CN104437549A - Novel surface plasma enhanced high-efficiency photocatalytic water splitting composite catalyst - Google Patents
Novel surface plasma enhanced high-efficiency photocatalytic water splitting composite catalyst Download PDFInfo
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- CN104437549A CN104437549A CN201410669637.XA CN201410669637A CN104437549A CN 104437549 A CN104437549 A CN 104437549A CN 201410669637 A CN201410669637 A CN 201410669637A CN 104437549 A CN104437549 A CN 104437549A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 80
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000004065 semiconductor Substances 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 150000001661 cadmium Chemical class 0.000 claims abstract description 5
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 81
- 239000002159 nanocrystal Substances 0.000 claims description 78
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 63
- -1 polytetrafluoroethylene Polymers 0.000 claims description 28
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 28
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 27
- 239000005864 Sulphur Substances 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 239000011669 selenium Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 14
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 13
- 238000006303 photolysis reaction Methods 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 12
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 4
- ORPNDFMZTDVBGA-UHFFFAOYSA-N (2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P ORPNDFMZTDVBGA-UHFFFAOYSA-N 0.000 claims description 3
- HUCQPHINKBNKRU-UHFFFAOYSA-N (4-methylphenyl)phosphane Chemical class CC1=CC=C(P)C=C1 HUCQPHINKBNKRU-UHFFFAOYSA-N 0.000 claims description 3
- 230000018199 S phase Effects 0.000 claims description 3
- 230000002708 enhancing effect Effects 0.000 claims description 3
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 3
- JWYFRSAIWSROES-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[SeH2] Chemical compound [O-2].[O-2].[Ti+4].[SeH2] JWYFRSAIWSROES-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 17
- 239000002096 quantum dot Substances 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 239000010931 gold Substances 0.000 description 107
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 59
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 238000013019 agitation Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- 229910052737 gold Inorganic materials 0.000 description 18
- 239000006228 supernatant Substances 0.000 description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 17
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000002211 L-ascorbic acid Substances 0.000 description 8
- 235000000069 L-ascorbic acid Nutrition 0.000 description 8
- 229960005070 ascorbic acid Drugs 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 101710134784 Agnoprotein Proteins 0.000 description 7
- 239000008346 aqueous phase Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 6
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 6
- 239000005642 Oleic acid Substances 0.000 description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- 125000001741 organic sulfur group Chemical group 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 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 description 2
- 208000026487 Triploidy Diseases 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to preparation and high-efficiency hydrogen production of a novel surface plasma enhanced high-efficiency photocatalytic water splitting composite catalyst Au/CdX (X refers to S, Se and the like). The Au/Cd core-shell structure nanocrystalline consists of Au particles serving as a core and a CdX semiconductor serving as a shell layer, wherein the size of the Au particles is 20-45nm; the CdX shell layer is a single crystalline layer of 2-12nm; and the crystal form is a hexagonal phase of wurtzite. The preparation method comprises the following steps: adding a precursor into hydrosol of the Au/Ag nanoparticles to be converted into Au/AgX; adding a cadmium salt and a phosphine ligand, reacting at the temperature of 50 to 80 DEG C to generate the Au/CdX catalyst. The photocatalytic water splitting hydrogen production efficiency of the catalyst is 20-30mol/g/h and is higher than that of pure CdS quantum dots of the same mass by over 1000 times. The water solubility is high, the inverted phase is not needed during the test, the operating device is simplified, and the time is shortened. Meanwhile, the material utilization rate is improved, the synthesis condition is mild, and the catalyst is environmentally friendly, feasible and low in cost and has wide application prospects in the field of photocatalysis.
Description
Technical field
The invention belongs to the energy and environmentally conscious materials field, be specifically related to a kind of efficient photodissociation aquatic products hydrogen Au/CdX (X represents S, the compound of Se and S and Se) nano-crystal with core-shell structure Catalysts and its preparation method.
Technical background
Current, the whole world is faced with the severe challenge of the problems such as energy shortage, environment deterioration and climate warming, and the regenerative resource that searching development and utilization is cleaned is the effective means solved the problem.Sunlight catalytic hydrogen production by water decomposition technology is pollution-free with it, easy to operate, solar energy can be converted into the focus that the advantages such as clean Hydrogen Energy become research.And the subject matter restricting catalysis material development is at present that present catalysis material is poor to separative efficiency to light induced electron/hole, thus cause the problems such as quantum yield is low, hydrogen generation efficiency is low.For expanding and promoting that catalysis material is applied on hydrogen energy source production development, urgently develop New Generation Optical catalysis material.
Noble metal nano particles, as Au, Ag, causes the resonance of free electron to produce surface plasmon resonance effect, thus makes it have very strong absorption and scattering effect in visible ray, black light, near-infrared region under the electromagnetic field effect of light.Surface plasma body resonant vibration is a kind of physical optics effect.Surface plasma body resonant vibration depends on the dielectric constant of the size of metal nanoparticle, pattern and surrounding environment.Noble metal is if Au is because of its good reactionlessness and its stronger visible, UV Absorption, scattering effect, utilize its surface plasmon resonance effect effectively to improve photo-generate electron-hole to effective separation, bring tremendous influence by the photocatalytic activity of hydrogen production by water decomposition reaction system.
The semiconductor of CdS (cadmium sulfide) to be energy gap be about 2.4eV, the semiconductor of CdSe (cadmium selenide) to be energy gap be about 1.8eV, has the photochemical catalyzing H2-producing capacity that excellent visible light-responded characteristic and principle meet very much.But CdX photo-generate electron-hole commute compound, separative efficiency is poor, thus makes light decomposition water hydrogen generation efficiency poor.Therefore in order to improve separative efficiency and the hydrogen generation efficiency of CdX photo-generated carrier, a large amount of researcher is devoted to study its NEW TYPE OF COMPOSITE photocatalyst structure, and wherein noble metal/semiconductor nano composite nanostructure greatly can improve the separative efficiency of photo-generated carrier and hydrogen generation efficiency and receive much concern because noble metal exists.
