CN104437549B - A kind of preparation method of efficient photocatalytic water composite catalyst - Google Patents
A kind of preparation method of efficient photocatalytic water composite catalyst Download PDFInfo
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Abstract
The present invention relates to preparation and the highly effective hydrogen yield of efficient photodissociation Aquatic product hydrogen catalyst Au/CdX (X represents S, Se etc.) that a kind of surface plasma strengthens.Au/CdX nano-crystal with core-shell structure is made up of as shell with CdX quasiconductor as core Au granule, and the size of Au granule is 20～45nm, and CdX shell is the single crystalline layer of 2～12nm, and crystal formation is the hexagonal phase of buergerite.Its preparation method is to add presoma to the hydrosol of Au/Ag nano-particle to be converted into Au/AgX, adds cadmium salt and Phosphine ligands and generates Au/CdX catalyst in 50～80 DEG C of reactions.The efficiency of this catalyst photolysis Aquatic product hydrogen reaches 20～30mmol/g/h, higher more than 1000 times than the simple same quality of CdS quantum dot.Its good water solubility, need not during test turn aqueous phase, i.e. simplifies operation device, shortens the time, improves the utilization rate of material simultaneously, and synthesis condition is gentle, green easy, low cost, has broad application prospects in photocatalysis field.
Description
Technical field
The invention belongs to the energy and environmentally conscious materials field, be specifically related to a kind of efficiently photodissociation Aquatic product hydrogen
Au/CdX (X represents the compound of S, Se and S and Se) nano-crystal with core-shell structure catalyst
And preparation method thereof.
Technical background
Currently, the whole world is faced with the tight of the problems such as energy shortage, ecological deterioration and climate warming
High challenge, the regenerative resource finding development and utilization cleaning is to solve effective hands of the problems referred to above
Section.Sunlight catalytic hydrogen production by water decomposition technology is pollution-free with it, easy operation, can be by solar energy
The advantages such as the Hydrogen Energy being converted into cleaning become the focus of research.And restrict photocatalysis material at present
Material development subject matter be present catalysis material to light induced electron/hole to separation efficiency
Difference, thus cause the problems such as quantum yield is low, hydrogen generation efficiency is low.For expanding and promoting photocatalysis
Material is applied on hydrogen energy source production development, urgently development New Generation Optical catalysis material.
Noble metal nano particles, such as Au, Ag, causes free electricity under the electromagnetic field effect of light
Son resonance produce surface plasmon resonance effect so that its visible ray, black light,
There are the strongest absorption and scattering effect in near-infrared region.Surface plasma body resonant vibration is a kind of physics
Optical effect.Surface plasma body resonant vibration depends on the size of metal nanoparticle, pattern and week
The dielectric constant in collarette border.Noble metal such as Au is because its preferable reactionlessness and it is stronger
Visible, UV Absorption, scattering effect, utilize its surface plasmon resonance effect effective
Improve photo-generate electron-hole to efficiently separating, by the photocatalysis to hydrogen production by water decomposition reaction system
Activity brings tremendous influence.
CdS (cadmium sulfide) be energy gap be the quasiconductor of about 2.4eV, CdSe (selenizing
Cadmium) be energy gap be the quasiconductor of about 1.8eV, have excellence visible light-responded characteristic
And the photochemical catalyzing H2-producing capacity met very much in principle.But CdX light induced electron-
Hole is to the most compound, and separation efficiency is poor, so that photolysis Aquatic product hydrogen efficiency is poor.Therefore to
Improving separation efficiency and the hydrogen generation efficiency of CdX photo-generated carrier, a large amount of researchers are endeavoured
In research its composite photo-catalyst structure, wherein noble metal/semiconductor nano composite nanostructure
The separation efficiency of photo-generated carrier and hydrogen generation efficiency can be greatly improved and standby owing to noble metal exists
Concerned.
The Au/ nanocrystalline major part of heterogeneous semiconductor dimeric structure reported is at organosol
In be prepared, the phase transfer between needing different colloidal sol mutually, step is complicated.Additionally, minority
During the Au/ heterogeneous semiconductor dimeric structure prepared at the hydrosol reported is nanocrystalline, partly lead
Body layer mostly is amorphous or polycrystalline, and because of the directivity of surface plasma enhancing, it is impossible to make
The effect that the nanocrystalline middle generation surface plasma of each Au/ heterogeneous semiconductor dimeric structure strengthens
Should, thus light hydrogen generation efficiency is relatively low.In view of drawbacks described above, creator of the present invention is through long-time
Research and practice finally obtain the present invention, solve above-mentioned problem in science.
Summary of the invention
It is an object of the invention to, it is provided that a kind of efficiently photodissociation that a kind of surface plasma strengthens
The preparation method of water composite catalyst, in order to solve above-mentioned technological deficiency.
For achieving the above object, the technical solution used in the present invention is, first provides a kind of high
Effect photodissociation Aquatic product hydrogen Au/CdX nano-crystal with core-shell structure catalyst, by Au nano-particle as core
With CdX Nano semiconductor as shell form, the size of described Au nano-particle be 20nm～
45nm, it is characterised in that described CdX shell is monocrystalline, crystal formation is the hexagonal phase of wurtzite,
Described CdX shell thickness is 2nm～12nm.
