CN1299997C - Metal sulfide semiconductor nanometer composite material using hydrotalcite as model and its preparation method - Google Patents
Metal sulfide semiconductor nanometer composite material using hydrotalcite as model and its preparation method Download PDFInfo
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- CN1299997C CN1299997C CNB2005100863492A CN200510086349A CN1299997C CN 1299997 C CN1299997 C CN 1299997C CN B2005100863492 A CNB2005100863492 A CN B2005100863492A CN 200510086349 A CN200510086349 A CN 200510086349A CN 1299997 C CN1299997 C CN 1299997C
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Abstract
The present invention provides a metal sulphide semiconductor nanometer composite material using hydrotalcites as a template, and a preparation method thereof, which belongs to the technical field of the composite material of a semiconductor. The method comprises the following steps: using LDHs as a template, replacing NO3<-> or Cl<-> after the ion exchange of metal complex anions, and entering the interlayer of the hydrotalcites to form a layered powder material whose metal complex anions account for 40 to 100% the total mole number of the intercalated anions; leading sufficient H2S gas into the powder, and thereby obtaining semiconductor nanoparticles intercalated layered hydrotalcites through gas phase reaction and solid phase reaction. The present invention has the advantages that the II to VI group semiconductor nanometer particles with outstanding photoelectric performance and catalytic performance are assembled to the interlayer of the hydrotalcites to realize high dispersion of the II to VI group semiconductor nanometer particles in the interlayer of the hydrotalcites; simultaneously, changeable plywood metal and organic ligands can be adjusted to obtain an organic and inorganic semiconductor nanometer composite material with well dispersed semiconductor nanoparticles whose particle diameter is adjustable.
Description
Affiliated field
The invention belongs to the semiconductor composite technical field, particularly providing a kind of is the metal sulfide semiconductor nanometer composite material and preparation method thereof of template with the hydrotalcite.
Background technology
Fast development along with nanoscale science and technology, metal sulfide semiconductor nanometer material (ZnS, CdS) causes people's attention gradually because of its special photoelectric property, and especially they are in huge applications potentiality that various fields showed such as luminescent material, photochemical catalysis, novel display material, solar cell, microelectronic devices.And the particle diameter of semi-conductor nano particles and distribution of sizes are determining the character and the application of nano material, for obtain to stablize, photoelectric properties, the effectively particle diameter and the distribution of sizes of control nanoparticle efficiently.Single semiconductor functional material of while, except that showing outstanding separately advantage, its inherent limitation is also arranged, therefore the function that relies on single-material to finish various complexity is unpractical, and this just makes the generation of synthetic method, performance cooperate optimization and the new effect of the semiconductor-based matrix material of research become the focus of current semiconductor material research.
The method that can prepare ZnS, CdS semiconductor nanometer composite material at present has a lot, and as the hot method of water (solvent), sol-gel method, template etc., every kind of preparation method has its advantage, but also exists shortcoming.Water (solvent) Re Fa can make the semiconductor nanoparticle of highly crystalline, but it needs high temperature, high pressure, airtight reaction system, and technology is comparatively complicated; Sol-gel method can directly make the organic composite semiconductor material that is evenly distributed, but its particle diameter is relatively large.Therefore how to obtain size single, be evenly distributed, the semiconductor nanometer composite material of stability and good reproducibility is still a very crucial problem, especially the preparation condition difference has a significant impact semi-conductive nano-scale, structure and morphology and photoelectric properties.Template is a kind of effective method for preparing nano composite material that developed recently gets up, be that template synthetic CdS nanoparticle has been realized the particle diameter of nanoparticle and effective control (Shouwu Guo of distribution of sizes to a certain extent wherein with organic ordered film (LB film), Leandro Konopny, RonitPopovitz-Biro, Hagai Cohen, Horia Porteanu, Efrat Lifshitz, and Meir Lahav, J.Am.Chem.Soc.1999,121,9589-9598), can be about 1.5～2.0nm at the synthetic thickness of interlayer by the length of modulation organic carboxyl acid molecular chain, diameter is about the discoid CdS nanoparticle of 3.0～4.5nm.But therefore LB membrance chemistry less stable and shortage heat resistanceheat resistant performance are preserved the synthetic nanoparticle in long-term stability, are prevented that it from taking place to have defective aspect reunion, limited its possible range of application.And be that the particle diameter of semi-conductor ZnS nanoparticle in the hard template synthetic ZnS nano composite material of representative can be less than 2.5nm with mesoporous material MCM-41, (Wen-Hua Zhang, Jian-Lin Shi, Hang-Rong Chen, Zi-Le Hua, and Dong-Sheng Yan, Chem.Mater.2001,13,648-654), and because mesoporous silicon material has good chemical stability and heat resistanceheat resistant performance, matrix material has had aspect stable and has significantly improved.Yet mesoporous material adjustable sex change aspect The Nomenclature Composition and Structure of Complexes is little, and its unreactiveness also caused not having synergistic effect between composite matrix layer and semi-conductor nano particles substantially, and this has also limited the semiconductor composite function development.
