CN106111129A - Photocatalyst for simultaneous hydrogen production and selective oxidation ethanol and preparation method thereof - Google Patents
Photocatalyst for simultaneous hydrogen production and selective oxidation ethanol and preparation method thereof Download PDFInfo
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- CN106111129A CN106111129A CN201610478639.XA CN201610478639A CN106111129A CN 106111129 A CN106111129 A CN 106111129A CN 201610478639 A CN201610478639 A CN 201610478639A CN 106111129 A CN106111129 A CN 106111129A
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- palladium
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- dioxide nanoplate
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 29
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 94
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 53
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 42
- 239000002055 nanoplate Substances 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 238000006303 photolysis reaction Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 claims description 5
- 239000002135 nanosheet Substances 0.000 claims description 3
- 241000790917 Dioxys <bee> Species 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 claims 2
- 229910003087 TiOx Inorganic materials 0.000 claims 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000005286 illumination Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1229—Ethanol
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of simultaneous hydrogen production and the photocatalyst of selective oxidation ethanol, is made up of palladium cube and titanium dioxide nanoplate；Wherein the cubical mass fraction of palladium is 1%, and palladium cubic granules size is: 7 17nm；The size of titanium dioxide nanoplate is: 50nm.Invention additionally discloses the concrete steps of its preparation method, this preparation method is simple.Gained titanium dioxide nanoplate palladium cube composite photocatalyst under simulated solar irradiation illumination, to while photodissociation alcohol produce hydrogen and selective oxidation ethanol there is high catalytic activity；And catalyst conveniently recycles and reuses after using.
Description
Technical field
The invention belongs to catalysis material preparation and photocatalysis technology field, be specifically related to a kind of simultaneous hydrogen production and selectivity
The photocatalyst of Oxidation of Alcohol.
Background technology
Since Honda report photoelectrolysis Aquatic product hydrogen in 1972, photodissociation Aquatic product hydrogen receives to be studied widely, but to mesh
Till before, the utilization rate of sunlight is the most on the low side, and at present in the system of research photodissociation Aquatic product hydrogen, major part is required for
Addition sacrifice agent, as electron donor, this not only adds the cost of system, and it is empty to also correspond to waste photoproduction in system
The energy in cave, is unfavorable for improving sunlight transformation efficiency.Recently, there are some researches show photodissociation Aquatic product hydrogen and selectivity can be had
Machine convert well be combined in a photocatalysis system so that single catalyst had dual-use function.This difunctional
Catalyst brings a kind of new Research Thinking to photocatalysis research field.
1,1-diethoxyethane receives more and more attention recently because it has a wide range of applications, for example as having
Machine solvent, chemical products reactant and fuel additive etc..Additionally, research shows, by appropriate 1,1-diethoxyethane
Joining and even can reduce the discharge of nitrogen oxides in combustion product in fuel, therefore it also has huge answering at environmental area
Use prospect.Generally, the preparation process of 1,1-diethoxyethane includes and is acetaldehyde and ethanol by oxidation of ethanol and glyoxalic acid is urged
Change aldolisation the two step.Except reactions steps is loaded down with trivial details, Ethanol Oxidation typically requires and uses some there is toxicity
Or corrosive strong oxidizer, such as ClO-, Cr (VI), Cl2Deng, these are all runed counter to and uneconomical with the concept of Green Chemistry
Environmental protection.And the photocatalysis technology in the past few years risen can be carried out under conditions of simple gentleness, thus avoid the problems referred to above, for
Selectivity organic synthesis 1,1-diethoxyethane provides a kind of new method and approach.
In numerous catalyst, TiO2Receive much concern with the advantage of its uniqueness, but, the one-component that we are conventionally used
Photocatalyst also exists that sunlight utilization rate is low and the problem such as quantum efficiency is low all the time.In order to improve the effect of conductor photocatalysis
Rate, being combined by noble metal (such as Au, Ag, Pd etc.) is to be widely studied a kind of of report to improve having of conductor photocatalysis efficiency
Efficacious prescriptions method.In these noble metals, precious metals pd is widely studied report because it has the catalytic performance of excellence.But crowd
In many reports, the impact of light-catalyzed reaction is often left in the basket by the pattern of Pd, but but catalysis activity is had significant impact.
