CN109317204A - Synthesis method of nickel cluster and Ni @ MOFs composite material - Google Patents
Synthesis method of nickel cluster and Ni @ MOFs composite material Download PDFInfo
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- CN109317204A CN109317204A CN201811205092.1A CN201811205092A CN109317204A CN 109317204 A CN109317204 A CN 109317204A CN 201811205092 A CN201811205092 A CN 201811205092A CN 109317204 A CN109317204 A CN 109317204A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 title abstract description 15
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 239000002184 metal Substances 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 12
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 53
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000010189 synthetic method Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 239000013049 sediment Substances 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 229910007926 ZrCl Inorganic materials 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- -1 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 230000000670 limiting effect Effects 0.000 abstract 1
- 150000002815 nickel Chemical class 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 239000010931 gold Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical class [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000013207 UiO-66 Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000000703 high-speed centrifugation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000155 isotopic effect Effects 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- ZFEZIAPMHMZNRS-UHFFFAOYSA-N 2-$l^{1}-sulfanyl-2-methylpropane Chemical compound CC(C)(C)[S] ZFEZIAPMHMZNRS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthesis method of nickel clusters, which comprises the following operations: reacting UIO-66-NH2、NiCl2.6H2Mixing O, tert-butyl mercaptan and sodium borohydride for reaction to obtain Ni14(S‑t‑Bu)18@UIO‑66‑NH2A composite material; mixing Ni14(S‑t‑Bu)18@UIO‑66‑NH2Soaking the composite material in dilute sulfuric acid solution to remove UIO-66-NH2Purifying to obtain Ni14A metal nanocluster. According to the technical scheme, the novel monodisperse metal nickel nanoclusters are synthesized by using regular pore channels of the metal organic framework material as a nano reactor, the pore channels have a limiting effect on nanoparticles and can control the growth of the nanoparticles, and then the framework of the metal organic framework material is broken through, so that the metal nanoclusters are released, and the nickel nanoclusters with accurate structures are obtained.
Description
Technical field
The present invention relates to metal nanometer clusters to synthesize field, and in particular to a kind of Ni cluster and Ni@MOFs composite material
Synthetic method.
Background technique
In recent years, largely the metal nanometer cluster with precision architecture is synthesized, such as Aurum clusters, Silver Clusters, copper group
Cluster and alloy cluster etc..Compared with metal nanoparticle, the metal nanometer cluster of precision architecture, which helps to understand to be catalyzed, to react
Journey explains mechanism of catalytic reaction.Due to the unique electronic structure of metal nanometer cluster and ultra-fine size (being less than 2nm) bring amount
Sub- dimensional effect causes the concern of domestic and foreign scholars.In all metallic catalysts, nickel is as a kind of base metal and magnetism gold
Belong to, is a kind of important metallic catalyst.So far, less about the research report of Ni cluster, the nickel that report comes out at present
Cluster has: Ni39(SC2H4Ph)24, Ni41(SC2H4Ph)25NCs, Ni6(SC2H4Ph)12Deng.
In order to control nanoparticle size size and monodispersity, there is the method thiol synthesis using solvent grading extraction
The gold nano grain of protection has obtained the gold particle that size range is 1.5~3.5nm, has also there is the method using dynamics Controlling
Synthesize that atom number is accurate, high yield Au25(SC2H4Ph)18.As the improvement and mass spectrum detection of cluster synthetic method are being rolled into a ball
Further development in cluster, to obtain metal nanometer cluster crystal, higher purity is important premise.Current metal
The synthetic method of cluster mainly has: liquid phase directly synthesizes and ligand exchange method etc., but in the process for obtaining single dispersion metal cluster
In, often face the problems such as separating-purifying step is complicated, yield is not high.For example, mass spectrographic research finds Au11:PPh3Nanometer
There is Au in cluster crude product9 -and Au10 -Generation, synthesize Au25:PPh3Crude product in the Au nano particle containing polydispersion.
Therefore, obtaining monodisperse, size uniformity, the metal nanometer cluster with precision architecture is particularly important.
Summary of the invention
The object of the present invention is to provide a kind of synthetic methods of Ni cluster.
