WO2006106493A1 - Mesoporous particles - Google Patents
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- WO2006106493A1 WO2006106493A1 PCT/IE2006/000024 IE2006000024W WO2006106493A1 WO 2006106493 A1 WO2006106493 A1 WO 2006106493A1 IE 2006000024 W IE2006000024 W IE 2006000024W WO 2006106493 A1 WO2006106493 A1 WO 2006106493A1
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- sol solution
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/283—Porous sorbents based on silica
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249986—Void-containing component contains also a solid fiber or solid particle
Definitions
- the present invention relates to the synthesis of mesoporous particles useful in the chromatography, absorbents and separation industries.
- HPLC high-performance liquid chromatography
- the chromatographic properties of the stationary phase are influenced by the size, shape, surface and porosity properties of the material.
- Stationary phases based on silica are very popular due to their stability to high pressure and variation in pH.
- porous micrometer-sized silica spheres between 3 and 7 ⁇ m in diameter, are often used as chromatography stationary phases due to their moderate surface areas (200 and 400 m 2 g "1 ) and good packing efficiency.
- milling is a commonly used technique to obtain silica particles of the required size but often results in the production of irregular shaped particles.
- Chromatography columns prepared with irregular shaped particles often show poor column longevity, due to the rearrangement of the particles in the packing during separation, ultimately resulting in poor separation efficiencies.
- particle size control using milling technology Producing particle size below 5 ⁇ m is extremely inefficient and expensive.
- the orientation of the internal pores is random, and the distribution of diameters within each particle is large, resulting in only moderate surface areas.
- Such materials are less effective at separating almost identical solutes, e.g. biphenyl from naphthalene.
- Mesoporous silica particles have been proposed as staducy phases for size- exclusion chromatography [2], HPLC [3], capillary-gas chromatography [4] and chiral HPLC [5].
- highly ordered mesoporous silica particles are difficult to prepare with controllable and reproducible pore diameters.
- poor hydrothermal stability and problems associated with directing the macroscopic particle size and shape often make the preparation of these materials problematic.
- the pre-sol solution contains a mixture of surfactants.
- the mixture of surfactants may include an ionic surfactant such as a cationic surfactant.
- the presol solution contains cetyltrimethylammonium bromide
- the surfactant includes a diblock (A-B) or triblock copolymer (A-B-A or A-B-C).
- the diblock (A-B) or triblock copolymers (A-B-A or A-B-C) may be copolymers having polyethylene oxide (PEO), polypropylene oxide (PPO) and polybutylene oxide (PBO) segments.
- the presol solution contains P 123 (PE ⁇ 2 oPP0 69 PE0 20 ).
- the supercritical fluid may be selected from any one or more of carbon dioxide, xenon, ammonia and alkanes of the formula C x H 2x+ i such as propane and butane wherein x is an integer between 1 and 6.
- the SCF is supercritical carbon dioxide.
- the macroscopic mesoporous particles are prepared under pressure to provide supercritical fluid conditions.
- the pressure may be between 10 and 1000 bar.Preferably the pressure is greater than 150 bar. In one case the particles are prepared at a pressure between 10 and 600 bar.
- the method comprises the step of washing, filtering and drying the mesoporous particles.
- the surfactant(s) may be removed from the mesoporous particles by calcination.
- the mesoporous particles may be calcined in air and/or air-ozone mixtures at a temperature between 200 and 600 0 C .
- the mesoporous particles may be calcined in air and/or air-ozone mixtures for between 1 and 24 hours.
- the surfactant(s) is removed from the mesoporous particles by microwave irradiation in the presence of an alcohol-type solvent.
- the alcohol-type solvent may be selected from any one or more of ethanol, methanol, 1- propanol and 2-propanol.
- the pre-sol solution is prepared by hydrolysis of a metal oxide precursor in the presence of a solvent, a surfactant mixture, an acid hydrolysis catalyst, water and a supercritical fluid.
- the surfactant mixture may be present at a concentration of less than 20% by weight of the pre-sol solution.In one caes the surfactant mixture is present at a concentration of less than 10% by weight of the pre-sol solution.
- the metal oxide precursor is selected from any one or more of tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetrapropoxysilane (TPOS), tetrabutoxysilane (TBOS), tetra-acetoxysilane, tetrachlorosilane and organic derivative thereof.
- the organic derivative may have the formula R n SiX( 4-n) wherein R is an organic radical and X is a hydrolysable group selected from any one or more of halide, acetoxy, alkoxy, teramethysilane and tetraethysilane and n is an integer between 1 and 4.
- the solvent may be an alcohol-type solvent.
