CN114512686B - Photoelectrocatalysis material and preparation method and application thereof - Google Patents
Photoelectrocatalysis material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 33
- 238000001354 calcination Methods 0.000 claims abstract description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000446 fuel Substances 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 230000007547 defect Effects 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 4
- 239000010931 gold Substances 0.000 claims abstract 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052737 gold Inorganic materials 0.000 claims abstract 2
- 238000007254 oxidation reaction Methods 0.000 claims description 35
- 230000003647 oxidation Effects 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 230000001699 photocatalysis Effects 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 230000031700 light absorption Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis 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
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 14
- 239000010936 titanium Substances 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 7
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 34
- 238000002484 cyclic voltammetry Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 19
- 238000005286 illumination Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000004435 EPR spectroscopy Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003487 electrochemical reaction Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- -1 titanium alkoxide Chemical class 0.000 description 2
- NFGXHKASABOEEW-UHFFFAOYSA-N 1-methylethyl 11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate Chemical compound COC(C)(C)CCCC(C)CC=CC(C)=CC(=O)OC(C)C NFGXHKASABOEEW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a photoelectrocatalysis material, a preparation method and application thereof, the photoelectrocatalysis material is titanium dioxide nanoparticle H-TiO with gold nanoparticle loaded on hydrogenation 2 A surface; H-TiO 2 Calcining for 5-15 hours at 500-1100 ℃ in hydrogen atmosphere. Compared with conventional Au/TiO 2 Compared with nano particles, the photoelectrocatalysis material provided by the invention has rich Ti 3+ The oxygen vacancy and other defect sites can be excited by ultraviolet light and visible light photons in sunlight to generate photo-generated carriers simultaneously, and can inhibit the recombination of electrons and holes, so that the charge transmission efficiency is improved, the ethanol electrooxidation reaction is further promoted, and the catalytic efficiency of the catalyst is improved. The photoelectrocatalysis material can enhance the electrocatalytic performance under the irradiation of sunlight, and has good application prospect in direct alcohol fuel cells.
Description
Technical Field
The invention relates to the field of catalyst preparation, in particular to a photoelectric catalytic material and a preparation method and application thereof.
Background
Fuel Cells (Fuel Cells) are electric energy conversion devices in a non-combustion process, which utilize Fuel gas and oxygen to continuously convert chemical energy into electric energy in an electrochemical reaction mode, and have the advantages of high energy conversion efficiency, portability, environmental friendliness, low carbon dioxide emission, no nitrogen oxides and sulfide tail gas and the like. At present, the main stream product in the industry uses hydrogen as fuel, but the hydrogen is high-pressure hydrogen, and has great potential safety hazard in storage and transportation. Direct Alcohol Fuel Cells (DAFCs) have wide sources of fuel and high safety, and are becoming more and more interesting. The direct alcohol fuel cell is an energy conversion device for converting chemical energy of organic micromolecular alcohols and oxygen into electric energy. The conversion efficiency of a direct alcohol fuel cell is closely related to the efficiency of the electrocatalytic oxidation reaction of the fuel at the anode. The traditional anode catalyst is Pt, but it has low electrocatalytic activity and is also easily poisoned by oxidized intermediates.
Therefore, the photocatalysis material is introduced to construct the electro-optic catalyst, the electro-optic catalyst can catalyze small organic molecules to generate electro-oxidation reaction under the action of certain voltage, and the photo-optic catalyst can absorb photons in solar spectrum to generate photo-generated carriers, so that the electro-optic reaction is enhanced, the electrochemical reaction kinetics is accelerated, the electro-optic catalytic performance is promoted, the electro-optic synergistic catalysis is realized, and finally, the working efficiency of the fuel cell can be effectively improved.
Document 1: wang Caiqin preparation of Au-based composite and its application in alcohol electrocatalytic oxidation and detection of biological small molecules [ doctor's article ]: university of su and chemical engineering, 2016: mention is made of Au-TiO 2 Nanocomposite catalyst, but TiO 2 Calcining at 600 ℃ in air for 3 hours, and has smaller catalytic activity on ethanol oxidation. This is in combination with TiO 2 The carrier has fewer surface defects, so that the interaction between the carrier and Au is weaker, and meanwhile, tiO 2 Only responds to ultraviolet light, and only shows photocatalytic performance under the condition of ultraviolet light.