The technical solution adopted by the present invention is that:
A kind of synthetic method of Ni cluster, which is characterized in that including operating as follows:
A01: by UIO-66-NH2、NiCl2.6H2O, tert-butyl mercaptan, sodium borohydride hybrid reaction synthesize to obtain Ni14(S-
t-Bu)18@UIO-66-NH2Composite material；
A02: by Ni14(S-t-Bu)18@UIO-66-NH2Composite material impregnates in dilution heat of sulfuric acid removes UIO-66-
NH2, can be prepared by Ni after purification14Metal nanometer cluster.
Specific scheme are as follows:
UIO-66-NH in step A012With NiCl2.6H2The molar ratio of O addition is 1:(5-10), UIO-66-NH2With tertiary fourth
The molar ratio of base mercaptan addition is 1:35, UIO-66-NH2Molar ratio with sodium borohydride addition is 1:1.3.
UIO-66-NH in step A012By ZrCl4, 2- amino terephthalic acid (TPA), N,N-dimethylformamide hybrid reaction close
At obtaining.
The concrete operations of step A01 are as follows: first by UIO-66-NH2It is dissolved in solvent A, adds NiCl2.6H2O is stirred
So that nickel ion enters in metal organic frame, tert-butyl mercaptan is then added, ice-water bath is stirred to react 4~6h, and stirring is anti-
The ethanol solution of sodium borohydride is added after answering, continue to be stirred to react 23~for 24 hours, it is then centrifuged for recycling to obtain sediment A, will sink
Starch A rotary evaporation can be prepared by Ni after removing unreacted ligand and by-product14(S-t-Bu)18@UIO-66-NH2Composite wood
Material.
The concrete operations of step A02 are as follows: by Ni14(S-t-Bu)18@UIO-66-NH2Composite material soaks in dilution heat of sulfuric acid
Bubble removes UIO-66-NH2, centrifugal treating recycles to obtain sediment B, sediment B dissolved with solvent B, centrifugal treating recycling
Then supernatant rotary evaporation removing solvent is obtained crude product, then carries out purifying to crude product with methanol and be made by supernatant
Ni14Metal nanometer cluster.
Produce UIO-66-NH2ZrCl in reaction4Molar ratio with the addition of 2- amino terephthalic acid (TPA) is 1:1, ZrCl4With N,
The molar ratio of dinethylformamide addition is 1:(1-2).
UIO-66-NH2The concrete operations of synthesis are as follows: first by ZrCl4, 2- amino terephthalic acid (TPA) ultrasonic dissolution to N, N- bis-
It in methylformamide, and is placed into the reaction kettle of polytetrafluoroethyllining lining, heated sealed reaction cools down after reaction
And be centrifuged and recycle to obtain sediment C, n,N-Dimethylformamide washing precipitate C is first used, then again with methanol is washed until N,
Dinethylformamide is replaced by methanol completely, can be prepared by UIO-66-NH after drying2。
Solvent A is the mixed liquor of tetrahydrofuran and methanol, and solvent B is methylene chloride or methanol.
The present invention also provides a kind of synthetic methods of Ni@MOFs composite material, which is characterized in that including operating as follows:
B01: by UIO-66-NH2、NiCl2.6H2O, tert-butyl mercaptan, sodium borohydride hybrid reaction synthesize to obtain Ni14(S-
t-Bu)18@UIO-66-NH2Composite material；
B02: using ethyl alcohol to Ni14(S-t-Bu)18@UIO-66-NH2Composite material is washed, and is carried out after washes clean
Calcination processing can be prepared by Ni14@UIO-66-NH2Composite material.
Specific: the temperature of calcination processing is 150~300 DEG C.
Compared with prior art, the technical effect that the present invention has are as follows: above-mentioned technical proposal utilizes metal organic frame material
Expect that the regular pore canal of (MOFs) is used as " nano-reactor ", synthesizes novel, single dispersion metal nickel nanocluster, duct is for receiving
The growth that rice grain has restriction effect, can control nano particle, then by breaking the frame of metal-organic framework material,
To release metal cluster, and then obtain the nickel nanocluster of precision architecture.This method is different from traditional liquid phase and closes
At the metal nanometer cluster of different sizes can be obtained by the MOFs in different ducts, therefore become a kind of novel conjunction
At method, new method and thinking also are proposed for the synthesis of metal nanometer cluster.
