CN101866960B - Method for preparing CdS-Bi2S3 composite nanocrystalline by utilizing partial cation exchange reaction - Google Patents
Method for preparing CdS-Bi2S3 composite nanocrystalline by utilizing partial cation exchange reaction Download PDFInfo
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Abstract
The invention relates to a method for preparing a CdS-Bi2S3 composite nanocrystalline by utilizing a partial cation exchange reaction, which is characterized by comprising: firstly, a flower-like SdS nanocrystalline is synthesized by a hydrothermal method; and then, the flower-like SdS nanocrystalline and a newly formed Bi2S3 nanocrystalline are combined by means of the partial cation exchange reaction so as to integrate the properties of Cds and Bi2S3 into the single composite nanocrystalline. The method has the advantages that in the process of synthesizing the composite nanocrystalline, nucleation and growth of the second phase material Bi2S3 can be avoided, thereby achieving effective composite of the CdS and the Bi2S3 in a nano-scale; and experimental operation is simple, the cost is cheap, and the requirement on experimental equipment is low. The method can be extended to the synthesis of other binary system nano composite materials.
Description
Technical field
The present invention relates to a kind of partial cation exchange reaction of utilizing and prepare CdS-Bi
2S
3The method of composite nanocrystalline.The CdS-Bi for preparing
2S
3Composite nanocrystalline is expected to be applied at opto-electronic devices such as solar cells.Belong to field of nanometer material technology.
Background technology
Nano material is inorganic nano-crystal especially, because it has produced the performance that many block of material did not have on less yardstick, receives much concern in recent years.But the character of single inorganic nano-crystal and function are limited after all.Can expand and improve single nanocrystalline performance by compound on nanoscale between the variety classes inorganic nano-crystal, strengthen original or obtain new performance.Although this is the strategy of normal application of material science research and engineering field, and new content has been given in the combination of nanometer technology.Need size little and have multiple materials with function such as miniaturization of devices, the inorganic composite nano crystalline substance just meets above-mentioned specification requirement.Therefore, many in recent years researchers are devoted to develop the synthesizing inorganic composite nanocrystalline.In general, synthetic two the main processes (two-step method) that experienced of inorganic composite nano crystalline substance: the first, what fertile material was nanocrystalline synthesizes; Second nanocrystalline with fertile material be the forming core point, carry out the nanocrystalline growth of second phase material.For example, the people such as Yu have synthesized earlier Au under the condition that has oleyl amine to exist nanocrystalline, then Au is nanocrystalline and Fe (CO)
5Octadecane alkene solution mix, again at 300 ℃ of lower reflux heatings, oleyl amine and oleic acid have also participated in synthetic reaction simultaneously.Then with the air under the room temperature it is oxidized to Au-Fe
3O
4(H.Yu, M.Chen, P.M.Rice, S.X.Wang, R.L.White, S.H.Sun, Nano Lett., 2005,5,379).Optionally grown in the CdS nanometer rods end of producing with high boiling solvent in advance PtNi and PtCo alloy nanometer crystals (S.E.Habas, P.D.Yang, T.Mokari, J.Am.Chem.Soc., 2008,130,3294) of people such as Mokari and for example.But this class synthetic method exists deficiency and inferior position: the nanocrystalline synthetic more complicated of one side fertile material, and cost is higher; On the other hand second phase material nanocrystalline nanocrystalline with parent be spontaneous nucleation, the growth that also exists when the forming core point carries out forming core, growth in liquid phase, need accurately to control the ratio and the concentration of the fertile material and second phase material in experiment, this has increased the complexity and the cost of synthesis technique undoubtedly.Therefore, a kind of method that is referred to as the partial cation