CN116676633A - Shape-adjustable Pt-TiO 2 Preparation method and application of catalyst - Google Patents
Shape-adjustable Pt-TiO 2 Preparation method and application of catalyst Download PDFInfo
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- CN116676633A CN116676633A CN202310452319.7A CN202310452319A CN116676633A CN 116676633 A CN116676633 A CN 116676633A CN 202310452319 A CN202310452319 A CN 202310452319A CN 116676633 A CN116676633 A CN 116676633A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000002105 nanoparticle Substances 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 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 239000002135 nanosheet Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000007790 solid phase Substances 0.000 claims abstract description 9
- WMRRGFKAQUKRPY-UHFFFAOYSA-N cesium oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].[Cs+] WMRRGFKAQUKRPY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005342 ion exchange Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 7
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 6
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000029219 regulation of pH Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000002484 cyclic voltammetry Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000002064 nanoplatelet Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000012876 topography Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 5
- 238000004630 atomic force microscopy Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000005298 paramagnetic effect Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The application relates to a Pt-TiO with adjustable morphology 2 A preparation method and application of a catalyst belong to the technical field of hydrogen energy production and manufacturing. The preparation method of the catalyst comprises the following steps: preparing lepidocrocite type layered cesium titanium oxide by a solid phase sintering method, and separating the oxide by an ion exchange stripping method to form ultrathin two-dimensional TiO 2 Nanoplatelets, then through controlling TiO 2 The pH value of the nanosheet suspension is used for obtaining TiO with different morphologies 2 Nanoparticles, finally utilizing TiO with different morphologies 2 The nano particles have different absorption properties to ultraviolet and visible light, and Pt loaded TiO can be obtained by mixing the nano particles with trace tetrachloroplatinic acid and exposing the mixture to ultraviolet and visible light 2 Form the Pt-TiO with adjustable morphology 2 The catalyst can be applied to the electrolysis of water to produce hydrogen, and the hydrogen production performance can be regulated and controlled. The preparation method has accurate shape control, easy operation, no toxicity and no harm,low cost and is suitable for mass production.
Description
Technical Field
The application belongs to the technical field of hydrogen energy production and manufacturing, and relates to a Pt-TiO with an adjustable morphology 2 A preparation method and application of the catalyst.
Background
Metallic platinum (Pt) has excellent hydrogen-generating catalytic activity when it is supported on an oxide, due to its suitable d-orbital electron number; the oxide of metallic titanium (Ti) is distinguished from a plurality of oxides by the characteristics of large reserves, low price, innocuity, environmental protection, and the like. Thus, from Pt and TiO 2 Formed Pt-TiO 2 The supported catalyst has great application prospect in the field of preparing hydrogen by electrocatalytic reaction. At present, the catalyst is commonly used for preparing Pt-TiO 2 The catalyst is prepared by impregnation, reduction (liquid phase reduction and solid phase H 2 Ar gas reduction), electrochemical deposition method, and the like. However, conventional preparation methods generally control TiO by a template agent, a long-chain surfactant, an oxidizing agent, or the like 2 Crystal growth of the substrate, and thus the introduction of an organic solvent or an organic ligand, is required, resulting in excessively high energy consumption of the preparation method and being not friendly to the environment; on the other hand, the traditional method needs to be heated and pressurized, so that the method has obvious defects in the aspects of environmental protection and energy conservation, and greatly limits the large-scale application of the method.
Therefore, in order to solve the problems existing in the traditional preparation method, it is very necessary to develop a green preparation method which is nontoxic and harmless, low in energy consumption, environment-friendly and adjustable in morphology.
Disclosure of Invention
Accordingly, one of the objects of the present application is to provide a Pt-TiO with adjustable morphology 2 A method for preparing the catalyst; the second purpose of the application is to provide a Pt-TiO with adjustable morphology 2 A catalyst; the third object of the present application is to provide a Pt-TiO with adjustable morphology 2 The application of the catalyst in the aspect of preparing hydrogen by electrocatalytic reaction; the fourth object of the application is to provide a method for preparing hydrogen by electrocatalytic.