- the alcohol-type solvent may be selected from any one or more of ethanol, methanol, 1-propanol, 2-propanol and 1- butanol.
- the acid catalyst is a mineral or organic acid.
- the acid catalyst may be selected from any one or more of hydrochloric (HCl), nitric, sulfuric, phosphoric, acetic and citric acid.
- HCl hydrochloric
- nitric nitric
- sulfuric sulfuric
- phosphoric phosphoric
- acetic citric acid.
- the acid catalyst may be present in a concentration range of between 0.001 M and IM.
- the pre-sol solution is prepared at a temperature of between -5 and 80°C.
- the pre-sol solution may be heated to a temperature of between 0 and 60 0 C.
- the pre-sol solution may be left to stand for at least 1 minute and up to 48 hours. In one case the pre-sol solution is left to stand for at least 1 minute and up to 24 hours.
- the ratio of the surfactants can be varied.
- the ratio P 123 : CTAB could be varied in a typical range of 0.007 : 0.001 to 0.007 : 0.10, preferably in the range of 0.007 : 0.005 to 0.007 : 0.06. These ratios are based on the TEOS having a ratio of 1.0 relative to P 123 and CTAB.
- the method comprises the step of adding a dopant compound to the pre-sol solution.
- the dopant compound may comprises aluminium or boron.
- the dopant compound may be selected from any one or more of aluminium nitrate, aluminium isopropoxide and triethyl borane.
- the invention also provides mesoporous particles synthesised by a method of the invention.
- the mesoporous particles have a mesopore diameter between 2 and 30 nm.
- the mesoporous particles may have a mesopore diameter between 2 and 15 nm.
- the mesoporous particles have a mesopore diameter between 5 and 15 nm.
- the particles may have a mesopore diameter of greater than 5 nm.
- the mesoporous particles may have a pore volume between 0.3 and lcm 3 g "] .
- the mesoporous particles may have a surface area between 300 and 1000m 2 g " ⁇
- the mesoporous particles may be in the form of spheres, rods, discs or ropes.
- the mesoporous particles have macroscopic diameters of between 1 and lO ⁇ m.
- the mesoporous particles may have macroscopic diameters between 1 and 5 ⁇ m. In one embodiment the mesoporous particles are in the form of spheres.
- the mesoporous particles are ordered in a single direction.
- the mesoporous particles may comprise a mesopore diameter greater than 5 nm, a pore volume between 0.3 and lcm 3 g ' ', a surface area between 300 and 1000m 2 g "] and macroscopic diameters between 1 and 1 O ⁇ m.
- the invention also provides mesoporous silica particles in the form of spheres, rods, discs or ropes prepared by a method as claimed in any of claims 1 to 49.
- a mesoporous particle comprising a mesopore diameter greater than 5 nm, a pore volume between 0.3 and lcm 3 g "1 , a surface area between 300 and 1000m 2 g " ' and macroscopic diameters between 1 and lO ⁇ m.
- the invention also provides mesoporous particle comprising a mesopore diameter greater than 5 nm, a pore volume between 0.3 and lcm 3 g " ', a surface area between 300 and 1000m 2 g "1 and macroscopic diameters between 1 and 5 ⁇ m.
- the invention also provides the use of macroscopic mesoporous particles of the invention in a chromatography stationary phase.
- the invention further provides a chromatography stationary phase comprising metal oxide macroscopic mesoporous particles of ordered pore structures prepared by preparing a pre-sol solution and hydrolysing and condensing the pre-sol solution under supercritical fluid conditions.
- the macroscopic mesoporous particles may comprise a pore diameter of greater than 5 nm, a pore volume between 0.3 and lcm 3 g "1 , a surface area between 300 and 1000m 2 g "1 and macroscopic diameters between 1 and lO ⁇ m.
- the pre-sol solution is prepared by hydrolysis of a metal oxide precursor in the presence of a solvent, a structural directing agent, an acid hydrolysis catalyst, water and a supercritical fluid.
- the structural directing agent comprises a surfactant.
- the structural directing agent comprises at least two surfactants.
- the surfactant(s) is present at a concentration of less than 20% by weight of the pre-sol solution.
- the surfactant(s) is present at a concentration of less than 10% by weight of the pre-sol solution.
- the surfactant is selected from any one or more of diblock (A-B) or triblock copolymers (A-B-A or A-B-C), polyalkyl ethers, anionic surfactants and cationic surfactants.
- the diblock (A-B) or triblock copolymers (A- B-A or A-B-C) may be copolymers having polyethylene oxide (PEO), polypropylene oxide (PPO) and polybutylene oxide (PBO) segments.
