CN106111129B - Photochemical catalyst and preparation method thereof for simultaneous hydrogen production and selective oxidation ethyl alcohol - Google Patents
Photochemical catalyst and preparation method thereof for simultaneous hydrogen production and selective oxidation ethyl alcohol Download PDFInfo
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- CN106111129B CN106111129B CN201610478639.XA CN201610478639A CN106111129B CN 106111129 B CN106111129 B CN 106111129B CN 201610478639 A CN201610478639 A CN 201610478639A CN 106111129 B CN106111129 B CN 106111129B
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 235000019441 ethanol Nutrition 0.000 title claims abstract description 26
- 239000001257 hydrogen Substances 0.000 title claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 230000003647 oxidation Effects 0.000 title claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 97
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 52
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 42
- 239000002055 nanoplate Substances 0.000 claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 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
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910003087 TiOx Inorganic materials 0.000 claims description 2
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- 238000005286 illumination Methods 0.000 abstract description 6
- 238000006303 photolysis reaction Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 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 20
- 239000000243 solution Substances 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 235000011167 hydrochloric acid Nutrition 0.000 description 5
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 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
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000004020 conductor Substances 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
- 239000006193 liquid solution Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 238000004064 recycling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 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 photochemical catalyst of simultaneous hydrogen production and selective oxidation ethyl alcohol, is made 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 specific steps of preparation method, and preparation method is simple for this.Gained titanium dioxide nanoplate palladium cube composite photocatalyst under simulated solar irradiation illumination, pair simultaneously photodissociation alcohol production hydrogen and selective oxidation ethyl alcohol have high catalytic activity；And catalyst is conveniently recycled and reused using rear.
Description
Technical field
It is prepared the invention belongs to catalysis material and photocatalysis technology field, and in particular to a kind of simultaneous hydrogen production and selectivity
The photochemical catalyst of Oxidation of Alcohol.
Background technology
Since Honda in 1972 reports photoelectrolysis aquatic products hydrogen, photodissociation aquatic products hydrogen receives extensive research, however arrives mesh
Before until, the utilization rate of sunlight is all universal relatively low, and is largely required in the system of research photodissociation aquatic products hydrogen at present
Sacrifice agent is added as electron donor, this not only adds the costs of system, and it is empty to also correspond to waste photoproduction in system
The energy in cave is unfavorable for improving sun phototranstormation efficiency.Recently, some researches show that can have photodissociation aquatic products hydrogen and selectivity
Machine conversion is combined in a photocatalytic system well, and the single catalyst to make has dual function.It is 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
Solvent, chemical products reactant and fuel additive etc..In addition, studies have shown that by suitable 1,1- diethoxyethane
It is added in fuel or even can reduce the discharge of nitrogen oxides in combustion product, therefore it also has huge answer in environmental area
Use foreground.In general, it is that acetaldehyde and ethyl alcohol and glyoxalic acid are urged that the preparation process of 1,1- diethoxyethane, which includes by oxidation of ethanol,
The two steps of change aldolisation.It usually requires to use some with toxicity in addition to reaction step is cumbersome, in Ethanol Oxidation
Or corrosive strong oxidizer, such as ClO-, Cr (VI), Cl2Deng these are all runed counter to the concept of Green Chemistry and uneconomical
Environmental protection.And the photocatalysis technology in the past few years risen can carry out under conditions of simple mild, so as to avoid the above problem, be
Selective organic synthesis 1,1- diethoxyethane provides a kind of new method and approach.
In numerous catalyst, TiO2It is concerned with its unique advantage, however, our conventionally used one-components
The problems such as photochemical catalyst is low low with quantum efficiency there is sun light utilization efficiency always.In order to improve the effect of conductor photocatalysis
Rate, by noble metal（Such as Au, Ag, Pd etc.）It is compound that be a kind of raising conductor photocatalysis efficiency for being widely studied report have
Efficacious prescriptions method.In these noble metals, precious metals pd is widely studied report because it is with excellent catalytic performance.However in crowd
In more reports, the influence of the pattern of Pd to light-catalyzed reaction is often ignored, but has significant impact to catalytic activity.
