CN108213414A - A kind of method and its application for coating MOF and improving gold nano cluster photostability - Google Patents
A kind of method and its application for coating MOF and improving gold nano cluster photostability Download PDFInfo
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- CN108213414A CN108213414A CN201711475768.4A CN201711475768A CN108213414A CN 108213414 A CN108213414 A CN 108213414A CN 201711475768 A CN201711475768 A CN 201711475768A CN 108213414 A CN108213414 A CN 108213414A
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Abstract
The invention discloses a kind of method for coating MOF and improving gold nano cluster photostability, this method includes the following steps：On gold nano cluster surface, liquid phase in-stiu coating sheet metal organic frame is as clad；The metal organic frame is zeolite imidazole ester frame structure material, and the thickness of the clad is 0.5~10nm.Metal organic frame cladding gold nano cluster composite material and its that the above method is prepared are also disclosed in photo catalytic reduction CO2Application in reaction.The advantage of the invention is that：Using in situ synthesis cladding thin layer MOF; MOF is not directly coated in gold nano cluster by surface modification; so as to improve its photostability; this method is low temperature liquid phase Moist chemical synthesis method; it will not have any impact to the performance of gold nano cluster; and method is simple for process, and reaction condition is mild, controllability is strong, low energy consumption, is easy to large-scale promotion application.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, are more particularly to a kind of cladding metal organic frame (MOF) and carry
It the method for high gold nano cluster photostability and its is used for.
Background technology
Golden (Au) nanocluster is to accumulate the little particle formed, size and Fermi's wavelength by several to hundreds of gold atoms
Quite, the property of based semiconductor is showed, there are good extinction and luminescent properties, in photocatalysis, fluorescent marker, biochemistry
The fields such as sensing, photoelectric material have potential application prospect.But due to its minimum size and high surface energy, gold nano
Cluster can reunite under illumination condition, gold nano grain be formed, so as to lose its unique optical property.Liu et al. people is led to
Cross illumination lure draw gold nano cluster reunite prepare gold nano grain [ACS Appl.Mater.Interfaces, 2015,7,
28105–28109].Au nanoclusters are used as powder TiO by P.V.Kamat et al.2The sensitizer of photochemical catalyst, in photocatalysis point
After during solution aquatic products hydrogen reaction 3h, gold nano cluster is largely agglomerated into gold nano grain, loses photocatalytic activity
[J.Am.Chem.Soc.,2014,136,6075-6082].Therefore, the photostability of gold nano cluster is improved to giving full play to it
Unique optical property has great importance.The method of traditional raising gold nano cluster photostability have element doping method and
Cladding process.The former adulterates the coordination environment for changing gold nano cluster by other elements, to improve its photostability [Gold
Bull(2015)48:161–167].Though the method can play stabilization to part gold nano cluster, which changes gold nano
The electronic structure of cluster in itself can influence its photoelectric properties, and the method is easily reunited without fundamentally solving gold nano cluster
The problem of.The latter is to coat gold nano cluster using inert material, come improve its stability [J.Phys.Chem.C, 2016,
120,29348-29357], but the cladding of non-porous inert material masks the active sites on gold nano cluster surface, so the method is deposited
In larger limitation.The research that simple gold nano cluster is applied to photocatalysis field at present is also rarely reported.As one
Kind novel based semiconductor material, it has unique advantage, especially, Aurum clusters can atom level accurately prepare, based on
Research provides good model catalyst.But gold nano cluster is easily reunited under light illumination, hinders its application.
Metal organic frame (MOFs) is that had by organic ligand and metal ion or cluster by what coordination assembled
The organic-inorganic hybrid material of periodical pore passage structure, it is adjustable etc. because being designed with high porosity, high-ratio surface and pore passage structure
Outstanding advantages are widely used in fields such as gas absorption separation, sensing and catalysis.In recent years, it by MOFs coatings or is coated to
Other materials are (such as：Metal/oxide nano-particle, dye molecule and protein molecule etc.) prepare the composite wood of nucleocapsid
Material solves the problems such as guest materials is reunited, component is lost in by the confinement of MOFs ducts and to give full play to MOFs ducts adjustable etc.