- PEO polyethylene oxide
- PPO polypropylene oxide
- PBO polybutylene oxide
- the surfactant is P 123 (PE0 20 PP0 69 PE0 2 o)
- the polyalkyl ethers comprise ethers of the formula C x H 2x+ ] -(CH 2 -CH 2 O) y H wherein x are integers between 12 and 18 and y are integers between 2 and 24.
- the polyalkyl ether is a Brij surfactant such as Brij 30.
- the anionic surfactant is sodium bis (2- ethylhexyl)sulfosuccinate (AOT).
- the cationic surfactant is cetyltrimethylammonium bromide (CTAB).
- the metal oxide precursor is selected from any one or more of tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetrapropoxysilane (TPOS), tetrabutoxysilane (TBOS), tetra-acetoxysilane, tetrachlorosilane and organic derivative thereof.
- TEOS tetraethoxysilane
- TMOS tetramethoxysilane
- TPOS tetrapropoxysilane
- TBOS tetrabutoxysilane
- the organic derivative has the formula R n SiX( 4-n ) wherein R is an organic radical and X is a hydrolysable group selected from any one or more of halide, acetoxy, alkoxy, teramethysilane and tetraethysilane and n is an integer between 1 and 4.
- the solvent is an alcohol-type solvent selected from any one or more of ethanol, methanol, 1-propanol, 2-propanol and 1-butanol.
- the acid catalyst is a mineral or organic acid selected from any one or more of hydrochloric (HCl), nitric, sulfuric, phosphoric, hydrofluoric (HF), acetic and citric acid.
- the acid catalyst is present in a concentration range of between 0.001 M and IM.
- the pre-sol solution is prepared at a temperature of between -5 and 80 0 C.
- the pre-sol solution is heated to a temperature of between -5 and 80 0 C for up to 2 hours.
- the invention also provides a method as hereinbefore described comprising the step of adding a dopant compound to the pre-sol solution to improve hydrothermal stability of the mesoporous materials produced.
- the dopant compound comprises aluminium or boron.
- the dopant compound may be selected from any one or more of aluminium nitrate, aluminium isopropoxide and tri ethyl borane.
- the pre-sol solution is left to stand for at least 1 minute and up to 48 hours depending on the degree of structural ordering required.
- the pre-sol solution is left to stand at a temperature of between 0 and 80°C.
- the mesoporous particles are dried at a temperature of between 200 and 55O 0 C.
- the pre-sol solution is hydrolysed and condensed using a supercritical fluid (SCF) or mixture of SCFs.
- SCF supercritical fluid
- the supercritical fluid is selected from any one or more of carbon dioxide, xenon, ammonia and alkanes of the formula C x H 2x+1 such as propane and butane wherein x is an integer between 1 and 6.
- the SCF is supercritical carbon dioxide.
- the particles are treated at a temperature of between 30 and 500 0 C and at a pressure between 1 and 1000 bar.
- One embodiment of the invention comprises the step of washing, filtering and drying the mesoporous particles.
- the particles are treated at a temperature between 250 and 550 0 C and at a pressure between 10 and 600 bar.
- the surfactant(s) is removed from the mesoporous particles by calcination.
- the mesoporous particles are calcined in air and/or air-ozone mixtures at a temperature between 200 and 600 0 C.
- the mesoporous particles are calcined in air and/or air-ozone mixtures for between 1 and • 24 hours.
- the surfactant(s) may be removed from the mesoporous particles by microwave irradiation in the presence of an alcohol-type solvent selected from any one or more of ethanol, methanol, 1-propanol and 2- propanol.
- the mesoporous particles have a mesopore diameter between 2 and 30 nm, preferably between 2 and 15 nm, most preferably greater than 5 nm.
- the mesoporous particles have a pore volume between 0.3 and lcm 3 g "1 , a surface area between 300 and 1000m 2 g "1 .
- the mesoporous particles may be in the form of spheres, rods, discs or ropes.
- the mesoporous particles have macroscopic diameters of between 1 and lO ⁇ m.
- the mesoporous particles may have macroscopic diameters between 1 and 5 ⁇ m and are in the form of spheres.
- the mesoporous particles are ordered in a single direction.
- the invention further provides mesoporous particles synthesised by a method as hereinbefore described.
- the invention also provides mesoporous particles prepared by a method hereinbefore descirbed comprising a mesopore diameter greater than 5 nm, a pore volume between 0.3 and lcm 3 g " ', a surface area between 300 and 1000m 2 g "1 and macroscopic diameters between 1 and lO ⁇ m.