At the problems referred to above, the previous important research direction of order be exactly select a kind of suitable template with prepare good stability and hypothallus and the ultra-fine semi-conductor nano particles of interlayer between the organic and inorganic composite semiconductor nano material of synergistic effect is arranged.
The bimetal complex hydroxide is called hydrotalcite (Layered Double Hydroxides again, be abbreviated as LDHs) be a kind of novel multifunctional stratified material, its chemical stability is good, has strong heat resistanceheat resistant performance, but and LDHs laminate metal ion modulation, interlayer anion has interchangeability, multiple functional negatively charged ion all can enter interlayer by ion-exchange, generate various functional composite materials, therefore can be with it as template, regulate and control laminate metal and interlayer anion as required simultaneously, and then the purpose that reaches regulating layer spacing and reaction environment is to realize the controlled preparation to the interlayer nanoparticle.
Summary of the invention
It is the metal sulfide semiconductor nanometer composite material and preparation method thereof of template with the hydrotalcite that the object of the invention is to provide a kind of, utilize the controlled and veneer structure orientation effect of interlayer ion interchangeability, laminate of LDHs, the semiconductor precursor positively charged ion is introduced interlayer with organic joining with the anionic form of thing, adopt gas-solid phase reaction at the synthetic metal sulfide semiconductor nanoparticle of LDHs interlayer confinement, and then realize the high dispersing of semi-conductor at the LDHs interlayer; But modulation laminate metal, change organic ligand prepare the organic and inorganic semiconductor nanometer composite material that semi-conductor is uniformly dispersed, particle diameter is controlled simultaneously.
Consisting of of metal sulfide semiconductor nanometer composite material of the present invention: interlayer anion is NO
3 -Perhaps Cl
-The hydrotalcite precursor, the metal complexes negatively charged ion is replaced NO through ion-exchange
3 -Perhaps Cl
-Enter hydrotalcite layers, constitute the anionic supramolecule stratified material that the metal complexes negatively charged ion accounts for interlayer anion mole number sum 40～100%, again to wherein feeding capacity H
2S gas, through gas-solid phase reaction obtain that organic ligand is pillared, the metal sulfide semiconductor nanoparticle high dispersing is in the hydrotalcite composite material of interlayer, wherein semi-conductor nano particles is perpendicular to the interlamellar spacing of the particle diameter on the laminate direction less than hydrotalcite.
The preparation process of the metal sulfide semiconductor nanometer composite material of high dispersing of the present invention is as follows:
A. preparing interlayer anion is NO
3 -Perhaps Cl
-, laminate monovalence, Tricationic mol ratio M
+/ M
3+=0.5 or laminate divalence, Tricationic mol ratio M
2+/ M
3+=2～4 hydrotalcite precursor;
B. oxide compound and citric acid, ethylenediamine tetraacetic acid (EDTA), the nitrilotriacetic acid(NTA) with Metal Zn or Cd reacts according to mol ratio respectively at 1: 1, and it is 7～9 that organic acid is transferred its pH value with metal oxide dissolving back with NaOH, prepares electronegative metal complexes;
C. be NO with metal complexes and interlayer anion
3 -Perhaps Cl
-Hydrotalcite at N
2Protection is also stirred down, and 25～65 ℃ were reacted 2～24 hours down, and product spends CO
2Water thorough washing, centrifugal can obtain the metal complexes intercalated houghite after 25～65 ℃ of following dryings;
D. metal complexes intercalated houghite powder being placed flow velocity is the H of 10～100ml/min
2Reacted in the S atmosphere 2～12 hours, product is at N
2Kept 12 hours in the atmosphere, can obtain the metal sulfide semiconductor nanoparticle intercalated hydrotalcite composite material.