The nanocrystalline major part of Au/ heterogeneous semiconductor dimeric structure reported is prepared in organosol, and need the phase transfer between different colloidal sol phase, step is complicated.In addition, during the Au/ heterogeneous semiconductor dimeric structure prepared at the hydrosol reported of minority is nanocrystalline, semiconductor layer mostly is amorphous or polycrystalline, and because the directionality of surface plasma enhancing, can not make the effect that the nanocrystalline middle generation surface plasma of each Au/ heterogeneous semiconductor dimeric structure strengthens, thus light hydrogen generation efficiency is lower.In view of above-mentioned defect, creator of the present invention obtains the present invention finally through long research and practice, solves above-mentioned problem in science.
Summary of the invention
The object of the invention is to, the preparation method of a kind of new and effective photocatalytic water composite catalyst providing a kind of surface plasma to strengthen, in order to solve above-mentioned technological deficiency.
For achieving the above object, the technical solution used in the present invention is, first a kind of efficient photodissociation aquatic products hydrogen Au/CdX nano-crystal with core-shell structure catalyst is provided, be made up of as shell as core and CdX Nano semiconductor Au nano particle, described Au nano particle is of a size of 20nm ~ 45nm, it is characterized in that, described CdX shell is monocrystalline, crystal formation is six side's phases of wurtzite, and described CdX shell thickness is 2nm ~ 12nm.
Secondly, a kind of method preparing above-mentioned efficient photodissociation aquatic products hydrogen Au/CdX nano-crystal with core-shell structure catalyst is provided, comprises the steps:
Step 1: the aqueous sol of Au/Ag nano-crystal with core-shell structure particle is joined in polytetrafluoroethylene (PTFE) reactor, add X precursor solution wherein, mix, 0.5h ~ 1h is reacted in 60 DEG C ~ 80 DEG C baking ovens, product centrifuge washing will be obtained, be distributed in the aqueous solution of deionized water and cationic surfactant, obtain Au/AgX nano-crystal with core-shell structure colloidal sol;
X is sulphur, selenium;
The molar concentration of the aqueous sol of described Au/Ag nano-crystal with core-shell structure particle is 0.005mol/L;
Step 2: add cadmium salt soln in described Au/AgX nano-crystal with core-shell structure colloidal sol, stir, add Phosphine ligands, forms solution a;
The volume that described Phosphine ligands adds is 80 μ l ~ 150 μ l.
Step 3: described solution a is added thermal response 1 ~ 4h in 50 DEG C ~ 80 DEG C, washs centrifugal, be precipitated thing b, is distributed in deionized water by described sediment b, obtains the colloidal sol of Au/CdX nano-crystal with core-shell structure.
Wherein, described sulphur precursor solution preparation method is: by n-dodecyl mereaptan, toluene, add in polytetrafluoroethylene (PTFE) reactor successively, stir, form solution c, sulphur powder is added in described solution c, stirred at ambient temperature 2min, sealing, reacts 15h, takes out as described sulphur presoma for subsequent use in 100 DEG C of baking ovens;
The volume ratio of described n-dodecyl mereaptan and described toluene is 1:(2 ~ 3), n-dodecyl mereaptan is 3:1 with the amount of substance ratio of sulphur powder.
Wherein, described selenium precursor solution preparation method is: by octadecylene, toluene, add in polytetrafluoroethylene (PTFE) reactor successively, stir, form solution c, titanium dioxide selenium powder is added in described solution, stirred at ambient temperature 2min, sealing, reacts 15h, takes out as selenium presoma for subsequent use in 100 DEG C of baking ovens;
The volume ratio of described octadecylene and toluene is 1:(2 ~ 3), octadecylene is 3:1 with the amount of substance ratio of sulphur powder.
Wherein, the volume that adds of described sulphur precursor solution adds 50ul ~ 100ul in the aqueous sol of the Au/Ag nano-crystal with core-shell structure particle of every 0.075mmol.
Wherein, the volume that adds of described selenium precursor solution adds 50ul ~ 100ul in the aqueous sol of the Au/Ag nano-crystal with core-shell structure particle of every 0.075mmol.
Wherein, described cationic surfactant is softex kw, and the concentration of its aqueous solution is 0.025mol/L ~ 0.05mol/L.
Wherein, described cadmium salt soln is Cd (NO
3)
24H
2the water of O or methanol solution, its mass concentration is 0.05g/ml, and addition is 0.6ml ~ 1.2ml.
Wherein, described Phosphine ligands is at least one in tributylphosphine, tri octyl phosphine, triphenylphosphine, three p-methylphenyl phosphines, three (o-methoxyphenyl) phosphine, Trimethyl phosphite, triethyl phosphite.
Compared with prior art, beneficial effect of the present invention is:
1. the invention provides noble metal Au surface plasma and strengthen the Au/CdS catalyst producing efficient photodissociation aquatic products hydrogen, owing to utilizing the CdS semiconductor shell with different-thickness, particularly CdS semiconductor thickness is 4nm ~ 6nm, when the size of metal core is 20nm ~ 45nm, thus realize by noble metal Au surface plasma bulk effect, significantly improve the efficiency that CdS semiconductor photochemical catalyst light decomposes aquatic products hydrogen, quality more same than simple CdS quantum dot, high more than 1000 times.
