CN108160088B - Platinum/platinum dichloride composite material with cubic crystal structure and nonlinear synthesis method and application thereof - Google Patents
Platinum/platinum dichloride composite material with cubic crystal structure and nonlinear synthesis method and application thereof Download PDFInfo
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- CN108160088B CN108160088B CN201711370825.2A CN201711370825A CN108160088B CN 108160088 B CN108160088 B CN 108160088B CN 201711370825 A CN201711370825 A CN 201711370825A CN 108160088 B CN108160088 B CN 108160088B
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 130
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 62
- 239000013078 crystal Substances 0.000 title claims abstract description 57
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000010355 oscillation Effects 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 12
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
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- 239000000203 mixture Substances 0.000 claims description 3
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- 238000003786 synthesis reaction Methods 0.000 claims description 3
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- 239000007788 liquid Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 13
- 238000012512 characterization method Methods 0.000 description 10
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- 238000002848 electrochemical method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- -1 Platinum group metals Chemical class 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 229910019032 PtCl2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
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- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/33—
-
- 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
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a platinum/platinum dichloride composite material with a cubic crystal structure and a nonlinear synthesis method and application thereof, wherein the method comprises the following steps: s1: reacting p-nitrophenol, sodium bromate and sulfuric acid at room temperature, and recording the chemical oscillation reaction by using an open circuit-time curve; s2: and during the reaction, adding a platinum dichloride raw material into the system at one time, taking out reaction liquid after the reaction is finished, and centrifuging and cleaning to obtain the platinum/platinum dichloride catalytic composite material with the cubic crystal structure. The preparation method combines nonlinear chemical oscillation with preparation of noble metal innovatively, so that the platinum/platinum dichloride catalytic composite material with a cubic crystal structure and excellent hydrogen production performance is obtained, and the platinum/platinum dichloride catalytic composite material can be used in the field of hydrogen production by electrolyzing water and has good application prospect and industrialization potential.
Description
Technical Field
The invention provides a composite material, a preparation method and application thereof, and more particularly provides a platinum/platinum dichloride composite material with a cubic crystal structure and a nonlinear synthesis method and application thereof, which can be used for hydrogen production by water electrolysis, belonging to the field of inorganic functional materials.
Background
With increasing environmental issues and non-renewable fossil fuels, new technologies are urgently needed to be developed to replace energy conversion and storage devices such as solar cells, lithium ion batteries, supercapacitors, fuel cells and the like to solve energy crisis. Recently, researchers have been keen to develop high-performance fuel cells in which catalyst performance is an important factor controlling improvement in fuel cell performance. Platinum group metals have attracted considerable attention naturally for their high melting point, good electrical conductivity, good corrosion resistance and high temperature stability and as the most effective catalysts in fuel cells. However, the high cost of Pt-based catalysts as one of the noble metals has made them impractical for commercial use in fuel cells. Therefore, research and development of new catalysts to reduce Pt loading and increase catalyst use efficiency and stability are urgently needed.
To date, many approaches to synthesizing Pt nanostructures have been explored and studied in this regard, such as: inorganic ion introduction, template induction, electrochemical reaction, seed growth, decomposition of organic Pt precursor at high temperature, etc. At present, researchers have synthesized platinum nanostructures with various morphologies such as linear, branched, spherical, rod-like, polyhedral and dendritic structures mainly by wet chemical methods and electrochemical methods.
The Sunshima project group of the editors successfully prepares the tetrahedron nanocrystals of Pt and Pd with high-index crystal faces exposed by an electrochemical method, and the materials show more excellent catalytic performance than the traditional Pt and Pd catalysts.
While Manfune F et al synthesized Pt particles with a particle size of about 6nm by laser radiation, and then synthesized nano platinum particles with an average particle size of 1.5nm by using sodium dodecyl sulfate as a stabilizer by a high-intensity UV pulse laser method and stirring uniformly.
Lee and its collaborators prepared five-twins Pt nanorods. Shviro et al synthesized hollow octahedral and cuboctahedral Pt-Ni-Au nanostructures by electro-corrosive reaction.