The preparation-obtained metal complexes of the present invention has negative charge, can stable existence between pH=6～10 in solution.
Organic acid part of the present invention is selected complexone or hydroxyl carboxylic complexing agent, comprising: ethylenediamine tetraacetic acid (EDTA) (EDTA), nitrilotriacetic acid(NTA) (NTA), teiethylene tetramine-hexacetic acid (TTHA), ethyl ether diamine tetraacetic acid (EEDTA), cyclohexanediaminetetraacetic acid (DCTA), pregnancy ethylenediamine tetraacetic acid (EDTA) (HDTA) and citric acid.
Metallic element of the present invention is Zn, Cd.
Hydrotalcite main body laminate of the present invention is selected monovalence metallic cation Li
+With trivalent metal cation Al
3+Combination or selection divalent metal Mg
2+, Ca
2+In any and trivalent metal cation Al
3+, Cr
3+In any combination.
Above-mentioned materials is carried out XRD, IR, TG-DTA, UV-vis, the success of elemental analysis demonstration metal complexes intercalation.The XRD structural parameter show that its laminate spacing increases greatly behind the metal complexes intercalation, and its unit cell parameters a value remains unchanged in the intercalation front and back, and product has complete laminate structure.With H
2After the S reaction, the XRD structural parameter show that laminate structure still is kept perfectly, and analyze with UV-vis and to show that all the LDHs interlayer has generated metal sulfide semiconductor nanoparticle, and semi-conductor nano particles is perpendicular to the interlamellar spacing of the particle diameter on the laminate direction less than hydrotalcite.
The invention has the advantages that: but the controlled and veneer structure orientation effect of intercalation assembleability, laminate of hydrotalcite stratified material utilized, have excellent photoelectric properties and catalytic performance metal sulfide semiconductor nanoparticle be assembled into hydrotalcite layers, realize the high dispersing of metal sulfide semiconductor nanoparticle in hydrotalcite layers; Also but modulation laminate metal and organic ligand prepare that metal sulfide semiconductor nanoparticle is uniformly dispersed, the organic and inorganic semiconductor nanometer composite material of adjustable grain simultaneously.
Embodiment:
Embodiment 1
Steps A: take by weighing 61.54g Mg (NO
3)
26H
2O and 45.02g Al (NO
3)
39H
2O is dissolved in 300ml and removes CO
2Water preparation mixing salt solution, other gets 28.80gNaOH and is dissolved in 300ml and removes CO
2In the water, under the room temperature rapidly with alkaline solution and mixing salt solution nucleation in the rotation liquid film reactor, gained slurries N
2Protect following 100 ℃ of crystallization 6h, the product centrifuge washing is to neutral; Take out small amount of sample and characterize behind the dry 24h down for 65 ℃, obtain Mg
2Al-NO
3LDHs, its Mg
2+/ Al
3+=2.
Step B: with 10.08g citric acid (C
6H
8O
7H
2O, 0.048mol) pressed powder adds and to fill in the there-necked flask of 200ml deionized water, adds 3.91g (0.048mol) ZnO solid after being heated to 60 ℃, continue to keep 60 ℃ of reactions, adding small amount of N aOH particle behind 0.5h in reactor, is 7～8 until reacting liquid pH value, and liquid becomes clarification.Solution is filtered, heats concentrated back constant-temperature evaporation, can obtain Powdered Na
2Zn (C
6H
5O
7) 3 (H
2O) crystal.
Step C: take by weighing 5.65g (0.016mol) Na
2Zn (C
6H
5O
7) title complex adds and to fill in the reactor of 100ml deionized water, treats that solid all dissolves the back and adds Mg
2Al-NO
3The LDHs precursor (5.50g, 0.004mol); The pH value of regulator solution is 7 after finishing, N
210h is reacted in protection normal temperature down down.Product spends CO
2Water washing, 65 ℃ of following dry 24h can obtain interlayer and contain Zn
2+Stratified material.