Detailed description of the invention
Fig. 1 is that Ni nanocluster is loaded in UIO-66-NH2Schematic diagram and its catalytic process in crystal duct；
Fig. 2 is the Ni produced in embodiment 314The ultraviolet-visible spectrogram of metal nanometer cluster；
Fig. 3 is the Ni produced in embodiment 314The MALDI-TOF mass spectrogram of metal nanometer cluster, wherein illustration is Ni14
(S-t-Bu)18Experiment with simulation isotopic peak；
Fig. 4 is the Ni produced in embodiment 314The TG of metal nanometer cluster schemes, weightlessness 66.8%；
Fig. 5 is the UIO-66 (NH produced in embodiment2)、Ni14@UIO-66-NH2、Ni14@UIO-66-NH2(150) and
Ni14@UIO-66-NH2XRD spectrum；
Fig. 6 is the UIO-66 (NH produced in embodiment2)、Ni14@UIO-66-NH2、Ni14@UIO-66-NH2(150) and
Ni14@UIO-66-NH2N2Adsorption and desorption isotherms figure；
Fig. 7 is the high power TEM figure for each product produced in embodiment, wherein figure (a) is Ni14@UIO-66-NH2High power
TEM figure, scale 10nm；Scheming (b) is unburnt Ni14@UIO-66-NH2The high power TEM of (1.4 ± 0.2nm) schemes, and scale is
5nm；Scheming (c) is Ni14@UIO-66-NH2(150) the high power TEM figure of (1.9 ± 0.2nm), scale 5nm；Scheming (d) is Ni14@
UIO-66-NH2(300) high power TEM figure, scale 5nm.
Specific embodiment
In order to which objects and advantages of the present invention are more clearly understood, the present invention is carried out with reference to embodiments specific
It is bright.It should be appreciated that following text is only used to describe one or more of specific embodiments of the invention, not to the present invention
The protection scope specifically requested carries out considered critical.
Reagent and operating method as used in this document, in addition to special instruction, according to the conventional general of this field
Thought is understood.
1 UIO-66-NH of embodiment2Synthesis
Utilize solvent structure UIO-66-NH2:
By the ZrCl of 298.4mg4130mL N, N- dimethyl formyl are dissolved into 232.1mg 2- amino terephthalic acid (TPA)
In amine (DMF), ultrasound is made it dissolve, and is placed into the reaction kettle of polytetrafluoroethyllining lining, and reaction kettle is sealed, and is placed in
It is reacted 24 hours in 120 DEG C of baking ovens, the product after natural cooling is precipitated by centrifuging and taking, and precipitating is washed for several times with DMF, then uses first
Alcohol washing is replaced by methanol completely until DMF, and precipitating is then placed in 80 DEG C of oven overnight drying, can be prepared by UIO-66-
NH2。
2 Ni of embodiment14(S-t-Bu)18@UIO-66-NH2The synthesis of composite material
Weigh the 100mg UIO-66-NH produced in embodiment 12Powder is added to the mixed of 8ml tetrahydrofuran and 2ml methanol
It in bonding solvent, is slowly stirred and forms it into light yellow uniform suspension, then by the NiCl of 45mg (0.42mmol)2·6H2O
Stirring 2 hours are added in above-mentioned suspension and are continued, Ni is made2+It is able to enter in the frame of MOF.Then by 0.290mL
(2.17mmol) tert-butyl mercaptan (S-t-Bu) is added thereto to form mixed liquor, is stirred to react it persistently in ice bath 5 hours,
The ethanol solution for being rapidly added 6ml sodium borohydride into reaction solution at this time (contains NaBH in solution4: 30mg), solution colour is vertical
Become black by orange-yellow, stir the reaction solution persistently 24 hours, products therefrom is by high speed centrifugation, rotary evaporation to remove
The by-product in unreacted ligand and liquid phase is removed, obtained sediment is Ni14(S-t-Bu)18@UIO-66-NH2Composite wood
Material.