At present, an electrochemical method and a wet chemical method are common methods for shape control synthesis, scientists have synthesized a large number of noble metal nano catalysts with different shapes by the two methods, but the electrochemical method has high experimental requirements and cannot be produced in large scale, and a proper functional molecule needs to be introduced by the wet chemical method. Therefore, based on the defects of the above synthesis method, self-organization and self-regulation of a chemical reaction system are utilized to obtain self-regulation (such as nonlinear oscillation) of reaction rate or functional molecule concentration, which has not been researched and applied yet, and obviously, the development of the novel dynamic regulation and control means provides unprecedented opportunities and challenges for realizing controllable preparation of a new-structure and high-performance noble metal nano-catalyst, which is the foundation and the dynamic dependence of the completion of the invention.
Disclosure of Invention
In order to overcome the drawbacks of the above-mentioned methods for synthesizing platinum group noble metals, a simple, fast, economical and environmentally friendly method for preparing a platinum group composite material having a regular morphology is sought and its application in the field of electrocatalysis is studied, and the present inventors have made intensive studies and, after having paid a lot of creative efforts, have completed the present invention.
In particular to a platinum/platinum dichloride catalytic composite material with a cubic crystal structure and a preparation method and application thereof.
More specifically, the present invention relates to the following aspects.
In a first aspect, the present invention relates to a process for the preparation of a platinum/platinum dichloride catalytic composite of cubic crystal structure, said process comprising the steps of:
s1: reacting p-nitrophenol, sodium bromate and sulfuric acid at room temperature, and recording the chemical oscillation reaction by using an open circuit-time curve;
s2: and during the reaction, adding a platinum dichloride raw material into the system at one time, taking out reaction liquid after the reaction is finished, and centrifugally cleaning to obtain the platinum/platinum dichloride catalytic composite material with the cubic crystal structure.
In the preparation method of the platinum/platinum dichloride catalytic composite material with the cubic crystal structure, in the step S1, a chemical oscillation system is adopted as a system consisting of p-nitrophenol, sodium bromate and sulfuric acid.
In the preparation method of the platinum/platinum dichloride catalytic composite material with cubic crystal structure of the present invention, in step S1, the reaction temperature is 10 to 50 ℃, for example, 10 ℃, 20 ℃, 30 ℃, 40 ℃ or 50 ℃, preferably 15 to 35 ℃, and most preferably 25 ℃.
In the preparation method of the platinum/platinum dichloride catalytic composite material with cubic crystal structure of the present invention, in step S1, the concentration of the p-nitrophenol is 0.001-0.02M, preferably 0.01M; the concentration of the sodium bromate is 0.01-0.06M, preferably 0.03M; the concentration of the sulfuric acid is 0.0-2.0M, preferably 1.0M.
In the preparation method of the platinum/platinum dichloride catalytic composite material with the cubic crystal structure, the step S2 is as follows:
s2-1: adding 0.001-0.006g of platinum dichloride into the chemical oscillation system, and ultrasonically dispersing the platinum dichloride with 3-5mL of high-purity water in advance;
s2-2: adding platinum dichloride dispersion liquid at a certain position after the chemical oscillation curve begins, wherein the sample adding positions are the top of the first period, the bottom of the second period, the top of the second period, the bottom of the third period and the top of the sixth period respectively, and reacting for 0.5-10 hours after adding to obtain reaction liquid;
s2-3: and centrifuging the reaction liquid at the centrifugal speed of 18000rpm for 3-6 minutes, washing the obtained precipitate with deionized water, acetone and absolute ethyl alcohol respectively for 2-3 times, and then adding the absolute ethyl alcohol for preservation to obtain the platinum/platinum dichloride catalytic composite material with the cubic crystal structure.
Wherein, in step S2-1, the platinum dichloride is used in an amount of 0.001-0.006g, preferably 0.0015-0.0035g, and most preferably 0.0025 g.
Wherein, in step S2-2, the loading site of the platinum dichloride dispersion is one or more of the top of the first cycle, the bottom of the second cycle, the top of the second cycle, the bottom of the third cycle, and the top of the sixth cycle, and the optimal loading site is the top of the first cycle of the chemical oscillation.
In step S2-2, the reaction time after the platinum dichloride is added to the reaction system is 0.5 to 10 hours, for example, 0.5 hour, 2.0 hours, 3.0 hours, or 10 hours.
The inventors have found that when such a preparation method is adopted, a platinum/platinum dichloride catalytic composite material with a specific appearance can be obtained, and when certain process parameters such as the concentration of raw materials, the reaction time and the like are changed, an electrocatalytic composite material with such a form cannot be obtained.
