A kind of calabash string structure cadmium sulfide-tellurium heterojunction photocatalysis composite and preparation side
Method and purposes
Technical field
The invention provides heterojunction composite of a kind of n-type semiconductor and p-type semiconductor and preparation method thereof with
On the way, more specifically, there is provided a kind of calabash string structure cadmium sulfide-tellurium heterojunction photocatalysis composite and preparation method and use
On the way, inorganic semiconductor material field is belonged to.
Background technology
In inorganic semiconductor material field, CdS is a kind of typical semiconductor, and the band gap of CdS photocatalysts is 2.4eV, conduction band
Current potential (- 0.87eVvs THE) and valence band current potential (1.5eV) position disclosure satisfy that the condition of complete photolysis water.Therefore, CdS can
Become one of semiconductor catalyst received much concern in sulfide systems to improve the utilization rate of sunlight.
But, CdS do not carry out surface modification and it is modified when, photolysis Aquatic product hydrogen activity is not high, and due to depositing
In photoetch, CdS occurs photodissociation phenomenon when by long-time illumination, so as to cause its activity decrease.
In order to overcome the defect, many scholar's research different preparation methoies, material modification means, light-catalyzed reaction system
The impact to CdS such as system.At present, CdS modified main method has doping, load cocatalyst (depositing noble metal, carried metal
Oxide or composite oxide of metal), composite semiconductor, photosensitization sensitization, Morphological control, construction hetero-junctions, in reaction system
Addition sacrifice agent etc..
In many CdS method of modifying, the correlational study for building hetero-junctions has been a great concern.And to visible ray
Or and near-infrared response p-type semiconductor elemental tellurium (Tellerium) for, its not only have good electric conductivity, pyroelectricity,
The physical propertys such as piezoelectricity and also there is preferably application in optics aspect.
Thus, it is contemplated that improving its photocatalysis hydrogen production from sulfuration cadmio tellurium heterojunction photocatalysis composite
It can be a kind of fine approach.
The CN104176704A of the applicant disclose a kind of mushroom cadmium sulfide-tellurium composite and preparation method thereof and
Purposes, the preparation method of the composite is as follows:(1) tellurium source presoma and cadmium source presoma are dissolved in organic solvent,
Organosulfur compound and alkaline compound are subsequently adding, under high pressure confined reaction;(2) reaction terminate after, pressure release to normal pressure,
And room temperature is naturally cooled to, centrifugation obtains solid, the solid is used successively water, absolute ethanol washing, vacuum drying obtain
To the mushroom cadmium sulfide-tellurium composite.The cadmium sulfide-tellurium composite has the good non-uniform topographical, form can
Control, and with excellent hydrogen manufacturing performance and effect, can be used for photolysis water hydrogen field.
Additionally, synthesis hetero-junctions sulfuration cadmio composite photocatalyst material method has many kinds.For example, cadmium sulfide/cadmium selenide
Lazer's zinc oxide nano-tube array can be obtained by chemical solution method synthesis;Cadmium sulfide/titanium dioxide nano-rod hetero-junctions
Can be obtained by chemical vapor deposition synthesis;Cadmium sulfide/Graphene composite photocatalyst material is obtained by hydro-thermal method synthesis.
But also there is many defects in the synthetic method of the above, such as:The requirement of chemical vapour deposition technique synthesis condition is harsh, and one
As need high-temperature heating, pour noble gases, control base reservoir temperature etc. is not easy to operation, is not suitable for a large amount of productions;And hydro-thermal method
It is more more than 10 hours to be synthesized the time, is not easy to a large amount of productions, and reaction carry out in a kettle. cannot home position observation
Crystal growing process is not easy to study mechanism of crystal growth.
Therefore, based on above-mentioned many defects, how to design a kind of simple, quick, method cost-effective and environmentally friendly to prepare
Composite tool with rule, the Novel cadmium sulfide/tellurium hetero-junctions of morphology controllable is of great significance, and especially urges in light
Change and have in hydrogen preparation field significant significance, and this basis that also exactly the present invention is accomplished is located and power is leaned on.
