CN106268884B - A kind of rear-earth-doped NaYF4/ Au@CdS composite photo-catalyst and preparation method thereof - Google Patents
A kind of rear-earth-doped NaYF4/ Au@CdS composite photo-catalyst and preparation method thereof Download PDFInfo
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- CN106268884B CN106268884B CN201610672371.3A CN201610672371A CN106268884B CN 106268884 B CN106268884 B CN 106268884B CN 201610672371 A CN201610672371 A CN 201610672371A CN 106268884 B CN106268884 B CN 106268884B
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- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 230000001699 photocatalysis Effects 0.000 claims abstract description 25
- 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
- 238000007146 photocatalysis Methods 0.000 claims abstract description 16
- 238000002407 reforming Methods 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 38
- 230000001376 precipitating effect Effects 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 25
- 229960004756 ethanol Drugs 0.000 claims description 22
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 229910002651 NO3 Inorganic materials 0.000 claims description 16
- 238000005119 centrifugation Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 14
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 12
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 12
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- -1 rare earth nitrate Chemical class 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 6
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002077 nanosphere Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000004201 L-cysteine Substances 0.000 claims 3
- 235000013878 L-cysteine Nutrition 0.000 claims 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- 230000005672 electromagnetic field Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000006193 liquid solution Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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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 invention discloses a kind of rear-earth-doped NaYF4/ Au@CdS composite photo-catalyst and preparation method thereof.It is with rear-earth-doped NaYF4For core, nanocrystalline for shell with CdS, Au nanoparticle is embedded in nucleocapsid interface；Wherein CdS and rear-earth-doped NaYF4The ratio between mole be 1:50 ~ 50:1；The mass fraction of Au is 0.1 ~ 10%.Gained NaYF4/ Au@CdS composite photo-catalyst absorbs near infrared light conversion using up-conversion and issues visible light, by causing the plasma resonance of Au nanostructure, and then induces near field electromagnetic field and efficiently excites CdS, realizes its response near infrared light.Therefore, in the reaction of photocatalysis hydrogen from ethanol reforming, which optimizes the utilization efficiency near infrared light, improves the utilization efficiency of sunlight in light-catalyzed reaction.
Description
Technical field
The invention belongs to photocatalysis fields, and in particular to a kind of rear-earth-doped NaYF4/ Au@CdS composite photo-catalyst and
Preparation method.
Background technique
Hydrogen is a kind of energy of the potential alternative conventional fossil fuel of clean and effective, utilizes mild photocatalysis technology
By renewable resource catalyzing manufacturing of hydrogen, this is the effective means for meeting environment and energy demand in sustainable development.As a kind of allusion quotation
The renewable biomass resources of type, bio-ethanol (concentration of alcohol is about 12wt%) mainly by wood materials, agricultural crop straw and
Municipal solid wastes organic fraction etc. is generated by microbial fermentation.At present for bio-ethanol utilization generally require by
The process of purification & isolation ethyl alcohol, technique is relative complex, higher cost.And photocatalytic hydrogen production by water decomposition can then directly obtain it is high-purity
Hydrogen avoids complicated purification process.Therefore develop the catalytically reforming hydrogen producing that high efficiency photocatalysis system realizes bio-ethanol, will be
A kind of efficient green approach using biomass energy generation has great Practical significance.