Step D: with the Na of step C preparation
2Zn (C
6H
5O
7) the title complex intercalated houghite inserts the H of certain pressure and flow velocity
2React 8h in the S atmosphere, can obtain the stratified material that interlayer contains the ZnS semi-conductor nano particles.
By X-ray diffractogram as can be known, title complex Zn (C
6H
5O
7)
2-After ion-exchange entered the LDHs interlayer, its laminate spacing increased to 1.217nm by the 0.867nm of precursor; Two kinds of LDHs have the obvious diffraction peak near 2 θ are 61 °, and corresponding unit cell parameters a is approximately 0.303nm, and Zn (C is described
6H
5O
7)
2-LDHs laminate electric density does not change before and after the intercalation, and the LDHs laminate obtains more complete maintenance.The IR spectrogram shows, the Mg for preparing
2Al-Zn (C
6H
5O
7) LDHs is at 1582cm
-1, 1399cm
-1COO has appearred in the place
-Characteristic peak, at 643cm
-1The stretching vibration peak of Zn-O has appearred in the place, proves title complex Zn (C
6H
5O
7)
2-The intercalation success.And Zn (C
6H
5O
7)
2-Intercalated houghite and H
2After the S reaction, near the diffraction peak that 2 θ are 28 °, has occurred ZnS by corresponding X-ray diffractogram as can be known, strong ZnS ultraviolet absorption peak appears in the UV-vis analysis revealed near 276nm, show all that below the LDHs interlayer has generated the ZnS semi-conductor nano particles, and the ZnS semi-conductor nano particles that generates of interlayer perpendicular to the particle diameter on the laminate direction less than LDHs net layer spacing 0.73nm.
Embodiment 2
Steps A: take that the steps A method obtains Mg in the similar embodiment 1
2Al-Cl LDHs precursor.Take by weighing 48.79gMgCl
26H
2O and 28.97g AlCl
36H
2O is dissolved in 300ml and removes CO
2Water preparation mixing salt solution, other gets 28.80g NaOH and is dissolved in 300ml and removes CO
2In the water, under the room temperature rapidly with alkaline solution and mixing salt solution nucleation in the rotation liquid film reactor, gained slurries N
2Protect following 100 ℃ of crystallization 6h, the product centrifuge washing is to neutral; Take out small amount of sample and characterize behind the dry 24h down for 65 ℃, obtain Mg
2Al-Cl LDHs, its Mg
2+/ Al
3+=2.
Step B: by the method for step B in the similar embodiment 1, with 7.76g nitrilotriacetic acid(NTA) (N (CH
2-COOH)
3, being called for short NTA, 0.04mol) the pressed powder adding fills in the there-necked flask of 200ml water, add 3.26g (0.04mol) ZnO solid behind the heated and boiled 15min, continue reflux, behind 0.5h, in reactor, add small amount of N aOH particle, until reacting liquid pH value is 7.Solution is filtered, heats concentrated back constant-temperature evaporation, can obtain Powdered Na
2ZnNTA (H
2O) crystal.
Step C: take step C method in the similar embodiment 1, take by weighing the adding of 4.71g (0.016mol) NaZnNTA title complex and fill in the reactor of 100ml deionized water, treat that solid all dissolves the back and adds Mg
2Al-Cl LDHs precursor (4.97g, 0.004mol); The pH value of regulator solution is 7 after finishing, N
212h is reacted in protection normal temperature down down.Product spends CO
2Water washing, 65 ℃ of following dry 24h can obtain interlayer and contain Zn
2+Stratified material.
Step D: take that step D method can obtain the stratified material that interlayer contains the ZnS semi-conductor nano particles in the similar embodiment 1.
By X-ray diffractogram as can be known, Mg
2Al-ZnNTA LDHs laminate spacing increases to 1.246nm by the 0.768nm of precursor, and the unit cell parameters a of the charateristic avsorption band correspondence of two kinds of LDHs is approximately 0.304nm near 2 θ are 61 °, and ZnNTA is described
-LDHs laminate electric density does not change before and after the intercalation, and the LDHs laminate obtains more complete maintenance.The IR spectrogram shows that the intercalation product is at 1610cm
-1, 1400cm
-1COO has appearred in the place
-Characteristic peak, at 1123cm
-1The stretching vibration peak of C-N has appearred in the place, proves title complex ZnNTA
-The intercalation success.And ZnNTA
-Intercalated houghite and H
2After the S reaction, near the diffraction peak that 2 θ are 28 °, has occurred ZnS by corresponding X-ray diffractogram as can be known, strong ZnS ultraviolet absorption peak appears in the UV-vis analysis revealed near 276nm, show all that below the LDHs interlayer has generated the ZnS semi-conductor nano particles, and the ZnS semi-conductor nano particles that generates of interlayer perpendicular to the particle diameter on the laminate direction less than LDHs net layer spacing 0.76nm.