2. the Au/CdX catalyst that the invention provides efficient photodissociation aquatic products hydrogen is directly preparing at aqueous phase, with at organic solvent compared with the material synthesized, it is better water-soluble, do not need to turn aqueous phase in the test carrying out Photocatalyzed Hydrogen Production, thus simplify operating means, the shortening time, improve the utilization rate of material simultaneously.
3. the invention provides the preparation method that surface plasma strengthens the Au/CdX catalyst producing efficient photodissociation aquatic products hydrogen, described method realizes in aqueous phase, lower than under the low temperature of 80 DEG C, use synthesis condition is gentle, device is simple, green is easy, cost is low, has broad application prospects in photocatalysis field.
Accompanying drawing explanation
Fig. 1 is the low resolved transmittance Electronic Speculum shape appearance figure of Au nano particle in the Au nano particle hydrosol;
Fig. 2 is the low resolved transmittance Electronic Speculum figure of the Au/CdS nano-crystal with core-shell structure that embodiment 1 obtains;
Fig. 3 a, 3b, 3c, 3d are respectively low resolved transmittance Electronic Speculum, the X-ray diffractogram of high-resolution-ration transmission electric-lens figure, Au/CdS nano-crystal with core-shell structure of Au/CdS nano-crystal with core-shell structure, the photoelectric respone signal graph of the film of Au/CdS nano-crystal with core-shell structure of the obtained Au/CdS nano-crystal with core-shell structure of embodiment 2;
Fig. 4 is the low resolved transmittance Electronic Speculum figure of the Au/CdS nano-crystal with core-shell structure that embodiment 3 obtains;
Fig. 5 is the photochemical catalyzing hydrogen output figure of five kinds of nano materials in embodiment 9.
Detailed description of the invention
In order to absolutely prove characteristic of the present invention and implement mode of the present invention, provide embodiment below.
In following examples, the preparation method of used sulphur presoma, selenium presoma and the gold nano grain hydrosol is as follows.
(1) preparation method of sulphur precursor solution
Get 3mL n-dodecyl mereaptan, 7mL toluene, add successively in the polytetrafluoroethylene (PTFE) reactor of 20mL, stir, form solution c, weigh 38.79mg sulphur powder and add in above-mentioned solution c, stirred at ambient temperature 2min, sealing, reacts 15h, takes out as sulphur presoma for subsequent use in 100 DEG C of baking ovens.
(2) preparation method of selenium precursor solution
Get 3mL octadecylene, 7mL toluene, add successively in the polytetrafluoroethylene (PTFE) reactor of 20mL, stir, form solution d, weigh 134.5mg selenium dioxide and add in above-mentioned solution d, stirred at ambient temperature 2min, sealing, reacts 15h, takes out as selenium presoma for subsequent use in 100 DEG C of baking ovens.
(3) preparation method of the gold nano grain hydrosol
Get 1.25mL 0.001mol/L chlorauric acid solution and 2.5mL 0.15mol/L softex kw (CTAB) solution mixes, add the sodium borohydride (NaBH configured in 0.3mL0.01mol/L ice bath under vigorous stirring
4) solution, and after Keep agitation 2min, left at room temperature 1h, forms gold seeds colloidal sol, by deionized water, described gold seeds colloidal sol is diluted 10 times afterwards.
Get 6.4mL 0.1mol/L softex kw (CTAB) solution, 0.8mL0.01mol/L chlorauric acid solution, 32mL deionized water, add successively in the round-bottomed flask of 100mL, stir, then add 3.8mL0.1mol/L ascorbic acid (A.A), stirring reaction 2min, add 2 above-mentioned gold seeds colloidal sols, left at room temperature 8-9h, for subsequent use.
Refer to shown in Fig. 1, it is the low resolved transmittance Electronic Speculum shape appearance figure of Au nano particle.The Au nano particle showing gained in figure detects through transmission electron microscope TEM (JEOL JEM1200EX, 100KV), and it is uniformly dispersed, size uniformity, and Au nano particle is of a size of 20nm ~ 45nm.
Embodiment 1
(1) hydrosol of gold nano grain described in 30mL is got in 50mL centrifuge tube, 7000rpm centrifuge washing 10min, reject supernatant, lower floor's gold nano grain is scattered in again in 10mL0.025mol/L softex kw (CTAB) solution, adds 0.7mL 0.1mol/L ascorbic acid (A.A), 0.2mL 0.01mol/L silver nitrate (AgNO wherein successively
3) solution, the NaOH (NaOH) adding 1.0mL 0.1mol/L regulates the PH to 10 of solution, and in 30 DEG C of water-baths, leave standstill 1h, obtain Au/Ag nano-crystal with core-shell structure colloidal sol, its concentration is 0.005mol/L.
(2) getting 15mL above-mentioned Au/Ag nano-crystal with core-shell structure colloidal sol joins in the polytetrafluoroethylene (PTFE) reactor of 20mL, then the precursor solution 60uL of described sulphur is added, mix, sealing, putting into 80 DEG C of baking ovens to react 1h and terminate, is then 1:1 deionized water by volume ratio, 7000rpm centrifuge washing 10min, abandoning supernatant, is scattered in 2mL H again by lower floor's material
2in O and 10mL 0.05mol/L CTAB solution, obtain Au/Ag
2the colloidal sol of S nano-crystal with core-shell structure.
(3) by above-mentioned Au/Ag
2the colloidal sol of S nano-crystal with core-shell structure is transferred in 50mL round-bottomed flask, under magnetic agitation, adds 0.8mL Cd (NO
3)
24H
2the O aqueous solution (0.05g/mL), room temperature lower magnetic force stirs 2min, add 80uL tributylphosphine (TBP), form solution a, by this solution a magnetic agitation reaction 2h in 50 DEG C of water-baths, take out the deionized water adding same volume, 7000r centrifuge washing 10min, abandoning supernatant, is precipitated thing b, sediment b is scattered in a small amount of deionized water again, obtains the colloidal sol of Au/CdS nano-crystal with core-shell structure.Refer to shown in Fig. 2, it is the low resolved transmittance Electronic Speculum shape appearance figure of Au/CdS nano-crystal with core-shell structure.The CdS shell dimensional thickness showing gained in figure is about 2nm ~ 3nm.