Summary of the invention
It is an object of the invention to provide a kind of simultaneous hydrogen production and the photocatalyst of selective oxidation ethanol, this catalyst by
TiO2Nanometer sheet and palladium cube composition.This catalyst can be catalyzed simultaneously photodissociation alcohol produce hydrogen and ethanol selectivity oxidation anti-
Should.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of simultaneous hydrogen production and the photocatalyst of selective oxidation ethanol, be made up of palladium cube and titanium dioxide nanoplate, its
The cubical mass fraction of middle palladium is 1%, and palladium cube size size is: 7-17 nm.
The preparation method of this catalyst, comprises the following steps:
(1) the cubical preparation of palladium:
By PVP, ascorbic acid, KBr, KCl and water mix and blend, after refluxing 10 minutes at 80 DEG C, by K2PdCl4Solution adds
In above-mentioned solution, reflux at 80 DEG C 3 h, is then centrifuged for, washs and is re-dispersed in water, obtains the colloid solution of palladium；
The concentration of the colloid solution of gained palladium is 1 mg/mL；Wherein the quality of KBr is 5 ~ 600mg；The quality of KCl is 0-185mg；
(2) preparation of titanium dioxide nanoplate:
By positive for the metatitanic acid of 5 mL four butyl esters (Ti (OBu)4) and the Fluohydric acid. mixing of 1 mL add in reactor and react 24 at 180 DEG C
H, then cools down, is centrifuged, washs, is dried to obtain titanium dioxide nanoplate；The size of gained titanium dioxide nanoplate is 50 nm.
(3) titanium dioxide nanoplate-palladium cube (TiO2NSs-Pd NCs) preparation of composite photocatalyst:
By 100 mg titanium dioxide nanoplate ultrasonic disperse in 100 mL aqueous solutions, take the palladium that 1 mL concentration is 1 mg/mL and stand
Cube is diluted to 10 mL, then palladium cube solution is dropwise instilled titanium dioxide nanoplate dispersion liquid, is stirred at room temperature 24
After h, it is centrifuged, washs, is dried to obtain titanium dioxide nanoplate-palladium cube composite photocatalyst；
In described step (1), the mean molecule quantity of PVP is 55000；
In described step (3), the titanium dioxide nanoplate ultrasonic disperse time is more than 10 minutes.
The application of titanium dioxide nanoplate-palladium cube composite photocatalyst:
(1) a certain amount of ethanol, TiO are taken2Nanometer sheet-palladium cube composite photocatalyst and trace concentrated hydrochloric acid are in reactor
In, stirring, illumination certain time, take a certain amount of gas inlet analysis of hplc gas-phase product, be then centrifuged for, recovery is urged
Agent, solution treats air inlet analysis of hplc；
(2) by photocatalysis reaction mixture air inlet analysis of hplc, by retention time and peak area qualitative, quantitative.
Composite photocatalyst irradiates 12 h under simulated solar irradiation, and its hydrogen output can reach 5.95-9.19 mmol,
And the conversion ratio of ethanol is 8.36-12.5%, wherein 1, the yield of 1-diethoxyethane is 927-1391 μm ol, selectivity
For 92.3-96.7%.
The remarkable advantage of the present invention is:
(1) preparation of this catalyst is simple, with solar energy for driving energy, can be catalyzed photodissociation alcohol simultaneously and produce hydrogen and selective oxidation second
Alcohol is 1, the sustainable development of 1-diethoxyethane, beneficially environment and the energy；
(2) photocatalytic activity of titanium dioxide nanoplate-palladium cube composite photocatalyst and selectivity is high, cycle performance
Good, production technology simple, can macroscopic view preparation, easily reclaim.
Accompanying drawing explanation
Fig. 1 is the palladium cubical TEM figure of 7 nm；
Fig. 2 is the TEM figure of titanium dioxide nanoplate-palladium cube composite photocatalyst prepared by 7 nm palladium cubes；
Fig. 3 is the XRD figure of titanium dioxide nanoplate-palladium cube composite photocatalyst.