Document 2: chinese patent CN 107115861B an Au-TiO 2 -x catalyst and its application 2019.10 discloses an Au-TiO 2 The-x catalyst comprises a carrier and an active component, wherein the carrier is composed of anatase phase TiO 2 The nano particles are obtained by calcining for 2-6 hours in a hydrogen atmosphere at 500-600 ℃, and the catalyst is applied to a water gas shift reaction, so that the hydrogen conversion rate is improved, but no suggestion of application in alcohol oxidation reaction is given.
Disclosure of Invention
In order to solve the problems of the prior photo-catalytic material Au-TiO 2 The inventors have unexpectedly found that TiO is a catalyst for catalyzing alcohol oxidation reactions to a low degree 2 Calcining for 5-15 hours at 500-1100 ℃ under hydrogen atmosphere to obtain H-TiO 2 The product has good electrochemical performance and high catalytic activity on alcohol oxidation, and solves the problems in the prior art, thereby completing the invention.
The invention aims to provide a photoelectrocatalysis material and a preparation method thereof. It is another object of the present invention to provide the use of the photoelectrocatalytic material of the present invention in an oxidation reaction of alcohols.
In order to achieve the purpose of the invention, the specific technical solution is as follows:
a photoelectrocatalysis material is prepared by loading Au nano-particles on hydrogenated titanium dioxide nano-particles H-TiO 2 A surface; the H-TiO 2 Calcining the nano particles for 5-15 hours at 500-1100 ℃ in hydrogen atmosphere.
A preparation method of a photoelectrocatalysis material comprises the following steps:
a. calcining the titanium dioxide nano-particles for 5-10 hours in a hydrogen atmosphere at 500-1100 ℃;
b. and d, uniformly dispersing the product obtained in the step a in ultrapure water, adding chloroauric acid and methanol solution, regulating the pH value of the solution to be alkaline by using sodium hydroxide solution, performing hydrothermal reaction, and finally washing, centrifuging and drying to obtain the required product.
Preferably, the calcination temperature in step a is 900-1100℃and the calcination time is 10-15 hours. More preferably, the calcination temperature in step a is 900℃and the calcination time is 10 hours.
Preferably, in step b, the pH of the solution is 9.
The titanium dioxide nanoparticles in step a are generally commercially available or self-prepared and can be used in any form as long as they are nano-scale. Preferably, self-prepared nano-titania particles may be prepared by a sol-gel process: firstly hydrolyzing and polycondensing inorganic salt of titanium or titanium alkoxide to obtain sol, further polycondensing the sol into gel, and drying to obtain the nano titanium dioxide product.
More preferably, the preparation method of the nano titanium dioxide particles comprises the following steps:
(1) Dispersing isopropyl titanate into absolute ethyl alcohol, wherein the mass ratio of the isopropyl titanate to the absolute ethyl alcohol is 3:8, after standing, washing with water and alcohol, and drying to obtain a precursor TiO 2 ；
(2) TiO as precursor 2 Calcining at 550 ℃ in air atmosphere to obtain original TiO 2 。
The photoelectrocatalysis material provided by the invention is applied to catalyzing alcohol oxidation reaction, in particular to application to micromolecular alcohol oxidation reaction.
Preferred small molecule alcohols are ethanol, methanol, isopropanol.