Secondly, it is provided that one prepares above-mentioned efficient photodissociation Aquatic product hydrogen Au/CdX nuclear shell structure nano
The method of brilliant catalyst, comprises the steps:
Step 1: the aqueous sol of Au/Ag nano-crystal with core-shell structure granule is joined polytetrafluoro
In ethylene reaction still, being added thereto to X precursor solution, mix homogeneously, in 60 DEG C～80 DEG C
Baking oven reacts 0.5h～1h, product centrifuge washing will be obtained, be distributed to deionized water and sun
In the aqueous solution of ionic surface active agent, obtain Au/AgX nano-crystal with core-shell structure colloidal sol；
X is sulfur, selenium；
The molar concentration of the aqueous sol of described Au/Ag nano-crystal with core-shell structure granule 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, form solution a；
The volume that described Phosphine ligands adds is 80 μ l～150 μ l.
Step 3: by described solution a in 50 DEG C～80 DEG C of reacting by heating 1～4h, washing is centrifugal,
It is precipitated thing b, described precipitate b is distributed in deionized water, obtains Au/CdX core
The colloidal sol that shell structural nano is brilliant.
Wherein, described sulfur precursor solution preparation method is: by n-dodecyl mereaptan, toluene, depend on
In secondary addition politef reactor, stir, form solution c, sulfur powder is added institute
State in solution c, stir 2min under room temperature, seal, 100 DEG C of baking ovens react 15h, takes
Go out as described sulfur presoma standby；
Described n-dodecyl mereaptan is 1:(2～3 with the volume ratio of described toluene), n-dodecyl mereaptan
With the amount of the material of sulfur powder than for 3:1.
Wherein, described selenium precursor solution preparation method is: by octadecylene, toluene, add successively
Enter in politef reactor, stir, form solution c, titanium dioxide selenium powder is added
In described solution, stir 2min under room temperature, seal, 100 DEG C of baking ovens react 15h,
Take out standby as selenium presoma；
Described octadecylene is 1:(2～3 with the volume ratio of toluene), octadecylene and the thing of sulfur powder
The amount of matter is than for 3:1.
Wherein, the addition volume of described sulfur precursor solution is the Au/Ag core of every 0.075mmol
The aqueous sol of shell structural nano crystalline substance granule adds 50ul～100ul.
Wherein, the addition volume of described selenium precursor solution is the Au/Ag core of every 0.075mmol
The aqueous sol of shell structural nano crystalline substance granule adds 50ul～100ul.
Wherein, described cationic surfactant is cetyl trimethylammonium bromide, and it is water-soluble
The concentration of liquid is 0.025mol/L～0.05mol/L.
Wherein, described cadmium salt soln is Cd (NO3)2·4H2The water of O or methanol solution, its matter
Amount concentration is 0.05g/ml, and addition is 0.6ml～1.2ml.
Wherein, described Phosphine ligands is tributylphosphine, tri octyl phosphine, triphenylphosphine, three pairs of first
In Phenylphosphine, three (o-methoxyphenyl) phosphine, NSC 6513, NSC 5284 extremely
Few one.
Compared with prior art, the invention have the benefit that
1. the present invention provides noble metal Au surface plasma to strengthen and produces efficient photodissociation Aquatic product hydrogen
Au/CdS catalyst, owing to utilizing, there is the CdS quasiconductor shell of different-thickness, especially
Be CdS semiconductor thickness be 4nm～6nm, when the size of metal core is 20nm～45nm, from
And realize by noble metal Au surface plasma bulk effect, CdS semiconductor light is greatly improved and urges
The efficiency of agent photolysis Aquatic product hydrogen, the simple same quality of CdS quantum dot of ratio is high by 1000
More than Bei.
2. the present invention provides the Au/CdX catalyst of efficient photodissociation Aquatic product hydrogen to be directly at aqueous phase
Connecing and prepare, compared with at organic solvent at the material of synthesis, its water solublity is more preferable, is carrying out
The test of Photocatalyzed Hydrogen Production need not turn aqueous phase, thus simplify operation device, shorten the time,
Improve the utilization rate of material simultaneously.
3. the invention provides surface plasma and strengthen the efficient photodissociation Aquatic product hydrogen of generation
The preparation method of Au/CdX catalyst, in a low temperature of described method is in aqueous phase, less than 80 DEG C
Realizing, use synthesis condition gentle, device is simple, and green easy, low cost, in photocatalysis
Field has broad application prospects.