Au/CdS prepared by the present invention is directly preparing at aqueous phase, and compared with the material synthesized in organic solvent, it is better water-soluble, do not need to turn aqueous phase in the test doing Photocatalyzed Hydrogen Production, thus simplify operating means, shorten the time, improve the utilization rate of material simultaneously.
Embodiment 2
(1) hydrosol of gold nano grain described in 30mL is got in 50mL centrifuge tube, 7000rpm centrifuge washing 10min, reject supernatant, lower floor's gold nano grain is scattered in again in 10mL0.025mol/L softex kw (CTAB) solution, adds 0.7mL 0.1mol/L ascorbic acid (A.A), 0.35mL 0.01mol/L silver nitrate (AgNO wherein successively
3) solution, the NaOH (NaOH) adding 1.0mL 0.1mol/L regulates the PH to 10 of solution, and in 30 DEG C of water-baths, leave standstill 1h, obtain Au/Ag nano-crystal with core-shell structure colloidal sol, its concentration is 0.005mol/L.
(2) getting 15mL above-mentioned Au/Ag nano-crystal with core-shell structure colloidal sol joins in the polytetrafluoroethylene (PTFE) reactor of 20mL, then the precursor solution 80uL of described sulphur is added, mix, sealing, putting into 80 DEG C of baking ovens to react 1h and terminate, is then 1:1 deionized water by volume ratio, 7000rpm centrifuge washing 10min, abandoning supernatant, is scattered in 2mL H again by lower floor's material
2in O and 10mL 0.05mol/L CTAB solution, obtain Au/Ag
2the colloidal sol of S nano-crystal with core-shell structure.
(3) by above-mentioned Au/Ag
2the colloidal sol of S nano-crystal with core-shell structure is transferred in 50mL round-bottomed flask, under magnetic agitation, adds 0.8mL Cd (NO
3)
24H
2the O aqueous solution (0.05g/mL), room temperature lower magnetic force stirs 2min, add 100uL tributylphosphine (TBP), form solution a, by this solution a magnetic agitation reaction 2h in 50 DEG C of water-baths, take out the deionized water adding same volume, 7000r centrifuge washing 10min, abandoning supernatant, is precipitated thing b, sediment b is scattered in a small amount of deionized water again, obtains the colloidal sol of Au/CdS nano-crystal with core-shell structure.
The Au/CdS nano-crystal with core-shell structure of gained detects through transmission electron microscope TEM (JEOL JEM1200EX, 100KV), shows it and has good monodispersity (as shown in Figure 3 a), CdS shell dimensional thickness is about 4nm ~ 6nm.Can show that the shell of CdS is monocrystalline from the high resolution transmission electron microscopy HRTEM (FEI Tecnai G2 F20 S-Twin, 200kV) of Fig. 3 b.Detect through powder x-ray diffraction (Bruker D8 Advance), reference JCPDS card CdS is 41-1049, JCPDS card Au is 04-0784, show its for shell CdS be six side's phases (as shown in Figure 3 c) of wurtzite, in Fig. 3 c, the longitudinal axis is diffracted intensity, transverse axis is the angle of diffraction, and solid black lines represents the peak shape of Au/CdS nano-crystal with core-shell structure.CHI650D type electrochemical workstation through Shanghai Chen Hua Instrument Ltd. is tested, and adopts three-electrode system, working electrode (the FTO electro-conductive glass of sample film forming), and Pt is to electrode, and calomel electrode reference electrode, prepares the Na of 0.1mol/L
2sO
4electrolyte, as shown in Figure 3 d, has good photoelectric respone signal.
This method realizes under lower than the low temperature of 80 DEG C, and synthesis condition is gentle, and device is simple, green easy, and reduces cost.
Embodiment 3
(1) hydrosol of gold nano grain described in 30mL is got in 50mL centrifuge tube, 7000rpm centrifuge washing 10min, reject supernatant, lower floor's gold nano grain is scattered in again in 10mL0.025mol/L softex kw (CTAB) solution, adds 0.7mL 0.1mol/L ascorbic acid (A.A), 0.5mL 0.01mol/L silver nitrate (AgNO wherein successively
3) solution, the NaOH (NaOH) adding 1.0mL 0.1mol/L regulates the PH to 10 of solution, and in 30 DEG C of water-baths, leave standstill 1h, obtain Au/Ag nano-crystal with core-shell structure colloidal sol, its concentration is 0.005mol/L.
(2) getting 15mL above-mentioned Au/Ag nano-crystal with core-shell structure colloidal sol joins in the polytetrafluoroethylene (PTFE) reactor of 20mL, then the precursor solution 100uL of described sulphur is added, mix, sealing, putting into 80 DEG C of baking ovens to react 1h and terminate, is then 1:1 deionized water by volume ratio, 7000rpm centrifuge washing 10min, abandoning supernatant, is scattered in 2mL H again by lower floor's material
2in O and 10mL 0.05mol/L CTAB solution, obtain Au/Ag
2the nanocrystalline colloidal sol of S nucleocapsid structure.