Compared with the prior art, the invention has the remarkable advantages that:
1. the photoelectric catalytic material provided by the invention uses TiO 2 Calcining the nano-particles for 5-15 hours in 500-1100 ℃ hydrogen atmosphere, thereby leading H-TiO to be 2 Is rich in Ti 3+ Defective sites such as oxygen vacancies, etc., to make H-TiO 2 Narrowing the band gap of H-TiO 2 The light absorption range of the light-emitting diode is expanded from an ultraviolet region to a visible light region, so that the light-emitting diode can be simultaneously excited by ultraviolet light and visible light photons in sunlight to generate photo-generated electrons and holes, and on one hand, au and H-TiO 2 The Schottky barrier is formed on the contact surface and can be used as an electron trap to effectively capture photo-generated electrons, and on the other hand, the existence of defect bits is beneficial to improving the charge transmission efficiency, inhibiting the recombination of photo-generated electron-hole pairs and improving the separation efficiency of electrons and holes, thereby prolonging the H-TiO (high-efficiency-TiO) 2 The hole life of the surface, the separated hole further participates in the ethanol oxidation reaction, and finally the photoelectrocatalysis efficiency is improved;
2. the Au provided by the invention has corrosion resistance, and is not easy to be poisoned by intermediate products generated in the alcohol electrooxidation reaction process, so that the photoelectrocatalysis material has better anti-poisoning capability.
Drawings
Fig. 1 is a scanning electron microscope fig. 1a and a transmission electron microscope fig. 1b of example 1 of the present invention.
Fig. 2 is an X-ray diffraction chart of example 1 and comparative example 1 of the present invention.
FIG. 3 is an X-ray diffraction pattern of examples 1-4 of the present invention.
FIG. 4 is an X-ray diffraction chart of example 1 and examples 5 to 6 of the present invention.
FIG. 5 is a graph showing diffuse reflectance spectra of example 1 and comparative example 1 of the present invention under different illuminations.
FIG. 6 is an electron spin resonance measurement chart of example 1 and comparative example 1 of the present invention;
wherein FIG. 6a is an electron spin resonance assay for example 1, comparative example 1 with/without illumination; FIG. 6b is a graph of electron spin resonance measurements of example 1 with/without illumination, respectively.
FIG. 7 is a cyclic voltammogram of example 1, comparative example 1 of the present invention in the absence of sunlight, visible light;
wherein fig. 7a is a cyclic voltammogram in the absence of light; FIG. 7b is a cyclic voltammogram under visible light; 7c is a cyclic voltammogram in sunlight; 7d is a summary bar graph of peak current density in cyclic voltammograms under different illumination.
FIG. 8 is a cyclic voltammogram of examples 1-4 of the present invention;
wherein fig. 8a is a cyclic voltammogram in the absence of light; FIG. 8b is a cyclic voltammogram under visible light; 8c is a cyclic voltammogram in sunlight; 8d is a summary bar graph of peak current density in cyclic voltammograms under different illumination.
FIG. 9 is a cyclic voltammogram of example 1, examples 5-6 of the present invention;
wherein fig. 9a is a cyclic voltammogram in the absence of light; FIG. 9b is a cyclic voltammogram under visible light; 9c is a cyclic voltammogram in sunlight; 9d is a summary bar graph of peak current density in cyclic voltammograms under different illumination.
Fig. 10 is a graph of current at 30 second intervals under sunlight 10a and a graph of ac impedance under sunlight 10b for example 1 of the present invention, comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, but the present invention is not limited thereto. The measurement methods not described in detail in the present invention are all conventional in the art.
The main instrument adopted in the embodiment of the invention is as follows: high resolution transmission electron microscope was purchased from JEOL corporation, japan, model JEM-1400; a field emission scanning electron microscope was purchased from JEOL corporation, japan, model JSM-7600F; x-ray powder diffractometer was purchased from Japanese Physics Co., ltd., model Rigaku Ultima IV; uv-vis diffuse reflectance spectroscopy is available from Perkin-Elmer, model Lambda 950; a spin electron resonator JEOL corporation, model JES-FA200; the electrochemical workstation was purchased from Shanghai Chenhua instruments Inc., model CHI660D.
The main reagent adopted in the embodiment of the invention is as follows: isopropyl titanate, absolute ethyl alcohol, sodium hydroxide, chloroauric acid and methanol are purchased from Shanghai national pharmaceutical chemical reagent Co., ltd.
