CN108160088A - A kind of platinum of cubic crystal structure/platinous chloride composite material and its non-linear synthetic method and application - Google Patents
A kind of platinum of cubic crystal structure/platinous chloride composite material and its non-linear synthetic method and application Download PDFInfo
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- CN108160088A CN108160088A CN201711370825.2A CN201711370825A CN108160088A CN 108160088 A CN108160088 A CN 108160088A CN 201711370825 A CN201711370825 A CN 201711370825A CN 108160088 A CN108160088 A CN 108160088A
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- platinum
- platinous chloride
- crystal structure
- cubic crystal
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 127
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 60
- 239000013078 crystal Substances 0.000 title claims abstract description 56
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 15
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 230000010355 oscillation Effects 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 150000004780 naphthols Chemical class 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 238000011835 investigation Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000003252 repetitive effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 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
- 239000002245 particle Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007704 wet chemistry method Methods 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
- 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
- 238000004458 analytical method Methods 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- VCHARIXNQOMKDN-UHFFFAOYSA-N bromic acid;sodium Chemical compound [Na].OBr(=O)=O VCHARIXNQOMKDN-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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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
-
- 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—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of platinum/platinous chloride composite material of cubic crystal structure and its non-linear synthetic method and applications, and described method includes following steps：S1：P-nitrophenol, sodium bromate and sulfuric acid are reacted at room temperature, with the open position circuit time curve record chemical oscillating reaction；S2：In reaction carries out, platinous chloride raw material is disposably added in into system, after reaction, reaction solution eccentric cleaning is taken out, so as to obtain the platinum of the cubic crystal structure/platinous chloride catalytic composite materials.The preparation method is to be combined by innovative vibrate nonlinear chemical with the preparation of noble metal, so as to obtain platinum/platinous chloride catalytic composite materials of the cubic crystal structure with excellent hydrogen manufacturing performance, water electrolysis hydrogen production field can be used it for, is had a good application prospect and industrialization potential.
Description
Technical field
The present invention provides composite materials and preparation method thereof and purposes, more specifically, provide a kind of available for electricity
Platinum/platinous chloride composite material of the cubic crystal structure of solution water hydrogen manufacturing and its non-linear synthetic method and application, belong to inorganic
Field of functional materials.
Background technology
With non-renewable, the urgent need development new technology alternative energy source conversion of more and more environmental problems and fossil fuel
And storage device such as solar cell, lithium ion battery, ultracapacitor and fuel cell etc. solve energy crisis.Recently,
Researchers, which place hope on, develops high performance fuel cell, and wherein catalyst performance is that control fuel battery performance improves
An important factor for.Platinum group metal is because of its fusing point height, good conductivity, corrosion-resistant and high-temperature stability is good and is used as in fuel cell most
Effective catalyst naturally causes the extensive concern of people.But Pt bases catalyst is as one kind in noble metal,
High cost is so that it can not commercial applications in a fuel cell.Therefore, new catalyst degradation Pt load capacity is researched and developed,
Service efficiency and the stability for increasing catalyst are extremely urgent.
So far, people have done many methods explored and work out a variety of synthesis Pt nanostructureds, example in this respect
Such as：Organic Pt presomas under the introducing of inorganic ions, template-mediated method, electrochemical reaction, seed mediated growth method and hot conditions
The methods of decomposition.At present, researchers mainly by wet chemistry method and electrochemical process synthesized threadiness, branch-like, it is spherical,
The platinum nanostructured of the different morphologies such as rodlike, polyhedron and dendritic morphology.
The Sun Shigang seminars of Xiamen University be successfully prepared using electrochemical process by the exposed Pt of high miller index surface and
The tetrahexahedron nanocrystal of Pd, these materials show catalytic performance more superior than traditional Pt and Pd catalyst.
And Manfune F et al. are then to have synthesized the Pt particles that grain size is about 6nm using the method for laser emission, it
It, using dodecyl sodium sulfate as stabilizer, after stirring evenly, is synthesized using the method for the UV pulse lasers of high intensity again afterwards
Mean particle size is the nano-platinum particle of 1.5nm.