(3) by above-mentioned Au/Ag
2the colloidal sol of S nano-crystal with core-shell structure is transferred in 50mL round-bottomed flask, under magnetic agitation, adds 1.2mL Cd (NO
3)
24H
2the O aqueous solution (0.05g/mL), room temperature lower magnetic force stirs 2min, add 150uL tributylphosphine (TBP), form solution a, by this solution a magnetic agitation reaction 2h in 50 DEG C of water-baths, take out the deionized water adding same volume, 7000r centrifuge washing 10min, abandoning supernatant, is precipitated thing b, sediment b is scattered in a small amount of deionized water again, obtains the colloidal sol of Au/CdS nano-crystal with core-shell structure.Refer to shown in Fig. 4, it is the low resolved transmittance Electronic Speculum shape appearance figure of Au/CdS nano-crystal with core-shell structure.The CdS shell dimensional thickness showing gained in figure is about 9nm ~ 12nm.
Embodiment 4
(1) hydrosol of gold nano grain described in 30mL is got in 50mL centrifuge tube, 7000rpm centrifuge washing 10min, reject supernatant, lower floor's gold nano grain is scattered in again in 10mL0.025mol/L softex kw (CTAB) solution, adds 0.7mL 0.1mol/L ascorbic acid (A.A), 0.35mL 0.01mol/L silver nitrate (AgNO wherein successively
3) solution, the NaOH (NaOH) adding 1.0mL 0.1mol/L regulates the PH to 10 of solution, and in 30 DEG C of water-baths, leave standstill 1h, obtain Au/Ag nano-crystal with core-shell structure colloidal sol, its concentration is 0.005mol/L.
(2) getting 15mL above-mentioned Au/Ag nano-crystal with core-shell structure colloidal sol joins in the polytetrafluoroethylene (PTFE) reactor of 20mL, then the precursor solution 80uL of described selenium is added, mix, sealing, putting into 80 DEG C of baking ovens to react 1h and terminate, is then 1:1 deionized water by volume ratio, 7000rpm centrifuge washing 10min, abandoning supernatant, is scattered in 2mL H again by lower floor's material
2in O and 10mL 0.05mol/L CTAB solution, obtain Au/Ag
2the colloidal sol of Se nano-crystal with core-shell structure.
(3) by above-mentioned Au/Ag
2the colloidal sol of Se nano-crystal with core-shell structure is transferred in 50mL round-bottomed flask, under magnetic agitation, adds 1mL Cd (NO
3)
24H
2the O aqueous solution (0.05g/mL), room temperature lower magnetic force stirs 2min, add 100uL tributylphosphine (TBP), magnetic agitation reaction 2h in 50 DEG C of water-baths, take out the deionized water adding same volume, 7000r centrifuge washing 10min, abandoning supernatant, the sediment obtained is scattered in a small amount of deionized water again, obtains the colloidal sol of Au/CdSe nano-crystal with core-shell structure.
Embodiment 5
(1) hydrosol of gold nano grain described in 30mL is got in 50mL centrifuge tube, 7000rpm centrifuge washing 10min, reject supernatant, lower floor's gold nano grain is scattered in again in 10mL0.025mol/L softex kw (CTAB) solution, adds 0.7mL 0.1mol/L ascorbic acid (A.A), 0.5mL 0.01mol/L silver nitrate (AgNO wherein successively
3) solution, the NaOH (NaOH) adding 1.0mL 0.1mol/L regulates the PH to 10 of solution, and in 30 DEG C of water-baths, leave standstill 1h, obtain Au/Ag nano-crystal with core-shell structure colloidal sol, its concentration is 0.005mol/L.
(2) getting 15mL above-mentioned Au/Ag nano-crystal with core-shell structure colloidal sol joins in the polytetrafluoroethylene (PTFE) reactor of 20mL, then the precursor solution 50uL of described sulphur is added, mix, sealing, put into 60 DEG C of baking ovens to react 0.5h and terminate, then use the deionized water of same volume, 7000rpm centrifuge washing 10min, abandoning supernatant, is scattered in 2mL H again by lower floor's material
2in O and 10mL 0.025mol/L CTAB solution, obtain Au/Ag
2the colloidal sol of S nano-crystal with core-shell structure.
(3) by above-mentioned Au/Ag
2the colloidal sol of S nano-crystal with core-shell structure is transferred in 50mL round-bottomed flask, under magnetic agitation, adds 0.8mL Cd (NO
3)
24H
2the O aqueous solution (0.05g/mL), room temperature lower magnetic force stirs 2min, add 80uL tri-n-octyl phosphine (T0P), form solution a, by this solution a magnetic agitation reaction 1h in 80 DEG C of water-baths, take out the deionized water adding same volume, 7000r centrifuge washing 10min, abandoning supernatant, is precipitated thing b, sediment b is scattered in a small amount of deionized water again, obtains the nanocrystalline colloidal sol of Au/CdS nucleocapsid structure.
Embodiment 6
(1) hydrosol of gold nano grain described in 30mL is got in 50mL centrifuge tube, 7000rpm centrifuge washing 10min, reject supernatant, lower floor's gold nano grain is scattered in again in 10mL0.025mol/L softex kw (CTAB) solution, adds 0.7mL 0.1mol/L ascorbic acid (A.A), 0.35mL 0.01mol/L silver nitrate (AgNO wherein successively
3) solution, the NaOH (NaOH) adding 1.0mL 0.1mol/L regulates the PH to 10 of solution, and in 30 DEG C of water-baths, leave standstill 1h, obtain Au/Ag nano-crystal with core-shell structure colloidal sol, its concentration is 0.005mol/L.
(2) getting 15mL above-mentioned Au/Ag nano-crystal with core-shell structure colloidal sol joins in the polytetrafluoroethylene (PTFE) reactor of 20mL, then the precursor solution 80uL of described sulphur is added, mix, sealing, put into 60 DEG C of baking ovens to react 0.8h and terminate, then use the deionized water of same volume, 7000rpm centrifuge washing 10min, abandoning supernatant, is scattered in 2mL H again by lower floor's material
2in O and 10mL 0.025mol/L CTAB solution, obtain Au/Ag
2s nano-crystal with core-shell structure colloidal sol.