The characterization method of each index comprises the following steps:
(1) Field emission Scanning Electron Microscope (SEM): the morphology was observed using a Hitachi S-4800 field emission scanning electron microscope. The catalyst sample is dispersed in ethanol after being ground, a small amount of sample is taken and placed on a copper sample table through conductive carbon gel, and the appearance of the nano material is observed under 15kV accelerating voltage after being dried.
(2) High Resolution Transmission Electron Microscopy (HRTEM): the morphology of the samples was observed using a JEOL 2010F (200 kV) field emission high resolution transmission electron microscope. The catalyst sample is dispersed in ethanol after being ground, after ultrasonic oscillation is carried out for 20min, suspension liquid drops on the upper layer are taken to be placed in a carbon film coated copper net, and after natural drying, the particle morphology and microstructure are observed under a200 kV electron beam.
(3) X-ray powder diffraction (XRD): the crystalline phase composition of the catalyst or support was carried out on a Rigaku Ultima IV diffractometer from Japanese Kabushiki Kaisha, using a theta/theta horizontal goniometer, cu-K.alpha. (lambda= 0.1541 nm) target radiation, tube voltage 20-60kv, tube current 2-60mA, scan range 10 DEG to 80 deg.
(4) Ultraviolet-visible Diffuse Reflectance Spectrometer (DRS): the absorption band edges were estimated by tangential extrapolation using a Lambda 950 diffuse reflectometer with a scan range of 200-800 nm.
(5) Electron Paramagnetic Resonance (EPR) assay: electron Paramagnetic Resonance (EPR) spectra were collected at 9.44GHz using a JES-FA200 spectrometer at room temperature, with an increase in light exposure of 420nm if required.
(6) Cyclic Voltammetry (CV): the catalyst was tested for its electrocatalytic performance to ethanol oxidation using the CHI660D electrochemical workstation, and the entire test was kept at room temperature. The test system adopts a standard three-electrode system, namely, a dry sample Glassy Carbon Electrode (GCE) is coated on the test system to serve as a working electrode, an Ag/AgCl electrode serves as a reference electrode, and a platinum sheet serves as an auxiliary electrode. In an alkaline system, the electrolyte solution is 1.0mol/L KOH solution, and the concentration of the organic micromolecular ethanol is 1.0mol/L. The measured curve is cyclic voltammogram, and is a main measure for measuring the electrocatalytic performance of the catalytic material to ethanol oxidation reaction. For comparison of sample performance, the relative magnitude of the peak current density value in the cyclic voltammetry curve is mainly compared, and if the peak current density value is large, the catalytic performance of the electrode material is relatively strong; conversely, it is relatively weak.
(7) Timing current method (CA): the chronoamperometry is to polarize 4000s at a constant potential and test the catalytic stability of ethanol when the current of the ethanol changes with time in the electrochemical oxidation process.
(8) Electrochemical alternating current impedance (EIS): for studying the kinetics and interfacial processes of the electrodes, and a smaller radius of the impedance arc reflects a higher electron transport efficiency of the catalyst, the electrochemical alternating current impedance (EIS) test being 10 -2 ～10 5 The frequency range of Hz, the amplitude of the alternating voltage was 5.0mV.
Example 1
(1) 3g of isopropyl titanate is weighed, poured into a surface dish, 10mL of absolute ethyl alcohol is added, the mixture is kept stand for 24 hours, and finally the mixture is washed with water and alcohol and dried for two times to obtain the precursor TiO 2 ；
(2) 50mg of precursor TiO 2 Calcining at 550 ℃ for 2 hours in air atmosphere to obtain original TiO 2 (denoted as P-TiO) 2 )；
(3) 50mg of P-TiO 2 Calcining at 900 deg.C under hydrogen atmosphere for 10 hr to obtain blue gray defect-rich TiO 2 (denoted as H-TiO) 2 )；
(4)H-TiO 2 Pouring 20mg into beaker, adding 50ml of ultrapure water, stirring uniformly, and then sequentially adding chloroauric acid solution with concentration of 3.03mg A 2.89mL and 2.13g of anhydrous methanol solution;
(5) Dripping 0.1mol/L sodium hydroxide solution into the solution, adjusting the pH value of the solution to 9, and performing hydrothermal reaction in a reaction kettle at 100 DEG C4 hours to obtain the target product (recorded as Au/H-TiO) 2 )。
Example 2
Example 1 was repeated in the same manner as described except that in step (3), the calcination was performed under a hydrogen atmosphere at a temperature of 500℃for 10 hours.
