The invention relates to a method for producing a zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure.
In the view of the current environmental challenges there is an urgent need to develop a more sustainable chemical industry through more efficient chemical transformations and by developing new highly selective and cost-effective catalysts. One approach towards enhanced catalytic performance of supported metal catalysts is to increase the active metal surface by synthesizing small metal nanoparticles (often <10 nm in diameter). However, small nanoparticles are often prone to sintering which decreases the catalytic activity over time. The development of sinter-stable heterogeneous nanoparticle catalysts is therefore of great importance, but also poses great challenges.
Zeolites are crystalline alumina silicate materials that exhibit a highly ordered porous structure with pores of molecular diameter. IUPAC identifies this type of porosity as microporous, as the size of the pores is not wider than 2 nm. The other groups of porosity are mesoporous (pore size between 2-50 nm) and macroporous. (pore size larger than 50 nm). Zeolites consist of tetrahedral TO4 units (T=Si or Al), which gives the framework an overall composition of TO2. These materials have a clearly organized framework throughout the crystals, giving rise to highly ordered pores and a large internal surface area. By replacing a silicon atom with an aluminium atom, it is possible to generate a deficit of charge, which is compensated by a cation located nearby. The cation is usually an alkali metal (such as sodium), alkali earth metal, or possibly a H+ ion. If the cation is a proton, the zeolite becomes a strong Brønsted acid. All these characteristics make zeolites useful for many applications.
Today, nearly 60 different natural occurring zeolites are known, while 201 can be prepared synthetically [R. W. Broach, D. Jan, D. A. Lesch, S. Kulprathipanja, E. Roland, and P. Kleinschmit. Zeolites. In Ullmann's Encyclopedia Of Industrial Chemistry. Wiley, 2012]. These zeolites have different structures, due to different Si—O—Al linkages, and a different number of Si or Al atoms linked in each unit cell. This also creates different pore system of one-, two, or three-dimensions in the zeolite. As the pores are very regular, and around the same size in diameter as molecules, it is possible for zeolites to function as molecular sieves. Due to their chemical structure and molecular sieve properties, zeolite catalysts exhibit high selectivity for a variety of chemical reactions. Since most of the surface area and the active sites are within the zeolite, the shape of the pores and channels give rise to shape selective catalysis. Commonly there is distinguished between three types of shape selectivity:
Encapsulation of metal nanoparticles in a zeolite structure may protect the individual nanoparticles from contact with other nanoparticles, thereby preventing sintering of the nanoparticles when these are subjected to elevated temperatures. It would also be possible to utilize the new material as a bifunctional catalyst, which owns it activity from the inherint catalytic activity of the zeolite and the catalytic properties of the metal nanoparticles.
In spite of the great technological, environmental and economic interests, general methods for the stabilization of metal nanoparticles against sintering are far from being fully developed, although for some specific systems it has been achieved by optimizing the interaction of nanoparticles with a support material or by encapsulation of the metal particles [A. B. Laursen, K. T. Højholt, L. F. Lundegaard, S. B. Simonsen, S. Helveg, F. Schüth, M. Paul, J.-D. Grunwaldt, S. Kegnæs, C. H. Christensen, and K. Egeblad. Angew. Chem. Int. Edit., 122:3582, 2010, High-Temperature-Stable Catalysts by Hollow Sphere Encapsulation, P. M. Amal, M. Comotti, F. Schüth, Angew. Chem. 2006, 118, 8404-8407, A Highly Reactive and Sinter-Resistant Catalytic System Based on Platinum Nanoparticles Embedded in the Inner Surfaces of CeO2 Hollow Fibers, Y. Dai, B. Lim, Y. Yang, C. M. Cobley, W. Li, E. C. Cho, B. Grayson, P. T. Fanson, C. T. Campbell, Y. Sun, and Y. Xia, Angew. Chem. Int. Ed. 2010, 49, 1-5, Encapsulation of Metal (Au, Ag, Pt) Nanoparticles into Mesoporous SBA-15 structure, J. Zhu, Z. Kónya, V. F. Puntes, I. Kiricsi, C. X. Miao, J. W. Agar, A. Paul Alivisatos, G. A. Somorjai, Langmuir 2003, 19, 4396-4410].
The encapsulation of nanoparticles is an area of increasing interest. This is a possible solution to the widely known problem of deactivation due to sintering.