Advantage makes composite material have the properties such as selection absorption, selective catalysis, becomes selective catalysis, sensing and drug conveying etc.
The research hotspot in field.Traditional method to guest materials cladding MOFs is broadly divided into two kinds：One kind is dipping osmosis,
Guest materials is filled in synthetic MOFs ducts, which is limited to MOF ducts size and fixes, and minimum ruler only can be filled
Very little nano material, and to guest materials, the distribution situation of position is difficult control in MOFs ducts；Another kind is packet in situ
Method is covered, is that MOF materials [Nature Chemistry 2012,4,310-316 are grown in guest materials surface in situ；Patent is public
The number of opening (CN 106117593A)], which has preferable universality and controllability, but the premise of the method is guest materials and growth
The metal ion or ligand of MOFs has interaction so that MOFs is grown in guest materials surface in situ.Existing original position
Cladding process needs first to be modified or wrapped up surfactant (such as to the surface of guest materials mostly：Polyvinylpyrrolidone, 16
Alkyl trimethyl ammonium bromide etc.), to promote the interaction of guest materials and MOFs presomas, but the ligand of surface modification and
Surfactant is difficult often removal, so as to influence the property of guest materials in itself.
In conclusion gold nano cluster photostability is poor, conventional method restricted application, and cannot fundamentally solve
The problem of certainly illumination is easily reunited.
Invention content
The technical problems to be solved by the invention are the provision of a kind of simple for process, mild condition that thickness is adjustable
MOF material in situ liquid phase coating the surface of gold nano cluster with improve the method for the photostability of gold nano cluster and its should
With.
The present invention is to solve above-mentioned technical problem by the following technical programs：
On the one hand, a kind of method for coating MOF and improving gold nano cluster photostability is provided, is included the following steps：In gold
Nanocluster surface liquid phase in-stiu coating sheet metal organic frame (MOF) is as clad, so as to make gold nano cluster uniform
It is dispersed in MOF to significantly improve the photostability of gold nano cluster；The metal organic frame is zeolite imidazole ester skeleton knot
Structure material, the thickness of the clad is 0.5~10nm.
Preferably, the method that cladding MOF improves gold nano cluster photostability includes the following steps：
By in gold nano cluster ultrasonic disperse to water, gold nano cluster dispersion liquid is formed, the gold nano cluster is disperseed
Liquid is cooled to 0~5 DEG C, adds in 2-methylimidazole thereto, and stirring adds the ice water solution of metal ion to after dissolving, then
5~180min of reaction is stood, centrifuges, wash, is dry, metal organic frame is made to coat gold nano cluster.
Preferably, the temperature of the ultrasonic disperse is no more than 20 DEG C, and the ultrasonic disperse carries out 30min under 90Hz.
Preferably, the metal ion is Zn2+Or Co2+。
Preferably, the molar ratio of 2-methylimidazole and metal ion is 1~6:1.
Preferably, the preparation method of the gold nano cluster includes：Golden source is soluble in water, add in the stirring of sulfydryl complex
To colourless, 6~72h is then reacted at 40~100 DEG C, adds in acetonitrile as precipitating reagent, centrifugation, with acetonitrile/water=3/1
Solution washing, the drying of (volume ratio), obtain gold nano cluster；Or
Golden source is soluble in water, and ammonium bromide and tetraoctyl ammonium bromide is dissolved in toluene, is vigorously stirred after two kinds of solution are mixed, and is stood and is divided
Layer removes water phase, collects oil phase, N is passed through into the oil phase2And 0 DEG C is cooled to, the benzene ethyl mercaptan with golden equimolar amounts is added in,
Stirring at low speed obtains colourless solution, then rapidly joins NaBH into the colourless solution under quick stirring4, N2Protection is lower to stir
Overnight, it is washed, dried with absolute ethyl alcohol, obtain gold nano cluster.