exchange reaction can remedy above-mentioned deficiency effectively.Cation exchange reaction is mutually a kind of reaction of conversion owing to difference in solubility in solution between two kinds of insoluble compounds.Under the guidance of this reaction mechanism, the ion of second-phase material only can react with the fertile material of solid phase is nanocrystalline in the solution, and it is nanocrystalline to form second-phase, and second-phase material oneself can be not individually in solution forming core, grow up.Therefore, only need to proportion control (ion of the second-phase material that namely adds is not enough to so that the nanocrystalline second-phase material nano crystalline substance that changes into fully of fertile material) in the scope of part exchange reaction with second-phase material ion that fertile material is nanocrystalline just can obtain composite nanocrystalline.People such as Alivisatos have synthesized the Ag of " ring " shape with regard to utilizing above-mentioned reaction principle
2The Cu of S-CdS composite nanocrystalline (R.D.Robinson, B.Sadtler, D.O.Demchenko, C.K.Erdonmez, L.W.Wang, A.P.Alivisatos, Science, 2007,317,355) and " match " shape
2S-CdS composite nanocrystalline (B.Sadtler, D.O.Demchenko, H.M.Zheng, S.M.Hughes, M.G.Merkle, U.Dahmen, L.W.Wang, A.P.Alivisatos, J.Am.Chem.Soc., 2009,131,5285).CdS is as a kind of typical II-IV family semiconductor, it is nanocrystalline to exist on opto-electronic device widely and use (L.Wang, Y.S.Liu, X.Jiang, D.H.Qin, Y.Cao, J.Phys.Chem.C 2007,111, and 9538).And Bi
2S
3A kind of more satisfactory thermoelectric material (B.X.Chen, C.Uher, Chem.Mater., 1997,9,1655) then.As these two kinds of functional materials are had the combination of Jun ground and the CdS-Bi of formation at nanoscale
2S
3Composite nanocrystalline has potential using value at photoelectron, thermoelectric microdevice.Therefore utilize the partial cation exchange reaction of high-efficient simple to synthesize CdS-Bi
2S
3Composite nanocrystalline has positive meaning.
Summary of the invention
Purpose of the present invention mouth provide a kind of efficient simple parts sun from
Exchange Frozen should close
CdS-B)
2S
3The method of composite nanocrystalline.Cation exchange reaction is mutually a kind of reaction of conversion owing to difference in solubility in solution between two kinds of insoluble compounds.
The present invention is implemented by following manner: it is nanocrystalline at first to utilize hydro thermal method to synthesize flower-shaped CdS; Then with this flower-shaped CdS nanocrystalline as in the ethylene glycol of the nanocrystalline Zai Wu of fertile material viscosity with free Bi
3*Carry out the partial cation exchange reaction.Control Bi
3+The addition of ion can obtain “ Si-rod " shape composite construction nanocrystalline and " nuclear! Shell " shape composite construction corner nanometer Tuan.The method that provides is easy and simple to handle, and cost is low, to equipment require lowly, can expand on other binary system nano composite materials synthetic.
Levy for of the present invention batch and be at first to have synthesized the nanocrystalline second-phase Bi that makes then the nanocrystalline and new formation of flower-shaped CdS by the partial cation exchange of flower-shaped CdS by hydro-thermal method
2S
3Nanocrystalline combination forms obvious interface, and then so that CdS and Bi
2S
3Performance can be integrated in the single composite nanocrystalline.
The concrete operations step is:
(A) the nanocrystalline synthetic concrete technology of flower-shaped CdS is:
(1) at first takes by weighing Cd (Ac)
22H
2O and thiocarbamide, thiocarbamide and Cd (Ac)
22H
2The mol ratio of O is 6-15, preferred thiocarbamide and the Cd (Ac) that recommends
22H
2The mol ratio of O is 8-10.
(2) with the above-mentioned Cd that takes by weighing (Ac)
22H
2O and thiocarbamide dissolve in the deionized water of 50mL together, and dissolve it ultrasonic half an hour fully, form the water white transparency aqueous solution.
(3) above-mentioned mixed aqueous solution being transferred to the polytetrafluoroethylene is in the stainless steel cauldron of liner (capacity is 80mL), is placed in the baking oven, reacts 2 hours down at 150 ℃.