In a second aspect, the present invention relates to a platinum/platinum dichloride catalytic composite material with cubic crystal structure obtained by the above preparation method.
The inventor finds that the platinum/platinum dichloride catalytic composite material with the cubic crystal structure has excellent electrocatalytic performance, so that the platinum/platinum dichloride catalytic composite material can be applied to the technical field of hydrogen production by electrolyzing water, and has good application prospect and industrialization potential.
Thus, in a third aspect, the present invention relates to the use of said platinum/platinum dichloride catalytic composite of cubic crystal structure for the electrolysis of water for the production of hydrogen.
In the application of the invention, the platinum/platinum dichloride catalytic composite material with the cubic crystal structure is used for preparing a working electrode for hydrogen production by electrolyzing water.
In a fourth aspect, the invention relates to an electrode comprising the platinum/platinum dichloride catalytic composite material with the cubic crystal structure, in particular to a working electrode for hydrogen production by electrolyzing water.
The inventor finds that the working electrode containing the platinum/platinum dichloride catalytic composite material with the cubic crystal structure has good electrocatalytic performance, so that the working electrode can be applied to the field of hydrogen production by electrolyzing water.
In a fifth aspect, the present invention also relates to a method of making a working electrode, the method comprising the steps of:
(A) taking a platinum/platinum dichloride catalytic composite material with a cubic crystal structure and naphthol, adding a proper amount of deionized water and absolute ethyl alcohol, uniformly mixing by ultrasonic waves, and dripping the mixture onto a clean glassy carbon electrode;
(B) and naturally drying the glassy carbon electrode coated with the platinum/platinum dichloride catalytic composite material with the cubic crystal structure to obtain the working electrode.
In the preparation method of the working electrode, the volume ratio of the absolute ethyl alcohol to the deionized water is 4: 1.
In the preparation method of the working electrode, in the step (a), 0.28mg of the platinum/platinum dichloride catalytic composite material with the cubic crystal structure is weighed and dispersed in 500 μ L of a mixture of absolute ethyl alcohol, deionized water and naphthol.
In the preparation method of the working electrode, the naphthol is a commonly-known raw material in the field of electrode preparation, can be obtained commercially through various channels, and is not described in detail herein.
In the preparation method of the electrode of the present invention, the amount of naphthol used in step (a) is not particularly limited, and the amount of naphthol used is conventional in the field of working electrodes, and those skilled in the art can make appropriate selections, which is not described herein again.
In the method for preparing the working electrode of the present invention, the preparation operations of the steps belong to conventional technical means in the electrode field, and are not described in detail herein.
The invention provides a platinum/platinum dichloride catalytic composite material with a cubic crystal structure, a preparation method and application thereof, and the inventor finds that the platinum/platinum dichloride catalytic composite material with a specific morphology obtained by the invention can be used for preparing hydrogen by electrolyzing water under the electrifying condition, has excellent hydrogen production performance, provides a brand-new and efficient electrolytic composite material for hydrogen production by electrolysis, and has great application potential and application value in the industrial field.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) and a corresponding open circuit potential-time curve diagram of a platinum/platinum dichloride catalytic composite material with a cubic crystal structure prepared in example 1 of the invention;
FIG. 2 is a TEM and HRTEM image of a cubic crystal structure platinum/platinum dichloride catalytic composite of example 1 of the present invention;
FIG. 3 is a graph of EDX and STEM-HAADF of a platinum/platinum dichloride catalytic composite of cubic crystal structure of example 1 of the present invention;
FIG. 4 is an XPS plot of a cubic crystal platinum/platinum dichloride catalytic composite of example 1 of the present invention;
FIG. 5 is a linear voltammogram scan of a cubic crystal platinum/platinum dichloride catalytic composite and platinum dichloride as a raw material prepared in example 1 of the present invention;
FIG. 6 is an open circuit-time diagram and corresponding SEM for different samples obtained using different raw material dosages;
FIG. 7 is an open circuit-time diagram and corresponding SEM for different samples taken using different reaction times;
FIG. 8 is an SEM image of different samples taken using different platinum dichloride addition sites;
FIG. 9 is an SEM image of different samples taken using different reaction temperatures;
FIG. 10 is an SEM image of different samples obtained using different concentrations of p-nitrophenol;
FIG. 11 is an SEM image of different samples taken with different concentrations of sodium bromate;
fig. 12 is an SEM image of different samples obtained using different concentrations of sulfuric acid.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the use and purpose of these exemplary embodiments are merely to exemplify the present invention, and do not set forth any limitation on the actual scope of the present invention in any form, and the scope of the present invention is not limited thereto.