(3) by above-mentioned Au/Ag
2the colloidal sol of S nano-crystal with core-shell structure is transferred in 50mL round-bottomed flask, under magnetic agitation, adds 0.8mL Cd (NO
3)
24H
2the O aqueous solution (0.05g/mL), room temperature lower magnetic force stirs 2min, add 0.025g triphenylphosphine, form solution a, by this solution a magnetic agitation reaction 4h in 80 DEG C of water-baths, take out the deionized water adding same volume, 7000r centrifuge washing 10min, abandoning supernatant, is precipitated thing b, sediment b is scattered in a small amount of deionized water again, obtains the colloidal sol of Au/CdS nano-crystal with core-shell structure.
Above-mentioned Phosphine ligands can also be at least one in Trimethyl phosphite, triethyl phosphite, three p-methylphenyl phosphines or three (o-methoxyphenyl) phosphine.
Embodiment 7
Test to do performance comparison with organic CdS quantum dot, the present embodiment is the concrete grammar of preparation organic C dS quantum dot.
(1) single dispersed nano silver particle colloidal sols is prepared
Get 10mL oleic acid, 10mL oleyl amine is in there-necked flask, and logical nitrogen bubble, weighs 0.17gAgNO
3add wherein, 30 DEG C of lower magnetic force stirring reaction 5min, then add 0.08gFe (NO wherein
3)
3﹒ 4H
2o, continue logical nitrogen gas stirring reaction 2min, temperature is set as 120 DEG C, heats up gradually and magnetic agitation, 1h is reacted again after being warmed up to 120 DEG C, stop reaction, by the liquid cools in single port flask to room temperature, adding is the ethanol that its triploid amasss, 5000r centrifuge washing 8min, be distributed in 80mL toluene, obtain monodispersed Argent grain toluene colloidal sol, and the particle diameter of Argent grain be 4nm ~ 6nm.
(2) organic sulfur precursor solution is prepared
Get 5mL oleyl amine, 10mL oleic acid, add successively in the round-bottomed flask of 50mL, stir, weigh 64mg sulphur powder and add in above-mentioned mixed liquor, stirred at ambient temperature 2min, magnetic agitation reaction 40min in 100 DEG C of oil baths, add 15mL toluene wherein, magnetic agitation is even, and it is for subsequent use as organic sulfur presoma that temperature is down to room temperature.
(3) 4nm ~ 6nm cadmium sulfide (CdS) quantum dot is prepared
Get the above-mentioned monodispersed Argent grain toluene colloidal sol of 6mL in the round-bottomed flask of 25mL, add organic sulfur presoma described in 3mL wherein, in 50 DEG C of stirred in water bath reaction 1h, add 30ml ethanol, 5000r centrifuge washing 8min, obtains monodispersed silver sulfide (Ag
2s) nano particle, is re-dispersed in 6mL ~ 10mL toluene.Under strong magnetic agitation, to Ag
2s Nano sol adds 0.2mL oleic acid, 0.1mL oleyl amine and 1mL Cd (NO
3)
24H
2o methanol solution (0.1g/mL), room temperature lower magnetic force stirs 1min, adds 0.1mL TBP, and magnetic agitation reaction 2h in 50 DEG C of water-baths, add 30ml ethanol, 5000r centrifuge washing 8min, obtaining particle diameter is 4nm ~ 6nm CdS quantum dot.
Embodiment 8
Test to do performance comparison with the Au/CdS nano-crystal with core-shell structure prepared in organic solvent, the present embodiment is the concrete grammar of preparation Au/CdS nano-crystal with core-shell structure.
(1) organic sulfur precursor solution is prepared
Get 5mL oleyl amine, 10mL oleic acid, add successively in the round-bottomed flask of 50mL, stir, weigh 64mg sulphur powder and add in above-mentioned mixed liquor, stirred at ambient temperature 2min, magnetic agitation reaction 40min in 100 DEG C of oil baths, add 15mL toluene wherein, magnetic agitation is even, and it is for subsequent use as sulphur presoma that temperature is down to room temperature.
(2) nanometer Au particle toluene colloidal sol is prepared
Get 5mL deionized water, 1mL1.0mol/L NaOH (NaOH), 4mL acetonitrile, 0.72mL oleic acid and 30mg gold chloride (HAuCl
44H
2o) mix, add 10 0.1mmol/L ascorbic acid and 13mL cyclohexane, stirring reaction 10h, add the ethanol that above-mentioned mixed liquor triploid is long-pending, 5000r centrifuge washing 8min, is distributed in 80mL toluene.
(3) organosol that CdS shell thickness is the Au/CdS nano-crystal with core-shell structure of 4nm ~ 6nm is prepared
The toluene colloidal sol getting the monodispersed Au of preparation in 8mL the present embodiment (2), in the round-bottomed flask of 25mL, adds 0.2mL oleyl amine and 1mL AgNO
3methanol solution (0.05g/mL), reacts 8h under 70 DEG C of oil baths, adds the ethanol of 30ml, 5000r centrifuge washing 8min, be distributed in 3.6mL toluene, add the above-mentioned organic sulfur presoma of 3mL wherein, stirred at ambient temperature reaction 1h, add 30ml ethanol, 5000r centrifuge washing 8min, is re-dispersed in 6 ~ 10mL toluene, under magnetic stirring, add 0.2mL oleic acid, 0.1mL oleyl amine and 1mLCd (NO
3)
24H
2o methanol solution (0.1g/mL), room temperature lower magnetic force stirs 1min, adds 0.1mL TBP, magnetic agitation reaction 2h in 50 DEG C of water-baths, add 30ml ethanol, 5000r centrifuge washing 8min, obtain the organosol that CdS shell thickness is the Au/CdS nano-crystal with core-shell structure of 4nm ~ 6nm.To the Au/CdS nano-crystal with core-shell structure of organic solvent, by volume for 1:2 adds the 5mg/mL Mercaptamine aqueous solution, in room temperature lower magnetic force stirring reaction 10min, obtain the Au/CdS nano-crystal with core-shell structure being dissolved in the hydrosol.