Embodiment 3
Steps A: obtain Mg by steps A method among the embodiment 1
2Al-NO
3The LDHs precursor.
Step B: by the method for step B in the similar embodiment 1, with 7.01g ethylenediamine tetraacetic acid (EDTA) (H
4C
10H
12N
2O
8, 0.024mol) the pressed powder adding is taken advantage of in the there-necked flask of 200ml deionized water, adds 3.08g (0.024mol) CdO solid behind the heated and boiled 15min, continue reflux, adding small amount of N aOH particle behind 0.5h in reactor, is 5～6 until reacting liquid pH value, and liquid becomes clarification.Solution is filtered, heats concentrated back constant-temperature evaporation, can obtain Powdered Na
2CdEDTA3 (H
2O) crystal.
Step C: take by weighing 8.01g (0.016mol) Na
2The adding of CdEDTA title complex fills in the reactor of 100ml deionized water, treats that solid all dissolves the Mg that the back adds heat
2Al-NO
3The LDHs precursor (5.50g, 0.004mol); The pH value of regulator solution is 6 after finishing, N
2Protect following 65 ℃ of constant temperature 10h.Product spends CO
2Water washing, 65 ℃ of following dry 24h can obtain interlayer and contain Cd
2+Stratified material.
Step D: take that step D method can obtain the stratified material that interlayer contains the CdS semi-conductor nano particles in the similar embodiment 1.
By X-ray diffractogram as can be known, Mg
2Al-CdEDTA LDHs laminate spacing increases to 1.521nm by the 0.874nm of precursor, and the unit cell parameters a of the charateristic avsorption band correspondence of two kinds of LDHs is approximately 0.306nm near 2 θ are 61 °, and CdEDTA is described
2-LDHs laminate electric density does not change before and after the intercalation, and the LDHs laminate obtains more complete maintenance.The IR spectrogram shows that the intercalation product is at 1596cm
-1, 1400cm
-1COO has appearred in the place
-Characteristic peak, at 1127cm
-1The stretching vibration peak of C-N has appearred in the place, proves the success of rare earth compounding EuNTA intercalation.And CdEDTA
2-Intercalated houghite and H
2After the S reaction, near the diffraction peak that 2 θ are 26.5 °, has occurred CdS by corresponding X-ray diffractogram as can be known, strong CdS ultraviolet absorption peak appears in the UV-vis analysis revealed near 460nm, show all that below the LDHs interlayer generates the CdS semi-conductor nano particles, and the CdS semi-conductor nano particles that generates of interlayer perpendicular to the particle diameter on the laminate direction less than LDHs net layer spacing 1.04nm.
Embodiment 4
Steps A: take by weighing 27.0g γ-Al (OH)
3Remove CO with 33.0gLiCl and 75ml
2Water mixed preparing slurries, gained slurries N
2Protect following 90 ℃ of crystallization 14h, the product centrifuge washing is to neutral; Take out small amount of sample and characterize behind the dry 24h down for 65 ℃, obtain LiAl
2-Cl LDHs precursor, its Li
+/ Al
3+=0.5.
Step B: press the method for step B among the embodiment 1, preparation Na
2Zn (C
6H
5O
7) title complex.
Step C: take by weighing 5.65g (0.016mol) Na
2Zn (C
6H
5O
7) title complex adds and to fill in the reactor of 100ml deionized water, treats that solid all dissolves the back and adds LiAl
2-Cl LDHs precursor (4.86g, 0.004mol); The pH value of regulator solution is 7 after finishing, N
210h is reacted in protection normal temperature down down.Product spends CO
2Water washing, 65 ℃ of following dry 24h can obtain interlayer and contain Zn
2+Stratified material.