Lee and its partner have prepared the Pt nanometer rods of five weight twins.Shviro et al. electricity consumption corrosion reactions synthesize
Hollow octahedron and cuboctahedron Pt-Ni-Au nanostructureds.
At present, electrochemical process and wet chemistry method are the common methods of shape controlled synthesis, and scientists pass through both sides
Method has synthesized the noble metal nano catalyst of a large amount of different-shapes, but electrochemical process is high to requirement of experiment and can not high-volume
Production, wet-chemical rule need to introduce suitable functional molecular.Therefore, the defects of being based on more than synthetic method, utilizes chemical reaction
The self-organizing of system and Self-controlled to obtain the Self-controlled (such as Non-Linear Ocsillation) of reaction rate or functional molecular concentration, do not have also
There is studied application, it is clear that the exploitation of this novel dynamics control measures, to realizing controllable preparation new construction, the expensive gold of high-performance
Belong to nanocatalyst and provide unprecedented opportunities and challenge, and this is also exactly where the basis that the present invention is accomplished and dynamic
Power is leaned on.
Invention content
For many defects existing for overcoming synthesis platinum-group noble metals method as indicated above, seek a kind of simple, fast
Speed, method cost-effective and environmentally friendly prepare the method for the platinum family composite material with regular morphology, and study it and led in electro-catalysis
Application in domain, present inventor has performed in-depth study, after a large amount of creative work has been paid, so as to complete this hair
It is bright.
Specifically, technical scheme of the present invention and content are related to a kind of platinum/platinous chloride catalysis of cubic crystal structure
Composite material and preparation method and application.
More particularly it relates to following many aspects.
The first aspect, the present invention relates to a kind of preparations of platinum/platinous chloride catalytic composite materials of cubic crystal structure
Method, described method includes following steps：
S1：P-nitrophenol, sodium bromate and sulfuric acid are reacted at room temperature, recorded with open position circuit-time graph
The chemical oscillating reaction；
S2：In reaction carries out, platinous chloride raw material is disposably added in into system, treats after reaction, to take out reaction
Liquid eccentric cleaning, so as to obtain the platinum of the cubic crystal structure/platinous chloride catalytic composite materials.
In the preparation method of platinum/platinous chloride catalytic composite materials of the cubic crystal structure of the present invention, in step
In rapid S1, p-nitrophenol, sodium bromate and sulfuric acid institute compositional system are chemical oscillation systems.
In the preparation method of platinum/platinous chloride catalytic composite materials of the cubic crystal structure of the present invention, in step
In rapid S1, reaction temperature is 10-50 DEG C, may be, for example, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C or 50 DEG C, preferably 15-35 DEG C, most
Preferably 25 DEG C.
In the preparation method of platinum/platinous chloride catalytic composite materials of the cubic crystal structure of the present invention, in step
In rapid S1, a concentration of 0.001-0.02M of the p-nitrophenol, preferably 0.01M；A concentration of 0.01- of the sodium bromate
0.06M, preferably 0.03M；A concentration of 0.0-2.0M of the sulfuric acid, preferably 1.0M.
It is described in the preparation method of platinum/platinous chloride catalytic composite materials of the cubic crystal structure of the present invention
Step S2 is specific as follows：
S2-1：The platinous chloride that 0.001-0.006g is added in into the chemical oscillation system is high-purity with 3-5mL in advance
Water ultrasonic disperse is uniform；
S2-2：Some site after the chemical oscillation curve starts adds in platinous chloride dispersion liquid, sample-adding site difference
It is anti-after addition for period 1 top, second round bottom, at the top of second round, at the top of period 3 bottom and period 6
0.5-10h is answered, obtains reaction solution；
S2-3：The reaction solution with the centrifugal speed of 18000rpm is centrifuged 3-6 minutes, the precipitation of gained is successively spent
Ionized water, acetone, absolute ethyl alcohol respectively wash 2-3 times, then add in absolute ethyl alcohol and preserve to get the cubic crystal structure
Platinum/platinous chloride catalytic composite materials.
