CN105772032A - Photocatalyst capable of directly converting solar energy into chemical energy and preparation method thereof - Google Patents
Photocatalyst capable of directly converting solar energy into chemical energy and preparation method thereof Download PDFInfo
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- CN105772032A CN105772032A CN201610010159.0A CN201610010159A CN105772032A CN 105772032 A CN105772032 A CN 105772032A CN 201610010159 A CN201610010159 A CN 201610010159A CN 105772032 A CN105772032 A CN 105772032A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 34
- 239000000126 substance Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 22
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000010970 precious metal Substances 0.000 claims abstract description 7
- 229910052737 gold Inorganic materials 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 9
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003808 methanol extraction Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- -1 octadecylene Chemical group 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- 229910019029 PtCl4 Inorganic materials 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 claims description 3
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 229910052763 palladium Inorganic materials 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 229960004217 benzyl alcohol Drugs 0.000 abstract 1
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 239000002159 nanocrystal Substances 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- LBBMOAOCCQOIAQ-UHFFFAOYSA-N methoxy(phenyl)borinic acid Chemical compound COB(O)C1=CC=CC=C1 LBBMOAOCCQOIAQ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a photocatalyst capable of directly converting solar energy into chemical energy and a preparation method thereof. Firstly, Cu7S4 nano crystals are obtained by a method of thermal decomposition of a single precursor, then a precious metal is introduced by a heat injection decomposition method to obtain a Cu7S4@M (M is Pd, Au, Ag or Pt) heterojunction, the heterojunction is applied as the photocatalyst capable of directly converting solar energy into chemical energy, and the photocatalyst shows excellent catalytic activity in Suzuki coupling, nitrobenzene reduction and benzene methanol oxidation reactions. The catalyst is composed of the semiconductor-precious metal heterojunction, has the characteristics of near infrared absorption, low price, high stability and excellent catalytic performance, broadens the sources of materials, saves the cost, provides the guiding role for design and preparation of high-efficiency photocatalysts, and also effectively converts solar energy into chemical energy in an environmentally friendly way.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly to one, solar energy is converted directly into chemistry
High efficiency photocatalyst of energy and preparation method thereof.
Background technology
The development of human society be unable to do without occurring and the use of advanced energy technology of high-grade energy.At Fossil fuel
Increasingly in the case of reducing, develop Renewable resource, it has also become the center of gravity of social development, and solar energy is made
For inexhaustible renewable and clean energy resource, more become the most important thing therein.Therefore, light is utilized
Catalyst directly converts the solar into chemical energy and has caused concern greatly.Up to now, semiconductor-semiconductor,
SEMICONDUCTOR-METAL and bimetallic hetero-junctions arise at the historic moment as potential photocatalyst, Organic substance light degradation,
Photolysis water hydrogen, CO2Conversion and the aspect such as organic synthesis played important function.And based on Pd nanometer
The material of structure be widely used in comprise Suzuki coupling, the reduction of Nitrobenzol and benzyl alcohol oxidation urge
Change reaction, but how to strengthen catalyst activity and reduce the consumption of noble metal and become the key point of research.
For the design of photocatalyst, one of effectively focus utilizing always research of sunlight.Although
Utilize the localized surface plasmons resonance effect of noble metal to strengthen the research of light conversion efficiency at plasma light
Catalyst, sensor and light thermal ablation application achieve certain achievement, but quasiconductor-noble metal is relative with it
Cheaply, the higher feature of light capture rate and gain great popularity.Therefore, research and development has near infrared absorption, valency
Lattice are cheap, high stability and the quasiconductor-noble metal hetero-junctions of remarkable catalytic performance, become high-efficiency solar light and urge
Change key and the urgent needs of reaction.And the sulfide nanocrystalline of copper has fabulous regulatable near infrared region
Plasmon absorption, this becomes the excellent selection making this photocatalyst.
Summary of the invention
The present invention is the demand meeting and solar energy being converted directly into chemical energy, is specifically designed a kind of near infrared region
Having the high efficiency photocatalyst of plasmon absorption, this catalyst is by Cu7S4@M (M=Pd, Au, Ag, Pt) is heterogeneous
Knot composition, can be as catalyst outstanding in photocatalysis organic synthesis.
The present invention, initially with the method thermally decomposing single presoma, obtains Cu7S4Nanocrystalline, then utilize heat note
Penetrate decomposition method and introduce noble metal, obtain Cu7S4@M (M=Pd, Au, Ag, Pt) hetero-junctions, is applied as
Solar energy is converted directly into the photocatalyst of chemical energy.