Accompanying drawing explanation
Fig. 1 is the low resolved transmittance Electronic Speculum pattern of Au nano-particle in the Au nano-particle hydrosol
Figure；
Fig. 2 is the low resolved transmittance electricity of the Au/CdS nano-crystal with core-shell structure that embodiment 1 prepares
Mirror figure；
Fig. 3 a, 3b, 3c, 3d are respectively the Au/CdS nuclear shell structure nano that embodiment 2 prepares
Brilliant low resolved transmittance Electronic Speculum, the high-resolution-ration transmission electric-lens figure of Au/CdS nano-crystal with core-shell structure,
The X-ray diffractogram of Au/CdS nano-crystal with core-shell structure, Au/CdS nano-crystal with core-shell structure
The photoelectric respone signal graph of thin film；
Fig. 4 is the low resolved transmittance electricity of the Au/CdS nano-crystal with core-shell structure that embodiment 3 prepares
Mirror figure；
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 the characteristic of the present invention and implement the mode of the present invention, reality is given below
Execute example.
In following example, used sulfur presoma, selenium presoma and gold nano grain are water-soluble
The preparation method of glue is as follows.
(1) preparation method of sulfur precursor solution
Taking 3mL n-dodecyl mereaptan, 7mL toluene, the politef being sequentially added into 20mL is anti-
Answer in still, stir, form solution c, weigh 38.79mg sulfur powder and add above-mentioned solution c
In, stir 2min under room temperature, seal, 100 DEG C of baking ovens react 15h, takes out as sulfur
Presoma is standby.
(2) preparation method of selenium precursor solution
Take 3mL octadecylene, 7mL toluene, be sequentially added into the politef reactor of 20mL
In, stir, form solution d, weigh 134.5mg selenium dioxide and add above-mentioned solution d
In, stir 2min under room temperature, seal, 100 DEG C of baking ovens react 15h, takes out as selenium
Presoma is standby.
(3) preparation method of the gold nano grain hydrosol
Take 1.25mL 0.001mol/L chlorauric acid solution and 2.5mL 0.15mol/L cetyl
Trimethylammonium bromide (CTAB) solution mix homogeneously, adds 0.3mL under vigorous stirring
Sodium borohydride (the NaBH of configuration in 0.01mol/L ice bath4) solution, and continuously stirred 2min
After, left at room temperature 1h, form gold seeds colloidal sol, with deionized water, described gold is planted afterwards
Sub-colloidal sol dilutes 10 times.
Take 6.4mL 0.1mol/L cetyl trimethylammonium bromide (CTAB) solution, 0.8mL
0.01mol/L chlorauric acid solution, 32mL deionized water, it is sequentially added into the round-bottomed flask of 100mL
In, stir, add 3.8mL0.1mol/L ascorbic acid (A.A), stirring reaction
2min, adds 2 above-mentioned gold seeds colloidal sols, and left at room temperature 8-9h is standby.
Referring to shown in Fig. 1, it is the low resolved transmittance Electronic Speculum shape appearance figure of Au nano-particle.
Figure showing, the Au nano-particle of gained is through transmission electron microscope TEM (JEOL JEM
1200EX, 100KV) detect, it is uniformly dispersed, size uniformity, the size of Au nano-particle
For 20nm～45nm.
Embodiment 1
(1) hydrosol of gold nano grain described in 30mL is taken in 50mL centrifuge tube, 7000rpm
Centrifuge washing 10min, reject supernatant, lower floor's gold nano grain is scattered in 10mL again
In 0.025mol/L cetyl trimethylammonium bromide (CTAB) solution, it is sequentially added into wherein
0.7mL 0.1mol/L ascorbic acid (A.A), 0.2mL 0.01mol/L silver nitrate (AgNO3)
Solution, adds the PH of sodium hydroxide (NaOH) regulation solution of 1.0mL 0.1mol/L extremely
10, in 30 DEG C of water-baths, stand 1h, obtain Au/Ag nano-crystal with core-shell structure colloidal sol, it is dense
Degree is 0.005mol/L.
(2) take 15mL above-mentioned Au/Ag nano-crystal with core-shell structure colloidal sol and join the poly-of 20mL
In tetrafluoroethene reactor, it is subsequently adding the precursor solution 60uL of described sulfur, mix homogeneously,
Seal, put into and 80 DEG C of baking ovens react 1h terminate, be then 1:1 deionized water by volume ratio,
7000rpm centrifuge washing 10min, abandoning supernatant, lower floor's material is scattered in 2mL H again2O
With in 10mL 0.05mol/L CTAB solution, obtain Au/Ag2S nano-crystal with core-shell structure molten
Glue.
(3) by above-mentioned Au/Ag2The colloidal sol of S nano-crystal with core-shell structure is transferred to 50mL round bottom and is burnt
In Ping, under magnetic agitation, add 0.8mL Cd (NO3)2·4H2O aqueous solution (0.05g/mL),
Magnetic agitation 2min under room temperature, adds 80uL tributylphosphine (TBP), forms solution a, will
This solution a in 50 DEG C of water-baths magnetic agitation reaction 2h, take out add same volume go from
Sub-water, 7000r centrifuge washing 10min, abandoning supernatant, it is precipitated thing b, will precipitation
Thing b is scattered in a small amount of deionized water again, obtains Au/CdS nano-crystal with core-shell structure
Colloidal sol.Referring to shown in Fig. 2, it is the low resolved transmittance of Au/CdS nano-crystal with core-shell structure
Electronic Speculum shape appearance figure.Figure showing, the CdS shell dimensional thickness of gained is about 2nm～3nm.