Wherein, in step S2-1, the dosage of the platinous chloride is 0.001-0.006g, preferably 0.0015-
0.0035g, most preferably 0.0025g.
Wherein, in step S2-2, the sample-adding site of platinous chloride dispersion liquid is at the top of the period 1, at the bottom of second round
At the top of portion, second round, one or more of at the top of period 3 bottom and period 6, the best site that adds in is the chemistry
Vibrate the top of period 1.
Wherein, in step S2-2, after adding in platinous chloride into reaction system, reaction time 0.5-10h, such as can
For 0.5h, 2.0h, 3.0h or 10h.
The inventors discovered that when using preparation method so, platinum/platinous chloride of specific appearance form can be obtained
Catalytic composite materials, and when concentration, reaction time for changing certain technological parameters such as raw material therein etc., then can not obtain as
The electro-catalysis composite material of this form.
The second aspect, the present invention relates to the cubic crystal structure platinum/platinous chloride obtained by above-mentioned preparation method to urge
Change composite material.
The inventors discovered that there is the platinum of the cubic crystal structure/platinous chloride catalytic composite materials excellent electricity to urge
Change performance, so as to be applied to water electrolysis hydrogen production technical field, have a good application prospect and industrialization potential.
Therefore, in terms of third, platinum/platinous chloride catalytic composite materials the present invention relates to the cubic crystal structure exist
Purposes in water electrolysis hydrogen production.
In the purposes of the present invention, platinum/platinous chloride catalytic composite materials of the cubic crystal structure are used for making
The working electrode of standby water electrolysis hydrogen production.
4th aspect, the present invention relates to a kind of platinum comprising the cubic crystal structure/platinous chloride catalysis composite woods
The working electrode of the electrode of material, especially water electrolysis hydrogen production.
Inventors discovered through research that the work of the platinum comprising the cubic crystal structure/platinous chloride catalytic composite materials
Make electrode with good electrocatalysis characteristic, so as to be applied to water electrolysis hydrogen production field.
5th aspect, the invention further relates to a kind of preparation methods of working electrode, and described method includes following steps：
(A) platinum/platinous chloride catalytic composite materials, the naphthols of cubic crystal structure are taken, adds in appropriate amount of deionized water and nothing
Water-ethanol, ultrasonic mixing is uniform, drips on clean glass-carbon electrode；
(B) glass-carbon electrode of the platinum for coating cubic crystal structure/platinous chloride catalytic composite materials is spontaneously dried,
Obtain the working electrode.
Wherein, in the preparation method of working electrode of the present invention, the volume ratio of absolute ethyl alcohol and deionized water is 4:
1。
Wherein, in the preparation method of working electrode of the present invention, in the step (A), the cubic crystal
The platinum of structure/platinous chloride catalytic composite materials weigh 0.28mg, are scattered in 500 μ L absolute ethyl alcohols, deionized water and naphthols
In mixture.
Wherein, in the preparation method of working electrode of the present invention, the naphthols is the common public affairs of electrode preparation field
Know raw material, can be by multiple channel and commercially-available, this is no longer going to repeat them.
Wherein, in the preparation method of electrode of the present invention, in the step (A), the dosage of the naphthols added in
It is not particularly limited, dosage belongs to the routine techniques in working electrode field, and those skilled in the art can carry out suitably
Selection, this is no longer going to repeat them.
Wherein, in the preparation method of working electrode of the present invention, the preparation manipulation of the step belongs to electrode field
In conventional technical means, this is no longer going to repeat them.
As described above, platinum/platinous chloride catalytic composite materials and its system the present invention provides a kind of cubic crystal structure
Preparation Method and purposes, the inventors discovered that, the platinum of specific specific morphology/platinous chloride catalytic composite materials that the present invention is obtained
Under power on condition, hydrogen can be prepared by being electrolysed in water, there is more excellent H2-producing capacity, carried for electrolytic hydrogen production
Completely new and efficient electrolytic composite materials have been supplied, there is huge application potential and application value in industrial circle.
