Background technology
Be a kind of typical semiconductor at inorganic semiconductor material field CdS, the band gap of CdS photocatalyst is 2.4eV, and conduction band current potential (-0.87eVvs THE) and valence band current potential (1.5eV) position can meet the condition of complete photolysis water.Therefore, CdS can improve the utilization ratio of sunlight and become one of semiconductor catalyst received much concern in sulfide systems.
But CdS is not when carrying out finishing and modification, and photolysis aquatic products hydrogen activity is not high, and owing to there is photoetch, CdS there will be photodissociation phenomenon when being subject to long-time illumination, thus causes its activity decrease.
In order to overcome this defect, the impacts on CdS such as different preparation methods, material modification means, light-catalyzed reaction system of many scholar's research.At present, the main method of CdS modification has in doping, load cocatalyst (depositing noble metal, metal oxide-loaded or composite oxide of metal), composite semiconductor, photosensitization sensitization, Morphological control, structure heterojunction, reaction system adds sacrifice agent etc.
In many CdS method of modifying, the correlative study building heterojunction has been a great concern.And for visible ray or and near infrared response p-type semiconductor elemental tellurium (Tellerium), it not only has the physical propertiess such as good electroconductibility, pyroelectricity, piezoelectricity but also also have good application in optics.
Therefore, it is contemplated that, select Cadmium Sulfide base tellurium heterojunction photocatalysis matrix material to be a kind of approach very well to improve its photocatalysis hydrogen production performance.
The CN104176704A of the applicant discloses a kind of mushroom Cadmium Sulfide-tellurium matrix material and its production and use, the preparation method of described matrix material is as follows: tellurium source presoma and cadmium source presoma dissolve in organic solvent by (1), then organosulfur compound and alkaline compound is added, under high pressure confined reaction; (2), after reaction terminates, pressure release to normal pressure, and naturally cools to room temperature, and centrifugation obtains solid, this solid is used water, absolute ethanol washing successively, vacuum-drying, obtains described mushroom Cadmium Sulfide-tellurium matrix material.Described Cadmium Sulfide-tellurium matrix material has good non-uniform topographical, form is controlled, and has excellent hydrogen manufacturing performance and effect, can be used for photolysis water hydrogen field.
In addition, synthesizing heterojunction Cadmium Sulfide base composite photocatalyst material method has a variety of.Such as, Cadmium Sulfide/cadmium selenide Lazer zinc oxide nano-tube array can be obtained by chemical solution method synthesis; Cadmium Sulfide/titanium dioxide nano-rod heterojunction can be obtained by chemical vapour deposition synthesis; Cadmium Sulfide/Graphene composite photocatalyst material is obtained by water heat transfer.
But above synthetic method also exists many defects, such as: chemical Vapor deposition process synthesis condition requires harsh, generally needs heat, pours rare gas element, control base reservoir temperature etc., be not easy to operation, be not suitable for a large amount of production; And the hydrothermal method Reactive Synthesis time is many more than 10 hours, be not easy to a large amount of production, and reaction is carried out being not easy to study mechanism of crystal growth by home position observation crystal growing process in a kettle..
Therefore, based on above-mentioned many defects, how to design a kind of simple, fast, the economic and method of environmental protection prepare there is rule, the matrix material tool of Novel cadmium sulfide/tellurium heterojunction of morphology controllable is of great significance, especially in photocatalysis hydrogen production field, there is significant significance, and this also just the basic place that is accomplished of the present invention and power lean on.
Summary of the invention
In order to overcome many defects that above-mentioned pointed synthesizing cadmium sulfide/tellurium heterojunction method exists, seek a kind of simple, fast, the economic and method of environmental protection prepares the method for Novel cadmium sulfide/tellurium heterojunction composite with rule, morphology controllable, and obtain the matrix material of Novel cadmium sulfide/tellurium heterojunction that this has rule, morphology controllable, and study its application in photocatalysis field, present inventor has performed deep research, after having paid a large amount of creative works, thus complete the present invention.