3 Ni of embodiment14The synthesis of metal nanometer cluster
By Ni obtained in embodiment 214(S-t-Bu)18@UIO-66-NH2Composite material, which is placed in dilution heat of sulfuric acid, to be impregnated,
So that UIO-66-NH2Structure collapse, centrifugation recycling sediment.It is then that this sediment is molten with methylene chloride/methanol mixed solvent
Solution, its supernatant of centrifuging and taking, using rotary evaporation this supernatant to remove solvent, obtained product is Ni14Metal nano group
Then cluster crude product purifies Ni14 metal nanometer cluster crude product with methanol repeatedly, can be prepared by after Economical Purification pure
Ni14Metal nanometer cluster.
4 Ni of embodiment14@UIO-66-NH2The synthesis of composite material
By Ni obtained in embodiment 214(S-t-Bu)18@UIO-66-NH2Composite material ethyl alcohol is repeated multiple times to wash away table
The solvent in face, the active sites for then removing some ligands by 150 DEG C, 300 DEG C of different temperatures calcination processing, exposing Ni cluster
Point can be prepared by Ni after calcination processing14@UIO-66-NH2Composite material.Wherein 150 DEG C of calcination processing products obtained therefroms are denoted as:
Ni14@UIO-66-NH2(150)；300 DEG C of calcination processing products obtained therefroms are denoted as: Ni14@UIO-66-NH2(300)。
Embodiment 5
It is detected to product is made in embodiment 2~4, the result of detection is as shown in table 1 and Fig. 2~7.
By UV-visible spectrum (Fig. 2) it is found that the absorption peak of nickel metal cluster obtained exists respectively in embodiment 3
300,375,465and 590nm did not met report so far, illustrated that this is a new nickel metal nanometer cluster.According to Ni metal
The MALDI-TOF mass spectrogram (Fig. 3) of cluster can carry out the simulation of isotopic peak, in conjunction with TG's (Fig. 4) as a result, can speculate the group
The molecular formula of cluster is Ni14(S-t-Bu)18, UIO-66-NH that Fig. 5,6 show the present invention crystal diffraction peak synthesized and simulation2Mark
Quasi- diffraction maximum is completely the same, unburnt Ni14@UIO-66-NH2、Ni14@MOF (150) and Ni14The XRD of@MOF (300) sample
Do not occur the diffraction maximum of nickel in map, illustrates that the size of nickel nanocluster is very small.Meanwhile as shown in table 1, from the ratio table of sample
From the point of view of the pore structures property such as area, pore volume and aperture, pure UIO-66-NH2Meet langmuirI type adsorption isotherm, than
Surface area reaches 687m2g-1.When nickel metal nanoparticle is loaded into wherein, Ni14@UIO-66-NH2There are many specific surface area decline,
Surface Ni cluster has successfully been filled into the duct of MOFs material.Work as Ni14@UIO-66-NH2Material calcination at a temperature of 150 DEG C
Afterwards, the ligand of Ni cluster falls off, so that specific surface area increases, but when temperature is increased to 300 DEG C, exposed nickel metal cluster can
Can partially it reunite.
TEM figure (Fig. 7) shows the Ni that the present invention obtains14@UIO-66-NH2Sample, wherein nickel metal cluster successfully loads
UIO-66-NH is arrived2In, Ni14@UIO-66-NH2、Ni14@UIO-66-NH2(150) and Ni14@UIO-66-NH2(300) ruler
Very little is respectively 1.4 ± 0.2nm, 1.9 ± 0.2nm, 2.1 ± 0.2nm.Therefore, with the raising of calcination temperature, Ni cluster may
There is agglomeration.Obtain the composite material of large specific surface area, moderate processing again to the active site of exposure Ni cluster
Temperature is 150 DEG C.