The preparation method of the photocatalyst that solar energy is converted directly into chemical energy of the present invention, it specifically walks
Rapid as follows:
A. by miscible in 1-2mL to the N of 30-40mg, N-di-t-butyl dithiocarbonic acid and 0.1-0.2mmol copper nitrate
In ethanol, it is evaporated after ultrasonic 15-20min and is scattered in 1-2mL oleyl amine, obtaining Cu (S2CNBut2) front
Drive body；
B. by the N of 20-30mg, N-di-t-butyl dithiocarbonic acid and 0.01-0.02mmol precious metal chemical complex, mixed
It is dissolved in 1-2mL methanol, is evaporated after ultrasonic 30-40min and is scattered in 1-2mL oleyl amine, obtain your gold
Belong to presoma；
C. by the lauryl mercaptan Hybrid Heating of 4-5mL oleyl amine, 6-7mL octadecylene and 0.05-0.1mL, at 200-210 DEG C
Time add step a prepare Cu (S2CNBut2) presoma, then lower the temperature, 185-195 DEG C of holding
Continue after 10-15min to cool, add the noble metal precursor body that step b prepares when 180-175 DEG C,
Continue to cool after keeping 10min at 170-165 DEG C；
D. cooling after 60-50 DEG C, add methanol extraction and be centrifuged, normal hexane washs, and obtains solar energy direct
Be converted to the photocatalyst of chemical energy, be scattered in chloroform.
Described precious metal chemical complex is PdCl2、HAuCl4、AgNO3、PtCl4。
By the above-mentioned prepared photocatalyst applications that solar energy is converted directly into chemical energy in photocatalysis Suzuki coupling
Reaction, the reduction reaction of Nitrobenzol and the oxidation reaction of benzyl alcohol.
The photocatalyst that solar energy is converted directly into chemical energy prepared by the present invention, due to Cu7S4@noble metal is tied
The near-infrared plasma strong absorption enhancement Cu that structure exists7S4Upper hot carrier, to the transfer of noble metal, strengthens
The catalytic reaction of precious metal surface.This enhancing mechanism effectively promotes sunlight in a series of light-catalyzed reactions
In utilization.Even if under the laser of the low power density that wavelength is 1500nm irradiates, the catalyst of the present invention depends on
So there is fabulous catalysis activity.It is 40mW/cm in optical power density2Sunlight under, Suzuki coupling,
Conversion efficiency in the reduction of Nitrobenzol and three kinds of organic reaction 2h of the oxidation of benzyl alcohol has all reached 80%-100%.
Additionally, after repeatedly circulation, the catalyst of the present invention has remained in that stability and the activity of height of structure.
Beneficial effects of the present invention: the invention discloses a kind of efficiency light that solar energy is converted directly into chemical energy
Catalyst and preparation method thereof, is especially including Suzuki coupling, the reduction of Nitrobenzol and the oxidation reaction of benzyl alcohol
In present brilliance catalysis activity.The catalyst of the present invention is made up of quasiconductor-noble metal hetero-junctions, has near
INFRARED ABSORPTION, cheap, high stability and the feature of remarkable catalytic performance, widened material source and saved
Cost, design and preparation for high efficiency photocatalyst provide directive function, accomplished with environmental friendliness simultaneously
Mode, solar energy is effectively converted into chemical energy.
Accompanying drawing explanation
The photocatalyst Cu that Fig. 1: embodiment 1 prepares7S4Common Electronic Speculum figure (a) of@Pd and high resolution electron microscopy figure (b) and
Cu7S4And Cu7S4XRD comparison diagram (c) of@Pd.
The photocatalyst Cu that Fig. 2: embodiment 2 prepares7S4@Au (a, d), the photocatalyst for preparing of embodiment 4
Cu7S4@Pt (b, e), the photocatalyst Cu for preparing of embodiment 37S4@Ag (c, common Electronic Speculum figure f) and high-resolution
Electronic Speculum figure.
There is Suzuki coupling reaction with phenylboric acid (a) with to methylphenylboronic acid (b) in Fig. 3: iodobenzene, under different time real respectively
Execute the Cu that example 1 prepares7S4@Pd photocatalyst is as the catalysis activity block diagram of reacting middle catalyst, and optical density is
0.45W/cm2, wavelength is under 808nm, 980nm and 1500nm laser irradiates；C is that 1500nm laser shines
Penetrate down, the comparison diagram of different catalysts conversion efficiency.
The oxidation reaction (a) of Fig. 4: benzyl alcohol and the reduction reaction (b) of Nitrobenzol under the differential responses time, embodiment 1
The Cu prepared7S4@Pd photocatalyst is 0.45 as the catalysis activity block diagram of reacting middle catalyst, optical density
W/cm2, wavelength is under 808nm, 980nm and 1500nm laser irradiates；C, d are respectively two reactions and exist
Under 1500nm laser irradiates, the comparison diagram of different catalysts conversion efficiency；E is the laser irradiation at different wave length
Under, the selectivity of product and conversion efficiency comparison diagram in the oxidation reaction of benzyl alcohol.