(4) be cooled to room temperature after, utilize centrifugal treating (10000rpm, 10min) that glassy yellow precipitation is collected, and with deionized water and each washed twice of absolute ethyl alcohol, be placed at last in the baking oven 60 ℃ of lower dryings 6 hours.
(5) the flower-shaped CdS nanocrystalline powder that will produce places drier standby.
(B) synthetic CdS-Bi
2S
3The specific embodiment of composite nanocrystalline is:
(a) take by weighing dry flower-shaped CdS nanocrystalline powder, be dispersed in then in the 50g ethylene glycol, sonicated 1 hour forms the suspension that newborn concentration is 0.0002-0.001M.
(b) be that the CTAB ethylene glycol solution (being that CTAB is dissolved in the solution that forms in the solvent ethylene glycol as solute) of 0.005-0.01M and the glycolic suspension of the above-mentioned flower-shaped CdS nanocrystalline powder of 15g mix with 20mL concentration, stir 15min.
(c) again toward wherein being added dropwise to the Bi (NO that 0.6-2mL concentration is 0.005-0.01M
3)
35H
2The O ethylene glycol solution is so that flower-shaped CdS is nanocrystalline and Bi (NO
3)
35H
2The mol ratio of O is in the 1.0-3.5 scope.Then at room temperature stir the oil bath heat treated 1.5 hours that places 77-90 ℃ behind the 15min again.
(d) after question response finishes, from oil bath, take out, be cooled to room temperature.The precipitation of utilizing centrifugal treating (10000rpm, 10min) will react gained is isolated from ethylene glycol solution, uses then each washed twice of deionized water and absolute ethyl alcohol.Last 60 ℃ of dryings 6 hours in baking oven.
A kind of partial cation exchange reaction of utilizing provided by the invention prepares CdS-Bi
2S
3The method of composite nanocrystalline is characterized in:
(1) easy hydro thermal method provides the degree of crystallinity height, and approximate monodispersed flower-shaped CdS is nanocrystalline.This approximate monodispersed flower-shaped CdS is nanocrystalline can fertile material be nanocrystalline preferably for next step partial cation exchange reaction provides.
(2) CdS and Bi
2S
3No matter in water or in the ethylene glycol, exist bigger difference in solubility.Particularly, the solubility of CdS will be much larger than Bi
2S
3But Bi is (NO
3)
35H
2O can't form the Bi with the CdS reaction in water
3+Ion, and following hydrolysis has taken place:
Bi(NO
3)
3+H
2O→BiONO
3↓+2HNO
3 (1)
In addition, Bi (NO
3)
35H
2O common are at other and also is difficult in machine solution such as absolute ethyl alcohol, dimethyl formamide and the acetone effectively dissolve.Found through experiments Bi (NO
3)
35H
2O can form water white solution in ethylene glycol, form Bi
3+Ion.Therefore, select the medium of ethylene glycol as reaction.Its cation exchange reaction is as follows:
3CdS+2Bi
3+→Bi
2S
3+3Cd
2+ (2)
Owing to do not add other sulphur source in the original ethylene glycol solution.Therefore, Bi
2S
3Formation can only depend on CdS, in ethylene glycol solution, be difficult to spontaneous nucleation, growth.This has just solved the difficult problem of the brilliant spontaneous nucleation of the difficult second-phase material nano of being avoided, growth in the common two-step method effectively.
(3) by after carrying out the partial cation exchange reaction with flower-shaped CdS is nanocrystalline, formed CdS-Bi
2S
3The version of composite nanocrystalline depends on the Bi (NO of adding
3)
35H
2The consumption of O ethylene glycol solution (0.005M): 0.6 and 1mL Bi (NO
3)
35H
2The consumption of O ethylene glycol solution has been facilitated the nanocrystalline formation of " nuclear-shell " shape composite construction; 1.3mL consumption facilitated the nanocrystalline formation of " nucleocapsid " shape composite construction and the coexistence of " ball-rod " shape composite construction; The consumption of 2mL has been facilitated the nanocrystalline formation of " ball-rod " shape composite construction.