The content of the invention
For many defects for overcoming synthesizing cadmium sulfide/tellurium hetero-junctions method as indicated above to exist, seek a kind of letter
Single, quick, method cost-effective and environmentally friendly has rule, the Novel cadmium sulfide/tellurium heterojunction composite of morphology controllable to prepare
Method, and obtain this have rule, the composite of the Novel cadmium sulfide/tellurium hetero-junctions of morphology controllable, and study its
Application in photocatalysis field, present inventor has performed in-depth study, after substantial amounts of creative work has been paid, so as to complete
Into the present invention.
Specifically, technical scheme and content are related to a kind of cadmium sulfide of calabash string structure-tellurium hetero-junctions light
Catalytic composite materials and preparation method thereof and purposes.
More particularly it relates to following many aspects.
One side, the present invention relates to a kind of cadmium sulfide of calabash string structure-tellurium heterojunction photocatalysis composite
Preparation method, methods described comprises the steps:
S1:Sulfur-bearing tellurium source presoma and cadmium source presoma are added in organic solvent, are sufficiently stirred for, mix homogeneously is obtained
To forerunner's reactant liquor;
S2:Forerunner's reactant liquor is carried out into two-part microwave heating isothermal reaction, so as to obtain the calabash string structure
Cadmium sulfide-tellurium heterojunction photocatalysis composite.
In the preparation method of the cadmium sulfide-tellurium heterojunction photocatalysis composite of the calabash string structure of the present invention,
In step sl, the sulfur-bearing tellurium source presoma is tellurium diethyl dithiocarbamate (TDEC).
In the preparation method of the cadmium sulfide-tellurium heterojunction photocatalysis composite of the calabash string structure of the present invention,
In step sl, cadmium source presoma is in cadmium diethyl dithiocarbamate (CED), cadmium acetate, dimethyl cadmium
Any one or arbitrarily various mixture, most preferably cadmium diethyl dithiocarbamate (CED).
In the preparation method of the cadmium sulfide-tellurium heterojunction photocatalysis composite of the calabash string structure of the present invention,
In step sl, the organic solvent is C1-6Alcohol, C2-6Glycol, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO)
Or any one in N-Methyl pyrrolidone (NMP), preferably C2-6Glycol, most preferably ethylene glycol.
In the preparation method of the cadmium sulfide-tellurium heterojunction photocatalysis composite of the calabash string structure of the present invention,
In step sl, the sulfur-bearing tellurium source presoma and the mass ratio of cadmium source presoma are 5:2-4, for example, can be 5:2、5:3
Or 4:4, most preferably 5:3.
In the preparation method of the cadmium sulfide-tellurium heterojunction photocatalysis composite of the calabash string structure of the present invention,
In step sl, the consumption of the organic solvent is not particularly limited, for example, can be to be easy to reaction and/or post processing
Amount, those skilled in the art can carry out suitably selecting and determining that this is no longer going to repeat them.
In the preparation method of the cadmium sulfide-tellurium heterojunction photocatalysis composite of the calabash string structure of the present invention,
Step S2 is specific as follows:
S2-1:Under the microwave power of 180-220W, forerunner's reactant liquor that step S1 is obtained is heated to by room temperature
90 DEG C, and kept for 4-6 minutes at such a temperature, obtain the first reactant liquor;
S2-2:By first reactant liquor under the microwave power of 450-550W, continue to be heated to 155-165 DEG C, and
Kept for 4-6 minutes at this temperature, obtain the second reactant liquor;
S2-3:Second reactant liquor is naturally cooled to into room temperature, and with 3-5 point of the centrifugal speed centrifugation of 10000rpm
Clock, precipitates gained priority dehydrated alcohol and deionized water is respectively washed 2-3 time, is then vacuum dried, and obtains final product the calabash bunch
The cadmium sulfide of structure-tellurium heterojunction photocatalysis composite.
Wherein, in step S2-1, forerunner's reactant liquor is heated to into 90 DEG C by room temperature, and keeps 4- at such a temperature
6 minutes, most preferably kept for 5 minutes.
