-3 nm.
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