Specifically, technical scheme of the present invention and content Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material relating to a kind of calabash bunch structure and preparation method thereof and purposes.
More specifically, the present invention relates to following many aspects.
First aspect, the present invention relates to a kind of preparation method of Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material of calabash bunch structure, described method comprises the steps:
S1: sulfur-bearing tellurium source presoma and cadmium source presoma are joined in organic solvent, fully stirs, mix, obtain forerunner's reaction solution;
S2: described forerunner's reaction solution is carried out two-part microwave heating isothermal reaction, thus the Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material obtaining described calabash bunch structure.
In the preparation method of the Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material of described calabash bunch structure of the present invention, in step sl, described sulfur-bearing tellurium source presoma is tellurium diethyl dithiocarbamate (TDEC).
In the preparation method of the Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material of described calabash bunch structure of the present invention, in step sl, described cadmium source presoma is selected from any one or mixture multiple arbitrarily in cadmium diethyl dithiocarbamate (CED), cadmium acetate, dimethyl cadmium, most preferably is cadmium diethyl dithiocarbamate (CED).
In the preparation method of the Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material of described calabash bunch structure of the present invention, in step sl, described organic solvent is C
1-6alcohol, C
2-6any one in glycol, DMF (DMF), dimethyl sulfoxide (DMSO) (DMSO) or N-Methyl pyrrolidone (NMP), is preferably C
2-6glycol, most preferably is ethylene glycol.
In the preparation method of the Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material of described calabash bunch structure of the present invention, in step sl, the mass ratio of described sulfur-bearing tellurium source presoma and described cadmium source presoma is 5:2-4, such as, can be 5:2,5:3 or 4:4, most preferably be 5:3.
In the preparation method of the Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material of described calabash bunch structure of the present invention, in step sl, the consumption of described organic solvent is not particularly limited, such as can be the amount being easy to reaction and/or aftertreatment, those skilled in the art can carry out suitable selection and determine, this is no longer going to repeat them.
In the preparation method of the Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material of described calabash bunch structure of the present invention, described step S2 is specific as follows:
S2-1: under the microwave power of 180-220W, the described forerunner's reaction solution obtained by step S1 is heated to 90 DEG C by room temperature, and keeps 4-6 minute at such a temperature, obtains the first reaction solution;
S2-2: by described first reaction solution under the microwave power of 450-550W, continue to be heated to 155-165 DEG C, and keep 4-6 minute at such a temperature, obtain the second reaction solution;
S2-3: described second reaction solution is naturally cooled to room temperature, and with the centrifugal 3-5 minute of the centrifugal speed of 10000rpm, gained precipitation priority dehydrated alcohol and deionized water are respectively washed 2-3 time, then vacuum-drying, obtains the Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material of described calabash bunch structure.
Wherein, in step S2-1, described forerunner's reaction solution is heated to 90 DEG C by room temperature, and keeps 4-6 minute at such a temperature, most preferably keep 5 minutes.
Wherein, in step S2-2, by the first reaction solution under the microwave power of 500W, continue to be heated to 155-165 DEG C, and keep 4-6 minute at such a temperature, most preferably keep 5 minutes.
The present inventor finds, when adopting preparation method so, Cadmium Sulfide-tellurium heterojunction photocatalysis the matrix material of specific appearance form can be obtained, and when changing some processing parameter wherein as raw material dosage ratio, microwave power, constant temperature time etc., then cannot obtain the optic catalytic composite material of form like this.
Second aspect, the present invention relates to the Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material of the calabash bunch structure obtained by above-mentioned preparation method.
The present inventor finds, the Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material of described calabash bunch structure has excellent photocatalysis performance, thus 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-purposes of tellurium heterojunction photocatalysis matrix material in photodissociation hydrogen manufacturing of described calabash bunch structure.
4th aspect, the present invention relates to a kind of method of photodissociation hydrogen manufacturing, described method is specially: joined by the Cadmium Sulfide of described calabash bunch structure of the present invention-tellurium heterojunction photocatalysis matrix material in the mixture of lactic acid and water composition, irradiate with solar simulator, the spectral filter of below 420nm is used to filter, and with the H of gas chromatographic detection output
2.