Au/CdS prepared by the present invention is directly to prepare at aqueous phase, and in organic solvent
The material of synthesis is compared, and its water solublity is more preferable, need not turn in the test do Photocatalyzed Hydrogen Production
Aqueous phase, thus simplify operation device, shorten the time, improve the utilization rate of material simultaneously.
Embodiment 2
(1) hydrosol of gold nano grain described in 30mL is taken in 50mL centrifuge tube, 7000rpm
Centrifuge washing 10min, reject supernatant, lower floor's gold nano grain is scattered in 10mL again
In 0.025mol/L cetyl trimethylammonium bromide (CTAB) solution, it is sequentially added into wherein
0.7mL 0.1mol/L ascorbic acid (A.A), 0.35mL 0.01mol/L silver nitrate (AgNO3)
Solution, adds the PH of sodium hydroxide (NaOH) regulation solution of 1.0mL 0.1mol/L extremely
10, in 30 DEG C of water-baths, stand 1h, obtain Au/Ag nano-crystal with core-shell structure colloidal sol, it is dense
Degree is 0.005mol/L.
(2) take 15mL above-mentioned Au/Ag nano-crystal with core-shell structure colloidal sol and join the poly-of 20mL
In tetrafluoroethene reactor, it is subsequently adding the precursor solution 80uL of described sulfur, mix homogeneously,
Seal, put into and 80 DEG C of baking ovens react 1h terminate, be then 1:1 deionized water by volume ratio,
7000rpm centrifuge washing 10min, abandoning supernatant, lower floor's material is scattered in 2mL H again2O
With in 10mL 0.05mol/L CTAB solution, obtain Au/Ag2S nano-crystal with core-shell structure molten
Glue.
(3) by above-mentioned Au/Ag2The colloidal sol of S nano-crystal with core-shell structure is transferred to 50mL round bottom and is burnt
In Ping, under magnetic agitation, add 0.8mL Cd (NO3)2·4H2O aqueous solution (0.05g/mL),
Magnetic agitation 2min under room temperature, adds 100uL tributylphosphine (TBP), forms solution a, will
This solution a in 50 DEG C of water-baths magnetic agitation reaction 2h, take out add same volume go from
Sub-water, 7000r centrifuge washing 10min, abandoning supernatant, it is precipitated thing b, will precipitation
Thing b is scattered in a small amount of deionized water again, obtains Au/CdS nano-crystal with core-shell structure
Colloidal sol.
The Au/CdS nano-crystal with core-shell structure of gained is through transmission electron microscope TEM (JEOL JEM
1200EX, 100KV) detection, show that it has good monodispersity (as shown in Figure 3 a),
CdS shell dimensional thickness is about 4nm～6nm.High resolution transmission electron microscopy from Fig. 3 b
HRTEM (FEI Tecnai G2F20S-Twin, 200kV) can draw the shell of CdS
It it is monocrystalline.Detect through powder x-ray diffraction (Bruker D8Advance), reference
JCPDS card CdS be 41-1049, JCPDS card Au be 04-0784, show that it is shell
Layer CdS is the hexagonal phase (as shown in Figure 3 c) of wurtzite, and in Fig. 3 c, the longitudinal axis is that diffraction is strong
Degree, transverse axis is the angle of diffraction, and solid black lines represents the peak shape of Au/CdS nano-crystal with core-shell structure.
Through the CHI650D type electrochemical workstation test of Shanghai Chen Hua Instrument Ltd., use three electricity
Polar body system, working electrode (the FTO electro-conductive glass of sample film forming), Pt is to electrode, calomel electricity
Pole reference electrode, the Na of preparation 0.1mol/L2SO4Electrolyte, as shown in Figure 3 d, has relatively
Good photoelectric respone signal.
This method realizes in a low temperature of less than 80 DEG C, and synthesis condition is gentle, and device is simple,
Green easy, and reduce cost.
Embodiment 3
(1) hydrosol of gold nano grain described in 30mL is taken in 50mL centrifuge tube, 7000rpm
Centrifuge washing 10min, reject supernatant, lower floor's gold nano grain is scattered in 10mL again
In 0.025mol/L cetyl trimethylammonium bromide (CTAB) solution, it is sequentially added into wherein
0.7mL 0.1mol/L ascorbic acid (A.A), 0.5mL 0.01mol/L silver nitrate (AgNO3)
Solution, adds the PH of sodium hydroxide (NaOH) regulation solution of 1.0mL 0.1mol/L extremely
10, in 30 DEG C of water-baths, stand 1h, obtain Au/Ag nano-crystal with core-shell structure colloidal sol, it is dense
Degree is 0.005mol/L.
(2) take 15mL above-mentioned Au/Ag nano-crystal with core-shell structure colloidal sol and join the poly-of 20mL
In tetrafluoroethene reactor, it is subsequently adding the precursor solution 100uL of described sulfur, mix homogeneously,
Seal, put into and 80 DEG C of baking ovens react 1h terminate, be then 1:1 deionized water by volume ratio,
7000rpm centrifuge washing 10min, abandoning supernatant, lower floor's material is scattered in 2mL H again2O
With in 10mL 0.05mol/L CTAB solution, obtain Au/Ag2S nucleocapsid structure nanocrystalline molten
Glue.