Step D: take that step D method can obtain the stratified material that interlayer contains the ZnS semi-conductor nano particles in the similar embodiment 1.
By X-ray diffractogram as can be known, LiAl
2-Zn (C
6H
5O
7) LDHs laminate spacing increases to 1.185nm by the 0.768nm of precursor, the unit cell parameters a of the charateristic avsorption band correspondence of two kinds of LDHs is approximately 0.306nm near 2 θ are 61 °, and Zn (C is described
6H
5O
7)
2-LDHs laminate electric density does not change before and after the intercalation, and the LDHs laminate obtains more complete maintenance.The IR spectrogram shows, the LiAl for preparing
2-Zn (C
6H
5O
7) LDHs is at 1590cm
-1, 1398cm
-1COO has appearred in the place
-Characteristic peak, at 645cm
-1The stretching vibration peak of Zn-O has appearred in the place, proves title complex Zn (C
6H
5O
7)
2-The intercalation success.And Zn (C
6H
5O
7)
2-Intercalated houghite and H
2After the S reaction, near the diffraction peak that 2 θ are 28 °, has occurred ZnS by corresponding X-ray diffractogram as can be known, strong ZnS ultraviolet absorption peak appears in the UV-vis analysis revealed near 276nm, show all that below the LDHs interlayer has generated the ZnS semi-conductor nano particles, and the ZnS semi-conductor nano particles that generates of interlayer perpendicular to the particle diameter on the laminate direction less than LDHs net layer spacing 0.71nm.
Embodiment 5
Steps A: obtain LiAl by steps A method in the similar embodiment 4
2-NO
3The LDHs precursor.Take by weighing 27.0g γ-Al (OH)
3With 45.0g Li (NO
3) remove CO with 75ml
2Water mixed preparing slurries, gained slurries N
2Protect following 90 ℃ of crystallization 14h, the product centrifuge washing is to neutral; Take out small amount of sample and characterize behind the dry 24h down for 65 ℃, obtain LiAl
2-NO
3LDHs, its Li
+/ Al
3+=0.5.
Step B: the method for taking step B in the similar embodiment 3, the adding of 7.01g EDTA (0.024mol) pressed powder is filled in the there-necked flask of 200ml deionized water, add 1.95g (0.024mol) ZnO solid behind the heated and boiled 15min, continue reflux, adding small amount of N aOH particle behind 0.5h in reactor, is 7 until reacting liquid pH value.Solution is filtered, heats concentrated back constant-temperature evaporation, can obtain Powdered Na
2Zn (EDTA) .3 (H
2O) crystal.
Step C: take the method for step C in the similar embodiment 1 to take by weighing 7.26g (0.016mol) Na
2The adding of Zn (EDTA) title complex fills in the reactor of 100ml deionized water, treats that solid all dissolves the LiAl that the back adds heat
2-NO
3The LDHs precursor (4.86g, 0.004mol); The pH value of regulator solution is 8 after finishing, N
2Protect following 65 ℃ of constant temperature 12h, product spends CO
2Water washing, 65 ℃ of following dry 24h can obtain interlayer and contain Zn
2+Stratified material.
By X-ray diffractogram as can be known, LiAl
2-ZnEDTALDHs laminate spacing increases to 1.487nm by the 0.735nm of precursor, and the unit cell parameters a of the charateristic avsorption band correspondence of two kinds of LDHs is approximately 0.306nm near 2 θ are 61 °, and ZnEDTA is described
2-LDHs laminate electric density does not change before and after the intercalation, and the LDHs laminate obtains more complete maintenance.The IR spectrogram shows that the intercalation product is at 1610cm
-1, 1399cm
-1COO has appearred in the place
-Characteristic peak, at 1110cm
-1The stretching vibration peak of C-N has appearred in the place, proves title complex ZnEDTA
2-The intercalation success.And ZnEDTA
2-Intercalated houghite and H
2After the S reaction, near the diffraction peak that 2 θ are 28 °, has occurred ZnS by corresponding X-ray diffractogram as can be known, strong ZnS ultraviolet absorption peak appears in the UV-vis analysis revealed near 276nm, show all that below the LDHs interlayer has generated the ZnS semi-conductor nano particles, and the ZnS semi-conductor nano particles that generates of interlayer perpendicular to the particle diameter on the laminate direction less than LDHs net layer spacing 0.73nm.