Wherein, in described photodissociation hydrogen production process, the volume ratio of lactic acid and water is 1:8-12, such as, can be 1:8,1:9,1:10,1:11 or 1:12.
Wherein, in described photodissociation hydrogen production process, the mass volume ratio of the mixture that the Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material of described calabash bunch structure forms with lactic acid and water is 1:1-3mg/ml, and namely described in every 1mg, matrix material joins in the mixture of 1-3ml.
Contriver finds, Cadmium Sulfide-tellurium heterojunction photocatalysis the matrix material of the concrete specific morphology that the present invention obtains is under illumination condition, water can be prepared hydrogen by photodissociation, there is very excellent hydrogen-producing speed, for photodissociation hydrogen manufacturing provides brand-new and efficient photodissociation matrix material, at industrial circle, there is huge application potential and industrial value.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
Embodiment 1
S1: in appropriate organic solvent ethylene glycol, add tellurium diethyl dithiocarbamate (TDEC) and cadmium diethyl dithiocarbamate (CED) that mass ratio is 5:3, fully stir with magnetic stirring apparatus, mix, obtain forerunner's reaction solution;
S2: described forerunner's reaction solution is carried out two-part microwave heating isothermal reaction, thus obtain Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material, be specially:
S2-1: under the microwave power of 200W, the described forerunner's reaction solution obtained by step S1 is heated to 90 DEG C by room temperature, and keeps 5 minutes at such a temperature, obtains the first reaction solution;
S2-2: by described first reaction solution under the microwave power of 500W, continues to be heated to 160 DEG C, and keeps 5 minutes at such a temperature, obtains the second reaction solution;
S2-3: described second reaction solution is naturally cooled to room temperature, and with the centrifugal speed of 10000rpm centrifugal 4 minutes, gained precipitation priority dehydrated alcohol and deionized water are respectively washed 2-3 time, then vacuum-drying, obtain Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material, by its called after H1.
Embodiment 2-3: the investigation of raw material dosage ratio
Except the tellurium diethyl dithiocarbamate (TDEC) using the ratio of different mass shown in following table 1 in step S1 and cadmium diethyl dithiocarbamate (CED), other operation is all same as embodiment 1, thus having carried out embodiment 2-3, the raw material dosage ratio used and matrix material name see the following form 1.
Matrix material obtained under table 1. different material amount ratio
Embodiment 4-9: the investigation of microwave power
Embodiment 4-5: except using the microwave power shown in following table 2 in step S2-1, other operation is all same as embodiment 1, thus has carried out embodiment 4-5.
Embodiment 6-7: except using the microwave power shown in following table 2 in step S2-2, other operation is all same as embodiment 1, thus has carried out embodiment 6-7.
Specifically see the following form 2.
Matrix material obtained under table 2. different microwave
The investigation of embodiment 10-11: two sections of microwave heating isothermal reactions
Embodiment 10: except dispensing step S2-1, other operation is entirely identical to embodiment 1, the described forerunner's reaction solution obtained by step S1 directly carries out step S2-2 and follow-up operation by room temperature under the microwave power of 500W, also namely not carrying out the first paragraph microwave heating isothermal reaction of step S2-1, is H10 by the material designation obtained.
Embodiment 11: except dispensing step S2-2, other operation is entirely identical to embodiment 1, the described forerunner's reaction solution obtained by step S1 only carries out the process of step S2-1, then the operation of step S2-3 is directly carried out, also namely not carrying out the second segment microwave heating isothermal reaction of step S2-2, is H11 by the material designation obtained.
