GB2457134A - Synthesis of Metal Oxide Nanoparticles - Google Patents
Synthesis of Metal Oxide Nanoparticles Download PDFInfo
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- GB2457134A GB2457134A GB0801123A GB0801123A GB2457134A GB 2457134 A GB2457134 A GB 2457134A GB 0801123 A GB0801123 A GB 0801123A GB 0801123 A GB0801123 A GB 0801123A GB 2457134 A GB2457134 A GB 2457134A
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 79
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 title claims description 5
- 238000003786 synthesis reaction Methods 0.000 title description 4
- 239000012074 organic phase Substances 0.000 claims abstract description 40
- 239000012071 phase Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 239000012702 metal oxide precursor Substances 0.000 claims abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims abstract 2
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims abstract 2
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract 2
- 230000007704 transition Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 claims 1
- 230000005501 phase interface Effects 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 18
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 238000005424 photoluminescence Methods 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract 1
- 150000004703 alkoxides Chemical class 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- 229910052726 zirconium Inorganic materials 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000002159 nanocrystal Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000235 small-angle X-ray scattering Methods 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005315 distribution function Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001464 small-angle X-ray scattering data Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
A method for the manufacture of metal oxide nanoparticles via a two-phase interface hydrolysis reaction under hydrothermal reaction conditions is disclosed. The method comprises providing a water phase and an organic phase where the organic phase contains a metal oxide precursor such as metal alkoxides or alkyls, placing the water and organic phases in a chamber and providing heat to reach hydrothermal reaction conditions thus hydrolyzing the metal oxide precursor to form metal oxide nanoparticles. The metal may be zirconium or titanium. The organic phase may be toluene, chloroform, iso-octane or ethyl acetate. The manufactured nanoparticles have good monodispersity, high crystallinity, as well as further advantageous properties such as strong photoluminescence and excellent photocatalytic properties. The nanoparticle size can be controlled by the manipulation of the hydrothermal reaction temperature.
Description
TITLE
[0001] Synthesis of Metal Oxide Nanoparticles.
CROSS RELATION TO OTHER APPLICATIONS
[0002] None.
FIELD OF iNVENTION
[0003] The present invention is directed to the field of the manufacture of metal oxide nanoparticles.
PRiOR ART
[0004] Methods for the manufacture of metal comprising nanoparticles are known in the literature.
For example.! Phys Chem. B 2006 110, 14262-14265, titled "Synthesis of FeNi3 alloyed nanoaprticles by hydrothermal reduction" by Xun Wang et a!, discloses the reduction of Ni(NO3) 91120 with hydrazine hydrate in strong alkaline media. Transmission electron microscope images show that the size of the nanoparticles increases with prolongation of the hydrothermal reaction time.
[0005] Furthermore, the paper in Nature 2005, 437. 121-124, titled "a general strategy for nanocrystal synthesis" by Qilong Liao a a!, discloses the manufacture of nanocrystals through the reduction of noble metal ions by ethanol at a temperature of 20 to 200 °C under hydrothermal or atmospheric conditions. *I * S
[0006] None of the prior art provides an enabling disclosure for the manufacture of metal oxide *** nanoparticles according to present invention. * S ** * S. *I S *** *
S
*5SSS* * S
BACKGROUND OF THE INVENTION
[0007] Inorganic semiconductor nanoparticles have attracted great interest in recent decades due to their implementation in a wide variety of applications including photo catalysis, electronic devices, S light-emitting devices, solar cells, bioimaging and biosensors. One of the most important factors regarding nanoparticles in these applications is that the size of the nanoparticles must be substantially uniform in order for the nanoparticles to function accordingly.
[0008] Although numerous methods for the manufacture of inorganic nanoparticles (also referred to as nanocrystals) have been developed, such as sol techniques, micelles or emulsion methods, sol-gel process, pyrolysis, chemical vapour deposition (CVD) and electrochemical methods, the prior art methods of manufacture suffer from complicated preparation and post-treatment procedures, problems of aggregation, size and poor monodispersity which greatly influence and hinder the desired properties of the nanoparticles and restrict their large-scale production and application in industry.
[0009] Currently simple methods that are suitable for the industrial production of monodispersed semiconductor nanoparticles with a tuneable size (especially under 10 nm), remain a challenge to the manufacturing industry.
SUMMARY OF INVENTION
[0001 0]The present invention teaches a method for the manufacture of metal oxide nanoparticles, preferably but is not limited to nanoparticles used in the semiconductor industry.