As traditional photocatalytic applications system, current most of research is concentrated mainly on ultraviolet-visible photoresponse
Photochemical catalyst on, and occupy the research of the near infrared light of solar spectrum energy about 44% and using relatively fewer.Although early period is
There is researcher that up-conversion luminescent material is introduced into conductor photocatalysis system, using the spectrum conversion function of up-conversion,
Expand utilization of the photocatalytic system near infrared light.I.e. up-conversion absorb near infrared light after conversion and emitting ultraviolet light and
(or) visible light, it is then directly absorbed by semiconductor, and then photocatalytic process occurs.However, due to up-conversion with partly lead
Its difference in reflectivity of body material is big, causes to lose in interface photon energy serious.So that the complex that both materials are constituted
It is the photocatalysis for often requiring to use the higher light source of energy density (such as laser) as excitation light source and causing compound system
Journey.And sunlight belongs to the light source of Energy distribution high granular, upper conversion base optic catalytic system is directly utilizing in sunlight closely
When infrared optical drive light-catalyzed reaction, the bottleneck that catalytic efficiency is low problem is often faced.In order to advanced optimize upper conversion base
Catalytic efficiency of the photochemical catalyst under near infrared light.Xu. et al. (Zhenhe Xu, Marta Quintanilla,
Fiorenzo Vetrone, Alexander O. Govorov, Mohamed Chaker and Dongling Ma, Adv. Funct. Mater.,2015,25,2950-2960) for the first time by plasma resonance nanostructure be integrated into upper conversion matrix/
It is successfully that Au is nano-particle modified in NaYF in semiconductors coupling system4:Yb3+, Er3+, Tm3+@TiO2Core-shell structure table
Face constructs NaYF4:Yb3+, Er3+, Tm3+@TiO2- Au trielement composite material.Since plasma resonance Au nanostructure is unique
Property (such as superpower light gathering can generate thermoelectron and induce the electromagnetic field etc. of enhancing), effectively improve compound
Catalytic efficiency of structure during near infrared light drives photocatalysis organic pollutant degradation.And up to the present, also only
There is conversion matrix/semiconductor/three component composite material of plasma resonance structure in this one kind to be reported.In the present invention, will etc. from
Sub-resonance nanostructure is introduced into the interface of up-conversion Yu semiconductor core shell structure, has constructed NaYF4:Yb3+/Er3+/
Au@CdS composite material.And for the first time by this kind of upper conversion matrix/three component composite catalyst of semiconductor/plasma resonance structure
Applied in photocatalytic reforming bio-ethanol hydrogen production reaction.In the photocatalytic process, since plasma resonance nanostructure is excellent
Characteristic optimizes the energy transfer efficiency between up-conversion and semiconductor light-catalyst.Metal plasma nano junction simultaneously
Structure also plays the role of electron trap and co-catalyst.The exactly multiple action of interface plasma nanostructure, mentions significantly
Comprehensive utilization ratio of the high composite material to solar energy.And composition, the space construction, system of composite material according to the present invention
Preparation Method and application field and upper conversion matrix/semiconductor/three component composite material of plasma resonance structure reported before are equal
It is different.
Summary of the invention
The object of the present invention is to provide a kind of rear-earth-doped NaYF4/ Au@CdS composite photocatalyst and preparation method thereof.Institute
The composite photo-catalyst obtained can efficiently utilize the utilization efficiency of near infrared light, to improve its utilization rate to solar energy, and will
It is applied to photocatalysis hydrogen from ethanol reforming.
A kind of rear-earth-doped NaYF4/ Au@CdS composite photo-catalyst, with rear-earth-doped NaYF4For core；With CdS nanometers
Material is shell；Au nanoparticle is embedded in nucleocapsid interface；Wherein CdS and rear-earth-doped NaYF4The ratio between mole be 1:
50~50:1；The mass fraction of Au is 0.1% ~ 10%.
The rear-earth-doped NaYF4Including sensitizer and activator, wherein sensitizer is Yb3+；Wherein activator is Er3 +；The ratio between the sensitizer and Y element mole are 1:5 ~ 20；The ratio between the activator and Y element mole are 1:10 ~ 100.
The rear-earth-doped NaYF4Its pattern is hexagonal prism, spherical shape or graininess, and size is 10nm ~ 10 μm.
The Au nanoparticle is nanosphere, nanometer rods or nanometer double cone structure；Its particle size range is 2 ~ 200nm.