- One aspect of the invention provides mesoporous silica particles in the form of spheres, rods, discs or ropes.
- the invention further provides a mesoporous particle comprising a mesopore diameter greater than 5 nm, a pore volume between 0.3 and lcm 3 g "1 , a surface area between 300 and 1000m 2 g " ' and macroscopic diameters between 1 and lO ⁇ m.
- the invention also provides use of macroscopic mesoporous particles as hereinbefore described in a chromatography stationary phase.
- the particles may be macroscopic mesoporous silica particles.
- the invention further provides a chromatography stationary phase comprising metal oxide macroscopic mesoporous particles of ordered pore structures prepared by preparing a pre-sol solution and hydrolysing and condensing the pre-sol solution under supercritical fluid conditions.
- the macroscopic mesoporous particles comprise a pore diameter of greater than 5 nm, a pore volume between 0.3 and lcm 3 g " ', a surface area between 300 and 1000m 2 g "i and macroscopic diameters between 1 and lO ⁇ m.
- a mesoporous particle comprises a sphere, rod, disc or rope and is taken to include a particle in which the mesopores are arranged within the particle in an ordered arrangement with symmetry described as hexagonal, cubic or lamellar.
- an ordered mesoporous structure is not the same as a random mesoporous arranged formed from tortuous mesopores resulting for example from trapped volumes between particles in a solid.
- the ordered mesoporous structures formed here are similar to materials previously described using the acronyms MCM (Mobil
- composition of Matter or SBA (Santa Barbara Adsorbents) and have a pore size range between 2 and 15 nm.
- An organic template is taken to include a defined structural arrangement originating from the assembly of surfactant molecules in a solvent as defined by the solvent- surfactant interactions.
- the organic template can also be described as a structural directing agent (SDA).
- Typical surfactants used as mesoporous SDAs are polyethylene oxide (PEO)- polypropylene oxide (PPO)-polyethylene oxide (PEO) triblock copolymer surfactants with the general chemical formula of PEO x -PPO y -PEO x .
- a co-surfactant, or SDA typically cetyltrimethylammonium bromide (CTAB), is used to control the macroscopic structure of the particles (sphere, rod, disc or rope).
- CTAB cetyltrimethylammonium bromide
- An inorganic precursor is a chemical compound that can be reacted with other chemical compounds to produce an oxide material. This oxide will form around the organic template structure to form an inorganic oxide skeleton which will survive treatments to remove the organic SDA component.
- An example of an inorganic precursor is a metal alkoxide such as tetraethoxysilane (TEOS).
- TEOS tetraethoxysilane
- SDAs, solvent and other materials TEOS hydrolyses to yield a molecule and molecular assemblies containing hydroxide groups. These hydroxyl group containing species react by elimination of water to produce -M-O-M- (M representing a metal ion and O and oxygen ion) bonds. This process is known as condensation.
- the product of the condensation reaction is a poorly chemically, structurally and stoichiometrically defined solid or gel containing metal oxide, metal hydroxide and metal-organic bonds.
- a dilute gel which flows easily on pouring is termed a sol.
- a supercritical fluid is defined as an element, compound or mixture above its critical temperature (T c ) or critical pressure (P c ) below which state changes can be effected by changes in temperature and/or pressure.
- a supercritical fluid treatment is defined as a procedure in which a pre-sol solution is hydrolysed and condensed in a supercritical fluid environment to form a sol of mesoporous silica particles.
- a pre-sol is a mixture of chemicals which under certain conditions will react to form a sol of mesoporous silica particles.
- Calcination is described as a thermal treatment under air.
- mixtures of air and ozone may be used as this ensures complete removal of organic materials.
- Fig. 1 is a flow diagram illustrating a process according to the invention
- Fig. 3 are transmission electron micrograph (TEM) images of a mesoporous silica sphere taken at two different magnifications at (a) lOOnm and (b) 25nm, prepared using Sc-CO 2 at a pressure of 206 bar, from a molar ratio of TEOS:P123:EtOH:CTAB:HCl of 1:0.007:9:0.027:22.6;
- TEM transmission electron micrograph
- Fig. 4 is a graph showing the PXRD patterns of mesoporous silica spheres processed in Sc-CO 2 using a chemical molar ratio of TEOS:P123:EtOH:CTAB:HCl of 1 :0.007:9:0.027:22.6 at varying CO 2 pressures
- Fig. 5 is a graph showing pore size distributions, calculated from N 2 sorption profiles, for sc-CO 2 treated and untreated samples of mesoporous silica spheres manufactured using the following molar ratio of TEOS:P123:EtOH:CTAB:HCl of 1:0.007:9:0.027:22.6 at (i) 0 bar, (ii) 137 bar and (iii) 486 bar; and
- Fig. 6 is a graph showing the UV-visible absorption data for biphenyl, 2,2- bipyridyl and 4,4-bipyridyl separated on a chromatographic column using sc- CO 2 treated mesoporous silica particles as the stationary phase (conditions: solvent 1 : hexane - elutes biphenyl; solvent 2: 50% hexane diethyl + trace amount acetic acid - elutes 2,2-bipyridyl and solvent 3: 100 % diethyl ether to elute 4,4-bipyridyl).