Wherein, in step S2-2, by the first reactant liquor under the microwave power of 500W, continue to be heated to 155-165 DEG C,
And kept for 4-6 minutes at such a temperature, most preferably kept for 5 minutes.
The inventors discovered that, when using preparation method so, the cadmium sulfide-tellurium that can obtain specific appearance form is different
Matter ties optic catalytic composite material, and when change some technological parameters such as raw material dosage ratio, microwave power, constant temperature time etc. therein
When, then cannot obtain the optic catalytic composite material of such form.
Second aspect the, the present invention relates to cadmium sulfide-tellurium of the calabash string structure obtained by above-mentioned preparation method is heterogeneous
Knot optic catalytic composite material.
The inventors discovered that, the cadmium sulfide-tellurium heterojunction photocatalysis composite of the calabash string structure has excellent
Photocatalysis performance, so as to can be applicable to photodissociation hydrogen producing technology field, has a good application prospect and industrialization potential.
Therefore, the 3rd aspect, the present invention relates to the cadmium sulfide of the calabash string structure-tellurium heterojunction photocatalysis composite wood
Purposes of the material in photodissociation hydrogen manufacturing.
4th aspect, the present invention relates to a kind of method of photodissociation hydrogen manufacturing, methods described is specially:By described in the present invention
The cadmium sulfide of calabash string structure-tellurium heterojunction photocatalysis composite is added in the mixture of lactic acid and water composition, uses the sun
Optical simulator irradiates, and is filtered using the optical filter of below 420nm, and with the H of gas chromatographic detection output2。
Wherein, in the photodissociation hydrogen production process, lactic acid is 1 with the volume ratio of water:8-12, for example, can be 1:8、1:9、1:
10、1:11 or 1:12.
Wherein, in the photodissociation hydrogen production process, the cadmium sulfide-tellurium heterojunction photocatalysis composite wood of the calabash string structure
The mass volume ratio of the mixture that material is constituted with lactic acid and water is 1:1-3mg/ml, i.e., composite described in per 1mg is added to
In the mixture of 1-3ml.
Inventor's discovery, the cadmium sulfide-tellurium heterojunction photocatalysis composite of the concrete specific morphology that the present invention is obtained
Under illumination condition, water can be prepared hydrogen by photodissociation, be photodissociation hydrogen manufacturing with very excellent hydrogen-producing speed
There is provided brand-new and efficient photodissociation composite, there is huge application potential and industrial value in industrial circle.
Description of the drawings
Fig. 1 is the low power scanning electron microscope of the cadmium sulfide-tellurium heterojunction photocatalysis composite obtained by the embodiment of the present invention 1
Figure (SEM).
Fig. 2 is the transmission electron microscope picture of the cadmium sulfide-tellurium heterojunction photocatalysis composite obtained by the embodiment of the present invention 1
(TEM) and local high resolution transmission electron microscopy (i.e. Fig. 2 (c) and Fig. 2 (d)).
Fig. 3 is the energy spectrum diagram (EDX) of the cadmium sulfide-tellurium heterojunction photocatalysis composite obtained by the embodiment of the present invention 1.
Fig. 4 is the X-ray diffractogram of the cadmium sulfide-tellurium heterojunction photocatalysis composite obtained by the embodiment of the present invention 1
(XRD)。
Fig. 5 be use different raw material dosages than when resulting different samples SEM figures.
When Fig. 6 is the two-part microwave heating isothermal reaction in the embodiment of the present invention 1 with total holding time (i.e. first paragraph
Retention time sum in (step S2-1) and second segment (step S2-2)) prolongation obtained from calabash string-like cadmium sulfide-tellurium
The growth course of heterojunction photocatalysis composite.
Fig. 7 is calabash string-like cadmium sulfide-tellurium heterojunction photocatalysis composite and the bright sulfur obtained by the embodiment of the present invention 1
Irradiation time-the hydrogen output pair of the simple physical mixture (CdS/Te) in photolysis water hydrogen of cadmium (CdS), cadmium sulfide/tellurium
Compare graph of a relation.
Specific embodiment
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, not constitutes any type of any restriction to the real protection scope of the present invention, more non-to incite somebody to action
Protection scope of the present invention is confined to this.