1 UIO-66 (NH of table2) package Ni cluster sample physicochemical structure property
The present invention has synthesized 14 nickel originals using its specific pore size using the template that MOFs material is that cluster synthesizes
The metal cluster of son.MOFs is also outstanding carrier simultaneously, being capable of stable metal cluster.This kind of metal cluster@MOF composite material
It will can be used for being catalyzed organic reaction, since metal cluster has good computation model, which will be helpful to Nanosurface catalysis
Mechanism, also provide more opportunities for heterogeneous catalysis.
6 UIO-66-NH of embodiment2Synthesis
Utilize solvent structure UIO-66-NH2:
By the ZrCl of 0.1mol4The N of 0.1mol, N- dimethyl formyl are dissolved into 0.1mol 2- amino terephthalic acid (TPA)
In amine (DMF), ultrasound is made it dissolve, and is placed into the reaction kettle of polytetrafluoroethyllining lining, and reaction kettle is sealed, and is placed in
It is reacted 24 hours in 120 DEG C of baking ovens, the product after natural cooling is precipitated by centrifuging and taking, and precipitating is washed for several times with DMF, then uses first
Alcohol washing is replaced by methanol completely until DMF, and precipitating is then placed in 80 DEG C of oven overnight drying, can be prepared by UIO-66-
NH2。
7 UIO-66-NH of embodiment2Synthesis
Utilize solvent structure UIO-66-NH2:
By the ZrCl of 0.1mol4The N of 0.2mol, N- dimethyl formyl are dissolved into 0.1mol 2- amino terephthalic acid (TPA)
In amine (DMF), ultrasound is made it dissolve, and is placed into the reaction kettle of polytetrafluoroethyllining lining, and reaction kettle is sealed, and is placed in
It is reacted 24 hours in 120 DEG C of baking ovens, the product after natural cooling is precipitated by centrifuging and taking, and precipitating is washed for several times with DMF, then uses first
Alcohol washing is replaced by methanol completely until DMF, and precipitating is then placed in 80 DEG C of oven overnight drying, can be prepared by UIO-66-
NH2。
8 Ni of embodiment14(S-t-Bu)18@UIO-66-NH2The synthesis of composite material
Weigh the UIO-66-NH of the 0.1mmol produced in embodiment 12Powder is added to 8ml tetrahydrofuran and 2ml methanol
In the mixed solvent, be slowly stirred and form it into light yellow uniform suspension, then by the NiCl of 0.5mmol2·6H2O is added
In above-mentioned suspension and continue stirring 2 hours, to make Ni2+It is able to enter in the frame of MOF.Then by the tert-butyl sulphur of 3.5mmol
Alcohol (S-t-Bu) is added thereto to form mixed liquor, is stirred to react it persistently in ice bath 5 hours, rapid into reaction solution at this time
The ethanol solution containing 0.13mol sodium borohydride is added, solution colour becomes black by orange-yellow immediately, continues the reaction solution
Stirring 24 hours, products therefrom, to remove the by-product in unreacted ligand and liquid phase, are obtained by high speed centrifugation, rotary evaporation
To sediment be Ni14(S-t-Bu)18@UIO-66-NH2Composite material.
Embodiment 9Ni14(S-t-Bu)18@UIO-66-NH2The synthesis of composite material
Weigh the UIO-66-NH of the 0.1mmol produced in embodiment 12Powder is added to 8ml tetrahydrofuran and 2ml methanol
In the mixed solvent, be slowly stirred and form it into light yellow uniform suspension, then by the NiCl of 1mmol2·6H2In O addition
Stirring 2 hours are stated in suspension and continued, Ni is made2+It is able to enter in the frame of MOF.Then by the tert-butyl mercaptan of 3.5mmol
(S-t-Bu) it is added thereto to form mixed liquor, is stirred to react it persistently in ice bath 5 hours, adds rapidly into reaction solution at this time
Enter the ethanol solution containing 0.13mol sodium borohydride, solution colour becomes black by orange-yellow immediately, stirs the reaction solution persistently
It mixes 24 hours, products therefrom, to remove the by-product in unreacted ligand and liquid phase, is obtained by high speed centrifugation, rotary evaporation
Sediment be Ni14(S-t-Bu)18@UIO-66-NH2Composite material.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the principle of the present invention, it can also make several improvements and retouch, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of Ni cluster, which is characterized in that including operating as follows:
A01: by UIO-66-NH2、NiCl2.6H2O, tert-butyl mercaptan, sodium borohydride hybrid reaction synthesize to obtain Ni14(S-t-
Bu)18@UIO-66-NH2Composite material；
A02: by Ni14(S-t-Bu)18@UIO-66-NH2Composite material impregnates in dilution heat of sulfuric acid removes UIO-66-NH2, it is pure
It can be prepared by Ni after change14Metal nanometer cluster.