Embodiment 6
Steps A: obtain LiAl by steps A method among the embodiment 4
2-Cl LDHs precursor.
Step B: take the method for step C in the similar embodiment 1, with 5.04g citric acid (C
6H
8O
7H
2O, 0.024mol) pressed powder adds and to fill in the there-necked flask of 100ml deionized water, adds 3.08g (0.024mol) CdO solid after being heated to 60 ℃, continue to keep 60 ℃ of reactions, adding small amount of N aOH particle behind 0.5h in reactor, is 7～8 until reacting liquid pH value, and liquid becomes clarification.Solution is filtered, heats concentrated back constant-temperature evaporation, can obtain Powdered Na
2Cd (C
6H
5O
7) 3 (H
2O) crystal.
Step C: take by weighing 8.01g (0.016mol) Na
2Cd (C
6H
5O
7) title complex adds and to fill in the reactor of 100ml deionized water, treats that solid all dissolves the back and adds LiAl
2-Cl LDHs precursor (4.97g, 0.004mol); The pH value of regulator solution is 7 after finishing, N
2Protection normal temperature is reaction 10h down.Product spends CO
2Water washing, 65 ℃ of following dry 24h can obtain interlayer and contain Cd
2+Stratified material.
Step D: take that step D method can obtain the stratified material that interlayer contains the CdS semi-conductor nano particles in the similar embodiment 1.
By X-ray diffractogram as can be known, LiAl
2-ZnEDTALDHs laminate spacing increases to 1.495nm by the 0.768nm of precursor, and the unit cell parameters a of the charateristic avsorption band correspondence of two kinds of LDHs is approximately 0.306nm near 2 θ are 61 °, and Cd (C is described
6H
5O
7)
2-LDHs laminate electric density does not change before and after the intercalation, and the LDHs laminate obtains more complete maintenance.The IR spectrogram shows that the intercalation product is at 1596cm
-1, 1400cm
-1COO has appearred in the place
-Characteristic peak, at 1115cm
-1The stretching vibration peak of C-N has appearred in the place, proves title complex Cd (C
6H
5O
7)
2-The intercalation success.And Cd (C
6H
5O
7)
2-Intercalated houghite and H
2After the S reaction, near the diffraction peak that 2 θ are 26.5 °, has occurred CdS by corresponding X-ray diffractogram as can be known, strong CdS ultraviolet absorption peak appears in the UV-vis analysis revealed near 465nm, show all that below the LDHs interlayer generates the CdS semi-conductor nano particles, and the CdS semi-conductor nano particles that generates of interlayer perpendicular to the particle diameter on the laminate direction less than LDHs net layer spacing 1.02nm.
Claims (6)
1. one kind is the metal sulfide semiconductor nanometer composite material of template with the hydrotalcite, it is characterized in that: getting interlayer anion is NO
3 -Perhaps Cl
-The hydrotalcite precursor, make a metal-organic complex negatively charged ion replace NO through ion-exchange
3 -Perhaps Cl
-Enter between the hydrotalcite precursor layer, constitute the anionic supramolecule stratified material that a metal-organic complex negatively charged ion accounts for interlayer anion mole number sum 40～100%, again to wherein feeding capacity H
2S gas, through gas-solid phase reaction obtain that organic ligand is pillared, the metal sulfide semiconductor nanoparticle high dispersing is in the hydrotalcite composite material of interlayer, wherein semi-conductor nano particles is perpendicular to the interlamellar spacing of the particle diameter on the laminate direction less than hydrotalcite, and metallic element is Zn or Cd.
2. according to right 1 described metal sulfide semiconductor nanometer composite material, it is characterized in that: hydrotalcite main body laminate is selected monovalence metallic cation Li
+With trivalent metal cation combination or selection divalent metal Mg
2+, Ca
2+In any and trivalent metal cation Al
3+, Cr
3+In any combination.
3. according to right 1 described metal sulfide semiconductor nanometer composite material, it is characterized in that: organic ligand is selected complexone or hydroxyl carboxylic complexing agent.