Embodiment 1
S1:To in appropriate organic solvent ethylene glycol, mass ratio is added to be 5:3 tellurium diethyl dithiocarbamate
(TDEC) and cadmium diethyl dithiocarbamate (CED), it is sufficiently stirred for magnetic stirring apparatuss, mix homogeneously obtains forerunner anti-
Answer liquid;
S2:Forerunner's reactant liquor is carried out into two-part microwave heating isothermal reaction, so as to obtain cadmium sulfide-tellurium hetero-junctions
Optic catalytic composite material, specially:
S2-1:Under the microwave power of 200W, forerunner's reactant liquor that step S1 is obtained is heated to into 90 DEG C by room temperature,
And kept for 5 minutes at such a temperature, obtain the first reactant liquor;
S2-2:By first reactant liquor under the microwave power of 500W, continue to be heated to 160 DEG C, and at such a temperature
Kept for 5 minutes, obtain the second reactant liquor;
S2-3:Second reactant liquor is naturally cooled to into room temperature, and is centrifuged 4 minutes with the centrifugal speed of 10000rpm,
Gained is precipitated into priority dehydrated alcohol and deionized water is respectively washed 2-3 time, be then vacuum dried, obtain final product cadmium sulfide-tellurium heterogeneous
Knot optic catalytic composite material, is named as H1.
Embodiment 2-3:The investigation of raw material dosage ratio
Except the tellurium diethyl dithiocarbamate (TDEC) and diethyl of the ratio of different quality shown in table 1 below used in step S1
Outward, other operations are homogeneously same as embodiment 1 to base aminodithioformic acid cadmium (CED), so as to be carried out a 2-3, are used
Raw material dosage ratio and composite name see the table below 1.
Obtained composite under the different material amount ratio of table 1.
Embodiment 4-9:The investigation of microwave power
Embodiment 4-5:In addition to the microwave power used in step S2-1 shown in table 2 below, other operations are homogeneously same as implementing
Example 1, so as to be carried out a 4-5.
Embodiment 6-7:In addition to the microwave power used in step S2-2 shown in table 2 below, other operations are homogeneously same as implementing
Example 1, so as to be carried out a 6-7.
It is specifically shown in table 2 below.
Obtained composite under the different microwave of table 2.
Embodiment 10-11:The investigation of two sections of microwave heating isothermal reactions
Embodiment 10:In addition to step S2-1 is dispensed, other operations are entirely identical to embodiment 1, will step S1 obtain
Forerunner's reactant liquor step S2-2 and follow-up operation are directly carried out under the microwave power of 500W by room temperature, namely do not have
The first paragraph microwave heating isothermal reaction of step S2-1 is carried out, is H10 by the material designation for obtaining.
Embodiment 11:In addition to step S2-2 is dispensed, other operations are entirely identical to embodiment 1, will step S1 obtain
Forerunner's reactant liquor only carry out the process of step S2-1, then directly carry out the operation of step S2-3, namely do not enter
The second segment microwave heating isothermal reaction of row step S2-2, is H11 by the material designation for obtaining.
Embodiment 12-:The investigation of organic solvent in step S1
Respectively by the organic solvent in S1 the step of embodiment 1 by ethylene glycol replace with 1,3- Propylene Glycol, 1,4- butanediols,
Ethanol, n-butyl alcohol, DMF, DMSO and NMP, other operations are constant, so as to sequentially be carried out a 12-18, gained are combined
Material is sequentially named as H12, H13, H14, H15, H16, H17 and H18.
Microscopic sdIBM-2+2q.p.approach
Multiple different handss have been carried out to the calabash string-like cadmium sulfide-tellurium heterojunction photocatalysis composite of the gained of embodiment 1
The microscopic sdIBM-2+2q.p.approach of section, it is as a result as follows:
1st, from the low power scanning electron microscope (SEM) photograph (SEM) of Fig. 1, the cadmium sulfide-tellurium composite pattern is homogeneous, structure is new
Grain husk, is the different knot matter of calabash string-like, and the external diameter of the different knot matter of these calabash string-like is highly identical, and length is 4.8-5.4 μm, nanometer rods width
For 300-320nm, nanosphere external diameter is 420-520nm.