(4) at CdS-Bi
2S
3During " ball-rod " shape composite construction is nanocrystalline, formed Bi
2S
3Form with nanometer rods exists, and arranges along the nanocrystalline tangential direction of CdS parent, forms the paniculate composite nanostructure of tool.Nanocrystalline and the Bi of CdS parent
2S
3Exist the interface that mutually combines between the nanometer rods.Can make CdS and Bi by this interface
2S
3Performance be combined in the single composite nanocrystalline; And the structure and morphology of branch can play a role in device application.
(5) experimental technique is simple, and operation is convenient, and is low to the experimental facilities requirement, can expand to synthesizing of other binary system nano composite materials.
Description of drawings
The XRD collection of illustrative plates of sample before and after Fig. 1 partial cation exchange reaction: (a) the CdS parent is nanocrystalline; (b) CdS-Bi
2S
3Composite nanocrystalline (77 ℃, 2mL Bi (NO
3)
35H
2O ethylene glycol solution (0.005M));
The TEM of sample figure before Fig. 2 partial cation exchange reaction: (a) flower-shaped CdS parent is nanocrystalline, upper right corner illustration be single flower-shaped CdS parent nanocrystalline choose electron diffraction diagram; (b) the HRTEM figure of the single sheet CdS nano crystal in position shown in the white box among the figure a;
The TEM of sample figure after Fig. 3 partial cation exchange reaction: (a) CdS-Bi
2S
3Composite nanocrystalline (77 ℃, 2mL Bi (NO
3)
35H
2O ethylene glycol solution (0.005M), upper right corner illustration are Bi shown in the black arrow
2S
3Nanometer rods choose electron diffraction diagram; (b) CdS-Bi
2S
3The HRTEM figure of composite nanocrystalline binding site;
The CdS-Bi for preparing under other process conditions of Fig. 4
2S
3The TEM figure of composite nanocrystalline: (a) 90 ℃, 2mL Bi (NO
3)
35H
2O ethylene glycol solution (0.005M); (b) 90 ℃, 0.6mL Bi (NO
3)
35H
2O ethylene glycol solution (0.005M); (c) 90 ℃, 1mL Bi (NO
3)
35H
2O ethylene glycol solution (0.005M); (d) 90 ℃, 1.3mL Bi (NO
3)
35H
2O ethylene glycol solution (0.005M); (b) (c) (d) upper right corner illustration is representational CdS-Bi in the sample separately
2S
3The TEM figure of composite nanocrystalline.
Embodiment
Further specify execution mode and effect with following indefiniteness embodiment:
At first take by weighing 0.0005mol Cd (Ac)
22H
2O (0.1333g) and 0.004mol thiocarbamide (0.3045g), i.e. thiocarbamide and Cd (Ac)
22H
2The O mol ratio is 8.With the above-mentioned Cd that takes by weighing (Ac)
22H
2O and thiocarbamide dissolve in the deionized water of 50mL together, and dissolve it ultrasonic half an hour fully, form the water white transparency aqueous solution.It is in the stainless steel cauldron of liner (capacity is 80mL) that above-mentioned mixed aqueous solution is transferred to the polytetrafluoroethylene, is placed in the baking oven, reacts 2 hours down at 150 ℃.After being cooled to room temperature, utilize centrifugal treating (10000rpm, 10min) that glassy yellow precipitation is collected, and with deionized water and each washed twice of absolute ethyl alcohol, be placed at last in the baking oven 60 ℃ of lower dryings 6 hours.Place drier standby the flower-shaped CdS nanocrystalline powder of producing.
Fig. 1 a is the nanocrystalline XRD figure spectrum of CdS parent, and all diffraction maximums all meet the standard card (JCPDS No.41-1049) of buergerite phase CdS.Fig. 2 a is the nanocrystalline TEM figure of CdS parent and chooses electron diffraction diagram.As can be seen from the figure, He Cheng CdS parent is nanocrystalline has a flower-shaped microstructure; This flower-shaped nanocrystalline CdS monocrystalline by several sheets is formed, whole nanocrystalline be polycrystalline.Fig. 2 b is the HRTEM figure of the single sheet CdS nano crystal shown in the white box among Fig. 2 a.Can find that therefrom these sheets CdS nano crystal has the trend of carrying out one-dimensional growth along [0001] direction, and this direction of growth is just along nanocrystalline tangential of integral body.