In order to achieve the above purpose, the present application provides the following technical solutions:
1. shape-adjustable Pt-TiO 2 A method for preparing a catalyst, said method comprising:
(1) Solid phase calcination: uniformly mixing cesium carbonate and titanium dioxide powder, reacting for 1h at 800 ℃, cooling, grinding into powder, heating to 800-850 ℃ in oxygen atmosphere, reacting for 10h, and cooling to obtain wurtzite type layered cesium titanium oxide;
(2) Ion exchange stripping: a. placing the lepidocrocite type layered cesium titanium oxide in the step (1) into a hydrochloric acid solution with the concentration of 1mol/L, carrying out ultrasonic treatment, standing for 24 hours, and removing supernatant to obtain a reaction product; b. repeating the step a for two times, centrifuging, washing with deionized water, and drying at 60 ℃ for 12 hours to obtain TiO 2 A nanosheet;
(3) pH regulation morphology: subjecting the TiO of step (2) 2 The nano sheet is placed in tetrabutylammonium hydroxide aqueous solution with the concentration of 60mmol/L, milky suspension is obtained after ultrasonic treatment, then water with the volume of 2 times of that of the milky suspension is added for dilution, the pH value is regulated to 1-13 by hydrochloric acid, then the nano sheet is transferred into a reaction kettle for reaction for 24 hours at 180 ℃ to obtain a product, and the product is washed by deionized water, centrifuged and dried overnight at 60 ℃ to obtain TiO with different morphologies 2 A nanoparticle;
(4) Ultraviolet visible light irradiation: tiO with different morphologies in the step (3) 2 Dispersing nano particles in ultrapure water, adding tetrachloroplatinic acid with the concentration of 1mg/ml, uniformly mixing, placing in ice bath, performing ultrasonic treatment to obtain dispersion liquid, keeping ice bath conditions unchanged, placing the dispersion liquid under ultraviolet visible light for 1h under a stirring state, centrifuging, cleaning, and freeze-drying to obtain the Pt-TiO with adjustable morphology 2 A catalyst.
Preferably, the molar ratio of cesium carbonate to titanium dioxide powder in step (1) is 1:1.35.
Preferably, the rate of temperature increase in step (1) is 5 ℃/min.
Preferably, the mass-to-volume ratio of the lepidocrocite type layered cesium titanium oxide to the hydrochloric acid solution in the step (2) is 1:100, g/mL.
Preferably, the TiO in step (3) 2 The mass volume ratio of the nano-sheet to the tetrabutylammonium hydroxide aqueous solution is 0.1:25, g:mL.
Preferably, in step (4), the morphologically distinct TiO 2 The mass volume ratio of the nano particles to the tetrachloroplatinic acid is 0.1:0.5-2.0; g is mL.
2. Pt-TiO with adjustable morphology prepared by the method 2 A catalyst.
3. The shape of the Pt-TiO is adjustable 2 The catalyst is used in electrocatalytic hydrogen production.
4. Method for preparing hydrogen by electrocatalytic reaction, wherein the morphology-adjustable Pt-TiO 2 Dispersing catalyst in deionized water, spin-coating on carbon electrode, drying to form film on the carbon electrode, and placing the film as working electrode on H 2 SO 4 In the solution, the voltage and the scanning speed are regulated by an electrochemical workstation, and the electrocatalytic preparation of hydrogen is carried out.
Preferably, the Pt-TiO 2 The mass volume ratio of the catalyst to the deionized water is 5:1, mg:mL; the H is 2 SO 4 The concentration of the solution is 0.5mol/L; the parameters of the electrochemical workstation are set to be that the cyclic voltammetry potential window voltage is 0.1-0.4V and the scanning speed is 5mV/s.
The application has the beneficial effects that: the application provides a Pt-TiO with adjustable morphology 2 A preparation method and application of the catalyst. The Pt-TiO 2 The catalyst takes cesium carbonate, titanium dioxide, hydrochloric acid, tetrabutylammonium hydroxide, tetrachloroplatinic acid and the like as reaction raw materials, and TiO is regulated and controlled by solid phase calcination, ion exchange stripping and pH 2 The four processes of the appearance of the nano sheet and irradiation of ultraviolet and visible light realize the adjustable appearance of Pt-TiO 2 Preparation of the catalyst. The preparation process does not involve complex instruments and the use of toxic and harmful reagents, and has the advantages of safety, no pollution, low cost, easy mass production and the like. In particular prepared Pt-TiO 2 The catalyst has the characteristics of adjustable morphology, low noble metal loading, adjustable active material loading, adjustable electronic structure and the like, particularly when certain defects and special surface states exist in the catalyst structure, the electronic structure of the catalyst is obviously improved, the catalyst has optimized reactant adsorption and desorption capacity, can efficiently perform electrocatalytic hydrogen production in sulfuric acid solution, has outstanding quality activity, has wide application prospect in the preparation and utilization fields of hydrogen energy, and is favorable for relieving the pressure of the shortage of current energy sources.