Invention content
The purpose of the present invention is to provide the photochemical catalyst of a kind of simultaneous hydrogen production and selective oxidation ethyl alcohol, the catalyst by
TiO2Nanometer sheet and palladium cube composition.The catalyst can be catalyzed simultaneously photodissociation alcohol production hydrogen and ethanol selectivity oxidation it is anti-
It answers.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of photochemical catalyst of simultaneous hydrogen production and selective oxidation ethyl alcohol, by palladium cube and titanium dioxide nanoplate group
At wherein the cubical mass fraction of palladium is 1%, and palladium cube size size is：7-17 nm.
The preparation method of the catalyst, includes the following steps：
（1）The cubical preparation of palladium：
By PVP, ascorbic acid, KBr, KCl and water are mixed, and flow back at 80 DEG C after ten minutes, by K2PdCl4Solution
It is added in above-mentioned solution, flow back 3 h at 80 DEG C, is then centrifuged for, washs and is re-dispersed into water, and the colloid for obtaining palladium is molten
Liquid；A concentration of 1 mg/mL of the colloidal solution of gained palladium；Wherein the quality of KBr is 5 ~ 600mg；The quality of KCl is 0-185mg；
（2）The preparation of titanium dioxide nanoplate：
By positive four butyl ester of the metatitanic acid of 5 mL（Ti(OBu)4）Hydrofluoric acid mixing with 1 mL is added in reaction kettle anti-at 180 DEG C
24 h are answered, then cools down, centrifuge, wash, be 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）The preparation of composite photocatalyst：
By 100 mg titanium dioxide nanoplates ultrasonic disperses in 100 mL aqueous solutions, take a concentration of 1 mg/mL's of 1 mL
Palladium cube is diluted to 10 mL, and palladium cube liquid solution is then instilled titanium dioxide nanoplate dispersion liquid dropwise, is stirred at room temperature
It after mixing 24 h, centrifuges, wash, being dried to obtain titanium dioxide nanoplate-palladium cube composite photocatalyst；
The step（1）The average molecular weight of middle PVP is 55000；
The step（3）In, the titanium dioxide nanoplate ultrasonic disperse time is more than 10 minutes.
The application of titanium dioxide nanoplate-palladium cube composite photocatalyst：
（1）Take a certain amount of ethyl alcohol, TiO2Nanometer sheet-palladium cube composite photocatalyst and micro concentrated hydrochloric acid are in reaction
It in device, stirs evenly, illumination certain time, takes a certain amount of gas inlet analysis of hplc gas-phase product, be then centrifuged for, recycle
Catalyst, solution are waited for into gas chromatographic analysis；
（2）By photocatalysis reaction mixture into gas chromatographic analysis, pass through retention time and peak area qualitative.
Composite photocatalyst irradiates 12 h under simulated solar irradiation, and hydrogen output can reach 5.95-9.19 mmol,
And the conversion ratio of ethyl alcohol is 8.36-12.5%, wherein the yield of 1,1- diethoxyethane is 927-1391 μm of ol, selectivity
For 92.3-96.7%.
The remarkable advantage of the present invention is：
（1）The catalyst preparation is simple, using solar energy as driving energy, can be catalyzed photodissociation alcohol production hydrogen and selective oxygen simultaneously
Change ethyl alcohol is 1,1- diethoxyethane, is conducive to the sustainable development of environment and the energy；
（2）The photocatalytic activity and high selectivity, cyclicity of titanium dioxide nanoplate-palladium cube composite photocatalyst
Energy is good, simple production process, macroscopical can prepare, easily recycling.
Description of the drawings
Fig. 1 is the cubical TEM figures of palladium of 7 nm；
Fig. 2 is the TEM figures of titanium dioxide nanoplate-palladium cube composite photocatalyst prepared by 7 nm palladium cubes；
Fig. 3 is the XRD diagram of titanium dioxide nanoplate-palladium cube composite photocatalyst.