Preferably, the Jin Yuan is selected from any one of gold chloride, chlorauride and gold potassium chloride.
Preferably, the sulfydryl complex is selected from reduced glutathione, benzene ethyl mercaptan, to mercaptobenzoic acid, two (two
Phenyl phosphino-) any one of methane and three (p-methoxyphenyl) phosphines, more it is selected as reduced glutathione.
Preferably, the number of the washing 3 times.
On the other hand, providing the metal that the method that above-mentioned cladding MOF improves gold nano cluster photostability is prepared has
Machine frame coats gold nano cluster composite material.
Another aspect also provides above-mentioned metal organic frame and coats gold nano cluster composite material in photo catalytic reduction CO2
Application in reaction.
Preferably, the application is realized by following steps：Gold nano cluster composite material is coated to metal organic frame
Middle addition sacrifice agent stirs lower logical CO2To discharge air, photo catalytic reduction CO is carried out using xenon source simulated solar irradiation2It is real
It tests.
Preferably, the sacrifice agent is the triethylamine solution or methanol solution that volume ratio is 5~20%.
The present invention has the following advantages compared with prior art：The present invention coats thin layer MOF using in situ synthesis, does not pass through
Surface modification directly coats MOF in gold nano cluster, and so as to improve its photostability, this method is low temperature liquid phase Moist chemical synthesis
Method will not have any impact to the performance of gold nano cluster, and method is simple for process, reaction condition is mild, controllability is strong,
Low energy consumption, is easy to large-scale promotion application；Obtained metal organic frame coats gold nano cluster composite material set MOF materials
Expect abundant duct and the excellent photoelectrochemical behaviour of gold nano cluster, abundant duct is the mass transfer of reactants and products molecule
Good channel is provided, and under the confinement of MOF materials, the reunion of gold nano cluster can be effectively prevented, so as to improve it
Photostability；Gold nano cluster favorable dispersibility in metal organic frame, photostability are substantially improved in composite material, can follow
Ring uses, and has a good application prospect in terms of photoelectric material.
Description of the drawings
Fig. 1 is solid gold nano cluster (Au prepared by embodiment 1x) transmission electron microscope photo；
Fig. 2 is that metal organic frame prepared by embodiment 1 coats gold nano cluster (Aux@MOF) composite material transmission electricity
Mirror photo；
Fig. 3 is Au prepared by embodiment 1xTransmission electron microscope photo after illumination reaction 3h；
Fig. 4 is Au prepared by embodiment 1xTransmission electron microscope photo after@MOF composite material illumination reactions 12h；
Fig. 5 is Au prepared by embodiment 1xUltraviolet-visible absorption spectroscopy figure after illumination reaction 3h；
Fig. 6 is Au prepared by embodiment 1xUltraviolet-visible absorption spectroscopy figure after@MOF composite material illumination reactions 12h；
Fig. 7 is Au prepared by embodiment 2xThe transmission electron microscope photo of@MOF composite materials；
Fig. 8 is Au prepared by embodiment 2xTransmission electron microscope photo after@MOF composite material illumination reactions 12h；
Fig. 9 is Au prepared by embodiment 3xThe transmission electron microscope photo of@MOF composite materials；
Figure 10 is Au prepared by embodiment 3xTransmission electron microscope photo after@MOF composite material illumination reactions 12h.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
A kind of metal organic frame cladding gold nano cluster (Aux@ZIF-8) composite material, it is prepared by following steps：
By 48.5mg HAuCl4·4H2O is dissolved in 30mL water, adds 50mg reduced glutathiones, and stirring 2h to solution is in colourless, so
The gold nano cluster solution for for 24 hours, obtaining yellow is reacted at 70 DEG C afterwards；90mL is added in into the gold nano cluster solution of the yellow
For acetonitrile as precipitating reagent, 8000rpm centrifuges sediment separate out after 5min, and will be heavy with the solution of acetonitrile/water=3/1 (volume ratio)
Starch is washed 3 times, and pure solid gold nano cluster is obtained after dry；Again by solid gold nano cluster (Au at 20 DEG Cx) with
90Hz ultrasounds 30min is distributed in 25mL water, forms gold nano cluster dispersion liquid；The gold nano cluster dispersion liquid formed is used
Ice-water bath is cooled to 0 DEG C, adds in 410mg 2-methylimidazoles thereto, and stirring is to dissolving, then by 3mL Zn containing 371mg
(NO3)2·6H2The ice water solution of O is added thereto, and stops stirring immediately, is stood reaction 5min, is centrifuged, three are washed with clear water
It is secondary, it is dry at 40 DEG C, obtain Aux@ZIF-8 composite materials.