Description of the drawings
Fig. 1 is the scanning electricity of cubic crystal structure platinum/platinous chloride catalytic composite materials obtained by the embodiment of the present invention 1
Mirror figure (SEM) and corresponding open circuit potential-time plot；
Fig. 2 is the TEM and HRTEM of cubic crystal structure platinum/platinous chloride catalytic composite materials of the embodiment of the present invention 1
Figure；
Fig. 3 is the EDX and STEM- of cubic crystal structure platinum/platinous chloride catalytic composite materials of the embodiment of the present invention 1
HAADF schemes；
Fig. 4 is the XPS figures of cubic crystal structure platinum/platinous chloride catalytic composite materials of the embodiment of the present invention 1；
Fig. 5 is cubic crystal structure platinum/platinous chloride catalytic composite materials and the raw material two obtained by the embodiment of the present invention 1
The linear voltammetric scan figure of platinum chloride；
Fig. 6 is the open position circuit-time diagram and corresponding SEM using the different obtained different samples of raw material dosage
Figure；
Fig. 7 is the open position circuit-time diagram and corresponding SEM using different reaction time obtained different samples
Figure；
Fig. 8 is the SEM figures that the obtained different samples in site are added in using different platinous chloride；
Fig. 9 is the SEM figures using the different obtained different samples of reaction temperature；
Figure 10 is the SEM figures using the obtained different samples of p-nitrophenol of various concentration；
Figure 11 is the SEM figures using the obtained different samples of sodium bromate of various concentration；
Figure 12 is the SEM figures using the obtained different samples of sulfuric acid of various concentration.
Specific embodiment
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, not forms any type of any restriction to the real protection scope of the present invention, more non-to incite somebody to action
Protection scope of the present invention is confined to this.
Embodiment 1
S1：P-nitrophenol, sodium bromate and sulfuric acid are placed in single water-bath electrolytic cell, it is anti-under 25.0 DEG C and atmospheric pressure
Should, and with its chemical oscillation curve of open circuit potential-time supervision in CHI electrochemical workstations, wherein p-nitrophenol, bromic acid
Sodium and sulfuric acid concentration ratio are 1：3：100.
S2：0.0025g 5mL deionized waters ultrasounds point are disposably added at the top of the period 1 of chemical oscillation curve
Platinous chloride after dissipating after reacting 2.0h, obtains reaction solution；
S3：The reaction solution is centrifuged 5 minutes with the centrifugal speed of 18000rpm, by the precipitation priority deionization of gained
Water, acetone, absolute ethyl alcohol respectively wash 2-3 times, then add in platinum/bis- of the absolute ethyl alcohol preservation to get the cubic crystal structure
Platinum chloride catalytic composite materials, are named as M1.
Embodiment 2-4：Dichloride claps the investigation of addition in step S2
Except the platinous chloride dosage in step S2 is replaced with (a) 0.0015g, (c) 0.0035g, (d) 0.0045g respectively
Outside, other operations are constant, so as to sequentially be carried out a 2-4, are respectively designated as C2-C4.
Embodiment 5-7：The investigation in reaction time in step S2
Except it will add in platinous chloride in step S2 after, the reaction time replaces with (a) 0.5h, (c) 3.0h, (d) respectively
Outside 10.0h, other operations are constant, so as to sequentially be carried out a 5-7, gained is compound so as to repetitive operation embodiment 1
Material is named as C5-C7 successively.
Embodiment 8-11：The investigation in dichloride site is added in step S2
Except by platinous chloride addition point in step S2 replace with respectively oscillation (B) second round bottom, (C) second round push up
Outer at the top of portion, (D) period 3 bottom and (E) period 6, other operations are constant, thus repetitive operation embodiment 1, so as to
A 8-11 is sequentially carried out, gained composite material is named as C8-C11 successively.