Specific implementation mode
Embodiment 1
By 105 mg PVP（Average molecular weight is about 55000）, 60 mg ascorbic acid, 5 mg KBr, 185 mg KCl
It is mixed, flows back at 80 DEG C after ten minutes, by 63 mg K with 8 mL water2PdCl4It is distributed to wiring solution-forming in 3 mL water
It is added in above-mentioned solution, flow back 3 h at 80 DEG C, is then centrifuged for, washs and be re-dispersed into water, obtains a certain concentration
Palladium colloidal solution（1 mg/mL）, the cubical size of gained palladium is 7 nm, as shown in Figure 1；
By positive four butyl ester of the metatitanic acid of 5 mL（Ti(OBu)4）Hydrofluoric acid mixing with 1 mL is added in reaction kettle at 180 DEG C
24 h are reacted, then cools down, centrifuge, wash, be dried to obtain titanium dioxide nanoplate:
By 100 mg titanium dioxide nanoplates ultrasonic disperses in 100 mL aqueous solutions, take a concentration of 1 mg/mL's of 1 mL
Palladium cube is diluted to 10mL, and palladium cube liquid solution is then instilled titanium dioxide nanoplate dispersion liquid dropwise, is stirred at room temperature
It after mixing 24 h, centrifuges, wash, being dried to obtain titanium dioxide nanoplate-palladium cube composite photocatalyst TiO2 NSs-
PdNCs-7；Its pattern forms two as shown in Fig. 2, as shown in Figure 2, palladium cube uniformly loads on titanium dioxide nanoplate
TiOx nano piece-palladium cube composite construction.The sample of gained is anatase crystal（As shown in Figure 3）, before illustrating load
Afterwards to TiO2Crystalline phase do not impact.
By 15 mg titanium dioxide nanoplates-palladium cube composite photocatalyst, 2 mL ethyl alcohol and 0.4 μ L concentrated hydrochloric acids
It is uniformly mixed, is placed in 12 h of illumination under simulated solar irradiation light (nm of 350 nm≤λ≤800), hydrogen output can reach 9.19
The conversion ratio of mmol, ethyl alcohol are 12.5%, and the yield of 1,1- diethoxyethane is 1391 μm of ol, and selectivity is 92.3%.
Embodiment 2
By 105 mg PVP（Molecular weight is about 75000）, 60 mg ascorbic acid, 200mg KBr, 70 mg KCl and 8
ML water is mixed, and flows back at 80 DEG C after ten minutes, by 63 mg K2PdCl4Wiring solution-forming in 3 mL water is distributed to be added
Into above-mentioned solution, flow back 3 h at 80 DEG C, is then centrifuged for, washs and is re-dispersed into water, obtains certain density palladium
Colloidal solution（1 mg/mL）；The cubical size of gained palladium is 14 nm；
By positive four butyl ester of the metatitanic acid of 5 mL（Ti(OBu)4）Hydrofluoric acid mixing with 1 mL is added in reaction kettle at 180 DEG C
24 h are reacted, then cools down, centrifuge, wash, be dried to obtain titanium dioxide nanoplate:
By 100 mg titanium dioxide nanoplates ultrasonic disperses in 100 mL aqueous solutions, take a concentration of 1 mg/mL's of 1 mL
Palladium cube is diluted to 10mL, and palladium cube is then instilled titanium dioxide nanoplate dispersion liquid dropwise, is stirred at room temperature 24
It after h, centrifuges, wash, being dried to obtain titanium dioxide nanoplate-palladium cube composite photocatalyst TiO2 NSs-PdNCs-
14；
By 15 mg titanium dioxide nanoplates-palladium cube composite photocatalyst, 2 mL ethyl alcohol and 0.4 μ L concentrated hydrochloric acids
It is uniformly mixed, is placed in 12 h of illumination under simulated solar irradiation light (nm of 350 nm≤λ≤800), hydrogen output can reach 8.33
The conversion ratio of mmol, ethyl alcohol are 9.87%, and the yield of 1,1- diethoxyethane is 1100 μm of ol, and selectivity is 93.2%.