(3) by above-mentioned Au/Ag2The colloidal sol of S nano-crystal with core-shell structure is transferred to 50mL round bottom and is burnt
In Ping, under magnetic agitation, add 1.2mL Cd (NO3)2·4H2O aqueous solution (0.05g/mL),
Magnetic agitation 2min under room temperature, adds 150uL tributylphosphine (TBP), forms solution a, will
This solution a in 50 DEG C of water-baths magnetic agitation reaction 2h, take out add same volume go from
Sub-water, 7000r centrifuge washing 10min, abandoning supernatant, it is precipitated thing b, will precipitation
Thing b is scattered in a small amount of deionized water again, obtains Au/CdS nano-crystal with core-shell structure
Colloidal sol.Referring to shown in Fig. 4, it is the low resolved transmittance of Au/CdS nano-crystal with core-shell structure
Electronic Speculum shape appearance figure.Figure showing, the CdS shell dimensional thickness of gained is about 9nm～12nm.
Embodiment 4
(1) hydrosol of gold nano grain described in 30mL is taken in 50mL centrifuge tube, 7000rpm
Centrifuge washing 10min, reject supernatant, lower floor's gold nano grain is scattered in 10mL again
In 0.025mol/L cetyl trimethylammonium bromide (CTAB) solution, it is sequentially added into wherein
0.7mL 0.1mol/L ascorbic acid (A.A), 0.35mL 0.01mol/L silver nitrate (AgNO3)
Solution, adds the PH of sodium hydroxide (NaOH) regulation solution of 1.0mL 0.1mol/L extremely
10, in 30 DEG C of water-baths, stand 1h, obtain Au/Ag nano-crystal with core-shell structure colloidal sol, it is dense
Degree is 0.005mol/L.
(2) take 15mL above-mentioned Au/Ag nano-crystal with core-shell structure colloidal sol and join the poly-of 20mL
In tetrafluoroethene reactor, it is subsequently adding the precursor solution 80uL of described selenium, mix homogeneously,
Seal, put into and 80 DEG C of baking ovens react 1h terminate, be then 1:1 deionized water by volume ratio,
7000rpm centrifuge washing 10min, abandoning supernatant, lower floor's material is scattered in 2mL H again2O
With in 10mL 0.05mol/L CTAB solution, obtain Au/Ag2Se nano-crystal with core-shell structure
Colloidal sol.
(3) by above-mentioned Au/Ag250mL round-bottomed flask transferred to by the colloidal sol of Se nano-crystal with core-shell structure
In, under magnetic agitation, add 1mL Cd (NO3)2·4H2O aqueous solution (0.05g/mL), room
Lower magnetic agitation 2min of temperature, adds 100uL tributylphosphine (TBP), magnetic in 50 DEG C of water-baths
Power stirring reaction 2h, the deionized water of taking-up addition same volume, 7000r centrifuge washing 10min,
Abandoning supernatant, is again scattered in the precipitate obtained in a small amount of deionized water, 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 taken in 50mL centrifuge tube, 7000rpm
Centrifuge washing 10min, reject supernatant, lower floor's gold nano grain is scattered in 10mL again
In 0.025mol/L cetyl trimethylammonium bromide (CTAB) solution, it is sequentially added into wherein
0.7mL 0.1mol/L ascorbic acid (A.A), 0.5mL 0.01mol/L silver nitrate (AgNO3)
Solution, adds the PH of sodium hydroxide (NaOH) regulation solution of 1.0mL 0.1mol/L extremely
10, in 30 DEG C of water-baths, stand 1h, obtain Au/Ag nano-crystal with core-shell structure colloidal sol, it is dense
Degree is 0.005mol/L.
(2) take 15mL above-mentioned Au/Ag nano-crystal with core-shell structure colloidal sol and join the poly-of 20mL
In tetrafluoroethene reactor, it is subsequently adding the precursor solution 50uL of described sulfur, mix homogeneously,
Seal, put into reaction 0.5h in 60 DEG C of baking ovens and terminate, then with the deionized water of same volume,
7000rpm centrifuge washing 10min, abandoning supernatant, lower floor's material is scattered in 2mL H again2O
With in 10mL 0.025mol/L CTAB solution, obtain Au/Ag2S nano-crystal with core-shell structure
Colloidal sol.
(3) by above-mentioned Au/Ag2The colloidal sol of S nano-crystal with core-shell structure is transferred to 50mL round bottom and is burnt
In Ping, under magnetic agitation, add 0.8mL Cd (NO3)2·4H2O aqueous solution (0.05g/mL),
Magnetic agitation 2min under room temperature, adds 80uL tri-n-octyl phosphine (T0P), forms solution a,
By this solution a magnetic agitation reaction 1h in 80 DEG C of water-baths, take out and add going of same volume
Ionized water, 7000r centrifuge washing 10min, abandoning supernatant, it is precipitated thing b, will be heavy
Shallow lake thing b is scattered in a small amount of deionized water again, obtains the nanometer of Au/CdS nucleocapsid structure
Brilliant colloidal sol.