[00011] The method comprises providing at least one water phase and at least one organic phase in a chamber of a hydrothermal apparatus. The organic phase is a solution of a metal oxide precursor. The metal oxide precursor is soluble in the organic phase and not the water phase. Once heated to a hydrothermal reaction temperature, hydrolysis and nucleation of the metal oxide precursor occurs at the interface of the organic phase and the water phase resulting in the simultaneous nucleation of the insoluble metal oxide nanoparticles. p * S..
* (00012] The method provides a simple yet novel method for the manufacture of metal oxide * * . nanoparticles. The method further allows the controlling of the size of the metal oxide nanoparticles by altering the hydrothermal reaction temperature.
I
* S. SS* * [00013] The present invention produces nanoparticles that have good monodispersity, are highly crystalline, and additionally possess strong photoluminescence and excellent photocatalytic activities.
(00014] The invention discloses a method for the manufacture of nanoparticles whereby the manipulation of the hydrothermal reaction temperature allows the manufacture of nanoparticles with a size below 10 nm.
[00015] Furthermore, the method also exhibits other distinct advantages, compared with other methods of manufacture reported previously. First, the preparation process is simple and cheap, and does not contain any complicated post-treatment procedure. Second, products (without coating) can be collected from the organic phase which effectively avoids grain aggregation induced by the capillary condensation in water environment. Third, the production yield is very high (almost 100 %) and the organic and water phases after reaction can be easily recycled.
[00016] The present invention can be used for the industrial manufacture of nanoparticles and help to reduce the cost of manufacture.
DESCRIPTION OF DRAWINGS
Figure 1. Depicts the manufacture of metal oxide nanoparticles under the separate two-phase hydrothermal reaction conditions.
Figure 2. Depicts a flow diagram for the steps to manufacture metal oxide nanoparticles under the separate two-phase hydrothermal reaction conditions.
FIgure 3. Shows low resolution TEM (a) and corresponding high resolution TEM images (b) of Zr02 nanoparticles prepared at 160 °C. Further magnified images show the coexistence of the tetragonal (c) and monoclinic Zr02 nanoparticles (d) in the samples.
Figure 4. Shows a) Size distribution function of Zr02 nanoparticles that calculated from the SAXS data. b) IRelationship [AH1] between the particle size (max probability of diameter) and the hydrothermal temperature.
Figure 5. Shows XRD patterns for ZrO2 nanoparticles that prepared at different temperatures. a): 100 °C; b) 120 °C; c) 140°C; d): 160 °C; e) 180°C; f) 200°C. Red lines: characteristic peaks for tetragonal * phase; Blue lines: characteristic peaks for monoclinic phase.
* : Figure 6. Shows fluorescence spectra of the Zr02 nanoparticles prepared at different temperatures (T), * : * * which IwerjAH2] dispersed in chloroform, a) Excitation spectra, in which obvious red-shift of the absorption peaks can be observed. b) Emission spectra (excitation wavelength: 285nm). Four main LI! peaks located at 331, 344, 401 and 423 nm in blue-light region can be observed. Inset: blue-light emission of Zr02 nanoparticles dispersed in chloroform (recorded by a CCD camera in dark room, irradiated by a black-light lamp (365 nm), left tube: with ZrO nanoarticles, right tube: without Zr02 nanoparticles).
Figure 7. Shows photocatalytic properties of the Zr02 nanoparticles with different particle sizes.
hydrogen output efficiency; specific reaction rate considering the specific surface area of the nanopartlcies.
Fugure 8. Shows average sizes of the Ti02 nanoparticles prepared at different temperatures.
Figure 9. Shows average particle size and specific surface area (BET) of the Zr02 nanoparticles prepared at different temperatures.
DETAILED DESCRIPTION OF THE INVENTION
(00017] The present invention teaches a method for the manufacture of metal oxide nanoparticles 10.
The invention is not limited to the use of the metal oxide nanoparticles 10 in a specific application, for example in photo catalysis, electronic devices, light-emitting devices, solar cells, bioimaging and biosensors etc. (0001 8]Under hydrothermal reaction temperatures an almost 1:1 ratio mixture of a water phase 20 and an organic phase 30 (which are immiscible at room temperature and pressure) will exhibit different characteristics. These different characteristics are due to the pressure increase that occurs when the temperature of the mixture of the water phase and the organic phase exceeds both the boiling point of the water phase 20 and the boiling point of the organic phase 30. The mixture of the water phase and the organic phase exhibit a non-liquid and non-gaseous state and, consequently, the mixture of the organic phase 30 and water phase 20 exists as tiny droplets. These tiny droplets diffuse with each other to form an interface. The tiny droplets of the organic phase 30 and water phase 20 exist with * "" substantially uniform sizes and can therefore be envisaged as a "nanoreactor".