Additional advantages, objects, and features of the application will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the application. The objects and other advantages of the application may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the present application will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 shows Pt-TiO of the present application 2 A preparation flow of the catalyst;
FIG. 2 shows Cs obtained in step (1) of example 2 0.35 TiO 2 XRD powder diffraction pattern of (2);
FIG. 3 shows Cs obtained in step (1) of example 2 0.35 TiO 2 Is a scanning electron microscope image of (2);
FIG. 4 shows TiO after stripping in step (2) of example 2 2 Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) images of the nanoplatelets, wherein (a) is AFM and (b) is SEM;
FIG. 5 shows the TiO after stripping in step (2) in examples 1 to 6 2 XRD powder diffraction patterns of the nano-sheets polymerized at different pH values;
FIG. 6 shows TiO values obtained in example 2 and example 4 at 180℃under different pH control in step (3) 2 Topography of the nanoparticle, wherein a is the TiO obtained hydrothermally at 180 ℃ at ph=3 2 Topography of nanoparticle, b is TiO obtained hydrothermally at 180 ℃ at ph=9 2 A topography of the nanoparticle;
FIG. 7 is the Pt-TiO obtained in step (4) in example 2 and example 4 2 The energy spectrum of the catalyst, wherein a is Pt-TiO obtained in example 2 2 The energy spectrum of the catalyst, b, is Pt-TiO obtained in example 4 2 Energy spectrum of the catalyst;
FIG. 8 is the Pt-TiO obtained in step (4) in example 2 and example 4 2 The ultraviolet-visible absorption spectrum of the catalyst, wherein a is TiO obtained with Pt supported at ph=3 2 Nanoparticle formed Pt-TiO 2 Ultraviolet-visible absorption spectrum of the catalyst (wherein the inset is an external optical diagram), b is TiO obtained with Pt supported at ph=9 2 Nanoparticle formed Pt-TiO 2 An ultraviolet visible absorption spectrum of the catalyst (wherein the inset is an apparent optical image);
FIG. 9 is the Pt-TiO obtained in step (4) in example 2 and example 4 2 Electron paramagnetic resonance diagram of the catalyst;
FIG. 10 is the Pt-TiO obtained in step (4) in example 2 and example 4 2 An X-ray photoelectron spectrum of the catalyst, wherein a is a Pt 4f spectrum, and b is a Ti 2p spectrum;
FIG. 11 is the Pt-TiO obtained in step (4) in example 2 and example 4 2 Electrocatalytic hydrogen production performance diagram of the catalyst.
Detailed Description
Other advantages and effects of the present application will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present application with reference to specific examples. The application may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present application. It should be noted that the illustrations provided in the following embodiments merely illustrate the basic idea of the present application by way of illustration, and the following embodiments and features in the embodiments may be combined with each other without conflict.