Detailed description of the invention
Embodiment 1
105 mg PVP(mean molecule quantities are about 55000), 60 mg ascorbic acid, 5 mg KBr, 185 mg KCl and 8
ML water mix and blend, after refluxing 10 minutes at 80 DEG C, by 63 mg K2PdCl4It is distributed to wiring solution-forming in 3 mL water add
In above-mentioned solution, reflux at 80 DEG C 3 h, is then centrifuged for, washs and is re-dispersed in water, obtains certain density palladium
Colloid solution (1 mg/mL), the cubical size of gained palladium is 7 nm, as shown in Figure 1；
By positive for the metatitanic acid of 5 mL four butyl esters (Ti (OBu)4) and the Fluohydric acid. mixing of 1 mL add in reactor 180 DEG C of reactions
24 h, then cool down, are centrifuged, wash, are dried to obtain titanium dioxide nanoplate:
By 100 mg titanium dioxide nanoplate ultrasonic disperse in 100 mL aqueous solutions, take the palladium that 1 mL concentration is 1 mg/mL and stand
Cube is diluted to 10mL, then palladium cube solution is dropwise instilled titanium dioxide nanoplate dispersion liquid, is stirred at room temperature 24
After h, it is centrifuged, washs, is dried to obtain titanium dioxide nanoplate-palladium cube composite photocatalyst TiO2 NSs-PdNCs-
7；As in figure 2 it is shown, as shown in Figure 2, palladium cube loads on titanium dioxide nanoplate its pattern uniformly, forms titanium dioxide
Nanometer sheet-palladium cube composite construction.The sample of gained is anatase crystal (as shown in Figure 3), right before and after load is described
TiO2Crystalline phase do not impact.
By 15 mg titanium dioxide nanoplates-palladium cube composite photocatalyst, 2 mL ethanol and 0.4 μ L concentrated hydrochloric acid
Mix homogeneously, is placed in illumination 12 h under simulated solar irradiation light (350 nm≤λ≤800 nm), and hydrogen output can reach 9.19
Mmol, the conversion ratio of ethanol is 12.5%, and the yield of 1,1-diethoxyethane is 1391 μm ol, and selectivity is 92.3%.
Embodiment 2
105 mg PVP(molecular weight are about 75000), 60 mg ascorbic acid, 200mg KBr, 70 mg KCl and 8 mL
Water mix and blend, after refluxing 10 minutes at 80 DEG C, by 63 mg K2PdCl4It is distributed to wiring solution-forming in 3 mL water join
Stating in solution, reflux at 80 DEG C 3 h, is then centrifuged for, washs and is re-dispersed in water, obtains the glue of certain density palladium
Liquid solution (1 mg/mL)；The cubical size of gained palladium is 14 nm；
By positive for the metatitanic acid of 5 mL four butyl esters (Ti (OBu)4) and the Fluohydric acid. mixing of 1 mL add in reactor 180 DEG C of reactions
24 h, then cool down, are centrifuged, wash, are dried to obtain titanium dioxide nanoplate:
By 100 mg titanium dioxide nanoplate ultrasonic disperse in 100 mL aqueous solutions, take the palladium that 1 mL concentration is 1 mg/mL and stand
Cube is diluted to 10mL, then palladium cube is dropwise instilled titanium dioxide nanoplate dispersion liquid, be stirred at room temperature 24 h it
After, it is centrifuged, washs, is dried to obtain titanium dioxide nanoplate-palladium cube composite photocatalyst TiO2NSs-PdNCs-14；
15 mg titanium dioxide nanoplates-palladium cube composite photocatalyst, 2 mL ethanol and 0.4 μ L concentrated hydrochloric acid are mixed
Uniformly, being placed in illumination 12 h under simulated solar irradiation light (350 nm≤λ≤800 nm), hydrogen output can reach 8.33
Mmol, the conversion ratio of ethanol is 9.87%, and the yield of 1,1-diethoxyethane is 1100 μm ol, and selectivity is 93.2%.