The NaYF4The preparation method of/Au@CdS composite photo-catalyst, comprising the following steps:
(1) NaYF is prepared4RE composite:
It is 50 ~ 70 DEG C in temperature, under conditions of mixing speed is 100 ~ 500r/min, by rare earth nitrate solution, surface
Activating agent and Fluorine source solution are uniformly mixed by volume for 1:1:1, are transferred to the reaction with Packed polytetrafluoroethyllining lining
In kettle, 160 ~ 180 DEG C are warming up to, preferable temperature is 180 DEG C, keeps the temperature 2 ~ 6h, and the preferably time is 3h；By products therefrom natural cooling
It to room temperature, is washed 2 ~ 6 times, is centrifuged with deionized water, dehydrated alcohol respectively, collect precipitating, vacuum drying obtains NaYF4, preferably
Vacuum drying temperature is 60 ~ 80 DEG C；
(2) NaYF is prepared4/ Au composite material:
A. the chlorauric acid solution of 200 ~ 1,000 5 ~ 20mg/mL of μ L is added in 10 ~ 100mL deionized water, with 0.1M ~
It is 8 ~ 10 that the aqueous slkali of 5M, which adjusts pH value, obtains golden precursor liquid, and wherein the concentration of Au is 10 ~ 500mg/L, and wherein aqueous slkali is preferred
For 1M NaOH aqueous solution；
B. by the NaYF of 100mg ~ 1g4RE composite is distributed in golden precursor liquid, then in 50 ~ 80 DEG C of constant temperatures
Under, it is dry to continue stirring until solution evaporation；Gained precipitating is immersed in the NaBH of 0.1M ~ 2M4Or KBH4In solution stand 30min ~
5h；Gained precipitating is washed 2 ~ 6 times with deionized water, dehydrated alcohol respectively finally, precipitating, vacuum drying, vacuum is collected by centrifugation
Drying temperature is 60 ~ 80 DEG C, obtains NaYF4/ Au composite material；
(3) NaYF is prepared4/ Au@CdS composite material:
A. willLCysteine and cadmium nitrate are dissolved in deionized water, are stirred evenly, whereinLCysteine and cadmium nitrate
Molar ratio 2:1;
B. by NaYF4/ Au is scattered inLIn cysteine and cadmium nitrate aqueous solution, wherein cadmium nitrate and NaYF4/ Au's rubs
The ratio between your amount is 1:50 ~ 50:1；After stirring 10min ~ 1h, the dehydrated alcohol of 5 ~ 9 times of volumes is added, continues to stir 2min ~ 1h；It moves
Enter in ptfe autoclave, be warming up to 150 ~ 180 DEG C, keeps the temperature 10 ~ 16h；By gained precipitating respectively with deionized water, anhydrous
Ethanol washing 2 ~ 6 times, precipitating is collected by centrifugation, vacuum drying obtains NaYF4/ Au@CdS composite photo-catalyst.
The concentration of rare earth nitrate aqueous solution as described in step (1) is 0.01M ~ 0.1M, and wherein rare earth nitrades are nitre
The mixture of sour yttrium, erbium nitrate or ytterbium nitrate；The concentration of the aqueous surfactant solution is 0.01M ~ 0.1M, wherein surface
Activating agent is disodium ethylene diamine tetraacetate (EDTA) or sodium citrate；The concentration of the Fluorine source aqueous solution is 0.01M ~ 1M,
Middle Fluorine source is at least one of sodium fluoride or potassium fluoride.
Gained NaYF4/ Au@CdS composite photo-catalyst is reacted for photocatalysis hydrogen from ethanol reforming:
By NaYF4/ Au@CdS composite photo-catalyst is put into ethanol water, and obtaining concentration is 0.1 ~ 10mg/mL's
Mixed solution carries out the reaction of photocatalysis hydrogen from ethanol reforming in standard atmospheric pressure inert atmosphere or vacuum at room temperature.
The content of ethyl alcohol is 1 ~ 100wt% in the ethanol water；The inert atmosphere conditions are nitrogen, helium, argon
One of gas or carbon dioxide are a variety of.
The rear-earth-doped NaYF of gained of the invention4/ Au CdS composite photo-catalyst is in simulated solar optical drive photocatalysis second
Excellent catalytic performance is shown in alcohol reforming hydrogen production reaction.
Detailed description of the invention
Fig. 1: (a) pure NaYF4:Yb3+/Er3+, (b) NaYF4:Yb3+/Er3+/ Au composite material, (c) NaYF4:Yb3+/Er3 +@CdS composite material and (d) NaYF4:Yb3+/Er3+The X-ray powder diffraction figure of/Au@CdS composite photo-catalyst；Figure 1B, C points
Not Wei in Figure 1A the amplification in region I and II XRD spectrum.
Fig. 2: (A) pure NaYF4:Yb3+/Er3+, (B) NaYF4:Yb3+/Er3+/ Au composite material, (C) NaYF4:Yb3+/Er3 +@CdS composite material and (D) NaYF4:Yb3+/Er3+The SEM of/Au@CdS composite photo-catalyst schemes.
Fig. 3: (A) NaYF4:Yb3+/Er3+/ Au@CdS composite photo-catalyst and (B) NaYF4:Yb3+, Er3+/ Au@CdS is multiple
The TEM of condensation material schemes；(C)NaYF4:Yb3+/Er3+The EDX of the single micron ball of/Au@CdS schemes.