Example 1
Shape-adjustable Pt-TiO 2 The preparation method of the catalyst comprises the following specific steps:
(1) Solid phase calcination: uniformly mixing cesium carbonate and anatase type titanium dioxide powder according to a molar ratio of 1:1.35, heating to 800 ℃ in a muffle furnace, reacting for 1h, cooling, grinding into powder, placing the powder in the muffle furnace again, heating to 800 ℃ at a speed of 5 ℃/min in an oxygen atmosphere, reacting for 10h, and cooling to obtain Cs 0.35 TiO 2 ；
(2) Ion exchange stripping: taking 1g of Cs in step (1) 0.35 TiO 2 Then placing the mixture in 100mL hydrochloric acid solution with the concentration of 1mol/L, standing for 24 hours after ultrasonic treatment to remove supernatant to obtain a reaction product, repeating the processes of adding acid, ultrasonic treatment, standing and removing supernatant on the basis of the reaction product twice, centrifuging for 3 times and washing with deionized water for 3 times, and drying in a drying oven at 60 ℃ for 12 hours to obtain TiO 2 A nanosheet;
(3) pH regulation morphology: taking 0.1g of TiO in the step (2) 2 The nanosheets are placed in 25mL tetrabutylammonium hydroxide aqueous solution with the concentration of 60mmol/L, milky suspension is obtained after ultrasonic treatment, then water with the volume of 2 times of that of the milky suspension is added for dilution, the pH value is regulated to 1 by hydrochloric acid, then the nanosheets are transferred into a reaction kettle for reaction for 24 hours at 180 ℃ to obtain a product, and the product is washed by deionized water, centrifuged and dried overnight at 60 ℃ to obtain TiO with the corresponding appearance of pH=1 2 A nanoparticle;
(4) Ultraviolet visible light irradiation: taking 0.1g of TiO with the corresponding morphology of pH=1 in the step (3) 2 Dispersing nano particles in 20mL of ultrapure water, adding 2mL of tetrachloroplatinic acid with the concentration of 1mg/mL, uniformly mixing, placing in an ice bath, performing ultrasonic treatment for 30min to obtain a dispersion liquid, keeping the ice bath condition unchanged, placing the dispersion liquid under a xenon lamp for exposure for 1h under a stirring state, centrifuging, cleaning, and freeze-drying to obtain Pt-TiO with the pH value of 1 corresponding to the morphology 2 A catalyst.
Example 2
The difference from example 1 is that ph=1 in step (3) is replaced with ph=3.
Example 3
The difference from example 1 is that ph=1 in step (3) is replaced with ph=6.
Example 4
The difference from example 1 is that ph=1 in step (3) is replaced with ph=9.
Example 5
The difference from example 1 is that ph=1 in step (3) is replaced with ph=12.
Example 6
The difference from example 1 is that ph=1 in step (3) is replaced with ph=13.
Example 7
The difference from example 1 is that 2mL of tetrachloroplatinic acid having a concentration of 1mg/mL in step (4) was replaced with 1.5mL of tetrachloroplatinic acid having a concentration of 1 mg/mL.
Example 8
The difference from example 1 is that 2mL of tetrachloroplatinic acid having a concentration of 1mg/mL in step (4) was replaced with 0.5mL of tetrachloroplatinic acid having a concentration of 1 mg/mL.
Pt-TiO in the present application 2 The preparation flow of the catalyst is shown in figure 1. As can be seen from FIG. 1, pt-TiO 2 The preparation process of the catalyst comprises four steps of solid phase calcination, ion exchange stripping, pH control morphology and ultraviolet and visible light irradiation. Organic substances are not introduced in the preparation process, so that the preparation method is low in energy consumption and environment-friendly, and belongs to a green preparation method with adjustable morphology.
Performance testing
For Cs obtained in step (1) of example 2 0.35 TiO 2 The X-ray powder diffraction test and the scanning electron microscope test were performed, and the experimental results are shown in FIG. 2 and FIG. 3, respectively. From FIG. 2, it can be seen that Cs synthesized by the solid phase calcination method 0.35 TiO 2 Is lepidocrocite type lamellar crystal; as can be seen from FIG. 3, the Cs obtained 0.35 TiO 2 Is a nano-sheet with the size of 400-500 nm. The peeled TiO in step (2) in example 2 was observed by an atomic force microscope and a scanning electron microscope, respectively 2 The morphology of the nanoplatelets, wherein (a) is atomic force microscopy and (b) is scanning electron microscopy in fig. 4. From FIG. 4, it can be seen that TiO after stripping 2 The morphology of the nano-sheet is that the thickness is 1-2 nm.
FIG. 5 shows the TiO after stripping in step (2) in examples 1 to 6 2 XRD powder diffraction patterns of nanoplatelets after polymerization at different pH. From FIG. 5, it can be seen that the peeled TiO 2 The nano-sheets can be assembled into crystals with different interlayer spacing under different pH adjustment.