- the method allows the preparation of uniform particles, with tunable mesoporous and macroscopic morphologies, in particular mesoporous silica particles in the form of spheres, rods, discs and ropes.
- the pore size and structure of the mesoporous layers can be predetermined.
- mesoporous silica is typically produced using a micelle-templated polymerisation method which produces uni- directional, size-monodisperse particles. In mesoporous silica powders the size of these pores can readily be tuned to between 2 and 30 nm [6]. However, most mesoporous silica spheres produced have mesopore diameters between 2 and 4 nm. The ability to control mesopore diameters has important implications for the use of these materials in size-exclusion chromatography. Also, for the effective separation of bio-macromolecules such as proteins, mesoporous silica spheres with large pore diameters, > 6 nm, are desirable.
- spherical particles of mesoporous silica can be produced without milling. A number of technologies have been reported for forming spherical mesoporous particles including spray-drying, oil-drop and pseudomorphic synthesis [3a,
- the mesoporous materials of the invention may also be relevant to the catalysis industry as support materials and to the general materials market, including highly specific chemical sensors and opto-electronic devices.
- the invention relates to the preparation of mesoporous particles with defined macroscopic dimensions, such as spheres, rods, discs and ropes using a supercritical fluid (SCF) assisted approach.
- SCF supercritical fluid
- the SCF process does not affect the hexagonal ordering in the mesoporous particles, a distinct advantage over conventional pore swelling techniques. Consequently, spherical particles, with macroscopic diameters between 1 and 10 ⁇ m, and highly ordered, size-tunable mesopores, between 2 and 15 nm in diameter can be produced by the SCF methodologies of the invention.
- Mesopore dimensions may be tuned utilizing a SCF, such as supercritical carbon dioxide (sc-CO 2 ), as part of the process.
- Spherical particles are produced in a similar manner to those reported by Zhang et al. [8].
- micelles formed from triblock copolymer surfactants of polyethylene (PEO)-polypropylene (PPO)- polyethylene oxide (PEO), such as P 123 (PEO 69 -PPO 20 -PEO 69 ), are mixed with a silica precursor, such as tertraethoxysilane (TEOS) and an ionic surfactant, such as cetyltrimethylammonium bromide (CTAB), under acid conditions (termed a pre-sol solution) and processed to form mesoporous materials.
- TEOS tertraethoxysilane
- CTAB cetyltrimethylammonium bromide
- the invention provides a method for synthesising swelled mesoporous silica materials with uni-directional and tunable mesoporous diameters.
- particles can be produced which are spherical and relatively size- monodispersed allowing for efficient column packing.
- the particles themselves are not aggregated or linked as reported in a number of other methods.
- the particles are thermally (up to 85O 0 C), mechanically and chemically robust. This results from the use of triblock copolymers to template the mesoporous spheres. Traditionally, ionic surfactants have been used as templating surfactants but these produce much less robust materials.
- the mesopore diameters of the particles can be controlled between 2 and 15 nm.
- Most mesoporous silica spheres produced to date have pore sizes between 2 and 4 nm.
- Sc-CO 2 has been shown to control the pore size within mesoporous silica powders with Angstrom-level precision [9b].
- the surfactants used may be but are not limited to any one or more of diblock (A-B) or triblock copolymers (A-B-A or A-B-C), with polyethylene oxide (PEO), polypropylene oxide (PPO) or polybutylene oxide (PBO) segments, polyalkyl ethers, e.g C x H 2x+ I -(CH 2 -CH 2 O) Z H (C x EOy) such as Brij surfactants, anionic surfactants, such as sodium bis (2-ethylhexyl)sulfosuccinate (AOT) and cationic surfactants, e.g. cetyltrimethylammonium bromide (CTAB) and Triton-X.
- A-B diblock
- A-B-A or A-B-C triblock copolymers
- PEO polyethylene oxide
- PPO polypropylene oxide
- PBO polybutylene oxide
- polyalkyl ethers e.g C
- the alcohol-type solvent used may be but is not limited to any one or more of ethanol, propanol or butanol.