Embodiment 3
105 mg PVP(molecular weight are about 150000), 60 mg ascorbic acid, 600mg KBr and the mixing of 8 mL water are stirred
Mix, after refluxing 10 minutes at 80 DEG C, by 63 mg K2PdCl4It is distributed to wiring solution-forming in 3 mL water and joins above-mentioned solution
In, reflux at 80 DEG C 3 h, is then centrifuged for, washs and is re-dispersed in water, obtains the colloid solution of certain density palladium
(1 mg/mL)；The cubical size of gained palladium is 17nm；
By positive for the metatitanic acid of 5 mL four butyl esters (Ti (OBu)4) and the Fluohydric acid. mixing of 1 mL add in reactor 180 DEG C of reactions
24 h, then cool down, are centrifuged, wash, are dried to obtain titanium dioxide nanoplate:
By 100 mg titanium dioxide nanoplate ultrasonic disperse in 100 mL aqueous solutions, take the palladium that 1 mL concentration is 1 mg/mL and stand
Cube is diluted to 10 mL, then palladium cube is dropwise instilled titanium dioxide nanoplate dispersion liquid, be stirred at room temperature 24 h it
After, it is centrifuged, washs, is dried to obtain titanium dioxide nanoplate-palladium cube composite photocatalyst TiO2NSs-PdNCs-17；
15 mg titanium dioxide nanoplates-palladium cube composite photocatalyst, 2 mL ethanol and 0.4 μ L concentrated hydrochloric acid are mixed
Uniformly, being placed in illumination 12 h under simulated solar irradiation light (350 nm≤λ≤800 nm), hydrogen output can reach 5.95
Mmol, the conversion ratio of ethanol is 8.36%, and the yield of 1,1-diethoxyethane is 927 μm ol, and selectivity is 92%.
Comparative example:
Preparation without the cubical titanium dioxide nanosheet photocatalyst of palladium:
By positive for the metatitanic acid of 5 mL four butyl esters (Ti (OBu)4) and the Fluohydric acid. mixing of 1 mL add in reactor 180 DEG C of reactions
24 h, then cool down, are centrifuged, wash, are dried to obtain titanium dioxide nanoplate TiO2NSs；
By 15 mg titanium dioxide nanosheet photocatalyst, 2 mL ethanol and 0.4 μ L concentrated hydrochloric acid mix homogeneously, it is placed in simulation too
Illumination 12 h under sunlight light (50 nm≤λ≤800 nm), hydrogen output is 0.018 mmol, and the conversion ratio of ethanol is 0.13%,
The yield of 1,1-diethoxyethane is 153 μm ol, and selectivity is 100%.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (6)
1. one kind is used for simultaneous hydrogen production and the photocatalyst of selective oxidation ethanol, it is characterised in that: by palladium cube and dioxy
Change titanium nanometer sheet composition；The cubical mass fraction of described palladium is 1%；Palladium cube size size is: 7-17nm；Described dioxy
The size changing titanium nanometer sheet is: 50 nm.
2. a preparation method for the photocatalyst of simultaneous hydrogen production as claimed in claim 1 and selective oxidation ethanol, it is special
Levy and be: comprise the following steps:
(1) the cubical preparation of palladium:
By PVP, ascorbic acid, KBr, KCl and water mix and blend, after backflow, add K2PdCl4Solution, then reflux, then from
The heart, wash and be re-dispersed in water, obtain the colloid solution of palladium；
(2) preparation of titanium dioxide nanoplate:
Positive for metatitanic acid four butyl esters and Fluohydric acid. are mixed and adds reaction kettle for reaction, then cool down, be centrifuged, wash, be dried to obtain two
TiOx nano sheet；
(3) preparation of titanium dioxide nanoplate-palladium cube composite photocatalyst:
By titanium dioxide nanoplate ultrasonic disperse prepared for step (2) in water, and after the colloid solution dilute with water of palladium, then by
Drip instill titanium dioxide nanoplate dispersion liquid, be stirred at room temperature, be centrifuged, wash, be dried to obtain titanium dioxide nanoplate-palladium stand
Cube composite photocatalyst.