2nd, from the transmission electron microscope picture (b) (TEM) of Fig. 2, there are sugarcoated haws on a stick string-like hetero-junctions, and sugarcoated haws on a stick string-like in figure
Club shaped structure outline on hetero-junctions is dark, and inside center is brighter, and the club shaped structure that this explanation synthesizes is hollow tubulose
Structure.
Fig. 2 (c), Fig. 2 (d) are respectively the high resolution transmission electron microscopy pictures of circle and Blocked portion in Fig. 2 (b).
Gem-pure lattice fringe can be seen from Fig. 2 (c), and the width of each lattice fringe is about the same, by measurement,
The width of the lattice fringe is 0.32nm, and this is consistent with (011) crystal face of hexagonal phase tellurium.
The illustration in the upper right corner is SEAD (SAED) style of sample in Fig. 2 (c), can be clearly from figure
Go out the point that diffraction pattern is aligned orderly, the club shaped structure on this sample for synthesizing of explanation is monocrystalline and non-polycrystalline, and can be with
Find (100), (011) and (012) crystal face of hexagonal phase tellurium.
It can also be seen that gem-pure lattice fringe in Fig. 2 (d), and the width of each lattice fringe is almost identical,
By measurement, the width for drawing lattice fringe is 0.36nm, and this is consistent with (100) crystal face of hexagonal phase cadmium sulfide
3rd, shown by Fig. 3 power spectrums (EDX) test:Contain tri- kinds of elements of Cd, S, Te in sample, illustrate the calabash string-like for preparing
Composite contains tri- kinds of elements of Cd, S, Te (wherein Cu elements come from the Cu net specimen holders needed for test sample).
4th, from the X-ray diffractogram (XRD) of Fig. 4, the XRD of sample is obtained as tellurium source as cadmium source and with TDEC with CED
In diffraction pattern, the diffraction maximum with solid black square frame labelling is the diffraction maximum of Te, and the diffraction maximum of five-pointed star labelling is CdS-Te
The diffraction maximum of CdS (002) in heterojunction composite sample.
Therefore, by comparing these diffraction maximums, it is known that the present invention is successfully synthesized by specific preparation method
CdS-Te heterojunction composites.
5th, Fig. 5 (a)-(c) is respectively the SEM figures of the H3 of the H2 of embodiment 2, the H1 of embodiment 1 and embodiment 3, thus may be used
See there is conclusive impact to the form of final product as the TDCE/CED mass ratioes of raw material, only when TDCE/CED is
5:When 3, the best calabash string-like of form could be produced.
6th, when Fig. 6 is the two-part microwave heating isothermal reaction in the embodiment of the present invention 1 with total holding time (i.e. first
Section (step S2-1) and second segment (step S2-2) in retention time sum) prolongation obtained from calabash string-like cadmium sulfide-
The growth course of tellurium heterojunction photocatalysis composite, the wherein total time corresponding to each figure are as follows:(a):6 minutes;(b):
6.25 minute;(c):6.5 minute;(d):6.75 minute;(e):7 minutes;(f):10 minutes.
As seen from Figure 6, when the total holding time of two sections of microwave heating isothermal reactions reaches 10 minutes, generate
The calabash string-like cadmium sulfide-tellurium heterojunction photocatalysis composite of form rule.
7th, Fig. 7 be calabash string-like cadmium sulfide-tellurium heterojunction photocatalysis composite obtained by the embodiment of the present invention 1 with it is pure
Cadmium sulfide (CdS), cadmium sulfide/irradiation time-hydrogen output pair of tellurium simple physical mixture (CdS/Te) in photolysis water hydrogen
Compare graph of a relation.
As can be seen from the figure the photocatalysis hydrogen production performance of CdS/Te is most weak, and hydrogen-producing speed is 25.979 μm of ol/gCdS, and
The calabash string-like cadmium sulfide of the embodiment of the present invention 1-tellurium heterojunction photocatalysis composite has best H2-producing capacity:Produce hydrogen speed
Rate is 158.70 μm of ol/gCdS, this is than pure CdS hydrogen-producing speeds (81.94 μm of ol/gCdS) about one times is higher by, even more far above sulfuration
Cadmium/tellurium simple physical mixture (CdS/Te).