- a suitable silating agent may be but is not limited to any one or more of tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetrapropoxysilane (TPOS), and tetrabutoxysilane (TBOS), tetra-acetoxysilane, tetrachlorosilane or organic derivative thereof represented by the formula R n SiX (4-n) where R is an organic radical and X is a hydrolysable group such as halide, acetoxy, alkoxy, teramethysilane, tetraethysilane.
- TEOS tetraethoxysilane
- TMOS tetramethoxysilane
- TPOS tetrapropoxysilane
- TBOS tetrabutoxysilane
- R n SiX (4-n) where R is an organic radical and X is a hydrolysable group such as hal
- a suitable supercritical fluid as a porogenic swelling agent may be, but is not limited to any one or more of carbon dioxide, xenon, ammonia and alkanes (C x H 2x+1 ) such as ethane, propane and butane.
- the metal oxide source used to prepare the sol may be but is not limited to, an alkoxide, carboxylate or halide of silicon, boron, cerium, lanthanum, yttrium, titanium, zirconium, vanadium, molybdenum, tungsten or hafnium.
- Control of the surfactant concentration used in the preparation of the silica mesoporous particles allows the resulting pore structure of the particle to be determined.
- Hexagonal and lamellar structures have parallel arrangements of pores and porous surfaces respectively.
- Cubic structures have channels running through the entire particle that allow transport to and from the surface. This may be a desirable characteristic for porous particles used in adsorbent, catalysis or sensor devices and applications.
- the swelling of the mesoporous particles is carried out at low concentrations of surfactant, preferably at concentrations less than 20 wt%.
- the swelling process involves the use of two surfactants and swelling is carried out during the hydrolysis process.
- the method of the invention provides the following advantages; 1. The ability to prepare robust mesoporous particles with greater thermal robustness than conventionally prepared materials and in certain cases alleviates significant experimental difficulties in the synthesis of these materials. 2.
- the use of SC-CO 2 leads to increased hexagonal mesoscopic ordering within the particles. 3.
- the method is simple and can be widely applied. 4.
- the method is not limited to particular surfactants or mixtures thereof and so the synthesis allows the control the pore size and structure of the mesoporous particles to be determined. 5.
- Mesoporous particles can be consistently formed. 6. The methods are consistent with techniques whereby mixed metal mesoporous oxide particles can be prepared.
- Mesoporous silica particles are prepared in several stages, as represented schematically in Fig. 1 and described below:
- Step 1 This is the SCF treatment and is responsible for achieving large pore mesoporous particles with very high thermal stability that exhibit high degrees of ordered mesoporosity.
- the silicon compound is mixed with the following ingredients: a suitable solvent, which in most cases is an alcohol, a mixture of structure directing agents (surfactant templates), an acid hydrolysis catalyst and controlled amount of water to produce a pre-sol solution.
- a suitable solvent which in most cases is an alcohol
- structure directing agents surfactant templates
- an acid hydrolysis catalyst controlled amount of water
- the pre-sol solution may be prepared at temperatures between -5 and 80 0 C.
- the pre-sol solution should be clear and free from any visible particles to produce high quality mesoporous particles.
- Step 2 The pre-sol solution prepared in step 1 may be prepared in a high pressure cell and exposed to a fluid such that the pressure and temperature of the fluid are above the critical values.
- the sample may be heated (up to 500 0 C) under pressure
- This process is to allow hydrolysis of the silicon compound and cross-linking of the inorganic polymer chains (condensation process) in a SCF atmosphere to form a sol of mesoporous particles.
- Step 3 The particles are removed from the SCF process, washed, filtered, air dried for up to 4 days and further calcined at temperatures between 200 and 550°C for periods of a few minutes to several days in air or air/ozone mixtures. Alternatively, the particles are exposed to microwave irradiation between 40 and 1000 watt in the presence of a solvent which in most cases is an alcohol to extract the SDA. Oxide particles are formed which consist of open pores, i.e. no organic surfactant is present.
- Step 4 The mesoporous particles can be packed into traditional chromatography columns, with typical dimensions such as diameter 1.0 cm and length 30 cm, using traditional 'wet filling' techniques, i.e. the mesoporous silica is wetted with a solvent to produce a slurry which is delivered into the column.
- a liquid sample of the mixture to be chromatographed is dissolved in a solvent, typically dichloromethane, and placed on top of the column.
- the starting column solvent hexane in the first two cases
- a hand pump can then be used to generate the required pressure to force the solvent through the column to separate the mixture's components.