Fig. 4: solid line is pure NaYF4:Yb3+/Er3+、NaYF4:Yb3+/Er3+/ Au composite material, NaYF4:Yb3+/Er3+@CdS
Composite material and NaYF4:Yb3+/Er3+The uv-visible absorption spectrum figure of/Au@CdS composite photocatalyst material；Dotted line is pure
NaYF4:Yb3+/Er3+Under 980nm laser excitation, up-conversion fluorescence emits spectrogram.
Fig. 5: pure NaYF4:Yb3+/Er3+、NaYF4:Yb3+/Er3+/ Au composite material, NaYF4:Yb3+/Er3+@CdS is compound
Material and NaYF4:Yb3+/Er3+The rate column of the photocatalysis hydrogen from ethanol reforming of/Au CdS composite material under the irradiation of different light
Shape figure, Fig. 5 A is under the light irradiation of 700nm；Fig. 5 B is under simulated solar irradiation (AM 1.5G) irradiation；Fig. 5 C is filtered in simulated solar irradiation
It goes after near-infrared ingredient under irradiating.
Specific embodiment
Embodiment 1
NaYF4:Yb3+/ Er3+The preparation of/Au@CdS composite photo-catalyst:
(1) NaYF is prepared4:Yb3+/Er3+Micron ball:
Under conditions of temperature is 60 DEG C, mixing speed is 300r/min, respectively by 1.408mmol Y (NO3)3•6H2O,
0.16mmol Yb(NO3)3•5H2O, 0.032mmol Er(NO3)3•5H2O is dissolved in 20mL water；1.6mmol EDTA is dissolved in
In 20mL water；After 14.4mmol NaF is dissolved in 20mL water, by the above rare earth nitrate solution, surfactant and Fluorine source solution
It mixes and continues to stir 1h, form reaction precursor liquid solution；Gained precursor liquid is moved into one with Packed 100mL polytetrafluoro
In the reaction kettle of ethylene liner, 180 DEG C are warming up to, keeps the temperature 3h；It is cooled to room temperature, washs 3 with deionized water, dehydrated alcohol respectively
It is secondary, precipitating is collected by centrifugation, vacuum drying obtains NaYF at 60 DEG C4:Yb3+/Er3+Micron ball；
(2) NaYF is prepared4:Yb3+/Er3+/ Au composite material:
A. the chlorauric acid solution of 417 μ L, 9.6mg/mL is added in 20mL deionized water, with 1M NaOH solution by its
PH value is adjusted to 9, obtains golden precursor liquid；
B. by (1) resulting NaYF the step of 400mg4:Yb3+/Er3+In the golden precursor liquid being distributed to, then by suspension
It is dry that solution evaporation is continued stirring until under 70 DEG C of constant temperatures, collects precipitating；Then gained precipitating is immersed in 1M NaBH4It is molten
In liquid, 2h is stood；Gained precipitating is washed 3 times with deionized water, dehydrated alcohol respectively, and precipitating is collected by centrifugation, and vacuum is dried at 60 DEG C
It is dry to obtain NaYF4:Yb3+/Er3+/ Au composite material；
(3) NaYF is prepared4:Yb3+/Er3+/ Au@CdS composite photo-catalyst:
A. by 0.4mmolLCysteine and 0.2mmol cadmium nitrate are dissolved in respectively in 10mL deionized water；By 400mg
The step of (2) resulting NaYF4:Yb3+/Er3+/ Au composite material disperses in its solution, and after stirring 1h, the anhydrous second of 70mL is added
Alcohol continues to stir 5min, obtains reaction precursor liquid；
B. reaction gained precursor liquid is moved into a reaction kettle with Packed 100mL polytetrafluoroethyllining lining, is risen
Temperature keeps the temperature 12h to 160 DEG C；Gained precipitating is washed 3 times with deionized water, dehydrated alcohol respectively, is collected by centrifugation precipitating, at 60 DEG C
Vacuum drying obtains NaYF4:Yb3+/Er3+/ Au@CdS composite photo-catalyst, structure by X-ray feature as shown in Figure 1, spread out
Peak is penetrated it is found that the material is the catalyst to be designed.The SEM and TEM of resulting materials are as shown in Figures 2 and 3.