So as to the calabash string-like cadmium sulfide-tellurium heterojunction photocatalysis composite of the present invention that proves to know clearly has excellent light
Solution catalyzing manufacturing of hydrogen performance, can be applicable to photodissociation hydrogen producing technology field.
The sign of other embodiments gained composite
A, the sign to H4-H9 find that the form of H4-H5 and H7-H8 is calabash string-like (but systematicness is less than H1);
And the form of H6 and H9 cannot be seen to be calabash string-like.
Thus demonstrate in step S2-1, microwave power is most preferably 200W, and in step S2-2, microwave power is most
Preferably 500W.
B, the sign of H10-H11 is found, H10-H11 fails the calabash string-like of formation rule, but have no rule can say,
Not of uniform size, different in size is bar-shaped.Thus demonstrate final for being formed using the isothermal reaction of such two-part microwave heating
The essential and necessity of calabash String structure.
C, the sign to H12-H18 find that the composite of gained is still calabash String structure, but its performance has than H1
A certain degree of reduction, subsequent hydrogen manufacturing performance test is specifically shown in.
Photolysis water hydrogen performance test
1st, the calabash string-like cadmium sulfide-tellurium heterojunction photocatalysis composite of the gained of embodiment 1 is used for into photolysis water hydrogen,
Specifically processing method is:
50mg samples are added in the mixture of 8ml lactic acid and 72ml water composition, are irradiated with solar simulator, used
The optical filter of below 420nm is filtered, and with the H of gas chromatographic detection output2。
It is combined when specimen in use is respectively calabash string-like cadmium sulfide-tellurium heterojunction photocatalysis obtained in the embodiment of the present invention 1
When material, commercially available bright sulfur cadmium (CdS) and cadmium sulfide/tellurium simple physical mixture (CdS/Te), irradiation time and hydrogen output
Between relation see accompanying drawing 7.As can be seen from the figure the photocatalysis hydrogen production performance of CdS/Te is most weak, and hydrogen-producing speed is only
25.979μmol/gCdS, and the calabash string-like cadmium sulfide of the embodiment of the present invention 1-tellurium heterojunction photocatalysis composite have it is best
H2-producing capacity:Hydrogen-producing speed is 158.70 μm of ol/gCdS, this is than pure CdS hydrogen-producing speeds (81.94 μm of ol/gCdS) it is higher by about one
Times, even more far above cadmium sulfide/tellurium simple physical mixture (CdS/Te).
Thus demonstrate calabash string-like cadmium sulfide of the present invention-tellurium heterojunction photocatalysis composite and there is excellent light
Solution water hydrogen manufacturing performance, can be used for photolysis water hydrogen field.
2nd, according to photolysis water hydrogen method same as described above, H12-H18 is tested, concrete hydrogen-producing speed sees below
Table, for the ease of comparing, will the hydrogen-producing speed of H1 of embodiment 1 list in the lump.
As can be seen here, although the pattern of H12-H18 is still calabash string-like, but its photodissociation hydrogen manufacturing performance is weaker than H1.But it is another
On the one hand, it is also possible to find out, compared with other solvents, the composite obtained by glycolic solvents have better performance (see
H1, H12-H13), wherein, the composite obtained when ethylene glycol is as organic solvent has best performance.
In sum, by above-mentioned all embodiments the preparation method of the present invention is can be seen that by specific technique
The synergistic combination and coordinative role of step and technological parameter etc., so as to obtained the calabash string-like cadmium sulfide with unique morphology-
Tellurium heterojunction photocatalysis composite, and it has good photolysis water hydrogen performance.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit the protection model of the present invention
Enclose.Additionally, it will also be appreciated that after the technology contents for having read the present invention, those skilled in the art can make each to the present invention
Plant and change, change and/or modification, all these equivalent form of value equally falls within the guarantor that the application appended claims are limited
Within the scope of shield.