Embodiment 9
To the hydrosol of the Au/CdS nano-crystal with core-shell structure prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 7 utilizes the CdS quantum dot of organic sulfur precursor power, the organosol of Au/CdS nano-crystal with core-shell structure prepared by embodiment 8 proceeds to aqueous phase becomes the Au/CdS nano-crystal with core-shell structure hydrosol, above-mentioned material is dried, take equal in quality, do the test of Photocatalyzed Hydrogen Production performance respectively.
Test process: get appropriate vulcanized sodium (Na
2s), potassium sulfite (K
2sO
3), be dissolved in 100mL deionized water respectively, until after dissolving completely, portion adds embodiment 1 gained Au/CdS nano-crystal with core-shell structure, portion adds embodiment 2 gained Au/CdS nano-crystal with core-shell structure, portion adds embodiment 3 gained Au/CdS nano-crystal with core-shell structure, portion adds embodiment 7 gained CdS quantum dot, portion adds embodiment 8 gained Au/CdS core-shell nano crystal structure photochemical catalyst, stir 5min respectively, reactor is connected with photolysis water hydrogen reaction system, and air in system is pumped.Under the 300W xenon lamp of simulated solar irradiation irradiates, the H2-producing capacity test platform of standard (photocatalytic hydrogen production by water decomposition on-line analysis system CEL-SPH2N) is utilized to test.In the atmosphere of nitrogen, adopt a sample with gas chromatograph (SP7800) every 25min.
The hydrogen output figure (as shown in Figure 5) of above-mentioned photocatalytic hydrogen production by water decomposition, in Fig. 5, curve a represents the Au/CdS nano-crystal with core-shell structure photocatalytic hydrogen production by water decomposition production curve of embodiment 1, curve b represents the Au/CdS nano-crystal with core-shell structure photocatalytic hydrogen production by water decomposition production curve of embodiment 2, curve c represents the Au/CdS nano-crystal with core-shell structure photocatalytic hydrogen production by water decomposition production curve of embodiment 3, curve d represents the CdS quantum dot photocatalytic hydrogen production by water decomposition production curve of embodiment 7, curve e represents Au/CdS nano-crystal with core-shell structure photocatalytic hydrogen production by water decomposition production curve prepared by embodiment 8, as can be seen from above-mentioned several curves, Au surface plasma bulk effect can make CdS become a kind of efficiency light and produce hydrogen catalyst, and CdS shell is that the efficiency of 4nm ~ 6nm time hydrogen production by water decomposition is best in the Au/CdS nano-crystal with core-shell structure synthesized in aqueous phase, test result reaches 20mmol/g/h ~ 30mmol/g/h.Its amounts of hydrogen produced in same time than the CdS quantum dot of homogenous quantities is high more than 1000 times.
The foregoing is only preferred embodiment of the present invention, is only illustrative for the purpose of the present invention, and nonrestrictive.Those skilled in the art is understood, and can carry out many changes and amendment in the spirit and scope that the claims in the present invention limit to it, even equivalence, but all will fall within the scope of protection of the present invention.
Claims (9)
1. the new and effective photocatalytic water composite catalyst of one of surface plasma enhancing, by Au nano particle, as core and CdX, (X represents S, the compound of Se and S, Se) semiconductor shell composition, described Au nano particle is of a size of 20nm ~ 45nm, it is characterized in that, described CdX shell is monocrystalline, and crystal formation is six side's phases of wurtzite, and described CdX shell thickness is 2nm ~ 12nm.
2. prepare the efficient photocatalytic water composite catalyst that surface plasma as claimed in claim 1 strengthens, the method for Au/CdX core-shell nano crystalline substance, is characterized in that, comprise the steps:
Step 1: the aqueous sol of Au/Ag nano-crystal with core-shell structure particle is joined in polytetrafluoroethylene (PTFE) reactor, add X precursor solution wherein, mix, 0.5h ~ 1h is reacted in 60 DEG C ~ 80 DEG C baking ovens, product centrifuge washing will be obtained, be distributed in the aqueous solution of deionized water and cationic surfactant, obtain Au/Ag
2the colloidal sol of X nano-crystal with core-shell structure;
X is the compound of sulphur, selenium or sulphur and selenium element;
The molar concentration of the aqueous sol of described Au/Ag nano-crystal with core-shell structure particle is 0.005mol/L;
Step 2: to described Au/Ag
2add cadmium salt soln in X nano-crystal with core-shell structure colloidal sol, stir, add Phosphine ligands, form solution a;
The volume that described Phosphine ligands adds is 80 μ l ~ 150 μ l.
Step 3: described solution a is added thermal response 1 ~ 4h in 50 DEG C ~ 80 DEG C, washs centrifugal, be precipitated thing b, is distributed in deionized water by described sediment b, obtains the colloidal sol of Au/CdX nano-crystal with core-shell structure.
3. the preparation method of a kind of new and effective photocatalytic water composite catalyst of surface plasma enhancing according to claim 2, it is characterized in that, described sulphur precursor solution preparation method is: by n-dodecyl mereaptan, toluene, add successively in polytetrafluoroethylene (PTFE) reactor, stir, form solution c, sulphur powder is added in described solution c, stirred at ambient temperature 2min, sealing, in 100 DEG C of baking ovens, react 15h, take out as described sulphur presoma for subsequent use;
The volume ratio of described n-dodecyl mereaptan and described toluene is 1:(2 ~ 3), n-dodecyl mereaptan is 3:1 with the amount of substance ratio of sulphur powder.