- TEOS Tetraethoxysilane
- CTAB cetyltrimethylammonium bromide
- Ethanol (EtOH) were used as the co-solvent.
- TEOS:P123:EtOH:CTAB:HCl was 1:0.007:9:0.027:22.6.
- Table 1 illustrates the molar composition and physiochemical properties of a variety of mesoporous silica particles synthesised. It will be apparent that by selection of the surfactant type, surfactant ratio, temperature and pressure the pore size and structure may be varied.
- TEOS:P123:HCl 1 :0.01 :0.24 b TEOS:P123:EtOH:CTAB:HCl 1 :0.007:9:0.027:22.6
- Powder X-ray diffraction (PXRD) profiles of the mesoporous particles were recorded on a Philips X'Pert diffractometer, equipped with a Cu-K 0 radiation source and accelerator detector.
- Fig. 1 is a flow diagram showing a process according to the invention, illustrating a general method of forming ordered mesoporous silica particles.
- a silica pre- sol solution is made. This may be made directly in a high-pressure cell or in a beaker and then transferred to the high-pressure cell. The hydrolysis and subsequent condensation of this pre-sol solution occurs under a SCF environment. As shown in block 2, the pre-sol solution is condensed as particles in a SCF environment. Finally, as shown in block 3, the particles are calcined to create SDA -free mesoporous particles.
- chromatography columns e.g. traditional columns or high pressure liquid chromatography (HPLC), and used as stationary phases for advanced chromatography (block 4).
- Fig. 2 shows the beneficial effect of using the SCF treatment to fo ⁇ n large pore mesoporous silica particles.
- Fig. 2 shows an example of a mesoporous silica sphere produced using a molar ratio of TEOS:P123:EtOH:CTAB:HCl of 1:0.007:9:0.027:22.6 and treated with SC-CO 2 at a pressure of 206 bar and at a temperature of 60°C.
- the SEM image confirms that the surface of the sphere is smooth and free from major defects.
- the particle size and morphology of the mesoporous silica spheres prepared in SC-CO 2 do not differ from those produced in the absence of Sc-CO 2 except that the mesopore diameters increase with increasing CO 2 pressure.
- Table 1 at higher CO 2 pressures (>150 bar) more spherical particulates are formed compared to non-treated samples and those treated a low CO 2 pressures ( ⁇ 150 bar).
- Samples prepared in the absence of CTAB do not retain the spherical morphology indicating that the co-surfactant is necessary for the production of particles of spherical morphology.
- Fig. 3 shows a TEM image illustrating the hexagonal arrangement of the mesopores in a SC-CO 2 prepared mesoporous silica sphere (obtained from the following reaction conditions: a TEOS:P123:EtOH:CTAB:HCl ratio of 1 :0.007:9:0.027:22.6 and a CO 2 pressure of 206 bar).
- the pore diameter was calculated to be 9.0 nm and the pore wall width was calculated to be approx. 2.1 nm, which are in agreement with nitrogen sorption data.
- the PXRD patterns shown in Fig. 4 demonstrates the effect OfCO 2 treatment on the d-spacing of the calcined mesoporous silica spheres prepared using the following molar ratio of TEOS:P123:EtOH:CTAB:HCl of 1 :0.007:9:0.027:22.6.
- the 2 ⁇ values can be seen to shift from 0.97 (untreated silica, line a) to 0.77 (sc-CO 2 treated at 482 bar, line (v) representing an increase in d-spacing from 9.2 to 11.4 nm.
- the variation in the pore diameter of mesoporous silica as a function of CO 2 pressure during the hydrolysis process is shown by the pore size distribution curves in Fig. 5. As the CO 2 pressure is increased the pore diameter increases.
- the untreated mesoporous silica templated from a P123/CTAB mixture displays a mean pore diameter of 6.2 nm while the mesoporous silica processed under a CO 2 pressure of 482 bar display a mean pore diameter of 10.9 nm.
- the increase in pore diameter represents a pore expansion of approximately 80 %.
- the SCF-treated mesoporous silica particles can be used as stationary phases for chromatography.
- the highly coloured nature of these chemical species means that the separation of these two components can be observed visually.
- UV- visible absorption data for the separation of the organo-bipyridyl compounds (2,2-bipyridyl and 4,4- bipyridyl) and biphenyl, using SCF-treated mesoporous silica spheres as a stationary phase is shown in Fig. 6.
- the specific mesoporous silica particles used in this example are those described above prepared using UCC/CTAB/EtOH/CO2(b), P123/CTAB, CO 2 pressure of 482 bar, particle size 3 ⁇ m and pore diameter of 10.9nm. Distinctive peaks were noticed for each of the individual species.