* S....
[000 19]The nanoreactors, due to their substantially uniform size, provide an environment for the manufacture of the nanoparticles 10 of substantially uniform sizes. The size of the nanoreactors : * "35 accordingly determines the size of the nanoparticles and will also consequently confine the further *.* . growth of nanoparticles.
* .*..* * . [00020] Under these circumstances where the mixture of the organic phase 30 and the water phase 20 are subjected to hydrothermal reaction temperatures and where the organic phase 30 contains a chemical substance that comprises hydrolysable groups, hydrolysis of the hydrolysable groups will occur at the interface of the water phase 20 and the organic phase 30. This hydrolysis results in a hydrolysed chemical substance with a substantially uniform particle size.
[00021) The process of diffusion at the interface of the droplets of the organic phase 30 by the water phase 20 is a dynamic process. The sizes of the tiny droplets (nanoreactors) and the diffusion at the interface of the organic phase 30 with the water phase 20 depends upon the hydrothermal reaction temperature. Therefore, if a hydrolysable chemical substance is present in the organic phase 30, a size of the nanoparticles can be controlled by altering the hydrothermal reaction temperature.
[00022) Where the chemical substances to be hydrolysed are metal oxide precursors 40, the metal oxide precursors 40 will be initially soluble in the organic phase 30. Once the metal oxide precursors 40 are hydrolysed to form a metal oxide nanoparticle 10, the metal oxide nanoparticle 10 will neither be soluble in the organic phase 30 or the water phase 20. The metal oxide nanoparticle 10 will crystallise from the mixture of the water phase 20 and the organic phase 30 during manufacture.
[00023] The hydrolysis reactions are carried out in a Teflon lined hydrothermal chamber 60 as shown inFigi.
[00024] In one aspect of the present invention shown in Fig. 2, the method for the preparation of nanoparticles commences as in step 200. The water phase 20 and the organic phase 30 are prepared as in step 210. The organic phase 30 contains a metal oxide precursor 40 dissolved in the organic phase 40 to form a solution. The solution is prepared in the open atmosphere and the ration of the organic phase tothewaterphase is 1:1.
[00025)The water phase 20 and the organic phase 30, which contains the metal oxide precursor 40 are * then placed in the sealed hydrothermal chamber 60 of a hydrothermal apparatus as in step 220. * 30 *.*e
* [00026] The mixture of the water phase 20 and the organic phase 30 is then heated to a hydrothermal * reaction temperature as in step 230. As discussed above, the hydrothermal reaction temperature "S...
* determines the size of the manufactured nanoparticles 10. * *
L: : [00027] Once the hydrothermal reaction temperature has been reached, hydrolysis 240 of the metal * oxide precursor 40 occurs almost instantaneously.
* .S*I* * S (p [00028] Upon hydrolysis 240 of the metal oxide precursor 40, the manufactured nanoparticles 10 fall from the solution as in step 250 as ultrafine, crystalline metal oxide nanoparticles 10.
[00029] The manufactured nanoparticles 10 are then collected and analysed as in step 260. The analysis is carried out by transmission electron microscopy (TEM), small angle X-Ray scattering (SAXS), X-Ray diffraction (XRD). Photoluminescent and photocatalytic activity of the manufactured nanoparticles are measured using a Perkinelmer 1s55 luminescence spectrometer and photocatalytic hydrogen production experiments [00030] Following the analysis 260 of the manufactured nanoparticles 10, the method is complete (step 270). The water phase 20 and the organic phase 30 may then be recycled by distillation.
Examples L5
[000311 The examples demonstrate the various aspects of the invention but are not intended to limit the invention when taken in conjunctions with the claims and the detailed description.
Example I Preparation of Zr02 nanoparticles [00032] A water phase 20 and an organic phase 30 of toluene which contains the metal oxide precursor 40 Zr(0C4H9)4 were placed in the hydrothermal chamber 60 and the hydrothermal reaction temperature set to 160 °C. The manufactured Zr02 nanoparticles 10 were prepared in 99.9 % yield.
[000331 Figure 3a shows a TEM of the manufactured Zz02 nanoparticle. The manufactured Zr02 nanoparticle shows excellent dispersity and no toluene coating as determined by proton NMR. Figure 3b displays a high resolution TEM depicting well ciystallised quantum dots of the manufactured Zr02 nanoparticle and a particle size of approximately 4.4nm is observed. a... * . .