4. the method for preparation according to claim 2 efficient photodissociation aquatic products hydrogen Au/CdX nano-crystal with core-shell structure catalyst, it is characterized in that, described selenium precursor solution preparation method is: by octadecylene, toluene, add successively in polytetrafluoroethylene (PTFE) reactor, stir, form solution c, titanium dioxide selenium powder is added in described solution, stirred at ambient temperature 2min, sealing, in 100 DEG C of baking ovens, react 15h, take out as selenium presoma for subsequent use;
The volume ratio of described octadecylene and toluene is 1:(2 ~ 3), octadecylene is 3:1 with the amount of substance ratio of sulphur powder.
5. the method for preparation according to claim 3 efficient photodissociation aquatic products hydrogen Au/CdX nano-crystal with core-shell structure catalyst, it is characterized in that, the volume that adds of described sulphur precursor solution adds 50ul ~ 100ul in the aqueous sol of the Au/Ag nano-crystal with core-shell structure particle of every 0.075mmol.
6. the method for preparation according to claim 4 efficient photodissociation aquatic products hydrogen Au/CdX catalyst, it is characterized in that, the volume that adds of described selenium precursor solution adds 50ul ~ 100ul in the aqueous sol of the Au/Ag nano-crystal with core-shell structure particle of every 0.075mmol.
7. the method for preparation according to claim 2 efficient photodissociation aquatic products hydrogen Au/CdX nano-crystal with core-shell structure catalyst, it is characterized in that, described cationic surfactant is softex kw, and the concentration of its aqueous solution is 0.025mol/L ~ 0.05mol/L.
8. the method for the catalyst of preparation according to claim 2 efficient photodissociation aquatic products hydrogen Au/CdX nano-crystal with core-shell structure, is characterized in that, described cadmium salt soln is Cd (NO
3)
24H
2the water of O or methanol solution, its mass concentration is 0.05g/ml, and addition is 0.6ml ~ 1.2ml.
9. the method for preparation according to claim 2 efficient photodissociation aquatic products hydrogen Au/CdX nano-crystal with core-shell structure catalyst, it is characterized in that, described Phosphine ligands is at least one in tributylphosphine, tri octyl phosphine, triphenylphosphine, three p-methylphenyl phosphines, three (o-methoxyphenyl) phosphine, Trimethyl phosphite, triethyl phosphite.
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| CN111036935A (en) * | 2019-12-13 | 2020-04-21 | 武汉工程大学 | Gap-adjustable Au layer, core of AgAu layer and CdS shell nano material, and preparation method and application thereof |
| CN113145133A (en) * | 2020-02-17 | 2021-07-23 | 山东大学 | Photocatalytic material based on metal-semiconductor composite structure, preparation method and magnetic field auxiliary application thereof |
| CN114703497A (en) * | 2022-04-26 | 2022-07-05 | 中南大学 | Plasma catalyst for photo-assisted electro-catalytic decomposition of water to produce hydrogen and preparation method |
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| CN105268966A (en) * | 2015-10-08 | 2016-01-27 | 北京理工大学 | Au@Cu2-deltaX nanoscale crystal and preparation method and application thereof |
| CN108367273A (en) * | 2015-11-16 | 2018-08-03 | 沙特基础工业全球技术公司 | The multilayer water-splitting photochemical catalyst of plasmon metal layer with plasma effect optimization |
| CN105521822A (en) * | 2016-01-08 | 2016-04-27 | 中国科学院理化技术研究所 | Bell-shaped nanospheres, preparation method therefor and application of bell-shaped nanospheres |
| CN105521822B (en) * | 2016-01-08 | 2018-07-13 | 中国科学院理化技术研究所 | One kind is rung a bell type nanoparticle and its preparation method and application |
| CN109641760A (en) * | 2016-09-01 | 2019-04-16 | 日立化成株式会社 | The manufacturing method of nanocrystal and the manufacturing method of steel |
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| CN107188125A (en) * | 2017-05-16 | 2017-09-22 | 南京航空航天大学 | Have both solar energy enhanced absorption and the nano-fluid and preparation method of thermocatalytic attribute |
| CN107188125B (en) * | 2017-05-16 | 2019-05-14 | 南京航空航天大学 | Have both the nano-fluid and preparation method of solar energy enhanced absorption and thermocatalytic attribute |
| CN107626330A (en) * | 2017-09-29 | 2018-01-26 | 浙江大学台州研究院 | P n-types La4O4Se3The preparation method of/CdS composite semiconductor light-catalysts |
| CN109261167A (en) * | 2018-09-15 | 2019-01-25 | 东莞理工学院 | A kind of Ag@Ag2The preparation method of S@CdS core shell nano core-shell material |
| CN109277563A (en) * | 2018-09-17 | 2019-01-29 | 东莞理工学院 | A method of preparing water phase Au@CdS nano core-shell material |
| CN111036935A (en) * | 2019-12-13 | 2020-04-21 | 武汉工程大学 | Gap-adjustable Au layer, core of AgAu layer and CdS shell nano material, and preparation method and application thereof |
| CN113145133A (en) * | 2020-02-17 | 2021-07-23 | 山东大学 | Photocatalytic material based on metal-semiconductor composite structure, preparation method and magnetic field auxiliary application thereof |
| CN114703497A (en) * | 2022-04-26 | 2022-07-05 | 中南大学 | Plasma catalyst for photo-assisted electro-catalytic decomposition of water to produce hydrogen and preparation method |
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