1 resulting materials of embodiment have good near infrared absorption function, as shown in Figure 4: gained NaYF4:Yb3+/Er3+/
In Au@CdS composite photo-catalyst, under near infrared light excitation, the visible light of Up-conversion emission can excite the plasma of Au total
Vibration, and then the near field electromagnetic field for inducing enhancing efficiently excites CdS, to realize energy from up-conversion to semiconductor material
Transmitting.
Embodiment 2:
NaYF4:Yb3+/ Er3+The preparation of/Au@CdS composite photo-catalyst:
(1) NaYF is prepared4:Yb3+/Er3+Micron ball:
Under conditions of temperature is 50 DEG C, mixing speed is 100r/min, respectively by 1.408mmol Y (NO3)3•6H2O,
0.28mmol Yb(NO3)3•5H2O, 0.141mmol Er(NO3)3•5H2O is dissolved in 20mL water；1.4mmol sodium citrate is molten
In 20mL water；After 20mmol NaF is dissolved in 20mL water, by the above rare earth nitrate solution, surfactant and Fluorine source solution
It mixes and continues to stir 1h, form reaction precursor liquid solution；Gained precursor liquid is moved into one with Packed 100mL polytetrafluoro
In the reaction kettle of ethylene liner, 160 DEG C are warming up to, keeps the temperature 2h；It is cooled to room temperature, washs 3 with deionized water, dehydrated alcohol respectively
It is secondary, precipitating is collected by centrifugation, vacuum drying obtains NaYF at 60 DEG C4:Yb3+/Er3+Micron ball；
(2) NaYF is prepared4:Yb3+/Er3+/ Au composite material:
A. the chlorauric acid solution of 200 μ L, 5mg/mL is added in 50mL deionized water, with 0.1M NaOH solution by its
PH value is adjusted to 8, obtains golden precursor liquid；
B. by (1) resulting NaYF the step of 600mg4:Yb3+/Er3+In the golden precursor liquid being distributed to, then by suspension
It is dry that solution evaporation is continued stirring until under 50 DEG C of constant temperatures, collects precipitating；Then gained precipitating is immersed in 0.1M NaBH4
In solution, 30min is stood；Gained precipitating is washed 3 times with deionized water, dehydrated alcohol respectively, is collected by centrifugation precipitating, at 60 DEG C very
It is empty obtained by drying to NaYF4:Yb3+/Er3+/ Au composite material；
(3) NaYF is prepared4:Yb3+/Er3+/ Au@CdS composite photo-catalyst:
A. by 0.2mmolLCysteine and 0.1mmol cadmium nitrate are dissolved in respectively in 10mL deionized water；
B. by (2) resulting NaYF the step of 600mg4:Yb3+/Er3+/ Au composite material disperses in its solution, stirring
After 30min, 70mL dehydrated alcohol is added, continues to stir 5min, obtains reaction precursor liquid；Reaction gained precursor liquid is moved into one
In reaction kettle with Packed 100mL polytetrafluoroethyllining lining, 150 DEG C are warming up to, keeps the temperature 10h；Gained precipitating is spent respectively
Ionized water, dehydrated alcohol wash 3 times, and precipitating is collected by centrifugation, and vacuum drying obtains NaYF at 60 DEG C4:Yb3+/Er3+/Au@CdS
Composite photo-catalyst.