Embodiment 12-13：Step S1, in S2 reaction temperature investigation
Except the reaction temperature in step S1, S2 is replaced with respectively, 35 DEG C of 15 DEG C of (A) and (C) is outer, it is other operate it is constant,
So as to repetitive operation embodiment 1, so as to sequentially be carried out a 12-13, gained composite material is named as C12- successively
C13。
Embodiment 14-15：The investigation of p-nitrophenol concentration in step S1
In addition to the concentration of p-nitrophenol in step S1 to be replaced with to (A) 0.0025M and (B) 0.005M respectively, Qi Tacao
Work is constant, and so as to repetitive operation embodiment 1, so as to sequentially be carried out a 14-15, gained composite material is named successively
For C14-C15.
Embodiment 16-17：The investigation of bromic acid na concn in step S1
In addition to the concentration of sodium bromate in step S1 to be replaced with to (A) 0.02M and (C) 0.05M respectively, other operations are not
Become, so as to repetitive operation embodiment 1, so as to sequentially be carried out a 16-17, gained composite material is named as C16- successively
C17。
Embodiment 18-19：The investigation of sulfuric acid concentration in step S1
In addition to the concentration of sulfuric acid in step S1 to be replaced with to (A) 0.5M and (C) 1.5M respectively, other operations are constant, from
And repetitive operation embodiment 1, so as to sequentially be carried out a 18-19, gained composite material is named as C18-C19 successively.
The preparation of electrode
The preparation method of the electrode includes the following steps：
(A) platinum/platinous chloride catalytic composite materials, the naphthols of cubic crystal structure are taken, adds in appropriate amount of deionized water and nothing
Water-ethanol, wherein water：Absolute ethyl alcohol is 1:4 (volume ratios), ultrasonic 30min are uniformly mixed, drip on glass-carbon electrode；
(B) glass-carbon electrode of the platinum for coating cubic crystal structure/platinous chloride catalytic composite materials is spontaneously dried,
Obtain the electrode.
Microscopic sdIBM-2+2q.p.approach
Platinum/platinous chloride catalytic composite materials of the cubic crystal structure of the gained of embodiment 1 have been carried out it is multiple not
It is as a result as follows with the microscopic sdIBM-2+2q.p.approach of means：
1st, the scanning electron microscope (SEM) photograph (SEM) of the platinum obtained by the embodiment of the present invention 1/platinous chloride catalytic composite materials and corresponding
Open circuit potential-time diagram.It, can be bright from open circuit potential-time diagram from SEM figures it can be seen that the material is cubic crystal structure
It shows after finding out addition platinous chloride, cycle of oscillation increase, amplitude enhancing.
2nd, from the TEM of Fig. 2 figures as can be seen that platinum/platinous chloride catalytic composite materials of cubic crystal structure are by dichloro
Change the quantum dot self assembly of platinum, this structure is more advantageous to the quick embedded and export of ion or proton, suitable for doing electrode
Material.
3rd, platinum/platinous chloride catalytic composite materials of cubic crystal structure are found out from EDX the and STEM-HAADF figures of Fig. 3
In have three kinds of platinum, chlorine, copper elements, wherein copper can be ignored from the copper mesh specimen frame used in test sample.From
STEM-HAADF schemes it is found that Pt elements (red) are mainly evenly distributed in the edge of cubic crystal structure, partly in it
Portion, and Cl elements (green) are mainly distributed on the middle section of cubic crystal structure.
4th, it can be seen that in sample from the XPS of Fig. 4 and come from conduct containing five kinds of elements of Pt, Cl, C, O, Si, Si elements
The silicon chip of carrier, without special consideration should be given to.The introducing of wherein O elements and C element is the band since sample does not clean up completely
Entered the organic matter generated in reaction process, still further determine that synthesized is that material mainly contains two kinds of members of Pt and Cl
Element.As shown in figure, the bond energy of sample display Pt 4f7/2 and the Pt 4f5/2 of gained demonstrate respectively in 73.3eV and 76.6eV
The existence form of platinum has 0 valency and divalent in products therefrom.After this result illustrates that platinous chloride raw material adds in oscillation system, part
It is reduced to simple substance platinum.