- Example 3 Synthesis of Aluminium Doped Mesoporous Silica Spheres A typical synthesis for the formation of Al-doped mesoporous silica spheres is outlined. 0.02 g of hexadecyltrimethylammonium bromide (CTAB) and 0.1 g of P123 surfactant was dissolved in 20 ml of 1.6 M HCl to which 0.2 g of aluminium nitrate nanohydrate (A1(NO 3 ) 3 .9H 2 O) was added. Once dissolved 0.2 ml of tetraethoxysilane (TEOS) was added to achieve better distribution of metal ions in the framework of the mesoporous materials.
- CTAB hexadecyltrimethylammonium bromide
- P123 surfactant was dissolved in 20 ml of 1.6 M HCl to which 0.2 g of aluminium nitrate nanohydrate (A1(NO 3 ) 3 .9H 2 O) was added.
- the pre-sol solution was transferred to a high pressure cell and pressurized with CO 2 at a pressure of 344 bar.
- the system was left to stand for between 1 and 7 days.
- the precipitated sample was washed and dried overnight at 80 0 C and calcined for 12 hours at 550 0 C.
- Variations to the above synthesis include changing the amount of Al (NO 3 ) 3 . 9H 2 O added.
- Low angle PXRD studies of the as-prepared samples showed 3 characteristic peaks that could be identified as the (100), (110) and (200) reflection typical of mesoporous silica materials.
- Surface area analysis showed the material to have a surface area of 598 m 2 g " '.
- the mean mesopore diameter in these particles was found to be 8.5 nm.
- Scanning electron microscopy (SEM) analysis confirmed the presence of monodispersed spheres of approximately 0.5 ⁇ m.
- Al-doped mesoporous silica may also be prepared by substituting Al(NO 3 ) 3 .9H 2 O with aluminium isopropoxide.
- Al-doped mesoporous silica spheres have potential applications as nanocatalysis, for example in fine chemical synthesis.
- Example 4 Synthesis of Boron Doped Mesoporous Silica Spheres
- a typical synthesis for the formation of Boron-doped mesoporous silica spheres is outlined. 0.02 g of hexadecyltrimethylammonium bromide (CTAB) and 0.1 g of Pl 23 surfactant was dissolved in 20 ml of 1.6 M HCl to which 0.2 g of triethyl boron (B(CH 2 CH 3 ) 3 ) was added. Once dissolved 0.2 ml of tetraethoxysilane (TEOS) was added to achieve a better distribution of metal ions in the framework of the mesoporous materials.
- CTAB hexadecyltrimethylammonium bromide
- Pl 23 surfactant was dissolved in 20 ml of 1.6 M HCl to which 0.2 g of triethyl boron (B(CH 2 CH 3 ) 3 ) was added. Once
- the pre-sol solution was then transferred to a high pressure cell and pressurized with CO 2 at a pressure of 206 bar.
- the system was left to stand for between 1 and 7 days.
- the precipitated sample was washed and dried overnight at 80 0 C and calcined for 12 hours at 500 0 C.
- Low angle PXRD studies showed 3 characteristic peaks that can be identified as the (100), (110) and (200) reflection typical of mesoporous silica materials. Surface area analysis showed the materials to have a surface area of 650 m 2 g "! .
- the mean mesopore diameters in these particles was found to be 7.5 nm.
- B-doped mesoporous silica spheres have potential applications as nanocatalysis, for example in fine chemical synthesis.
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Abstract
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EP20060728130 EP1866250A1 (en) | 2005-04-05 | 2006-04-05 | Mesoporous particles |
US11/887,930 US20090029146A1 (en) | 2005-04-05 | 2006-04-05 | Mesoporous Particles |
JP2008504900A JP2008535756A (en) | 2005-04-05 | 2006-04-05 | Mesoporous particles |
AU2006231725A AU2006231725A1 (en) | 2005-04-05 | 2006-04-05 | Mesoporous particles |
CA 2604869 CA2604869A1 (en) | 2005-04-05 | 2006-04-05 | Mesoporous particles |
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EP (1) | EP1866250A1 (en) |
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- 2006-04-05 EP EP20060728130 patent/EP1866250A1/en not_active Withdrawn
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- 2006-04-05 JP JP2008504900A patent/JP2008535756A/en active Pending
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AU2006231725A1 (en) | 2006-10-12 |
EP1866250A1 (en) | 2007-12-19 |
JP2008535756A (en) | 2008-09-04 |
US20090029146A1 (en) | 2009-01-29 |
CA2604869A1 (en) | 2006-10-12 |
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