FIG. 6 shows TiO values obtained in example 2 and example 4 at 180℃under different pH control in step (3) 2 Topography of the nanoparticle, wherein a is the TiO obtained hydrothermally at 180 ℃ at ph=3 2 Topography of nanoparticle, b is TiO obtained hydrothermally at 180 ℃ at ph=9 2 Topography of nanoparticles. As can be seen from fig. 6, tiO 2 The morphology of (2) is affected by pH, different pH, tiO 2 Is different in both morphology and size.
For Pt-TiO obtained in step (4) in example 2 and example 4 2 The catalyst was subjected to energy spectrum test, and the experimental results are shown in fig. 7. FIG. 7 a shows the Pt-TiO composition obtained in example 2 2 The energy spectrum of the catalyst, b, is Pt-TiO obtained in example 4 2 The energy spectrum of the catalyst shows that Pt-TiO can be obtained by the corresponding preparation methods in example 2 and example 4 2 TiO supported catalyst with different morphology 2 The surface is uniformly loaded with a small amount of Pt. FIG. 8 is the Pt-TiO obtained in step (4) in example 2 and example 4 2 The ultraviolet-visible absorption spectrum of the catalyst, wherein a is TiO obtained with Pt supported at ph=3 2 Nanoparticle formed Pt-TiO 2 Ultraviolet-visible absorption spectrum of the catalyst (wherein the inset is an external optical diagram), b is TiO obtained with Pt supported at ph=9 2 Nanoparticle formed Pt-TiO 2 The ultraviolet visible absorption spectrum of the catalyst (wherein the inset is an apparent optical image). As can be seen from FIGS. 8 a and b, pt-TiO obtained in example 2 and example 4 2 The catalysts have different spectral absorption responses, wherein Pt-TiO at ph=3 2 The catalyst has absorption in the ultraviolet visible band, while Pt-TiO at ph=9 2 The catalyst has the absorption of the full ultraviolet visible light wave band, thereby showing that Pt-TiO at different pH values 2 The catalysts have different electronic structures. FIG. 9 is the Pt-TiO obtained in step (4) in example 2 and example 4 2 Electron paramagnetic resonance diagram of the catalyst. As can be seen from FIG. 9, pt-TiO obtained in example 2 and example 4 2 The catalysts have different electron paramagnetic responses, wherein Pt-TiO at ph=3 2 The catalyst had only a single electron paramagnetic response, while Pt-TiO at ph=9 2 The catalyst has Ti 3+ Single electron and Pt + Signals, thus indicating Pt-TiO at different pH values 2 The catalysts have significantly different surface states. FIG. 10 is a diagram ofPt-TiO obtained in step (4) in example 2 and example 4 2 X-ray photoelectron spectrum of the catalyst, wherein a is Pt 4f spectrum, and b is Ti 2p spectrum. As can be seen from FIG. 10, pt-TiO obtained in example 2 and example 4 2 The catalyst has different electronic states, wherein Pt-TiO under ph=3 conditions 2 Pt in the catalyst has a higher valence state, pt 2+ Pt-TiO at ph=9 2 Pt in the catalyst having a Pt valence of low valence + . FIG. 11 is the Pt-TiO obtained in step (4) in example 2 and example 4 2 Electrocatalytic hydrogen production performance diagram of the catalyst. As can be seen from FIG. 11, pt-TiO obtained in example 2 and example 4 2 The catalysts have different catalytic properties, wherein Pt-TiO at ph=9 2 The catalyst shows more excellent electrocatalytic hydrogen production activity.
In summary, the application provides a Pt-TiO with adjustable morphology 2 A preparation method and application of the catalyst. The preparation method of the catalyst comprises four processes of solid phase sintering, ion exchange stripping, pH control morphology and ultraviolet and visible light irradiation. The preparation method has the advantages of accurate shape control, easy operation, no toxicity, no harm and low cost, and is suitable for large-scale production. Formed Pt-TiO 2 The catalyst has wide application prospect in the electrolysis of water to produce hydrogen.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present application, which is intended to be covered by the claims of the present application.