Example 1
S1: p-nitrophenol, sodium bromate and sulfuric acid are placed in a single water bath electrolytic cell, reacted at 25.0 ℃ and atmospheric pressure, and the chemical oscillation curve is monitored by using the open circuit potential-time in the CHI electrochemical workstation, wherein the concentration ratio of the p-nitrophenol, the sodium bromate and the sulfuric acid is 1: 3: 100.
s2: adding 0.0025g of platinum dichloride subjected to ultrasonic dispersion by 5mL of deionized water at one time at the top of the first period of the chemical oscillation curve, and reacting for 2.0h to obtain reaction liquid;
s3: and centrifuging the reaction liquid at the centrifugal speed of 18000rpm for 5 minutes, washing the obtained precipitate with deionized water, acetone and absolute ethyl alcohol respectively for 2-3 times, and then adding the absolute ethyl alcohol for preservation to obtain the platinum/platinum dichloride catalytic composite material with the cubic crystal structure, wherein the name of the platinum/platinum dichloride catalytic composite material is M1.
Examples 2 to 4: examination of the amount of addition of the beat of dichloro in step S2
Examples 2 to 4, designated as C2 to C4, were sequentially carried out without changing the operations except that the platinum dichloride amount in step S2 was replaced with (a)0.0015g, (C) 0.0035g, and (d)0.0045g, respectively.
Examples 5 to 7: examination of reaction time in step S2
Example 1 was repeated except that the reaction times were changed to (a)0.5h, (C)3.0h, and (d)10.0h after platinum dichloride was added in step S2, to thereby repeat examples 5 to 7, and the resulting composite material was sequentially named as C5-C7.
Examples 8 to 11: examination of addition of Dichlorination site in step S2
Example 1 was repeated except that the platinum dichloride addition point in step S2 was replaced with shaking (B) the bottom of the second cycle, (C) the top of the second cycle, (D) the bottom of the third cycle, and (E) the top of the sixth cycle, respectively, to thereby conduct examples 8-11 in this order, and the resulting composite material was named C8-C11 in this order.
Examples 12 to 13: examination of reaction temperature in Steps S1 and S2
Example 1 was repeated by repeating the operations of examples 12 to 13 except that the reaction temperatures in steps S1 and S2 were changed to (A)15 ℃ and (C)35 ℃ respectively, and the resulting composite materials were named C12 to C13 in this order.
Examples 14 to 15: examination of p-nitrophenol concentration in step S1
Example 1 was repeated except that the concentration of p-nitrophenol in step S1 was changed to (A)0.0025M and (B)0.005M, respectively, to thereby conduct examples 14 to 15 in this order, and the resulting composite material was named C14-C15 in this order.
Examples 16 to 17: examination of sodium bromate concentration in step S1
Example 1 was repeated by repeating the operations of examples 16 to 17 in this order except that the concentrations of sodium bromate in step S1 were changed to (A)0.02M and (C)0.05M, respectively, and the resulting composite materials were named C16-C17 in this order.
Examples 18 to 19: examination of sulfuric acid concentration in step S1
Example 1 was repeated except that the concentration of sulfuric acid in step S1 was changed to (A)0.5M and (C)1.5M, respectively, to thereby carry out examples 18 to 19 in this order, and the resulting composite material was named C18-C19 in this order.
Preparation of the electrodes
The preparation method of the electrode comprises the following steps:
(A) taking a platinum/platinum dichloride catalytic composite material with a cubic crystal structure and naphthol, and adding a proper amount of deionized water and absolute ethyl alcohol, wherein the weight ratio of water: carrying out ultrasonic treatment for 30min with absolute ethyl alcohol at a volume ratio of 1:4, mixing uniformly, and dripping onto a glassy carbon electrode;
(B) and naturally drying the glassy carbon electrode coated with the platinum/platinum dichloride catalytic composite material with the cubic crystal structure to obtain the electrode.