Embodiment 6
(1) hydrosol of gold nano grain described in 30mL is taken in 50mL centrifuge tube, 7000rpm
Centrifuge washing 10min, reject supernatant, lower floor's gold nano grain is scattered in 10mL again
In 0.025mol/L cetyl trimethylammonium bromide (CTAB) solution, it is sequentially added into wherein
0.7mL 0.1mol/L ascorbic acid (A.A), 0.35mL 0.01mol/L silver nitrate (AgNO3)
Solution, adds the PH of sodium hydroxide (NaOH) regulation solution of 1.0mL 0.1mol/L extremely
10, in 30 DEG C of water-baths, stand 1h, obtain Au/Ag nano-crystal with core-shell structure colloidal sol, it is dense
Degree is 0.005mol/L.
(2) take 15mL above-mentioned Au/Ag nano-crystal with core-shell structure colloidal sol and join the poly-of 20mL
In tetrafluoroethene reactor, it is subsequently adding the precursor solution 80uL of described sulfur, mix homogeneously,
Seal, put into reaction 0.8h in 60 DEG C of baking ovens and terminate, then with the deionized water of same volume,
7000rpm centrifuge washing 10min, abandoning supernatant, lower floor's material is scattered in 2mL H again2O
With in 10mL 0.025mol/L CTAB solution, obtain Au/Ag2S nano-crystal with core-shell structure is molten
Glue.
(3) by above-mentioned Au/Ag2The colloidal sol of S nano-crystal with core-shell structure is transferred to 50mL round bottom and is burnt
In Ping, under magnetic agitation, add 0.8mL Cd (NO3)2·4H2O aqueous solution (0.05g/mL),
Magnetic agitation 2min under room temperature, adds 0.025g triphenylphosphine, forms solution a, and this is molten
Liquid a is magnetic agitation reaction 4h in 80 DEG C of water-baths, takes out the deionized water adding same volume,
7000r centrifuge washing 10min, abandoning supernatant, it is precipitated thing b, by precipitate b weight
Newly it is scattered in a small amount of deionized water, obtains the colloidal sol of Au/CdS nano-crystal with core-shell structure.
Above-mentioned Phosphine ligands can also be NSC 6513, NSC 5284, three p-methylphenyls
In phosphine or three (o-methoxyphenyl) phosphine at least one.
Embodiment 7
In order to do performance comparison experiment with organic CdS quantum dot, the present embodiment is organic for preparing
The concrete grammar of CdS quantum dot.
(1) single dispersed nano silver particle colloidal sols is prepared
Taking 10mL oleic acid, 10mL oleyl amine, in there-necked flask, leads to nitrogen bubble, weighs 0.17g
AgNO3It is added thereto, magnetic agitation reaction 5min at 30 DEG C, then is added thereto to 0.08g
Fe(NO3)34H2O, continues logical nitrogen gas stirring reaction 2min, temperature is set as 120 DEG C,
Gradually heating up and magnetic agitation, react 1h after being warmed up to 120 DEG C again, stopped reaction, by single port
Liquid in flask is cooled to room temperature, and addition is the ethanol that its triploid is long-pending, and 5000r is centrifugal to be washed
Wash 8min, be distributed in 80mL toluene, obtain monodispersed Argent grain toluene colloidal sol, and silver
The particle diameter of granule is 4nm～6nm.
(2) organic sulfur precursor solution is prepared
Taking 5mL oleyl amine, 10mL oleic acid, be sequentially added in the round-bottomed flask of 50mL, stirring is all
Even, weigh 64mg sulfur powder and add in above-mentioned mixed liquor, stir 2min under room temperature, at 100 DEG C
In oil bath, magnetic agitation reaction 40min, is added thereto to 15mL toluene, and magnetic agitation is uniform,
It is standby as organic sulfur presoma that temperature is down to room temperature.
(3) 4nm～6nm cadmium sulfide (CdS) quantum dot is prepared
Take the above-mentioned monodispersed Argent grain toluene colloidal sol of 6mL in the round-bottomed flask of 25mL, to
Wherein add organic sulfur presoma described in 3mL, react 1h in 50 DEG C of stirred in water bath, add
30ml ethanol, 5000r centrifuge washing 8min, obtain monodispersed Argentous sulfide. (Ag2S) nanometer
Granule, is re-dispersed in 6mL～10mL toluene.Under strong magnetic agitation, to Ag2S receives
Rice colloidal sol adds 0.2mL oleic acid, 0.1mL oleyl amine and 1mL Cd (NO3)2·4H2O methanol solution
(0.1g/mL), magnetic agitation 1min under room temperature, add 0.1mL TBP, in 50 DEG C of water-baths
Middle magnetic agitation reaction 2h, adds 30ml ethanol, 5000r centrifuge washing 8min, obtains grain
Footpath is 4nm～6nm CdS quantum dot.