I *ISS
*....io [00034] The reaction of Example I was then carried out at different hydrothermal reaction temperatures and the manufactured nanoparticles 10 were investigated by SAXS. The curves of *1*II distribution function (Figure 4a) show good monodispersity for all samples prepared at different S...
**** temperatures with the average size of the manufactured nanoparticles 10 increasing monotonously : ** from 1.Onm to approximately 6.1 urn when the temperature was increased from 110 °C to 240 °C (Figure 4b). The XRD patterns (Figure 5) show that the samples have very good crystallinity, which as....
* a increases with the increase of preparation temperature.
[00035] Photoluminescent and photocatalytic activities of the manufactured Zr03 was measured.
When the size of the manufactured Zr02 nanoparticle decreases to a value that is comparable to the Bohr exciton radius of the manufactured Zr02 nanoparticles, e.g. 10 nm or less, the manufactured Zr02 nanoparticles will exhibit some unique properties because of the nanosize effect, such as photoluminescent properties. In order to veri1y the performance of the manufactured Zr02 nanoparticles 10, the luminescent properties and the photocatatytic properties were further investigated. As shown in the excitation spectra (Figure 6a), the absorption peaks for the Zr02 nanoparticles exhibit obvious red-shift from 278.0 -284.0 nm to -288.5 rim when the size of the nanoparticles increases from -1.0 nm (prepared at I = 110 °C) to -6.1 rim (T 240 °C), indicating a distinct quantum size effect. The emission spectra (Figure 6b) show four emission peaks in blue light region for all the samples. As a result, strong blue light emission (inset of Figure 4b) when irradiated by a UV-light lamp (365 nm) can be clearly observed even at daytime. These features are related to the near band-edge transitions and a mid-gap trap state that results from incomplete surface passivation such as surface defects and oxygen vacancies, and the change of the corresponding band gap with the decrease of the nanocrystal size.
[00036] The manufactured Zr02 nanoparticles also show excellent and size-dependent photocatalytic activity. Figure 7 shows the relationship between the nanoparticle size and the photocatalytic efficiency of the Zr02 nanoparticles (as denoted by the hydrogen output in the photocatalytic hydrogen production experiment). It can be observed that the photocatalytic efficiency increases firstly with the increase of crystal size and reach a maximum value of 1676 mo1gh' at the size of -5.5 nm (prepared at 210°C) and then decreases dramatically when the size increases further. Because the specific surface area (SSA) is an important factor influencing the photocatalytic efficiency, SSA values were measured from the samples prepared at different temperatures. As shown in Figure 9, the SSA values increase significantly with the decrease of the reaction temperatures. The specific reaction rate of the photocatalytic reaction after considering the SSA values is also included in Figure 7. It can be observed that 5.5 nm also shows a highest specific reaction rate, which indicates that the .. : ciystallinity is another important factor influencing the photocatalytic efficiency of Zr02 *1I1I * * * .ibO nanoparticles. In order to make a comparison, a further investigatelon into the photocatalytic activity of the commercial Zr02 (Beijing Chemical Plant, China) and Ti02 (p25, Degussa) powders was S....
* performed, which show hydrogen output efficiencies of about 673 and 300 tmo1g1h', respectively. It S...
indicates that the manufactured Zr02 nanoparticles have excellent photocatalytic activity that are E.: :* superior to the commercially available metal oxide nanoaprticles.
I..... * S
Example 2 Preparation of Ti02 nanoparticles [00037] A water phase 2 and an organic phase 30 of toluene which contains the metal oxide precursor 40 Ti(0C4H9)4 were placed in the hydrothermal chamber 60 and the hydrothermal reaction temperature varied stepwise from 100 °C to 200 °C.
[00038) The average size of the manufactured nanoparticle 10, shows an increase from approximately 1.0 nm to approximately 22 nm (Figure 8). Figure 8 also shows the dimensions of the particles indicating a spherical morphology of the manufactured nanoparticles 10. * * S ** * S... * S S... a *S * 0 *.. * S *.* * *0 * S S *SS * *
* a**.*
S
Claims (8)
- IClaims 1. A method for the manufacture of metal oxide nanoparticles (10) comprising: providing at least one water phase (20); providing at least one organic phase (30), wherein the at least one organic phase (30) contains a metal oxide precursor (40); placing the at least one water phase (20) and the at least one organic phase (30) in a same chamber (60) providing heat to reach a hydrothermal temperature, thus hydrolysing the metal oxide precursor (40) to form the metal oxide nanoparticles (10).
- 2. The method according to claim 1, wherein the formation of the metal oxide nanoparticles (10) is at a two phase interface reached by heating the at least one water phase (20) and at least one organic phase (30 to the hydrothermal temperature.