Embodiment 3:
NaYF4:Yb3+/ Er3+The preparation of/Au@CdS composite photo-catalyst:
(1) NaYF is prepared4:Yb3+/Er3+Micron ball:
Under conditions of temperature is 70 DEG C, mixing speed is 500r/min, respectively by 1.408mmol Y (NO3)3•6H2O,
0.08mmol Yb(NO3)3•5H2O, 0.0141mmol Er(NO3)3•5H2O is dissolved in 20mL water；1.5mmol EDTA is dissolved in
In 20mL water；It is after 6mmol NaF is dissolved in 20mL water, the above rare earth nitrate solution, surfactant solution and Fluorine source is molten
Liquid mixes and continues to stir 1h, forms reaction precursor liquid solution；Gained precursor liquid is moved into one with Packed 100mL poly- four
In the reaction kettle of vinyl fluoride liner, 170 DEG C are warming up to, keeps the temperature 6h；It is cooled to room temperature, is washed respectively with deionized water, dehydrated alcohol
It washs 3 times, precipitating is collected by centrifugation, vacuum drying obtains NaYF at 60 DEG C4:Yb3+/Er3+Micron ball；
(2) NaYF is prepared4:Yb3+/Er3+/ Au composite material:
A. the chlorauric acid solution of 1000 μ L, 20mg/mL is added in 100mL deionized water, it will with 5M NaOH solution
Its pH value is adjusted to 10, obtains golden precursor liquid；
B. by (1) resulting NaYF the step of 100mg4:Yb3+/Er3+In the golden precursor liquid being distributed to, then by suspension
It is dry that solution evaporation is continued stirring until under 80 DEG C of constant temperatures, collects precipitating；Then gained precipitating is immersed in 2M KBH4Solution
In, stand 3h；Gained precipitating is washed 3 times with deionized water, dehydrated alcohol respectively, and precipitating, vacuum drying at 60 DEG C is collected by centrifugation
Obtain NaYF4:Yb3+/Er3+/ Au composite material；
(3) NaYF is prepared4:Yb3+/Er3+/ Au@CdS composite photo-catalyst:
A. by 0.6mmolLCysteine and 0.3mmol cadmium nitrate are dissolved in respectively in 5mL deionized water；
B. by (2) resulting NaYF the step of 200mg4:Yb3+/Er3+/ Au composite material disperses in its solution, stirring
After 10min, 80mL dehydrated alcohol is added, continues to stir 5min, obtains reaction precursor liquid；Reaction gained precursor liquid is moved into one
In reaction kettle with Packed 100mL polytetrafluoroethyllining lining, 180 DEG C are warming up to, keeps the temperature 16h；Gained precipitating is spent respectively
Ionized water, dehydrated alcohol wash 3 times, and precipitating is collected by centrifugation, and vacuum drying obtains NaYF at 60 DEG C4:Yb3+/Er3+/Au@CdS
Composite photo-catalyst.
Comparative example 1
NaYF4:Yb3+/Er3+The preparation of@CdS composite material:
(1) NaYF is prepared4:Yb3+/Er3+Micron ball:
Under conditions of temperature is 60 DEG C, mixing speed is 300r/min, respectively by 1.408mmol Y (NO3)3•6H2O,
0.16mmol Yb(NO3)3•5H2O, 0.032mmol Er(NO3)3•5H2O is dissolved in 20mL water；1.6mmol EDTA is dissolved in
In 20mL water；After 14.4mmol NaF is dissolved in 20mL water, by the above rare earth nitrate solution, surfactant and Fluorine source solution
It is mixed by volume for 1:1:1 and continues to stir 1h, form reaction precursor liquid solution；Gained precursor liquid is moved into one with close
In the reaction kettle of the 100mL polytetrafluoroethyllining lining of envelope, 180 DEG C are warming up to, keeps the temperature 3h；Products therefrom naturally cools to room temperature,
It is washed 3 times with deionized water, dehydrated alcohol respectively, precipitating is collected by centrifugation, vacuum drying obtains NaYF at 60 DEG C4:Yb3+/Er3+
Micron ball；
(2) NaYF is prepared4:Yb3+/Er3+@CdS composite material:
By 0.4mmolLCysteine and 0.2mmol cadmium nitrate are dissolved in respectively in 10mL deionized water.By 400mg first
Walk resulting NaYF4:Yb3+/Er3+Disperse in its solution, after stirring 1h, 70mL dehydrated alcohol is added, continues to stir 5min, obtain
Reaction precursor liquid；Gained precursor liquid is moved into a reaction kettle with Packed 100mL polytetrafluoroethyllining lining, is warming up to
160 DEG C, keep the temperature 12h；Gained precipitating is washed 3 times with deionized water, dehydrated alcohol respectively, is collected by centrifugation precipitating, at 60 DEG C very
It is empty obtained by drying to NaYF4:Yb3+/Er3+@CdS composite material.
Application Example 1
Infrared optical drive produces hydrogen:
The pure NaYF synthesized in 15mg embodiment 1 is weighed respectively4:Yb3+/Er3+, NaYF4:Yb3+/Er3+/ Au composite wood
Material, NaYF4:Yb3+/Er3+/ Au@CdS composite photo-catalyst and NaYF4:Yb3+/Er3+@CdS composite material, is added to 10mL second
In alcoholic solution (wherein ethyl alcohol 1.5mL, deionized water 8.5mL), after ultrasonic disperse, suspension is moved into 50mL capacity cylinder stone
In English reaction tube, the argon gas of an atmospheric pressure is vacuumized and filled；Under the irradiation of λ > 700nm light (light source is 300W xenon lamp), grind
Study carefully its photocatalytic reforming bio-ethanol hydrogen manufacturing performance at room temperature.