Preparation method the most according to claim 2, it is characterised in that: in step (1), the mean molecule quantity of PVP is 55000.
Preparation method the most according to claim 2, it is characterised in that: in step (1), the quality of KBr is 5 ~ 600 mg；KCl
Quality be 0-185 mg.
Preparation method the most according to claim 2, it is characterised in that: step (2) described reactor reaction condition is temperature
180 DEG C, response time 24 h.
6. an application for titanium dioxide nanoplate as claimed in claim 1-palladium cube composite photocatalyst, its feature
It is: produce in the reaction of hydrogen and ethanol selectivity oxidation for photodissociation alcohol simultaneously.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109420495A (en) * | 2017-08-30 | 2019-03-05 | 中国科学院大连化学物理研究所 | It is applied in load type palladium nano cubic body catalyst and preparation and hydrogen peroxide synthesis |
| CN111921540A (en) * | 2020-08-22 | 2020-11-13 | 湖南第一师范学院 | Preparation method of three-way catalyst for automobile exhaust, product and application thereof |
| CN112479158A (en) * | 2020-11-30 | 2021-03-12 | 江南大学 | Method for producing hydrogen from methanol |
| CN113083323A (en) * | 2021-04-13 | 2021-07-09 | 中国科学技术大学 | Copper-modified palladium-titanium dioxide nano composite material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101775638A (en) * | 2010-03-24 | 2010-07-14 | 中国科学院长春应用化学研究所 | Preparation method of palladium nano crystal |
| CN102120184A (en) * | 2011-01-25 | 2011-07-13 | 中国科学院山西煤炭化学研究所 | Noble metal-carrying titanium dioxide catalyst and preparation method and use thereof |
| CN104368338A (en) * | 2014-11-06 | 2015-02-25 | 上海电力学院 | Preparation method of amino-modified Pd/TiO2 photocatalyst |
| CN104493153A (en) * | 2014-12-08 | 2015-04-08 | 中国科学院深圳先进技术研究院 | Palladium nanoparticles and preparation method thereof |
| CN105664929A (en) * | 2016-01-19 | 2016-06-15 | 福州大学 | Nano-plate with precious metal and method for preparing nano-plate |
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2016
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| CN101775638A (en) * | 2010-03-24 | 2010-07-14 | 中国科学院长春应用化学研究所 | Preparation method of palladium nano crystal |
| CN102120184A (en) * | 2011-01-25 | 2011-07-13 | 中国科学院山西煤炭化学研究所 | Noble metal-carrying titanium dioxide catalyst and preparation method and use thereof |
| CN104368338A (en) * | 2014-11-06 | 2015-02-25 | 上海电力学院 | Preparation method of amino-modified Pd/TiO2 photocatalyst |
| CN104493153A (en) * | 2014-12-08 | 2015-04-08 | 中国科学院深圳先进技术研究院 | Palladium nanoparticles and preparation method thereof |
| CN105664929A (en) * | 2016-01-19 | 2016-06-15 | 福州大学 | Nano-plate with precious metal and method for preparing nano-plate |
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| JIAGUO YU ET AL.: "Hydrogen Production by Photocatalytic Water Splitting over Pt/TiO2 Nanosheets with Exposed (001) Facets", 《J. PHYS. CHEM.》 * |
| MUHUA LUO ET AL.: "Shape-controlled synthesis of Pd nanoparticles for effective photocatalytic hydrogen production", 《RSC ADV.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109420495A (en) * | 2017-08-30 | 2019-03-05 | 中国科学院大连化学物理研究所 | It is applied in load type palladium nano cubic body catalyst and preparation and hydrogen peroxide synthesis |
| CN111921540A (en) * | 2020-08-22 | 2020-11-13 | 湖南第一师范学院 | Preparation method of three-way catalyst for automobile exhaust, product and application thereof |
| CN112479158A (en) * | 2020-11-30 | 2021-03-12 | 江南大学 | Method for producing hydrogen from methanol |
| CN113083323A (en) * | 2021-04-13 | 2021-07-09 | 中国科学技术大学 | Copper-modified palladium-titanium dioxide nano composite material and preparation method and application thereof |
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