Take by weighing dry flower-shaped CdS nanocrystalline powder 0.005g, be dispersed in then in the 50g ethylene glycol, sonicated 1 hour forms the suspension that newborn concentration is 0.0002M.With 20mL concentration is that the CTAB ethylene glycol solution of 0.005M and the glycolic suspension of the above-mentioned flower-shaped CdS nanocrystalline powder of 15g mix, and stirs 15min.Again toward wherein being added dropwise to the Bi (NO that 2mL concentration is 0.005M
3)
35H
2The O ethylene glycol solution at room temperature stirs 15min and was placed in 77 ℃ the oil bath heat treated 1.5 hours.Question response takes out from oil bath after finishing, and is cooled to room temperature.The precipitation of utilizing centrifugal treating (10000rpm, 10min) will react gained is isolated from ethylene glycol solution, uses then each washed twice of deionized water and absolute ethyl alcohol.Last 60 ℃ of dryings 6 hours in baking oven.
Fig. 1 b is the CdS-Bi of embodiment 2 gained
2S
3The XRD collection of illustrative plates of composite nanocrystalline except the nanocrystalline diffraction maximum of the CdS parent of buergerite, belongs to the Bi of quadrature phase
2S
3Diffraction maximum (JCPDS No.17-0320) also appearred.The CdS-Bi that embodiment 2 synthesizes
2S
3The microstructure of composite nanocrystalline is shown in Fig. 3 a.As can be seen from the figure, Bi
2S
3That form with nanometer rods exists.SEAD figure by Fig. 3 a illustration learns Bi
2S
3Nanometer rods is monocrystalline.These Bi
2S
3Nanometer rods is all along tangentially the arranging of the nanocrystalline integral body of CdS parent, and whole composite nanocrystalline has had the complicated structure of apparatus derivatorius-" ball-rod " shape composite construction, and this will play a role in microdevice.By observing the HRTEM figure (Fig. 3 b) of binding site, the nanocrystalline and Bi of CdS parent
2S
3Mutually combine by interface, (0002)/(001) between the nanometer rods; Bi
2S
3Nanometer rods is that self c-axis direction is carried out one-dimensional growth along [001], this and Bi
2S
3In (001) mask have higher surface energy relevant.Because Bi
2S
3The direction of nanometer rods one-dimensional growth almost is parallel to the direction of single flake nano monocrystalline one-dimensional growth in the CdS parent, and the direction of single flake nano monocrystalline one-dimensional growth is tangential along parent integral body in the CdS parent, so Bi
2S
3Nanometer rods also all is tangentially arranging along the nanocrystalline integral body of CdS parent.
Embodiment 3
Take by weighing dry flower-shaped CdS nanocrystalline powder 0.005g, be dispersed in then in the 50g ethylene glycol, sonicated 1 hour forms the suspension that newborn concentration is 0.0002M.With 20mL concentration is that the CTAB ethylene glycol solution of 0.005M and the glycolic suspension of the above-mentioned flower-shaped CdS nanocrystalline powder of 15g mix, and stirs 15min.Again toward wherein being added dropwise to the Bi (NO that 2mL concentration is 0.005M
3)
35H
2The O ethylene glycol solution at room temperature stirs 15min and was placed in 90 ℃ the oil bath heat treated 1.5 hours.Question response takes out from oil bath after finishing, and is cooled to room temperature.The precipitation of utilizing centrifugal treating (10000rpm, 10min) will react gained is isolated from ethylene glycol solution, uses then each washed twice of deionized water and absolute ethyl alcohol.Last 60 ℃ of dryings 6 hours in baking oven.All the other are with embodiment 2.Fig. 4 a is the CdS-Bi of present embodiment preparation
2S
3The TEM figure of composite nanocrystalline.From this figure as seen, along with the raising of reaction temperature, " ball-rod " shape composite construction of composite nanocrystalline does not change, the Bi of formation
2S
3The quantity of nanometer rods has increased.