Example 3
Example 1 was repeated in the same manner as described except that in step (3), the calcination was performed under a hydrogen atmosphere at a temperature of 700℃for 10 hours.
Example 4
Example 1 was repeated in the same manner as described except that in step (3), the calcination was performed under a hydrogen atmosphere at a temperature of 1100℃for 10 hours.
Example 5
Example 1 was repeated in the same manner as described except that in step (3), the time was changed to 900℃and the calcination was carried out under a hydrogen atmosphere for 5 hours.
Example 6
Example 1 was repeated in the same manner as described except that in step (3), the time was changed to 900℃and the calcination was carried out under a hydrogen atmosphere for 15 hours.
Comparative example 1
According to the same steps as described example 1 was repeated in a manner such that, however, the operation of step (3) is omitted, and white TiO is obtained in step (2) 2 And (3) carrying out the operation of the steps (4) and (5) to obtain the target product.
The catalysts prepared in examples 1 to 6 and comparative example 1 above were examined for their catalytic activity analysis, SEM analysis, TEM, XRD and Raman analysis, EPR analysis, XPS analysis, and photoelectric property analysis, and the results were as follows:
as is evident from FIG. 1, the Au nanoparticles of example 1 are supported on H-TiO as is evident from the scanning electron microscope image and the transmission electron microscope (FIG. 1a, FIG. 1 b) 2 Nanoparticle surfaces.
As shown in FIG. 2, the TiO of example 1 2 The crystal form of (2) was changed to the rutile form as compared with the crystal form of comparative example 1. In the figure, the angle 2 theta is about 27.4 degrees, 36.0 degrees, 39.2 degrees, 41.17 degrees, 54.3 degrees, 56.6 degrees, 62.7 degrees, 64.1 degrees, 68.9 degrees and 69.7 degreesIs typical of rutile TiO 2 The diffraction peak of the 2 theta angle of 38.17 degrees and 77.58 degrees corresponds to the diffraction peaks of the (111) and (311) crystal planes of the Au face-centered cubic structure. The presence of these diffraction peaks, on the one hand, illustrates the presence of nano Au in the prepared oxide supported Au catalyst.
As shown in FIG. 3, the diffraction peaks of examples 2-4 remain the same as in example 1. As shown in FIG. 4, the diffraction peaks of examples 5-6 remain the same as in example 1. This demonstrates that the catalysts to be protected according to the invention are structurally consistent and are all typically rutile TiO 2 Meanwhile, the catalyst contains nano Au.
As shown in fig. 5, the absorption wavelength of example 1 is significantly extended to the visible light region by the diffuse reflection spectrum test, whereas comparative example 1, comparative example 2 is not significantly extended to the visible light region.
As shown in FIG. 6, the electron spin resonance test shows that the electron spin resonance peak of example 1 has the highest intensity in the absence of light and illumination, indicating that the calcination in a hydrogen atmosphere causes TiO to react 2 Form Ti in 3+ Defects such as oxygen vacancies (FIG. 6 a). Due to the introduction of Ti 3+ Or oxygen vacancy, to cause TiO 2 Introducing a local state into the conduction band bottom of the reactor, thereby leading to TiO 2 The light absorption range of the light-emitting diode is expanded, and the light-emitting diode has the visible light and even infrared light absorption performance. Ti (Ti) 3+ Or oxygen vacancy and other defects can not only improve TiO 2 The hydrophilicity of the polymer is improved, the conductivity is improved, the photo-generated electrons and holes are generated by excitation under visible light, the transmission rate of the electrons and the holes is accelerated, and the recombination of the electrons and the holes is restrained, so that the separation efficiency of the electrons and the holes is changed, the separated holes further participate in ethanol oxidation reaction, and finally the photoelectric conversion efficiency is improved. The intensity of the electron spin formants of example 1 under light was also higher than under no light conditions (fig. 6 b), further confirming that example 1 was photo-responsive to visible light.