As a result as shown in Figure 5A: under the same terms, NaYF4:Yb3+/Er3+/ Au@CdS composite photo-catalyst is near infrared light
Under irradiation, photocatalytic reforming bio-ethanol hydrogen-producing speed is apparently higher than pure NaYF4:Yb3+/Er3+, NaYF4:Yb3+/Er3+/Au
Composite material and NaYF4:Yb3+/Er3+@CdS composite material.
Application Example 2
Simulated solar optical drive produces hydrogen:
The pure NaYF synthesized in 15mg embodiment 1 is weighed respectively4:Yb3+/Er3+, NaYF4:Yb3+/Er3+/ Au composite wood
Material, NaYF4:Yb3+/Er3+/ Au@CdS composite photo-catalyst and NaYF4:Yb3+/Er3+@CdS composite material, is added to 10ml second
In alcoholic solution (wherein ethyl alcohol 1.5mL, deionized water 8.5mL), after ultrasonic disperse, suspension is moved into 50mL capacity cylinder stone
In English reaction tube, the argon gas of an atmospheric pressure is vacuumized and filled；Simulated solar irradiation (AM 1.5G) irradiation under, study its
Photocatalytic reforming bio-ethanol hydrogen manufacturing performance at room temperature.
As a result as shown in Figure 5 B, under the same conditions, under simulated solar irradiation (AM 1.5G) irradiation, NaYF4:Yb3+/Er3 +/ Au@CdS composite photo-catalyst photocatalysis hydrogen from ethanol reforming rate is substantially better than NaYF pure in embodiment 14:Yb3+/Er3+,
NaYF4:Yb3+/Er3+/ Au composite material and NaYF4:Yb3+/Er3+@CdS composite material.
Application Example 3
The simulated solar optical drive for filtering off infrared light produces hydrogen variation:
Weigh the NaYF synthesized in 15mg embodiment 14:Yb3+/Er3+/ Au@CdS composite material, it is molten to be added to 10ml ethyl alcohol
In liquid (wherein ethyl alcohol 1.5mL, deionized water 8.5mL), after ultrasonic disperse, it is anti-that suspension is moved into 50mL capacity cylindrical quartz
Ying Guanzhong vacuumizes and fills the argon gas of an atmospheric pressure；It is shone in the simulated solar irradiation (AM 1.5G) for filtering off near infrared light ingredient
It penetrates down, studies its photocatalysis hydrogen from ethanol reforming performance at room temperature.
As a result as shown in Figure 5 C, under the same conditions, NaYF after simulated solar irradiation filters off near-infrared ingredient4:Yb3+/Er3 +/ Au@CdS composite photo-catalyst photocatalysis hydrogen from ethanol reforming rate is significantly lower than its hydrogen-producing speed under simulated solar irradiation.
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, is all covered by the present invention.