Fig. 5: a, b is respectively Cu7S4Indirect band gap (a) and the plane graph of direct band gap (b)；C is Cu7S4Circulation volt
Peace curve；D is Cu7S4Energy level arrangement；E, f are respectively metal Pd and p-type semiconductor Cu7S4Before contact
After energy band diagram solution.
Fig. 6: a, b is Pd, Cu7S4、Cu7S4+Pd、Cu7S4The local surface plasma resonance of@Pd photocatalyst
Absorption spectrum and Finite-Difference Time-Domain Method simulation drawing；C is that Finite-Difference Time-Domain Method simulation is arranged and electric field intensity ratio
Figure；D-f is respectively under Compound eye, the photocatalyst Cu that embodiment 1 prepares7S4@Pd surrounding electric field is strong
The two-dimensional distribution of degree.
Detailed description of the invention
Embodiment 1
A. by the HS of 43.1mg2CNBut2Miscible with 0.1mmol copper nitrate in 1mL ethanol, ultrasonic 15min
After be evaporated and be scattered in 1mL oleyl amine, obtain Cu (S2CNBut2) presoma；
B. by the HS of 21.5mg2CNBut2With 0.01mmol PdCl2, miscible in 1mL methanol, ultrasonic 30min
After be evaporated and be scattered in 1mL oleyl amine, obtain Pd (S2CNBut2)2Presoma；
C. by the lauryl mercaptan Hybrid Heating of 4mL oleyl amine, 6mL octadecylene and 0.08mL, step is added when 205 DEG C
Cu (the S that rapid a prepares2CNBut2) presoma, then lower the temperature, continue cold after keeping 10min at 190 DEG C
But lower the temperature, add the Pd (S that step b prepares when 180 DEG C2CNBut2)2Presoma, 170 DEG C of holdings
Continue after 10min to cool；
D. cooling after 60 DEG C, add methanol extraction and be centrifuged, normal hexane washs, and obtains directly turning solar energy
It is changed to the photocatalyst of chemical energy, is scattered in 2mL chloroform.
Embodiment 2
A. by the HS of 43.1mg2CNBut2Miscible with 0.1mmol copper nitrate in 1mL ethanol, ultrasonic 15min
After be evaporated and be scattered in 1mL oleyl amine, obtain Cu (S2CNBut2) presoma；
B. by the HS of 21.5mg2CNBut2With 0.01mmol HAuCl4, miscible in 1mL methanol, ultrasonic 30min
After be evaporated and be scattered in 1mL oleyl amine, obtain Au (S2CNBut2)3Presoma；
C. by the lauryl mercaptan Hybrid Heating of 4mL oleyl amine, 6mL octadecylene and 0.08mL, step is added when 205 DEG C
Cu (the S that rapid a prepares2CNBut2) presoma, then lower the temperature, continue cold after keeping 10min at 190 DEG C
But lower the temperature, add the Au (S that step b prepares when 180 DEG C2CNBut2)3Presoma, 170 DEG C of holdings
Continue after 10min to cool；
D. cooling after 60 DEG C, add methanol extraction and be centrifuged, normal hexane washs, and obtains directly turning solar energy
It is changed to the photocatalyst of chemical energy, is scattered in 2mL chloroform.
Embodiment 3
A. by the HS of 43.1mg2CNBut2Miscible with 0.1mmol copper nitrate in 1mL ethanol, ultrasonic 15min
After be evaporated and be scattered in 1mL oleyl amine, obtain Cu (S2CNBut2) presoma；
B. by the HS of 21.5mg2CNBut2With 0.01mmol AgNO3, miscible in 1mL methanol, ultrasonic 30min
After be evaporated and be scattered in 1mL oleyl amine, obtain Ag (S2CNBut2) presoma；
C. by the lauryl mercaptan Hybrid Heating of 4mL oleyl amine, 6mL octadecylene and 0.08mL, step is added when 205 DEG C
Cu (the S that rapid a prepares2CNBut2) presoma, then lower the temperature, continue cold after keeping 10min at 190 DEG C
But lower the temperature, add the Ag (S that step b prepares when 180 DEG C2CNBut2) presoma, 170 DEG C of holdings
Continue after 10min to cool；
D. cooling after 60 DEG C, add methanol extraction and be centrifuged, normal hexane washs, and obtains directly turning solar energy
It is changed to the photocatalyst of chemical energy, is scattered in 2mL chloroform.