2. the synthetic method of Ni cluster according to claim 1, which is characterized in that UIO-66-NH in step A012With
NiCl2.6H2The molar ratio of O addition is 1:(5-10)；UIO-66-NH2Molar ratio with tert-butyl mercaptan addition is 1:35, UIO-
66-NH2Molar ratio with sodium borohydride addition is 1:1.3.
3. the synthetic method of Ni cluster according to claim 1, which is characterized in that UIO-66-NH in step A012By ZrCl4、
2- amino terephthalic acid (TPA), N,N-dimethylformamide hybrid reaction synthesize to obtain.
4. the synthetic method of Ni cluster according to claim 1, which is characterized in that the concrete operations of step A01 are as follows: first will
UIO-66-NH2It is dissolved in solvent A, adds NiCl2.6H2O is stirred so that nickel ion enters in metal organic frame, with
After add tert-butyl mercaptan, ice-water bath is stirred to react 4~6h, after being stirred to react be added sodium borohydride ethanol solution,
Continue to be stirred to react 23~for 24 hours, be then centrifuged for recycling to obtain sediment A, by sediment A rotary evaporation remove unreacted ligand and
It can be prepared by Ni after by-product14(S-t-Bu)18@UIO-66-NH2Composite material.
5. the synthetic method of Ni cluster according to claim 1, which is characterized in that the concrete operations of step A02 are as follows: by Ni14
(S-t-Bu)18@UIO-66-NH2Composite material impregnates in dilution heat of sulfuric acid removes UIO-66-NH2, centrifugal treating recycles heavy
Starch B dissolves sediment B with solvent B, and centrifugal treating recycles supernatant, then removes supernatant rotary evaporation molten
Agent obtains crude product, is then carried out purifying obtained Ni to crude product with methanol14Metal nanometer cluster.
6. the synthetic method of Ni cluster according to claim 3, which is characterized in that produce UIO-66-NH2ZrCl in reaction4With
The molar ratio of 2- amino terephthalic acid (TPA) addition is 1:1, ZrCl4Molar ratio with N,N-dimethylformamide addition is 1:(1-
2)。
7. the synthetic method of Ni cluster according to claim 6, which is characterized in that UIO-66-NH2The concrete operations of synthesis are as follows:
First by ZrCl4, 2- amino terephthalic acid (TPA) ultrasonic dissolution be placed into polytetrafluoroethylene (PTFE) into n,N-Dimethylformamide
In the reaction kettle of liner, heated sealed reaction cools down after reaction and is centrifuged and recycle to obtain sediment C, first uses N, N- diformazan
Base formamide washing precipitate C, then again with methanol is washed until n,N-Dimethylformamide is replaced by methanol completely, after drying
It can be prepared by UIO-66-NH2。
8. the synthetic method of Ni cluster according to claim 4, it is characterised in that: solvent A is the mixed of tetrahydrofuran and methanol
Liquid is closed, solvent B is methylene chloride or methanol.
9. a kind of synthetic method of Ni@MOFs composite material, which is characterized in that including operating as follows:
B01: by UIO-66-NH2、NiCl2.6H2O, tert-butyl mercaptan, sodium borohydride hybrid reaction synthesize to obtain Ni14(S-t-
Bu)18@UIO-66-NH2Composite material；
B02: using ethyl alcohol to Ni14(S-t-Bu)18@UIO-66-NH2Composite material is washed, and calcination is carried out after washes clean
Processing can be prepared by Ni14@UIO-66-NH2Composite material.
10. the synthetic method of Ni@MOFs composite material according to claim 9, which is characterized in that calcination processing temperature be
150~300 DEG C.
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