Embodiment 12-: the investigation of organic solvent in step S1
Respectively the organic solvent in the step S1 of embodiment 1 is replaced with 1 by ethylene glycol, ammediol, 1,4-butyleneglycol, ethanol, propyl carbinol, DMF, DMSO and NMP, other operation is all constant, thus carried out embodiment 12-18 in turn, by gained matrix material called after H12, H13, H14, H15, H16, H17 and H18 in turn.
microscopic sdIBM-2+2q.p.approach
Carried out the microscopic sdIBM-2+2q.p.approach of multiple means of different to the cucurbit string-like Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material of embodiment 1 gained, result is as follows:
1, from the low power scanning electron microscope (SEM) photograph (SEM) of Fig. 1, described Cadmium Sulfide-tellurium matrix material pattern is homogeneous, novel structure, for the different knot matter of cucurbit string-like, the external diameter height of these cucurbit string-like different knot matter is identical, length is 4.8-5.4 μm, nanometer rod is wide is 300-320nm, and nanometer ball external diameter is 420-520nm.
2, from the transmission electron microscope picture (b) (TEM) of Fig. 2, sugarcoated haws on a stick string-like heterojunction is had in figure, and club shaped structure outline on sugarcoated haws on a stick string-like heterojunction is comparatively dark, inside center is brighter, and this illustrates that the club shaped structure synthesized is hollow tubular structure.
Fig. 2 (c), Fig. 2 (d) are the high resolution transmission electron microscopy image of circle and Blocked portion in Fig. 2 (b) respectively.Can see gem-pure lattice fringe from Fig. 2 (c), and the width of each lattice fringe is about the same, by measuring, the width of described lattice fringe is 0.32nm, and this is consistent with (011) crystal face of six side's phase telluriums.
In Fig. 2 (c), the illustration in the upper right corner is selected area electron diffraction (SAED) style of sample, clearly can find out that from figure diffractogram arranges orderly point, club shaped structure on the sample that this explanation synthesizes is monocrystalline but not polycrystalline, and can find (100), (011) and (012) crystal face of six side's phase telluriums.
Also can see gem-pure lattice fringe in Fig. 2 (d), and the width of each lattice fringe is almost identical, by measuring, show that the width of lattice fringe is 0.36nm, this is consistent with (100) crystal face of six side's phase Cadmium Sulfides
3, shown by Fig. 3 power spectrum (EDX) test: containing Cd, S, Te tri-kinds of elements in sample, illustrate that the cucurbit string-like matrix material of preparation contains Cd, S, Te tri-kinds of elements (wherein Cu element comes from the Cu net specimen holder of test needed for sample).
4, from the X-ray diffractogram (XRD) of Fig. 4, take CED as cadmium source and be that tellurium source obtains in the XRD diffraction pattern of sample with TDEC, diffraction peak with solid black square frame mark is the diffraction peak of Te, and the diffraction peak of pentagram mark is the diffraction peak of CdS (002) in CdS-Te heterojunction composite sample.
Therefore, by these diffraction peaks of comparison, known the present invention has successfully synthesized CdS-Te heterojunction composite by specific preparation method.
5, Fig. 5 (a)-(c) is respectively the SEM figure of the H3 of the H2 of embodiment 2, the H1 of embodiment 1 and embodiment 3, as can be seen here, the form of TDCE/CED mass ratio on final product as raw material has conclusive impact, only have when TDCE/CED is 5:3, the cucurbit string-like that form is best could be produced.
6, the prolongation with total holding time (the hold-time sum in first paragraph (step S2-1) and second segment (step S2-2)) when Fig. 6 is two-part microwave heating isothermal reaction in the embodiment of the present invention 1 and the process of growth of the cucurbit string-like Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material obtained, the total time wherein corresponding to each figure is as follows: (a): 6 minutes; (b): 6.25 minutes; (c): 6.5 minutes; (d): 6.75 minutes; (e): 7 minutes; (f): 10 minutes.
As seen from Figure 6, when the total holding time of described two sections of microwave heating isothermal reactions reaches 10 minutes, generate the cucurbit string-like Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material of form rule.
7, Fig. 7 is cucurbit string-like Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material obtained by the embodiment of the present invention 1 and bright sulfur cadmium (CdS), Cadmium Sulfide/tellurium simple physical mixture (CdS/Te) irradiation time in photolysis water hydrogen-hydrogen output relativity figure.