Embodiment 8
In order to do performance pair with the Au/CdS nano-crystal with core-shell structure of preparation in organic solvent
Than experiment, the present embodiment is the concrete grammar preparing Au/CdS nano-crystal with core-shell structure.
(1) organic sulfur precursor solution is prepared
Taking 5mL oleyl amine, 10mL oleic acid, be sequentially added in the round-bottomed flask of 50mL, stirring is all
Even, weigh 64mg sulfur powder and add in above-mentioned mixed liquor, stir 2min under room temperature, at 100 DEG C
In oil bath, magnetic agitation reaction 40min, is added thereto to 15mL toluene, and magnetic agitation is uniform,
It is standby as sulfur presoma that temperature is down to room temperature.
(2) nanometer Au granule toluene colloidal sol is prepared
Take 5mL deionized water, 1mL1.0mol/L sodium hydroxide (NaOH), 4mL acetonitrile,
0.72mL oleic acid and 30mg gold chloride (HAuCl4·4H2O) mix homogeneously, adds 10
0.1mmol/L ascorbic acid and 13mL hexamethylene, stirring reaction 10h, add above-mentioned mixed liquor
The ethanol that triploid is long-pending, 5000r centrifuge washing 8min, it is distributed in 80mL toluene.
(3) having of the Au/CdS nano-crystal with core-shell structure that CdS shell thickness is 4nm～6nm is prepared
Machine colloidal sol
Take the toluene colloidal sol of the monodispersed Au prepared in 8mL the present embodiment (2) in 25mL
Round-bottomed flask in, add 0.2mL oleyl amine and 1mL AgNO3Methanol solution (0.05g/mL),
Under 70 DEG C of oil baths, react 8h, add the ethanol of 30ml, 5000r centrifuge washing 8min, divide
It is scattered in 3.6mL toluene, is added thereto to 3mL above-mentioned organic sulfur presoma, stir under room temperature
Reaction 1h, adds 30ml ethanol, 5000r centrifuge washing 8min, is re-dispersed into 6～10mL
In toluene, under magnetic stirring, 0.2mL oleic acid, 0.1mL oleyl amine and 1mL are added
Cd(NO3)2·4H2O methanol solution (0.1g/mL), magnetic agitation 1min under room temperature, add 0.1
ML TBP, in 50 DEG C of water-baths magnetic agitation reaction 2h, add 30ml ethanol, 5000r from
Heart washing 8min, obtains the Au/CdS nucleocapsid structure that CdS shell thickness is 4nm～6nm and receives
The organosol of meter Jing.To the Au/CdS nano-crystal with core-shell structure of organic solvent, by volume
5mg/mL Mercaptamine aqueous solution, at room temperature magnetic agitation reaction is added for 1:2
10min, obtains being dissolved in the Au/CdS nano-crystal with core-shell structure of the hydrosol.
Embodiment 9
To the Au/CdS nuclear shell structure nano prepared by embodiment 1, embodiment 2, embodiment 3
The brilliant hydrosol, embodiment 7 utilizes CdS quantum dot prepared by organic sulfur presoma, embodiment
The organosol of the Au/CdS nano-crystal with core-shell structure of 8 preparations proceeds to aqueous phase becomes Au/CdS core
The shell structural nano crystalline substance hydrosol, dries above-mentioned material, weighs equal in quality, do light respectively and urge
Change the test of H2-producing capacity.
Test process: take appropriate sodium sulfide (Na2S), potassium sulfite (K2SO3), it is dissolved in respectively
In 100mL deionized water, until after being completely dissolved, a addition embodiment 1 gained Au/CdS
Nano-crystal with core-shell structure, a addition embodiment 2 gained Au/CdS nano-crystal with core-shell structure,
The a embodiment 3 gained Au/CdS nano-crystal with core-shell structure that adds, a addition embodiment 7
Gained CdS quantum dot, a addition embodiment 8 gained Au/CdS core-shell nano crystal structure light
Catalyst, stirs 5min respectively, is connected with photolysis water hydrogen response system by reactor, and
Air in system is pumped.Under the 300W xenon lamp of simulated solar irradiation irradiates, utilize standard
H2-producing capacity test platform (photocatalytic hydrogen production by water decomposition on-line analysis system CEL-SPH2N) enters
Row test.In the atmosphere of nitrogen, adopt one with gas chromatograph (SP7800) every 25min
Secondary sample.
The hydrogen output figure (as shown in Figure 5) of above-mentioned photocatalytic hydrogen production by water decomposition, in Fig. 5
Curve a represents that the Au/CdS nano-crystal with core-shell structure photocatalytic hydrogen production by water decomposition of embodiment 1 produces
Discharge curve, curve b represent the Au/CdS nano-crystal with core-shell structure photocatalysis Decomposition of embodiment 2
Water hydrogen manufacturing production curve, curve c represent the Au/CdS nano-crystal with core-shell structure light of embodiment 3
Catalytic decomposition water hydrogen manufacturing production curve, curve d represent the CdS quantum dot photocatalysis of embodiment 7
Hydrogen production by water decomposition production curve, curve e represents Au/CdS nucleocapsid structure prepared by embodiment 8
Nano-crystalline photocatalysis hydrogen production by water decomposition production curve, it can be seen that Au from above-mentioned several curves
Surface plasma bulk effect can make CdS become a kind of efficiency light and produce conjunction in hydrogen catalyst, and aqueous phase
In the Au/CdS nano-crystal with core-shell structure become, CdS shell is 4nm～6nm time decomposition water system
The efficiency of hydrogen is best, and test result reaches 20mmol/g/h～30mmol/g/h.It compares homogeneity
The amounts of hydrogen that the CdS quantum dot of amount produced within the identical time is high more than 1000 times.