As shown in FIG. 7, the cyclic voltammogram test in the ethanol electrooxidation reaction is usually based on the oxidation peak current or current density in the normal sweep section to evaluate the catalytic activity of the catalyst. As shown, example 1 showed a significant oxidation peak around a scan voltage of 0.15V under various illumination conditions, indicating that the electrocatalytic oxidation performance was exhibited for ethanol oxidation, and the highest oxidation peak current density (fig. 7a,7b,7 c) was exhibited compared to comparative example 1, indicating that example 1 had the optimal electrocatalytic oxidation performance. From the summary bar graph of example 1 under different illumination (fig. 7 d), it can be seen that the peak current density of example 1 is significantly increased under the illumination, which means that the catalytic performance is significantly enhanced, especially under the sun illumination (fig. 7 d), the current density is increased by 18.3%, and also increased by 5.4% under the visible light. Due to the defects, example 1 can be excited to generate photo-generated electrons and holes under visible light, and the catalytic performance of ethanol oxidation under illumination is improved the most compared with comparative example 1.
Examples 1-4 pass cyclic voltammogram testing in an ethanol electrooxidation reaction, as shown in figure 8. Examples 2-4 were identical to example 1 and exhibited distinct oxidation peaks at about 0.15V at different light conditions, indicating that electrocatalytic oxidation performance was exhibited for ethanol oxidation (fig. 8a,8b,8 c). Although the catalytic performance of examples 2-4 was not as strong as example 1, the lowest current density peak of example 3 also exceeded 7mA cm -2 While the peak current density of comparative example 1 was only 5mA cm -2 Left and right. As shown in fig. 8d, the summarized columns under different illumination can be seen more intuitively, and the peak current densities of examples 2-4 are improved under both visible illumination and simulated sunlight, which indicates that both visible illumination and solar illumination can promote the improvement of the catalytic performance of examples 2-4.
Examples 1,5-6 pass cyclic voltammogram testing in ethanol electrooxidation reactions as shown in figure 9. Examples 5-6 were identical to example 1, and all showed significant oxidation peaks at around 0.15V at different light conditions, indicating electrocatalytic oxidation performance for ethanol oxidation (fig. 8a,8b,8 c). Although the catalytic performance of examples 5-6 was not as strong as example 1, the lowest current density peak of example 5 also exceeded 6mA cm -2 While the peak current density of comparative example 1 was only 5mA cm -2 Left and right. As shown in FIG. 8d, summaries under different illuminationThe columns can be seen more intuitively, and the peak current densities of examples 5-6 are not much different, indicating that the catalytic performance is much better under different light conditions. The peak current density of example 5 was not much different in the absence of light under visible light, indicating that the catalytic performance was comparable under visible light. The peak current density of example 6 was increased under both visible and simulated sunlight, indicating that both visible and solar illumination promoted the increase in catalytic performance of example 6.
For a more visual understanding of the peak cyclic voltammogram test current density for each of the examples and comparative examples, it can be seen from table 1:
table 1 cyclic voltammogram test current density peak data table for each of examples and comparative examples
As shown in fig. 10, the response of example 1 to light is very sensitive in passing a timed current curve (fig. 10 a) at 30 second intervals under illumination. Comparative example 1 is insensitive to the response to light. It can be seen from the graph that the current density of example 1 is at the highest level throughout the scan, which illustrates that the electrode produced in example 1 has the best long term stability to ethanol oxidation. As shown in fig. 10b, the radius of the impedance arc (diameter of impedance arc, DIA) on the electrode prepared in example 1 is greater than that of comparative example 1. In general, DIA can account for the magnitude of the electron transfer resistance of an electrode to some extent. The smaller the radius of the impedance arc, the smaller the electron transfer resistance on the electrode is, which is beneficial to the transfer of electrons on the electrode in the electrochemical reaction process; conversely, the larger the radius of the impedance arc, the larger the electron transfer resistance on the electrode is, which is unfavorable for the transfer of electrons on the electrode in the electrochemical reaction process. By means of fig. 10b, the minimum radius of the impedance arc of example 1 illustrates the fastest electron transport speed in example 1.