Embodiment 4
Take by weighing dry flower-shaped CdS nanocrystalline powder 0.005g, be dispersed in then in the 50g ethylene glycol, sonicated 1 hour forms the suspension that newborn concentration is 0.0002M.With 20mL concentration is that the CTAB ethylene glycol solution of 0.005M and the glycolic suspension of the above-mentioned flower-shaped CdS nanocrystalline powder of 15g mix, and stirs 15min.Again toward wherein being added dropwise to the Bi (NO that 0.6mL concentration is 0.005M
3)
35H
2The O ethylene glycol solution at room temperature stirs 15min and was placed in 90 ℃ the oil bath heat treated 1.5 hours.Question response takes out from oil bath after finishing, and is cooled to room temperature.The precipitation of utilizing centrifugal treating (10000rpm, 10min) will react gained is isolated from ethylene glycol solution, uses then each washed twice of deionized water and absolute ethyl alcohol.Last 60 ℃ of dryings 6 hours in baking oven.All the other are with embodiment 2.Fig. 4 b is the CdS-Bi of present embodiment preparation
2S
3The TEM figure of composite nanocrystalline.Relatively be somebody's turn to do figure and Fig. 4 a as seen, along with adding Bi
3+The minimizing of amount, the structure of the composite nanocrystalline of formation has become " nuclear-shell " shape composite construction from " ball-rod " shape composite construction.Bi
2S
3Shell thickness is smaller, shown in the illustration of Fig. 4 b upper right corner, only has 2-3nm.
Take by weighing dry flower-shaped CdS nanocrystalline powder 0.005g, be dispersed in then in the 50g ethylene glycol, sonicated 1 hour forms the suspension that newborn concentration is 0.0002M.With 20mL concentration is that the CTAB ethylene glycol solution of 0.005M and the glycolic suspension of the above-mentioned flower-shaped CdS nanocrystalline powder of 15g mix, and stirs 15min.Again toward wherein being added dropwise to the Bi (NO that 1mL concentration is 0.005M
3)
35H
2The O ethylene glycol solution at room temperature stirs 15min and was placed in 90 ℃ the oil bath heat treated 1.5 hours.Question response takes out from oil bath after finishing, and is cooled to room temperature.The precipitation of utilizing centrifugal treating (10000rpm, 10min) will react gained is isolated from ethylene glycol solution, uses then each washed twice of deionized water and absolute ethyl alcohol.Last 60 ℃ of dryings 6 hours in baking oven.All the other are with embodiment 2.Fig. 4 c is the CdS-Bi of present embodiment preparation
2S
3The TEM figure of composite nanocrystalline.The embodiment 4 that compares is along with Bi
3+The increase of addition, " nuclear-shell " shape composite construction does not change, Bi
2S
3The thickness of shell has been increased to 10-15nm (shown in Fig. 4 c illustration) from 2-3nm.