The foregoing is only presently preferred embodiments of the present invention, the most illustrative
, and nonrestrictive.Those skilled in the art understands, is limited in the claims in the present invention
Spirit and scope in it can be carried out many changes and modifications, even equivalence, but fall within
In protection scope of the present invention.
Claims (8)
1. the preparation method of an efficient photocatalytic water composite catalyst, it is characterised in that described light
Solve water composite catalyst to be made up of with CdX quasiconductor shell as core Au nano-particle, described
The size of Au nano-particle is 20nm～45nm, and described CdX shell is monocrystalline, and crystal formation is
The hexagonal phase of wurtzite, described CdX shell thickness is 2nm～12nm, wherein, X generation
Table S, Se and S, Se compound；
Preparation method comprises the steps:
Step 1: the aqueous sol of Au/Ag nano-crystal with core-shell structure granule is joined polytetrafluoro
In ethylene reaction still, being added thereto to X precursor solution, mix homogeneously, in 60 DEG C～80 DEG C
Baking oven reacts 0.5h～1h, will obtain product centrifuge washing, be distributed to deionized water and positive from
In the aqueous solution of sub-surface activating agent, obtain Au/Ag2The colloidal sol of X nano-crystal with core-shell structure；
What X was sulfur, selenium or sulfur with selenium element is compound；
The molar concentration of the aqueous sol of described Au/Ag nano-crystal with core-shell structure granule is
0.005mol/L；
Step 2: to described Au/Ag2X nano-crystal with core-shell structure colloidal sol adds cadmium salt soln,
Stir, add Phosphine ligands, form solution a；
The volume that described Phosphine ligands adds is 80 μ L～150 μ L；
Step 3: by described solution a in 50 DEG C～80 DEG C of reacting by heating 1～4h, washing is centrifugal,
It is precipitated thing b, described precipitate b is distributed in deionized water, obtains Au/CdX core
The colloidal sol that shell structural nano is brilliant.
The preparation method of efficient photocatalytic water composite catalyst the most according to claim 1, its
Being characterised by, sulfur precursor solution preparation method is: by n-dodecyl mereaptan, toluene, add successively
Enter in politef reactor, stir, form solution c, sulfur powder is added described solution
In c, stir 2min under room temperature, seal, 100 DEG C of baking ovens react 15h, takes out conduct
Described sulfur presoma is standby；
Described n-dodecyl mereaptan is 1:(2～3 with the volume ratio of described toluene), n-dodecyl mereaptan
With the amount of the material of sulfur powder than for 3:1.
The preparation method of efficient photocatalytic water composite catalyst the most according to claim 1, its
Being characterised by, selenium precursor solution preparation method is: by octadecylene, toluene, be sequentially added into poly-
In tetrafluoroethene reactor, stir, form solution c, titanium dioxide selenium powder is added described molten
In liquid, stir 2min under room temperature, seal, 100 DEG C of baking ovens react 15h, takes out conduct
Selenium presoma is standby；
Described octadecylene is 1:(2～3 with the volume ratio of toluene), octadecylene and described titanium dioxide
The amount of the material of selenium powder is than for 3:1.
The preparation method of efficient photocatalytic water composite catalyst the most according to claim 2,
It is characterized in that, the addition volume of described sulfur precursor solution is the Au/Ag of every 0.075mmol
The aqueous sol of nano-crystal with core-shell structure granule adds 50 μ L～100 μ L.
The preparation method of efficient photocatalytic water composite catalyst the most according to claim 3,
It is characterized in that, the addition volume of described selenium precursor solution is the Au/Ag of every 0.075mmol
The aqueous sol of nano-crystal with core-shell structure granule adds 50 μ L～100 μ L.
The preparation method of efficient photocatalytic water composite catalyst the most according to claim 1, its
Being characterised by, described cationic surfactant is cetyl trimethylammonium bromide, and it is water-soluble
The concentration of liquid is 0.025mol/L～0.05mol/L.
The preparation method of efficient photocatalytic water composite catalyst the most according to claim 1,
It is characterized in that, described cadmium salt soln is Cd (NO3)2·4H2The water of O or methanol solution, its
Mass concentration is 0.05g/mL, and addition is 0.6mL～1.2mL.
The preparation method of efficient photocatalytic water composite catalyst the most according to claim 1, its
Being characterised by, described Phosphine ligands is tributylphosphine, tri octyl phosphine, triphenylphosphine, three pairs of first
In Phenylphosphine, three (o-methoxyphenyl) phosphine, NSC 6513, NSC 5284 extremely
Few one.
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