The photoelectric catalytic material provided by the invention uses TiO 2 Calcining the nano-particles for 5-15 hours in 500-1100 ℃ hydrogen atmosphere, thereby leading H-TiO to be 2 Is rich in Ti 3+ Defective sites such as oxygen vacancies and the like,thereby making H-TiO 2 Narrowing the band gap of H-TiO 2 The light absorption range of the catalyst is expanded from an ultraviolet region to a visible region, the performance of the original catalyst is changed, and finally the photoelectrocatalysis efficiency is improved.
Claims (6)
1. A preparation method of a photo-catalytic material for alcohol electro-catalytic oxidation reaction of a fuel cell, the method is characterized in that: the photoelectrocatalysis material is gold nanoparticles loaded on the surface of hydrogenated titanium dioxide nanoparticles H-TiO 2; the H-TiO2 is obtained by calcining precursor TiO2 for 2 hours in an air atmosphere at 550 ℃ and then calcining the precursor TiO2 for 10 hours in a hydrogen atmosphere at 900-1100 ℃ or calcining the precursor TiO2 for 10-15 hours in a hydrogen atmosphere at 900 ℃; through the steps, the H-TiO2 has the defects of Ti3+ and oxygen vacancies, and the light absorption range of the H-TiO2 is further expanded from an ultraviolet light region to a visible light region; the crystal form of the photoelectrocatalysis material prepared by the steps is rutile, and the XRD diffraction peak 2 theta is 27.4 degrees, 36.0 degrees, 39.2 degrees, 41.17 degrees, 54.3 degrees, 56.6 degrees, 62.7 degrees, 64.1 degrees, 68.9 degrees, 69.7 degrees, 38.17 degrees and 77.58 degrees.
2. The method for preparing the photocatalytic material for the electrocatalytic oxidation reaction of fuel cell alcohols according to claim 1, wherein the method comprises the following steps: the H-TiO2 is obtained by calcining for 2 hours in an air atmosphere at 550 ℃ and calcining for 10 hours in a hydrogen atmosphere at 900 ℃.
3. The method for preparing the photocatalytic material for the electrocatalytic oxidation reaction of fuel cell alcohols according to claim 1, comprising the following steps:
a. calcining the titanium dioxide nano-particles for 2 hours in an air atmosphere at 550 ℃;
b. calcining the product obtained in the step a for 10 hours in a hydrogen atmosphere at 900-1100 ℃ or calcining for 10-15 hours in a hydrogen atmosphere at 900 ℃;
c. and c, uniformly dispersing the product obtained in the step b in ultrapure water, adding chloroauric acid and methanol solution, regulating the pH value of the solution to be alkaline by using sodium hydroxide solution, performing hydrothermal reaction, and finally washing, centrifuging and drying to obtain the required product.
4. A method for preparing a photocatalytic material for the electrocatalytic oxidation of fuel cell alcohols according to claim 3, wherein: in the step b, the calcination temperature is 900-1100 ℃ and the calcination time is 10 hours.
5. The method for preparing the photocatalytic material for the electrocatalytic oxidation reaction of fuel cell alcohols according to claim 4, wherein the method comprises the following steps: in step b, the calcination time was 10 hours and the calcination temperature was 900 ℃.
6. The method for preparing the photocatalytic material for the electrocatalytic oxidation reaction of fuel cell alcohols according to claim 1, wherein the method comprises the following steps: the alcohol is small molecular alcohol which is used for the electrocatalytic oxidation reaction of the fuel cell; the photoelectrocatalytic material has enhanced electrocatalytic oxidation properties under visible light.
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