Embodiment 6
Take by weighing dry flower-shaped CdS nanocrystalline powder 0.005g, be dispersed in then in the 50g ethylene glycol, sonicated 1 hour forms the suspension that newborn concentration is 0.0002M.With 20mL concentration is that the CTAB ethylene glycol solution of 0.005M and the glycolic suspension of the above-mentioned flower-shaped CdS nanocrystalline powder of 15g mix, and stirs 15min.Again toward wherein being added dropwise to the Bi (NO that 1.3mL concentration is 0.005M
3)
35H
2The O ethylene glycol solution at room temperature stirs 15min and was placed in 90 ℃ the oil bath heat treated 1.5 hours.Question response takes out from oil bath after finishing, and is cooled to room temperature.The precipitation of utilizing centrifugal treating (10000rpm, 10min) will react gained is isolated from ethylene glycol solution, uses then each washed twice of deionized water and absolute ethyl alcohol.Last 60 ℃ of dryings 6 hours in baking oven.All the other are with embodiment 2.Fig. 4 d is the CdS-Bi of present embodiment preparation
2S
3Composite nanocrystalline TEM figure.The embodiment 5 that compares is along with Bi
3+The continuation of addition increases, and shown in Fig. 4 d illustration, the composite construction of the composite construction of " ball-rod " shape and " nuclear-shell " shape coexists.2-5 in conjunction with the embodiments is along with Bi
3+The increase gradually of addition, CdS-Bi
2S
3The structure of composite nanocrystalline develops into " ball-rod " shape composite construction from " nuclear-shell " shape composite construction gradually.
Claims (8)
1. one kind is utilized the partial cation exchange reaction to prepare CdS-Bi
2S
3The method of composite nanocrystalline, it is nanocrystalline to it is characterized in that at first synthesizing flower-shaped CdS by hydro-thermal method, passes through the partial cation exchange reaction then so that flower-shaped CdS is nanocrystalline and the second-phase Bi of formation
2S
3Nanocrystalline combination forms obvious interface, and then so that CdS and Bi
2S
3Performance be integrated in the single composite nanocrystalline, comprise (A) and (B) two greatly the step:
(A) the nanocrystalline synthesis technique of flower-shaped CdS comprises:
(a1) at first take by weighing Cd (Ac)
22H
2O and thiocarbamide, thiocarbamide and Cd (Ac)
22H
2The mol ratio of O is 6-15, and with Cd (Ac)
22H
2O and thiocarbamide dissolve in the deionized water of 50mL together, and dissolve it ultrasonic half an hour fully, form the water white transparency aqueous solution;
(a2) to be transferred to the polytetrafluoroethylene be in the stainless steel cauldron of liner to the aqueous solution that step a1 is formed, and is placed in the baking oven, 150 ℃ of reactions 2 hours down;
(a3) be cooled to room temperature after, at 10000rpm, under the 10min centrifugal treating condition, and glassy yellow precipitation collected, use again each washed twice of deionized water and absolute ethyl alcohol, be placed at last in the baking oven 60 ℃ lower dry 6 hours;
(a4) the flower-shaped CdS nanocrystalline powder that will produce places drier standby;
(B) CdS-Bi
2S
3The synthesis technique of composite nanocrystalline comprises:
(b1) it is some to take by weighing the flower-shaped CdS nanocrystalline powder of step (A) preparation, be dispersed in then in the 50g ethylene glycol, and sonicated 1 hour, forming concentration is the suspension of 0.0002-0.001M;
(b2) be that the CTAB ethylene glycol solution of 0.005-0.01M and the glycolic suspension of the flower-shaped CdS nanocrystalline powder that 15g step b1 prepares mix with 20mL concentration, stir 15min;
(b3) again in the mixed liquor of step b2, being added dropwise to 0.6-2mL concentration is the Bi (NO of 0.005-0.01M
3)
35H
2The O ethylene glycol solution is so that flower-shaped CdS is nanocrystalline and Bi (NO
3)
35H
2The mol ratio of O is in the 1.0-3.5 scope; Then at room temperature stir oil bath heat treated 1-2 hour that places again 77-90 ℃ behind the 15min;
(b4) after the reaction for the treatment of step b3 finishes, from oil bath, take out, be cooled to room temperature, and under 10000rpm and 10min condition centrifugal treating, the sediment of reaction gained is isolated from ethylene glycol solution, used then each washed twice of deionized water and absolute ethyl alcohol; Last 60 ℃ of dryings 6 hours in baking oven.
2. by the described preparation of claim 1 CdS-Bi
2S
3The method of composite nanocrystalline is characterized in that the thiocarbamide described in the step (A) and Cd (Ac)
22H
20 mol ratio is 8-10.