Electrochemical property test
1st, prepared by Fig. 5 is platinum/platinous chloride catalytic composite materials of cubic crystal structure electrode and platinous chloride are former
Linear voltammetric scan figure of the electrode made from material under sweep speed 10mV/s.It can be seen from the figure that the production of platinous chloride
Hydrogen better performances, but the platinum of prepared cubic crystal structure/platinous chloride catalytic composite materials current density is big, illustrates conduction
Property is better than platinous chloride very much.
By above-mentioned Fig. 5 as it can be seen that the platinum of the obtained cubic crystal structure of the method for the present invention/platinous chloride catalytic composite materials
With more excellent chemical property, the catalyst of water electrolysis hydrogen production is thus can be used as, there is good answer in electrochemical field
With prospect and industrial production potential.
The microscopic sdIBM-2+2q.p.approach of composite material obtained by other embodiments
A, the characterization of C2-C4 is found, microscopic pattern height is similar to C1, changes PtCl as Fig. 6 finds out2Dosage,
Open circuit potential-time diagram amplitude increase, period are elongated, and four kinds of difference PtCl are analyzed to obtain by corresponding SEM image2Addition all
The product of cubic crystal structure can be generated, but comparatively, works as PtCl2Dosage be 0.0045g when, the cubic crystal knot of generation
Structure is most, accounts about 60%.
B, the characterization of C5-C7 is found, microscopic pattern height is similar to C1, changes the reaction time as Fig. 7 finds out, shakes
It swings curve to continue to, and amplitude increases, the period is elongated, and reaction time too short (0.5h) or mistake are analyzed to obtain by corresponding SEM image
The product of long (10.0h) synthesis is undesirable, and the reaction time is too short, and raw material has little time to assemble, so only a small amount of cubic crystal
Body structure, and the reaction time is long, the organic matter generated in system is more to be coated on product, it is difficult to be cleaned.
C, the characterization of C8-C11 is found, microscopic pattern height is similar to C1, it was found from the SEM image analysis in Fig. 8
Addition platinous chloride is more late, and cubic crystal structure is fewer in product, therefore following Experimental Research selects to make at the top of the period 1
For sample-adding point.
D, the characterization of C12-C13 being found, microscopic pattern height is similar to C1, while is found out by SEM image in Fig. 9,
Product coalescence under the conditions of low temperature (15 DEG C) is difficult to detach, in contrast preferable under the conditions of 25 DEG C and 35 DEG C, due at room temperature
It is easy to operate and facilitate control, therefore 25 DEG C are selected as subsequently probing into temperature.
E, the characterization of C14-C15 is found, microscopic pattern height is similar to C1, is analyzed from the SEM image in Figure 10
The concentration of p-nitrophenol is bigger, and in contrast generated cubic crystal structure is more, i.e., reducing agent is conducive to nanometer
The generation of cubic crystal structure.
F, the characterization of C16-C17 is found, microscopic pattern height is similar to C1, is analyzed from the SEM image in Figure 11
NaBrO3Concentrations on product generation without especial influence, in contrast [NaBrO3Generated cubic crystal knot during]=0.04M
Structure is most.
G, the characterization of C18-C19 is found, microscopic pattern height is similar to C1, is analyzed from the SEM image in Figure 12
H2SO4Concentrations on product generation without especial influence.
In conclusion selection of the present invention by suitable reactants and condition, and synthesize and obtained cubic crystal structure
Platinum/platinous chloride catalytic composite materials, by the study found that the composite material has excellent chemical property, having good
Good industrial applications potentiality and market value.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limitation protection model of the invention
It encloses.In addition, it should also be understood that, after reading the technical contents of the present invention, those skilled in the art can make the present invention each
Kind change, modification and/or variation, all these equivalent forms equally fall within the guarantor that the application the appended claims are limited
Within the scope of shield.