As can be seen from the figure the photocatalysis hydrogen production performance of CdS/Te is the most weak, and hydrogen-producing speed is 25.979 μm of ol/g
cdS, and the cucurbit string-like Cadmium Sulfide of the embodiment of the present invention 1-tellurium heterojunction photocatalysis matrix material has best H2-producing capacity: hydrogen-producing speed is 158.70 μm of ol/g
cdS, this is than pure CdS hydrogen-producing speed (81.94 μm of ol/g
cdS) exceed about one times, especially far above Cadmium Sulfide/tellurium simple physical mixture (CdS/Te).
Thus proof is known clearly, cucurbit string-like Cadmium Sulfide of the present invention-tellurium heterojunction photocatalysis matrix material has excellent photodissociation catalyzing manufacturing of hydrogen performance, can be applicable to photodissociation hydrogen producing technology field.
the sign of other embodiment gained matrix material
A, find the sign of H4-H9, the form of H4-H5 and H7-H8 is cucurbit string-like (but systematicness will be worse than H1); And the form of H6 and H9 cannot find out it is cucurbit string-like.
Demonstrate thus in step S2-1, microwave power most preferably is 200W, and in step S2-2, microwave power most preferably is 500W.
B, find the sign of H10-H11, H10-H11 fails the cucurbit string-like of formation rule, but have no rule can say, not of uniform size, different in size bar-shaped.Demonstrate thus and adopt two-part microwave heating isothermal reaction like this for the essential and necessity forming final cucurbit String structure.
C, find the sign of H12-H18, the matrix material of gained is still cucurbit String structure, but its performance has reduction to a certain degree than H1, specifically sees hydrogen manufacturing performance test subsequently.
photolysis water hydrogen performance test
1, the cucurbit string-like Cadmium Sulfide of embodiment 1 gained-tellurium heterojunction photocatalysis matrix material is used for photolysis water hydrogen, concrete treatment process is:
50mg sample is joined in the mixture of 8ml lactic acid and 72ml water composition, irradiate with solar simulator, use the spectral filter of below 420nm to filter, and with the H of gas chromatographic detection output
2.
When specimen in use is respectively the embodiment of the present invention 1 obtained cucurbit string-like Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material, commercially available bright sulfur cadmium (CdS) and Cadmium Sulfide/tellurium simple physical mixture (CdS/Te), the relation between irradiation time and hydrogen output is shown in accompanying drawing 7.The photocatalysis hydrogen production performance of CdS/Te is the most weak as can be seen from the figure, and hydrogen-producing speed is only 25.979 μm of ol/g
cdS, and the cucurbit string-like Cadmium Sulfide of the embodiment of the present invention 1-tellurium heterojunction photocatalysis matrix material has best H2-producing capacity: hydrogen-producing speed is 158.70 μm of ol/g
cdS, this is than pure CdS hydrogen-producing speed (81.94 μm of ol/g
cdS) exceed about one times, especially far above Cadmium Sulfide/tellurium simple physical mixture (CdS/Te).
Demonstrate cucurbit string-like Cadmium Sulfide of the present invention-tellurium heterojunction photocatalysis matrix material thus to there is excellent photolysis water hydrogen performance, can be used for photolysis water hydrogen field.
2, according to photolysis water hydrogen method same as described above, test H12-H18, concrete hydrogen-producing speed sees the following form, and for the ease of comparing, will list in the lump the hydrogen-producing speed of H1 of embodiment 1.
As can be seen here, although the pattern of H12-H18 is still cucurbit string-like, its photodissociation hydrogen manufacturing performance is weaker than H1.But then, also can find out, with other solvent phase ratio, the matrix material obtained by glycolic solvents has better properties (see H1, H12-H13), and wherein, ethylene glycol has best performance as the matrix material obtained during organic solvent.
In sum, as can be seen from above-mentioned all embodiments, described preparation method of the present invention is by the synergistic combination of specific processing step and processing parameter etc. and coordinative role, thus obtain the cucurbit string-like Cadmium Sulfide-tellurium heterojunction photocatalysis matrix material with unique morphology, and it has good photolysis water hydrogen performance.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.