4. according to right 3 described metal sulfide semiconductor nanometer composite materials, it is characterized in that: complexone comprises: ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA), teiethylene tetramine-hexacetic acid, ethyl ether diamine tetraacetic acid, cyclohexanediaminetetraacetic acid, pregnancy ethylenediamine tetraacetic acid (EDTA); Hydroxyl carboxylic complexing agent is a citric acid.
5. according to right 1 described metal sulfide semiconductor nanometer composite material, it is characterized in that: a metal-organic complex has negative charge, can stable existence in pH=6～10 scopes in solution.
6. method for preparing metal sulfide semiconductor nanometer composite material is characterized in that: concrete preparation technology is:
A. preparing interlayer anion is NO
3 -Perhaps Cl
-, laminate monovalence, Tricationic mol ratio M
+/ M
3+=0.5 or divalence, Tricationic mol ratio M
2+/ M
3+=2～4 hydrotalcite precursor;
B. oxide compound and citric acid, ethylenediamine tetraacetic acid (EDTA), the nitrilotriacetic acid(NTA) with Metal Zn or Cd reacts according to mol ratio respectively at 1: 1, it is 7～9 that organic acid is transferred its pH value with metal oxide dissolving back with NaOH, prepares electronegative a metal-organic complex;
C. be NO with electronegative a metal-organic complex and interlayer anion
3 -Perhaps Cl
-The hydrotalcite precursor at N
2Protection is also stirred down, and 25～65 ℃ were reacted 2～24 hours down, and product spends CO
2Water thorough washing, centrifugal obtains a metal-organic complex intercalated houghite powder after 25～65 ℃ of following dryings;
D. a metal-organic complex intercalated houghite powder is placed the H of 10～100ml/min
2Reacted in the S atmosphere 2～12 hours, product is at N
2Kept 12 hours in the atmosphere, obtain metal sulfide semiconductor nanometer composite material.
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| CN101343540B (en) * | 2008-08-28 | 2011-02-16 | 上海交通大学 | Method for preparing quantum point with hyperbranched polymer supermolecule nano-reactor |
| CN102335627B (en) * | 2011-06-28 | 2013-03-06 | 太原理工大学 | Preparation method of metal complex functionalized hydrotalcite-like nano-layer sheet |
| CN102931247B (en) * | 2012-10-23 | 2014-12-24 | 北京化工大学 | Preparation method of polyaniline and II-VI family semiconductor compound photovoltaic conversion film |
| CN103191783B (en) * | 2013-04-18 | 2014-11-05 | 北京化工大学 | Zinc sulfide-benzoic acid nano composite photocatalytic material and preparation method thereof |
| CN106047348B (en) * | 2016-05-24 | 2018-02-06 | 合肥工业大学 | A kind of β NaYF4:The preparation method of Yb, Tm@CdS core shell nanostructureds |
| CN105948086B (en) * | 2016-05-30 | 2018-01-30 | 长沙学院 | Citric acid pillared hydrotalcite supramolecular materials and its intercalation assemble method |
| CN109759087B (en) * | 2019-01-16 | 2022-02-08 | 安徽大学 | NiS/MgAl-LDH photocatalyst and preparation method and application thereof |
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| CN1381510A (en) * | 2001-04-18 | 2002-11-27 | 中国科学院理化技术研究所 | Process for preparing composite nano metal sulfide particle/polymer material |
| CN1472165A (en) * | 2002-07-29 | 2004-02-04 | 北京化工大学 | Method for preparing magnetic ferrite from layered precursor |
| CN1608998A (en) * | 2004-09-16 | 2005-04-27 | 复旦大学 | Prepn process of metal oxide and sulfide nanometer linear array |
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| US5318936A (en) * | 1992-09-23 | 1994-06-07 | Uop | Catalyst for sweetening a sour hydrocarbon fraction containing metal oxide solid solution and magnesium oxide |
| CN1381510A (en) * | 2001-04-18 | 2002-11-27 | 中国科学院理化技术研究所 | Process for preparing composite nano metal sulfide particle/polymer material |
| CN1472165A (en) * | 2002-07-29 | 2004-02-04 | 北京化工大学 | Method for preparing magnetic ferrite from layered precursor |
| CN1616495A (en) * | 2003-11-13 | 2005-05-18 | 北京化工大学 | Preparing nano sheet type polymer using LDHs as template and its preparing method |
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