Microscopic characterization
The platinum/platinum dichloride catalytic composite material with cubic crystal structure obtained in example 1 was subjected to microscopic characterization by a plurality of different means, and the results are as follows:
1. a Scanning Electron Microscope (SEM) image and a corresponding open circuit potential-time image of the platinum/platinum dichloride catalytic composite material prepared in example 1 of the present invention. The material is seen to be in a cubic crystal structure from an SEM image, and the oscillation period is increased and the amplitude is enhanced after platinum dichloride is added is obviously seen from an open-circuit potential-time image.
2. As can be seen from a TEM image of FIG. 2, the platinum/platinum dichloride catalytic composite material with the cubic crystal structure is synthesized by self-assembly of the quantum dots of platinum dichloride, and the structure is more favorable for rapid embedding and leading-out of ions or protons and is suitable for being used as an electrode material.
3. From the EDX and STEM-HAADF graphs of fig. 3, it is seen that the platinum/platinum dichloride catalytic composite material of cubic crystal structure contains three elements of platinum, chlorine and copper, wherein the copper element is derived from the copper mesh sample holder used for the test sample and is negligible. As can be seen from the STEM-HAADF graph, Pt elements (red) are mainly uniformly distributed in the edge of the cubic crystal structure and partially in the interior thereof, and Cl elements (green) are mainly distributed in the middle of the cubic crystal structure.
4. It can be seen from XPS of FIG. 4 that the sample contains five elements of Pt, Cl, C, O and Si, and the Si element is derived from the silicon wafer as the carrier, and is not particularly considered. The introduction of the O element and the C element is caused by the fact that a sample is not completely cleaned and brings organic matters generated in the reaction process, so that the synthetic material is further determined to mainly contain two elements of Pt and Cl. As shown in the figure, the obtained sample shows that the bonding energies of Pt 4f7/2 and Pt 4f5/2 are 73.3eV and 76.6eV respectively, and the existence form of platinum in the obtained product is verified to have 0 valence and 2 valence. This result demonstrates that the platinum dichloride feedstock is partially reduced to elemental platinum after being added to the shaking system.
Electrochemical performance test
1. FIG. 5 is a linear voltammetric scan of an electrode made from a platinum/platinum dichloride catalytic composite having a cubic crystal structure and an electrode made from a platinum dichloride feedstock at a scan rate of 10 mV/s. As can be seen from the figure, the hydrogen production performance of the platinum dichloride is better, but the prepared platinum/platinum dichloride catalytic composite material with the cubic crystal structure has large current density, which shows that the electric conductivity is much better than that of the platinum dichloride.
As can be seen from the figure 5, the platinum/platinum dichloride catalytic composite material with the cubic crystal structure obtained by the method has excellent electrochemical performance, so that the platinum/platinum dichloride catalytic composite material can be used as a catalyst for hydrogen production by electrolyzing water, and has good application prospect and industrial production potential in the electrochemical field.
Microscopic characterization of the composite materials obtained in other examples
A. Characterization of C2-C4 found that the microscopic morphology was highly similar to C1, with the change in PtCl seen in FIG. 62The open circuit potential-time diagram has increased amplitude and longer period, and four types of the complex are obtained by corresponding SEM image analysisSame PtCl2All of them give a cubic crystal structure, but in comparison, when PtCl is used2The amount of (C) used is 0.0045g, the cubic crystal structure produced is at most, about 60%.
B. The characterization of C5-C7 shows that the microscopic morphology is highly similar to that of C1, as shown in fig. 7, the change of the reaction time still continues the oscillation curve, the amplitude increases, the period becomes longer, the corresponding SEM image analysis shows that the product synthesized by too short reaction time (0.5h) or too long reaction time (10.0h) is not ideal, the reaction time is too short, the raw materials are not ready to assemble, so that only a small amount of cubic crystal structure is provided, and the reaction time is too long, and more organic matters generated in the system are coated on the product, so that the cleaning is difficult.
C. Characterization of C8-C11 found that the microstructure was highly similar to C1, and from SEM image analysis in fig. 8 it was found that the later the platinum dichloride was added, the less the cubic crystal structure in the product, so the first cycle top was selected as the point of addition for all of the following experimental studies.
D. Characterization of C12-C13 found that the microscopic morphology was highly similar to C1, while the product coalescence under low temperature (15 ℃) conditions was difficult to separate, relatively good at 25 ℃ and 35 ℃, as seen by the SEM images in fig. 9, 25 ℃ was chosen as the subsequent probing temperature due to ease of handling and ease of control at room temperature.