Embodiment 4
A. by the HS of 43.1mg2CNBut2Miscible with 0.1mmol copper nitrate in 1mL ethanol, ultrasonic 15min
After be evaporated and be scattered in 1mL oleyl amine, obtain Cu (S2CNBut2) presoma；
B. by the HS of 21.5mg2CNBut2With 0.01mmol PtCl4, miscible in 1mL methanol, ultrasonic 30min
After be evaporated and be scattered in 1mL oleyl amine, obtain Pt (S2CNBut2)4Presoma；
C. by the lauryl mercaptan Hybrid Heating of 4mL oleyl amine, 6mL octadecylene and 0.08mL, add when 205 DEG C
Cu (the S that step a prepares2CNBut2) presoma, then lower the temperature, continue after keeping 10min at 190 DEG C
Cool, add the Pt (S that step b prepares when 180 DEG C2CNBut2)4Presoma, at 170 DEG C
Continue to cool after keeping 10min；
D. cooling after 60 DEG C, add methanol extraction and be centrifuged, normal hexane washs, and obtains directly turning solar energy
It is changed to the photocatalyst of chemical energy, is scattered in 2mL chloroform.
Application examples 1
A. Cu embodiment 1 prepared7S4@Pd photocatalyst 1mg joins in 2mL water, ultrasonic 30 times,
Can be uniformly dispersed in water to granule；
B. by 20mg cetyl trimethylammonium bromide, 0.08mmol iodobenzene, 0.08mmol phenylboric acid and
The sodium hydroxide of 15mg joins in the dispersion liquid of step a, is transferred in the quartz glass bottle of 5mL, adds
Magneton stirs；
C. adjust the light intensity of simulated solar irradiation, use 100mW/cm2Light source irradiate quartz glass bottle, light application time is
1h, is then turned off light source, continues stirring 30min；
D. with the reactant liquor of dichloromethane extraction step c, and it is spin-dried for Rotary Evaporators, by 4mL chromatograph methanol constant volume
After walk efficient liquid phase chromatographic analysis.
Claims (3)
1. the preparation method of the photocatalyst that solar energy is converted directly into chemical energy, it is characterised in that its
Specifically comprise the following steps that
A. by miscible in 1-2mL to the N of 30-40mg, N-di-t-butyl dithiocarbonic acid and 0.1-0.2mmol copper nitrate
In ethanol, it is evaporated after ultrasonic 15-20min and is scattered in 1-2mL oleyl amine, obtaining Cu (S2CNBut2) front
Drive body；
B. by the N of 20-30mg, N-di-t-butyl dithiocarbonic acid and 0.01-0.02mmol precious metal chemical complex, mixed
It is dissolved in 1-2mL methanol, is evaporated after ultrasonic 30-40min and is scattered in 1-2mL oleyl amine, obtain your gold
Belong to presoma；
C. by the lauryl mercaptan Hybrid Heating of 4-5mL oleyl amine, 6-7mL octadecylene and 0.05-0.1mL, at 200-210 DEG C
Time add step a prepare Cu (S2CNBut2) presoma, then lower the temperature, 185-195 DEG C of holding
Continue after 10-15min to cool, add the noble metal precursor body that step b prepares when 180-175 DEG C,
Continue to cool after keeping 10min at 170-165 DEG C；
D. cooling after 60-50 DEG C, add methanol extraction and be centrifuged, normal hexane washs, and obtains solar energy direct
Be converted to the photocatalyst of chemical energy, be scattered in chloroform.
The preparation of a kind of photocatalyst that solar energy is converted directly into chemical energy the most according to claim 1
Method, it is characterised in that described precious metal chemical complex is PdCl2、HAuCl4、AgNO3、PtCl4。
What preparation method the most according to claim 1 and 2 prepared is converted directly into chemical energy by solar energy
The application of the oxidation reaction of photocatalyst photocatalysis Suzuki coupling reaction, the reduction reaction of Nitrobenzol and benzyl alcohol.
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| WO2010061212A1 (en) * | 2008-11-25 | 2010-06-03 | Johnson Matthey Plc | Reduced copper sulphide sorbent for removing heavy metals |
| CN103962157A (en) * | 2014-05-19 | 2014-08-06 | 北京化工大学 | Nano-structure CoSx/C cathode electro-catalytic material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010061212A1 (en) * | 2008-11-25 | 2010-06-03 | Johnson Matthey Plc | Reduced copper sulphide sorbent for removing heavy metals |
| CN103962157A (en) * | 2014-05-19 | 2014-08-06 | 北京化工大学 | Nano-structure CoSx/C cathode electro-catalytic material and preparation method thereof |
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| JIABIN CUI ET AL.: "Near-Infrared Plasmonic-Enhanced Solar Energy Harvest for Highly Efficient Photocatalytic Reactions", 《NANO LETTERS》 * |
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