3. by the described preparation of claim 1 CdS-Bi
2S
3The method of composite nanocrystalline is characterized in that CdS that hydro-thermal method synthesizes is nanocrystalline and has flower-shaped microstructure, and be the buergerite phase that the flower-like nanometer crystalline substance is made up of several sheets CdS nano crystal.
4. by the described preparation of claim 3 CdS-Bi
2S
3The method of composite nanocrystalline is characterized in that sheet CdS nano crystal is along [0001] direction one-dimensional growth.
5. by the described preparation of claim 1 CdS-Bi
2S
3The method of composite nanocrystalline is characterized in that the Bi (NO as 0.005M
3)
35H
2When O ethylene glycol solution consumption is 2mL, CdS-Bi
2S
3The structure of composite nanocrystalline presents " ball-rod " shape composite construction; Bi
2S
3Form with nanometer rods is arranged in the tangential of the nanocrystalline integral body of CdS, and Bi
2S
3Nanometer rods is monocrystalline, belongs to the quadrature phase.
6. by the described preparation of claim 1 CdS-Bi
2S
3The method of composite nanocrystalline is characterized in that the Bi (NO as 0.005M
3)
35H
2When O ethylene glycol solution consumption is 0.6-1mL, CdS-Bi
2S
3The structure of composite nanocrystalline presents " nuclear-shell " shape composite construction; Along with adding Bi
3+The increase of amount, Bi
2S
3The thickness of shell is increased to 10-15nm from 2-3nm.
7. by the described preparation of claim 1 CdS-Bi
2S
3The method of composite nanocrystalline is characterized in that the Bi (NO as 0.005M
3)
35H
2When O ethylene glycol solution consumption is 1.3mL, CdS-Bi
2S
3The structure of composite nanocrystalline presents the coexistence of " nuclear-shell " shape composite construction and " ball-rod " shape composite construction, i.e. CdS-Bi
2S
3The structure of composite nanocrystalline develops into " ball-rod " shape composite construction from " nuclear-shell " shape composite construction gradually.
8. by the described preparation of claim 5 CdS-Bi
2S
3The method of composite nanocrystalline is characterized in that the nanocrystalline and Bi of CdS
2S
3Mutually combine with interface, (0002)/(001) between the nanometer rods; Along with the raising of reaction temperature, Bi
2S
3The quantity of nanometer rods increases.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101086497A CN101866960B (en) | 2010-02-10 | 2010-02-10 | Method for preparing CdS-Bi2S3 composite nanocrystalline by utilizing partial cation exchange reaction |
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| CN102008966B (en) * | 2010-11-08 | 2012-07-04 | 安徽师范大学 | Sulfur group hetero-structure nano material, preparation method and application thereof |
| CN103272617A (en) * | 2013-06-08 | 2013-09-04 | 哈尔滨工业大学 | CdS/Bi2S3 composite photocatalyst and preparation method thereof |
| CN103617891B (en) * | 2013-11-27 | 2016-04-27 | 中国科学院化学研究所 | A kind of indium tin oxide nanowire array composite and preparation method thereof and application in solar cells |
| CN106693994A (en) * | 2016-12-14 | 2017-05-24 | 中南大学 | Preparation and application of core-shell structure bismuth sulfide@copper sulfide composite microspheres |
| CN108269935A (en) * | 2016-12-30 | 2018-07-10 | Tcl集团股份有限公司 | A kind of quantum dot film and preparation method thereof |
| CN107010653A (en) * | 2017-04-29 | 2017-08-04 | 天津大学 | The cubical method of zinc blende-type cadmium sulfide nano is synthesized using cation exchange |
| US10934176B2 (en) | 2018-09-27 | 2021-03-02 | Imam Abdulrahman Bin Faisal University | Methods of degrading organic pollutants and preventing or treating microbe using Bi2S3-CdS particles |
| CN109261197A (en) * | 2018-10-18 | 2019-01-25 | 新乡学院 | A kind of ammonia nitrogen waste water processing coal ash molecular sieve/ZnO/Bi2S3Preparation method |
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