E. The characterization of C14-C15 found that the microscopic morphology was highly similar to C1, and the higher the concentration of p-nitrophenol, the more cubic crystal structure produced, i.e., the more reducing agent, was in favor of the nano-cubic crystal structure, as analyzed from the SEM image in fig. 10.
F. Characterization of C16-C17 found that the microscopic morphology was highly similar to C1, and the NaBrO was analyzed from the SEM image in FIG. 113The concentration of (A) has no particular influence on the formation of the product, in contrast to [ NaBrO ]3]The cubic crystal structure produced is the most when the crystal is 0.04M.
G. Characterization of C18-C19 found that the microscopic morphology was highly similar to C1, and H was analyzed from the SEM image in FIG. 122SO4The concentration of (A) has no particular influence on the formation of the product.
In conclusion, the platinum/platinum dichloride catalytic composite material with a cubic crystal structure is synthesized by selecting appropriate reactants and conditions, and researches show that the composite material has excellent electrochemical performance, and has good industrial application potential and market value.
It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should also be understood that various alterations, modifications and/or variations can be made to the present invention by those skilled in the art after reading the technical content of the present invention, and all such equivalents fall within the protective scope defined by the claims of the present application.
Claims (5)
1. A method for the non-linear synthesis of a platinum/platinum dichloride catalytic composite material with a cubic crystal structure, comprising the steps of:
s1: carrying out chemical oscillation reaction on p-nitrophenol, sodium bromate and sulfuric acid at room temperature;
s2: during the reaction, adding a platinum dichloride raw material into the system at one time, taking out reaction liquid after the reaction is finished, and centrifugally cleaning to obtain the platinum/platinum dichloride catalytic composite material with the cubic crystal structure;
in step S1, the reaction temperature is 10-50 ℃;
in step S2, the platinum dichloride is used in an amount of 0.001 to 0.006 g;
in step S2, the reaction time after adding platinum dichloride is 0.5-10 h;
in step S1, the concentration of the p-nitrophenol is 0.001-0.02M; the concentration of the sodium bromate is 0.01-0.06M; the concentration of the sulfuric acid is 0.0-2.0M;
the step S1 records the chemical oscillation reaction by using an open-position circuit-time curve, and the step S2 is specifically as follows:
s2-1: 3-5mL of high-purity water is used for ultrasonic dispersion before the platinum dichloride raw material is added into the chemical oscillation system;
s2-2: adding platinum dichloride dispersion liquid into a sample adding site after the open circuit-time curve begins, wherein the sample adding site is one or more of the top of the first period, the bottom of the second period, the top of the second period, the bottom of the third period and the top of the sixth period, and reacting for 0.5-10 hours after adding to obtain a reaction liquid;
s2-3: and centrifuging the reaction liquid for 3-6 minutes, washing the obtained precipitate with deionized water, acetone and absolute ethyl alcohol respectively, and then adding absolute ethyl alcohol for storage to obtain the platinum/platinum dichloride catalytic composite material with the cubic crystal structure.
2. A platinum/platinum dichloride catalytic composite material of cubic crystal structure obtained by the non-linear synthesis process of claim 1.
3. An electrode comprising the cubic crystalline structured platinum/platinum dichloride catalytic composite of claim 2.
4. A method of making a working electrode, the method comprising the steps of:
(A) taking the platinum/platinum dichloride catalytic composite material with the cubic crystal structure and naphthol as defined in claim 2, adding a proper amount of deionized water and absolute ethyl alcohol, uniformly mixing by ultrasonic waves, and dripping the mixture on a clean glassy carbon electrode;
(B) and naturally drying the glassy carbon electrode coated with the platinum/platinum dichloride catalytic composite material with the cubic crystal structure to obtain the working electrode.
5. The method of claim 4, wherein the step of preparing the working electrode comprises: deionized water: the volume ratio of the absolute ethyl alcohol is 1: 4.
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| CN102709575A (en) * | 2012-03-14 | 2012-10-03 | 温州大学 | High CO-resistant anode catalyst of direct alcohol fuel cells and preparation and application |
| CN105085578A (en) * | 2015-08-28 | 2015-11-25 | 合肥祥晨化工有限公司 | Platinum complex crystal |
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| CN102709575A (en) * | 2012-03-14 | 2012-10-03 | 温州大学 | High CO-resistant anode catalyst of direct alcohol fuel cells and preparation and application |
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