- 3. The method according to any of the above claims, wherein the at least one water phase (20) and the at least one organic phase (30) are placed in a hydrothermal chamber (60).
- 4. The method according to any of the above claims wherein a ratio of organic phase (30) and water phase (20) is substantially a 1:1 ratio.
- 5. The method according to any of the above claims, wherein the organic phase is selected from a group comprising of toluene, chloroform, isooctane and ethyl acetate. * S *
- 6. A method according to any of the above claims, wherein the metal oxide precursor (50) is *5*S selected from a group comprising a metal alkyl-oxides and metal alkyls.S*5SS*S * S * : : : L
- 7. A method according to any of the above claims, wherein a metal in the metal oxide precursor is . : :* selected from group two metal of the transition elements of the periodic table.
- 8. A method according to any of the above claims, wherein the hydrothermal temperature is selected to control the size of the metal oxide nanoparticles (10).
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0801123A GB2457134A (en) | 2008-01-22 | 2008-01-22 | Synthesis of Metal Oxide Nanoparticles |
| PCT/EP2009/050544 WO2009092684A2 (en) | 2008-01-22 | 2009-01-19 | Synthesis of metal oxide nanoparticles |
| EP09704125A EP2244981A2 (en) | 2008-01-22 | 2009-01-19 | Synthesis of metal oxide nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0801123A GB2457134A (en) | 2008-01-22 | 2008-01-22 | Synthesis of Metal Oxide Nanoparticles |
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| Publication Number | Publication Date |
|---|---|
| GB0801123D0 GB0801123D0 (en) | 2008-02-27 |
| GB2457134A true GB2457134A (en) | 2009-08-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| GB0801123A Withdrawn GB2457134A (en) | 2008-01-22 | 2008-01-22 | Synthesis of Metal Oxide Nanoparticles |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2244981A2 (en) |
| GB (1) | GB2457134A (en) |
| WO (1) | WO2009092684A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3530625A3 (en) | 2015-07-23 | 2019-10-30 | Shoei Chemical Inc. | Metal oxide nanocrystals |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6413489B1 (en) * | 1997-04-15 | 2002-07-02 | Massachusetts Institute Of Technology | Synthesis of nanometer-sized particles by reverse micelle mediated techniques |
| CN1524796A (en) * | 2003-02-28 | 2004-09-01 | 中国科学院过程工程研究所 | Method for synthesizing ferric oxide nanometer powder by hydrothermal back extraction |
| CN1821086A (en) * | 2005-12-28 | 2006-08-23 | 中国科学院长春应用化学研究所 | Method for synthesizing organic ligand coated zirconium oxide nano crystal |
| US20060247322A1 (en) * | 2004-12-15 | 2006-11-02 | Industrial Technology Research Institute | Process for preparing nanofluids with rotating packed bed reactor |
| CN101070192A (en) * | 2007-06-13 | 2007-11-14 | 天津大学 | Method for synthesizing spinel structure magnesium frrite nano particles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ220463A (en) * | 1986-06-26 | 1988-11-29 | Mobil Oil Corp | Two-phase synthesis of crystalline binary oxides |
-
2008
- 2008-01-22 GB GB0801123A patent/GB2457134A/en not_active Withdrawn
-
2009
- 2009-01-19 WO PCT/EP2009/050544 patent/WO2009092684A2/en active Application Filing
- 2009-01-19 EP EP09704125A patent/EP2244981A2/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6413489B1 (en) * | 1997-04-15 | 2002-07-02 | Massachusetts Institute Of Technology | Synthesis of nanometer-sized particles by reverse micelle mediated techniques |
| CN1524796A (en) * | 2003-02-28 | 2004-09-01 | 中国科学院过程工程研究所 | Method for synthesizing ferric oxide nanometer powder by hydrothermal back extraction |
| US20060247322A1 (en) * | 2004-12-15 | 2006-11-02 | Industrial Technology Research Institute | Process for preparing nanofluids with rotating packed bed reactor |
| CN1821086A (en) * | 2005-12-28 | 2006-08-23 | 中国科学院长春应用化学研究所 | Method for synthesizing organic ligand coated zirconium oxide nano crystal |
| CN101070192A (en) * | 2007-06-13 | 2007-11-14 | 天津大学 | Method for synthesizing spinel structure magnesium frrite nano particles |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009092684A2 (en) | 2009-07-30 |
| EP2244981A2 (en) | 2010-11-03 |
| WO2009092684A3 (en) | 2009-10-08 |
| GB0801123D0 (en) | 2008-02-27 |
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