Claims (10)
1. Shape-adjustable Pt-TiO 2 The preparation method of the catalyst is characterized in that: the preparation method comprises the following steps:
(1) Solid phase calcination: uniformly mixing cesium carbonate and titanium dioxide powder, reacting for 1h at 800 ℃, cooling, grinding into powder, heating to 800-850 ℃ in oxygen atmosphere, reacting for 10h, and cooling to obtain wurtzite type layered cesium titanium oxide;
(2) Ion exchange stripping: a. placing the lepidocrocite type layered cesium titanium oxide in the step (1) into a hydrochloric acid solution with the concentration of 1mol/L, carrying out ultrasonic treatment, standing for 24 hours, and removing supernatant to obtain a reaction product; b. repeating the step a for two times, centrifuging, washing with deionized water, and drying at 60 ℃ for 12 hours to obtain TiO 2 A nanosheet;
(3) pH regulation morphology: subjecting the TiO of step (2) 2 The nano sheet is placed in tetrabutylammonium hydroxide aqueous solution with the concentration of 60mmol/L, milky suspension is obtained after ultrasonic treatment, then water with the volume of 2 times of that of the milky suspension is added for dilution, the pH value is regulated to 1-13 by hydrochloric acid, then the nano sheet is transferred into a reaction kettle for reaction for 24 hours at 180 ℃ to obtain a product, and the product is washed by deionized water, centrifuged and dried overnight at 60 ℃ to obtain TiO with different morphologies 2 A nanoparticle;
(4) Ultraviolet visible light irradiation: tiO with different morphologies in the step (3) 2 Dispersing nano particles in ultrapure water, adding tetrachloroplatinic acid with the concentration of 1mg/ml, uniformly mixing, placing in ice bath, performing ultrasonic treatment to obtain dispersion liquid, keeping ice bath conditions unchanged, placing the dispersion liquid under ultraviolet visible light for 1h under a stirring state, centrifuging, cleaning, and freeze-drying to obtain the Pt-TiO with adjustable morphology 2 A catalyst.
2. The method of manufacturing according to claim 1, characterized in that: the molar ratio of cesium carbonate to titanium dioxide powder in step (1) is 1:1.35.
3. The method of manufacturing according to claim 1, characterized in that: the heating rate in the step (1) is 5 ℃/min.
4. The method of manufacturing according to claim 1, characterized in that: the mass-volume ratio of the lepidocrocite type layered cesium titanium oxide to the hydrochloric acid solution in the step (2) is 1:100, g:mL.
5. The method according to claim 1The preparation method is characterized in that: the TiO in step (3) 2 The mass volume ratio of the nano-sheet to the tetrabutylammonium hydroxide aqueous solution is 0.1:25, g:mL.
6. The method of manufacturing according to claim 1, characterized in that: the TiO with different morphologies in the step (4) 2 The mass volume ratio of the nano particles to the tetrachloroplatinic acid is 0.1:0.5-2.0; g is mL.
7. Morphology-adjustable Pt-TiO prepared by the method according to any one of claims 1-6 2 A catalyst.
8. The morphology-tunable Pt-TiO of claim 7 2 The catalyst is used in electrocatalytic hydrogen production.
9. A method for preparing hydrogen by electrocatalytic reaction, which is characterized by comprising the following steps: morphology-tunable Pt-TiO as defined in claim 7 2 Dispersing catalyst in deionized water, spin-coating on carbon electrode, drying to form film on the carbon electrode, and placing the film as working electrode on H 2 SO 4 In the solution, the voltage and the scanning speed are regulated by an electrochemical workstation, and the electrocatalytic preparation of hydrogen is carried out.
10. The method according to claim 9, wherein: the Pt-TiO 2 The mass volume ratio of the catalyst to the deionized water is 5:1, mg:mL; the H is 2 SO 4 The concentration of the solution is 0.5mol/L; the parameters of the electrochemical workstation are set to be that the cyclic voltammetry potential window voltage is 0.1-0.4V and the scanning speed is 5mV/s.
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| CN117684321B (en) * | 2023-11-08 | 2024-05-31 | 中山市福维环境科技有限公司 | Moisture permeable material and preparation method and application thereof |
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| CN117684321A (en) * | 2023-11-08 | 2024-03-12 | 中山市福维环境科技有限公司 | Moisture permeable material and preparation method and application thereof |
| CN117684321B (en) * | 2023-11-08 | 2024-05-31 | 中山市福维环境科技有限公司 | Moisture permeable material and preparation method and application thereof |
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