Claims (5)
1. a kind of rear-earth-doped NaYF4The preparation method of/Au@CdS composite photo-catalyst, it is characterised in that: the complex light is urged
Agent is with rear-earth-doped NaYF4For core；Using CdS nanometer material as shell；Au nanoparticle is embedded in nucleocapsid interface；Wherein
CdS and rear-earth-doped NaYF4The ratio between mole be 1:50 ~ 50:1；The mass fraction of Au is 0.1 ~ 10%；The rare earth is mixed
Miscellaneous NaYF4Including sensitizer and activator, wherein sensitizer is Yb3+；Wherein activator is Er3+；The sensitizer and Y element
The ratio between mole is 1:5 ~ 20；The ratio between the activator and Y element mole are 1:10 ~ 100；The rear-earth-doped NaYF4
Its pattern is hexagonal prism, spherical shape or graininess, and size is 10nm ~ 10 μm；The Au nanoparticle be nanosphere, nanometer rods or
Nanometer double cone structure；Its particle size range is 2 ~ 200nm；The preparation method of the composite photo-catalyst, comprising the following steps:
(1) NaYF is prepared4RE composite:
At 50 ~ 70 °C, under 100-500r/min mixing speed, by rare earth nitrate aqueous solution, surfactant water
Solution and Fluorine source aqueous solution are uniformly mixed by volume for 1:1:1, are transferred in reaction kettle, are warming up to 160 ~ 180 DEG C, and heat preservation 2 ~
Products therefrom is naturally cooled to room temperature, is washed respectively with deionized water, dehydrated alcohol by 6h, centrifugation, collects precipitating, and vacuum is dried
It is dry, obtain NaYF4RE composite；
(2) NaYF is prepared4/ Au composite material:
A. the chlorauric acid solution of 200 ~ 1,000 5 ~ 20mg/mL of μ L is added in 10 ~ 100mL deionized water, with 0.1M ~ 5M's
It is 8 ~ 10 that aqueous slkali, which adjusts pH value, obtains golden precursor liquid, and wherein the concentration of Au is 10 ~ 500mg/L；
B. by the NaYF of 100mg ~ 1g4RE composite is distributed in golden precursor liquid, is then continued under 50 ~ 80 DEG C of constant temperatures
Stirring is dry to solution evaporation；Gained precipitating is immersed in standing 30min ~ 5h in the reducing solution of 0.1M ~ 2M；Finally by gained
Precipitating is washed with deionized water, dehydrated alcohol respectively, precipitating is collected by centrifugation, vacuum drying obtains NaYF4/ Au composite material；
(3) NaYF is prepared4/ Au@CdS composite photo-catalyst:
A. L-cysteine and cadmium nitrate are dissolved in deionized water, are stirred evenly, wherein L-cysteine and cadmium nitrate rub
You compare 2:1;
B. by NaYF4/ Au is scattered in L-cysteine and cadmium nitrate aqueous solution, wherein cadmium nitrate and NaYF4The mole of/Au
The ratio between be 1:50 ~ 50:1；After stirring 10min ~ 1h, the dehydrated alcohol of 5 ~ 9 times of volumes is added, stirs evenly, moves into polytetrafluoroethyl-ne
In alkene reaction kettle, 150 ~ 180 DEG C are warming up to, keeps the temperature 10 ~ 16h；Gained precipitating is washed with deionized water, dehydrated alcohol respectively,
Precipitating is collected by centrifugation, vacuum drying obtains NaYF4/ Au@CdS composite photo-catalyst.
2. rear-earth-doped NaYF according to claim 14The preparation method of/Au@CdS composite photo-catalyst, feature exist
In: the concentration of rare earth nitrate aqueous solution as described in step (1) be 0.01M ~ 0.1M, wherein rare earth nitrades be yttrium nitrate,
Erbium nitrate, ytterbium nitrate three's mixture；The concentration of the aqueous surfactant solution is 0.01M ~ 0.1M, wherein surface-active
Agent is disodium ethylene diamine tetraacetate (EDTA) or sodium citrate；The concentration of the Fluorine source aqueous solution is 0.01M ~ 1M, wherein fluorine
Source is at least one of sodium fluoride or potassium fluoride.
3. rear-earth-doped NaYF according to claim 14The preparation method of/Au@CdS composite photo-catalyst, feature exist
In: aqueous slkali described in step (2) a is NaOH or KOH solution；Solute in reducing solution described in step (2) b is
NaBH4Or KBH4。
4. a kind of rear-earth-doped NaYF of method preparation as described in claim 14The application of/Au@CdS composite photo-catalyst,
It is characterized in that: by NaYF4In the ethanol water that/Au@CdS composite photo-catalyst is put into, it is 0.1 ~ 10mg/mL that concentration, which is made,
Mixed solution, in standard atmospheric pressure inert atmosphere or vacuum, at room temperature carry out the reaction of photocatalysis hydrogen from ethanol reforming.
5. rear-earth-doped NaYF according to claim 44The application of/Au@CdS composite photo-catalyst, it is characterised in that:
The content of ethyl alcohol is 1 ~ 100wt% in the ethanol water；The inert atmosphere conditions are nitrogen, helium, argon gas or dioxy
Change one of carbon or a variety of.
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| CN103316703A (en) * | 2013-07-08 | 2013-09-25 | 中国科学院城市环境研究所 | High-efficiency near-infrared light compound photocatalyst and preparation method thereof |
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