With the prepared Au of transmission electron microscope (TEM) observationx@ZIF-8 composite materials, the results are shown in Figure 2, can be with by Fig. 2
Find out the ZIF-8 for having coated that a layer thickness is about 1nm around the gold nano cluster of size 1.3nm or so, gold nano cluster exists
It is uniformly dispersed in ZIF-8.TEM photos after the illumination of 12h are as shown in figure 4, from fig. 4, it can be seen that Aux@ZIF-8
What pattern essentially unchangedization of composite material, the size of gold nano cluster also change without.It is observed with transmission electron microscope (TEM) pure
Gold nano cluster and by 3h illumination after pure gold nano cluster, as a result as shown in figures 1 and 3, from Fig. 1 and figure
3 as can be seen that the size of gold nano cluster increases 3nm or so (Fig. 3) by original 1.3nm (Fig. 1) after illumination.By
Ultraviolet-visible spectrometer measures after pure gold nano cluster illumination reaction 3h and AuxAfter@ZIF-8 composite material illumination reactions 12h
UV-vis DRS collection of illustrative plates, as a result as shown in Figure 5 and Figure 6, it can be seen that the UV, visible light of pure gold nano cluster is overflow instead
The plasma resonance absorption peak that collection of illustrative plates has apparent gold is penetrated, illustrates that pure gold nano cluster has occurred seriously during the reaction
Agglomerated into gold nano grain (Fig. 5), and coat the Au of MOFxThe plasma resonance of cash is not gone out after@ZIF-8 reactions
It absorbs (Fig. 6).The result of comprehensive TEM and UV-vis DRS can obtain, gold nano cluster after MOF is coated, light is steady
It is qualitative to have obtained significantly being promoted.
The Au that will be preparedx@ZIF-8 composite materials are used for photo catalytic reduction CO2Reaction：Take 10mgAux@ZIF-8 are compound
Material is added in 10mL 5% (volume ratio) triethanolamine solution, stirs lower logical CO230min utilizes xenon to discharge air
Lamp source simulated solar irradiation carries out photo catalytic reduction CO2Experiment quantitative determines the amount of product using gas chromatograph.It is surveyed
Product has CO and H2, generating rate is respectively 0.15 μm of ol/gh, H of CO2 3.26μmol/g·h。
Embodiment 2
A kind of metal organic frame cladding gold nano cluster Aux@ZIF-67 composite materials, are prepared by following steps：
By 48.5mg HAuCl4·4H2O is dissolved in 30mL water, adds 50mg reduced glutathiones, and stirring 2h to solution is in colourless, so
The gold nano cluster solution for for 24 hours, obtaining yellow is reacted at 70 DEG C afterwards；90mL is added in into the gold nano cluster solution of the yellow
For acetonitrile as precipitating reagent, 8000rpm centrifuges sediment separate out after 5min, and will be heavy with the solution of acetonitrile/water=3/1 (volume ratio)
Starch is washed 3 times, and pure solid gold nano cluster is obtained after dry；Again by solid gold nano cluster (Au at 10 DEG Cx) with
90Hz ultrasounds 30min is distributed in 25mL water, forms gold nano cluster dispersion liquid；The gold nano cluster dispersion liquid formed is used
Ice-water bath is cooled to 0 DEG C, adds in 600mg 2-methylimidazoles thereto, and stirring is to dissolving, then by 3mL Co containing 370mg
(NO3)2·6H2The ice water solution of O is added thereto, and stops stirring immediately, is stood reaction 20min, is centrifuged, three are washed with clear water
It is secondary, it is dry at 40 DEG C, obtain lilac Aux@ZIF-67 composite materials.