Embodiment 3
By 105 mg PVP（Molecular weight is about 150000）, 60 mg ascorbic acid, 600mg KBr and 8 mL water mix
Stirring, flows back after ten minutes at 80 DEG C, by 63 mg K2PdCl4It is distributed to wiring solution-forming in 3 mL water and is added to above-mentioned solution
In, flow back 3 h at 80 DEG C, is then centrifuged for, washs and is re-dispersed into water, obtains the colloidal solution of certain density palladium
（1 mg/mL）；The cubical size of gained palladium is 17nm；
By positive four butyl ester of the metatitanic acid of 5 mL（Ti(OBu)4）Hydrofluoric acid mixing with 1 mL is added in reaction kettle at 180 DEG C
24 h are reacted, then cools down, centrifuge, wash, be dried to obtain titanium dioxide nanoplate:
By 100 mg titanium dioxide nanoplates ultrasonic disperses in 100 mL aqueous solutions, take a concentration of 1 mg/mL's of 1 mL
Palladium cube is diluted to 10 mL, and palladium cube is then instilled titanium dioxide nanoplate dispersion liquid dropwise, is stirred at room temperature 24
It after h, centrifuges, wash, being dried to obtain titanium dioxide nanoplate-palladium cube composite photocatalyst TiO2 NSs-PdNCs-
17；
By 15 mg titanium dioxide nanoplates-palladium cube composite photocatalyst, 2 mL ethyl alcohol and 0.4 μ L concentrated hydrochloric acids
It is uniformly mixed, is placed in 12 h of illumination under simulated solar irradiation light (nm of 350 nm≤λ≤800), hydrogen output can reach 5.95
The conversion ratio of mmol, ethyl alcohol are 8.36%, and the yield of 1,1- diethoxyethane is 927 μm of ol, and selectivity is 92%.
Comparative example：
Preparation without the cubical titanium dioxide nanosheet photocatalyst of palladium：
By positive four butyl ester of the metatitanic acid of 5 mL（Ti(OBu)4）Hydrofluoric acid mixing with 1 mL is added in reaction kettle at 180 DEG C
24 h are reacted, then cools down, centrifuge, washing, being dried to obtain titanium dioxide nanoplate TiO2NSs；
15 mg titanium dioxide nanosheet photocatalysts, 2 mL ethyl alcohol and 0.4 μ L concentrated hydrochloric acids are uniformly mixed, mould is placed in
12 h of illumination under quasi- sunlight light (nm of 50 nm≤λ≤800), hydrogen output are 0.018 mmol, and the conversion ratio of ethyl alcohol is
0.13%, the yield of 1,1- diethoxyethane is 153 μm of ol, and selectivity is 100%.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (4)
1. a kind of preparation method for simultaneous hydrogen production and the photochemical catalyst of selective oxidation ethyl alcohol, it is characterised in that：It is stood by palladium
Cube and titanium dioxide nanoplate composition；The cubical mass fraction of palladium is 1%；Palladium cube size size is：7-
17nm；The size of the titanium dioxide nanoplate is：50 nm；Specific preparation method includes the following steps：
（1）The cubical preparation of palladium：
By PVP, ascorbic acid, KBr, KCl and water are mixed, and after reflux, add K2PdCl4Solution, then flow back, then from
The heart is washed and is re-dispersed into water, obtains the colloidal solution of palladium；
（2）The preparation of titanium dioxide nanoplate：
Positive four butyl ester of metatitanic acid and hydrofluoric acid are mixed to be added in reaction kettle and reacted, then cools down, centrifuge, wash, be dried to obtain two
TiOx nano piece；
（3）The preparation of titanium dioxide nanoplate-palladium cube composite photocatalyst：
By step（2）Titanium dioxide nanoplate ultrasonic disperse obtained in water, and after the colloidal solution of palladium is diluted with water, then by
Drop instills titanium dioxide nanoplate dispersion liquid, is stirred at room temperature, and centrifuges, washs, to be dried to obtain titanium dioxide nanoplate-palladium vertical
Cube composite photocatalyst.
2. preparation method according to claim 1, it is characterised in that：Step（1）The average molecular weight of middle PVP is 55000.
3. preparation method according to claim 1, it is characterised in that：Step（1）The quality of middle KBr is 5 ~ 600 mg；KCl
Quality be 0-185 mg, wherein the quality of KCl be 0mg.
4. preparation method according to claim 1, it is characterised in that：Step（2）The reaction kettle reaction condition is temperature
180 DEG C, 24 h of reaction time.
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| CN201610478639.XA CN106111129B (en) | 2016-06-28 | 2016-06-28 | Photochemical catalyst and preparation method thereof for simultaneous hydrogen production and selective oxidation ethyl alcohol |
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| CN106111129B true CN106111129B (en) | 2018-09-18 |
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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 |
| CN111921540B (en) * | 2020-08-22 | 2021-04-20 | 湖南第一师范学院 | Preparation method of three-way catalyst for automobile exhaust, product and application thereof |
| CN112479158B (en) * | 2020-11-30 | 2022-08-02 | 江南大学 | Method for producing hydrogen from methanol |
| CN113083323B (en) * | 2021-04-13 | 2022-07-15 | 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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