Claims (10)
1. a kind of non-linear synthetic method of the platinum of cubic crystal structure/platinous chloride catalytic composite materials, the method includes
Following steps：
S1：P-nitrophenol, sodium bromate and sulfuric acid are subjected to chemical oscillating reaction at room temperature；
S2：Reaction carry out in, platinous chloride raw material is disposably added in into system, treat after reaction, take out reaction solution from
The heart cleans, and obtains platinum/platinous chloride catalytic composite materials of the cubic crystal structure.
2. non-linear synthetic method as described in claim 1, it is characterised in that：In step sl, reaction temperature 10-50
℃。
3. non-linear synthetic method as described in claim 1, in step s 2, the dosage of the platinous chloride is 0.001-
0.006g。
4. non-linear synthetic method as described in claim 1, in step s 2, the reaction time added in after platinous chloride is
0.5-10h。
5. non-linear synthetic method as described in claim 1, it is characterised in that：In step sl, the p-nitrophenol
A concentration of 0.001-0.02M；A concentration of 0.01-0.06M of the sodium bromate；A concentration of 0.0-2.0M of the sulfuric acid.
6. non-linear synthetic method as described in claim 1, it is characterised in that：The step S1 is with open position circuit-time
The curve record chemical oscillating reaction, the step S2 are specific as follows：
S2-1：The high purity water ultrasonic disperse of 3-5mL is used before the platinous chloride raw material added in into the chemical oscillation system；
S2-2：Sample-adding site after the open position circuit-time graph starts adds in platinous chloride dispersion liquid, which is
Period 1 top, second round bottom, at the top of second round, at the top of period 3 bottom and period 6 in one or more
It is a, 0.5-10h is reacted after addition, obtains reaction solution；
S2-3：The reaction solution is centrifuged 3-6 minutes, the precipitation of gained is successively distinguished with deionized water, acetone, absolute ethyl alcohol
Then washing adds in platinum/platinous chloride catalytic composite materials of the absolute ethyl alcohol preservation to get the cubic crystal structure.
7. a kind of platinum/dichloro of cubic crystal structure obtained by any one of the claim 1-6 non-linear synthetic methods
Change platinum catalysis composite material.
8. a kind of electrode of platinum/platinous chloride catalytic composite materials comprising cubic crystal structure described in claim 7.
9. a kind of preparation method of working electrode, described method includes following steps：
(A) platinum/platinous chloride catalytic composite materials and naphthols of the cubic crystal structure described in claim 7 are taken, are added in appropriate
Deionized water and absolute ethyl alcohol, ultrasonic mixing is uniform, drips on clean glass-carbon electrode；
(B) by the glass-carbon electrode of the platinum for coating cubic crystal structure/platinous chloride catalytic composite materials spontaneously dry to get
To the working electrode.
10. a kind of preparation method of working electrode according to claim 9, it is characterised in that：Deionized water：Absolute ethyl alcohol
Volume ratio be 1:4.
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| CN111085219A (en) * | 2019-12-27 | 2020-05-01 | 大连理工大学 | Carbon-supported nickel oxide-modified platinum-rhodium nanorod electrocatalyst for alkaline hydrogen evolution reaction and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061067A (en) * | 2010-12-17 | 2011-05-18 | 苏州大学 | Composite material with three-order nonlinear optical property and preparing method thereof |
| 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 |
-
2017
- 2017-12-19 CN CN201711370825.2A patent/CN108160088B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061067A (en) * | 2010-12-17 | 2011-05-18 | 苏州大学 | Composite material with three-order nonlinear optical property and preparing method thereof |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 马世昌: "《化学物质词典》", 30 April 1999 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111085219A (en) * | 2019-12-27 | 2020-05-01 | 大连理工大学 | Carbon-supported nickel oxide-modified platinum-rhodium nanorod electrocatalyst for alkaline hydrogen evolution reaction and preparation method and application thereof |
| CN111085219B (en) * | 2019-12-27 | 2021-04-30 | 大连理工大学 | Carbon-supported nickel oxide-modified platinum-rhodium nanorod electrocatalyst for alkaline hydrogen evolution reaction and preparation method and application thereof |
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