With the prepared Au of transmission electron microscope (TEM) observationx@ZIF-67 composite materials, the results are shown in Figure 7, can be with by Fig. 7
Find out, AuxCladdings of the thin layer ZIF-67 to gold nano cluster, and the thickness of ZIF-67 are realized in@ZIF-67 composite materials
About 1.5nm, gold nano cluster dispersed phase in ZIF-67 are good.TEM photos after the illumination of 12h as shown in figure 8,
From figure 8, it is seen that by the illumination of 12h, gold nano cluster pattern keeps good, does not reunite, illustrates ZIF-67's
Cladding can improve AuxThe photostability of gold nano cluster in@ZIF-67 composite materials.
The Au that will be preparedx@ZIF-67 composite materials are used for photo catalytic reduction CO2Reaction：Take 10mgAux@ZIF-67 are answered
Condensation material is added in 10mL 20% (volume ratio) methanol solution, stirs lower logical CO230min utilizes xenon lamp to discharge air
Light source analogy sunlight carries out photo catalytic reduction CO2Experiment quantitative determines the amount of product using gas chromatograph.The production surveyed
Object has CO and H2, generating rate is respectively CO0.052 μm of ol/gh, H2 6.31μmol/g·h。
Embodiment 3
A kind of metal organic frame cladding gold nano cluster (Aux@ZIF-8) composite material, it is prepared by following steps：
By 164.7mg HAuCl4·4H2O is dissolved in 5mL water, and 255.8mg ammonium bromide and tetraoctyl ammonium bromides are dissolved in 10mL toluene, and two kinds of solution mix
It closes, is vigorously stirred 15min, stratification removes water phase, collects oil phase, leads to N230min, and 0 DEG C is cooled to, addition and gold etc.
The benzene ethyl mercaptan of mole, stirring at low speed 1h obtain colourless solution；Then it is rapidly joined under quick stirring into colourless solution
155mg NaBH4, N2It is stirred overnight under protection, is washed three times with absolute ethyl alcohol, pure solid gold nano group is obtained after dry
Cluster；Again by solid gold nano cluster (Au at 20 DEG Cx) be distributed in 25mL water with 90Hz ultrasounds 30min, form gold nano group
Cluster dispersion liquid；The gold nano cluster dispersion liquid formed is cooled to 0 DEG C with ice-water bath, adds in 1.64g 2- methyl miaows thereto
Azoles, stirring is to dissolving, then by 5mL Zn containing 1.48mg (NO3)2·6H2The ice water solution of O is added thereto, and stops stirring immediately, quiet
Reaction 30min is put, centrifuges, is washed three times with clear water, it is dry at 40 DEG C, obtain Aux@ZIF-8 composite materials.
With the prepared Au of transmission electron microscope (TEM) observationx@ZIF-8 composite materials, the results are shown in Figure 9, can be with by Fig. 9
Find out, AuxCladdings of the thin layer ZIF-8 to gold nano cluster is realized in@ZIF-8 composite materials, and the thickness of ZIF-8 is about
0.8nm, gold nano cluster dispersed phase in ZIF-8 are good.TEM photos after the illumination of 12h are as shown in Figure 10, from figure
10 as can be seen that pass through the illumination of 12h, and gold nano cluster pattern keeps good, does not reunite, illustrates the cladding of ZIF-8
Au can be improvedxThe photostability of gold nano cluster in@ZIF-8 composite materials.
The Au that will be preparedx@ZIF-8 composite materials are used for photo catalytic reduction CO2Reaction：Take 10mgAux@ZIF-8 are compound
Material is added in 10mL 5% (volume ratio) triethanolamine solution, stirs lower logical CO230min utilizes xenon to discharge air
Lamp source simulated solar irradiation carries out photo catalytic reduction CO2Experiment quantitative determines the amount of product using gas chromatograph.It is surveyed
Product is mainly H2, generating rate is 2.55 μm of ol/gh.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (9)
- A kind of 1. method for coating MOF and improving gold nano cluster photostability, which is characterized in that the method includes following steps Suddenly：On gold nano cluster surface, liquid phase in-stiu coating sheet metal organic frame is as clad；The metal organic frame is Zeolite imidazole ester frame structure material, the thickness of the clad is 0.5~10nm.
- 2. the method that cladding MOF according to claim 1 improves gold nano cluster photostability, which is characterized in that including Following steps：In gold nano cluster ultrasonic disperse to water, gold nano cluster dispersion liquid will be formed, the gold nano cluster dispersion liquid is cold But to 0~5 DEG C, 2-methylimidazole is added in thereto, and stirring adds the ice water solution of metal ion to after dissolving, then stands 5~180min is reacted, centrifuges, wash, is dry, metal organic frame is made to coat gold nano cluster.
- 3. the method that cladding MOF according to claim 2 improves gold nano cluster photostability, which is characterized in that described The temperature of ultrasonic disperse is no more than 20 DEG C, and the ultrasonic disperse carries out 30min under 90Hz.
- 4. the method that cladding MOF according to claim 2 improves gold nano cluster photostability, which is characterized in that described Metal ion is Zn2+Or Co2+。
- 5. the method that cladding MOF according to claim 2 improves gold nano cluster photostability, which is characterized in that 2- first The molar ratio of base imidazoles and metal ion is 1~6:1.
- 6. the method that cladding MOF according to claim 2 improves gold nano cluster photostability, which is characterized in that described The preparation method of gold nano cluster includes：Golden source is soluble in water, it adds in sulfydryl complex and stirs to colourless, 6~72h is then reacted at 40~100 DEG C, add in Acetonitrile is centrifuged, is that the solution of acetonitrile/water=3/1 wash, dried with volume ratio, obtain gold nano cluster as precipitating reagent； OrGolden source is soluble in water, and ammonium bromide and tetraoctyl ammonium bromide is dissolved in toluene, is vigorously stirred after two kinds of solution are mixed, stratification is gone Fall water phase, collect oil phase, N is passed through into the oil phase2And 0 DEG C is cooled to, add in the benzene ethyl mercaptan with golden equimolar amounts, low speed Colourless solution is stirred to get, then rapidly joins NaBH into the colourless solution under quick stirring4, N2It is stirred overnight under protection, It is washed, dried with absolute ethyl alcohol, obtain gold nano cluster.
- 7. the method that cladding MOF according to claim 6 improves gold nano cluster photostability, which is characterized in that described Jin Yuan is selected from any one of gold chloride, chlorauride and gold potassium chloride.The sulfydryl complex is selected from reduced glutathione, benzene ethyl mercaptan, to mercaptobenzoic acid, two (diphenylphosphino) first Any one of alkane and three (p-methoxyphenyl) phosphines.
- 8. the method that the cladding MOF described in a kind of any one of claim 1 to 7 improves gold nano cluster photostability is prepared into The metal organic frame cladding gold nano cluster composite material arrived.
- 9. a kind of application of MOF claddings gold nano cluster composite material according to any one of claims 8, which is characterized in that by the gold Belong to organic frame cladding gold nano cluster composite material and be used for photo catalytic reduction CO2Reaction.
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