Several methods have been developed to produce sinter-stable nanoparticle catalyst, including encapsulating in mesoporous silica matrix or by using a protective shell [P. M. Amal, M. Comotti, and F. Schuth. Angew. Chem. Int. Ed., 45:8224, 2006, N. Ren and Y.-H. Yang and. J. Catal., 251:182, 2007, S. H. Joo, J. Y. Park, C.-K. Tsung, Y. Yamada, and P. Yang. Nature Mater., 8:126, 2009, and L. W. Beakley, S. E. Yost, R. Cheng, and B. D. Chandler. Appl. Catal. A, 292:124, 2005].
By encapsulating metal nanoparticles in a zeolite matrix, the zeolites micropores allow small substrates to access the active sites, while big molecules are excluded. The confined space of the active sites may also enhance the formation of one product over another by shape selectivity. In addition, the thermal stability of zeolites and high surface area, makes zeolites particularly useful for this application. Post treatment deposition of nanoparticles inside zeolites has been reported in literature [T. M. Salama, R. Ohnishi, T. Shido, and M. Ichikawa. J. Catal., 156:169, 1996, Y.-M. Kang and B.-Z. Wan. Appl. Catal. A: General, 128:53, 1995, and Z. X. Gao, Q. Sun, H.-Y. Chen, X. Wang, and W. M. H. Sachtler. Catal. Lett., 2001:1, 72].
A limitation of these methods is however that they require zeolites containing cages. By post-synthesis treatments the nanoparticles are in the cages and/or in the pores of the zeolite and it can be difficult to control the metal loading and the size and location of the nanoparticles. Both Laursen et al. [A. B. Laursen, K. T. Højholt, L. F. Lundegaard, S. B. Simonsen, S. Helveg, F. Schüth, M. Paul, J.-D. Grunwaldt, S. Kegns, C. H. Christensen, and K. Egeblad. Angew. Chem. Int. Edit., 122:3582, 2010] an Højholt et al. [K. T. Højholt, A. B. Laursen, S. Kegns, and C. H. Christensen. Top. Catal., 54:1026, 2011] have successfully synthesised a MFI zeolite containing gold nanoparticles (size 1-3 nm), which showed to be highly stably versus sintering. In addition, the gold nanoparticles were only accessible through the micropores of the zeolite. The synthesis is however time-consuming and requires expensive additives and a complicated reaction procedure.
US 2005/239634 A1 discloses a crystalline inorganic material organized in a mesostructure, where the inorganic material can be a metal oxide. The document further discloses a method for producing mesostructured zeolites.
Laursen et al discloses in Ang. Chem. Int. Ed., 49 (2010), p. 3504-3507 a bottom-up approach for the preparation of hybrid zeolite-nanoparticle materials containing small metal nanoparticles dispersed throughout the zeolite crystals. The nanoparticles are contained inside the zeolites. The bottom-up approach is an approach where the metal nanoparticles are encapsulated in an amorphous silica matrix and then hydrothermally treated for zeolite crystallisation to take place. This method is however cumbersome.
So, despite the growing demand, a fast, efficient and economically process for manufacturing zeolite or zeotype encapsulated metal nanoparticles which are sinter-resistant that can be scaled up for industrial application has not yet been reported.
Disclosed herein in a first aspect of the invention is a method for producing a zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure.
By formation of transition metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype is meant that only a small fraction, i.e. substantially none, of the nanoparticles and/or cluster will be found on the external surfaces of the structure. Thus, the nanoparticles and/or cluster will primarily be situated inside or on the internal surfaces of the structure.
By transition metal, metal oxide or metal sulphide nanoparticles—also referred to as metal nanoparticles—are meant particles typically between 1-100 nm that may or may not have size-related properties that differs significantly from the bulk material.
By transition metal, metal oxide or metal sulphide clusters—also referred to as metal clusters—are meant a small ensemble of metal atoms grouped close together which can have direct metal bonding interactions or interactions through a bridging ligand. Typically, clusters are smaller than nanoparticles.
The method according to the first aspect of the invention comprises the steps of a) treating a zeolite, zeolite-like or zeotype structure with an alkaline solution in the presence of a surfactant thereby obtaining a zeolite, zeolite-like or zeotype structure having a partly dissolved structure, and b) heating the partly dissolved zeolite, zeolite-like or zeotype structure to an elevated temperature between 110-200° C. thereby obtaining a zeolite, zeolite-like or zeotype structure with an additional porosity situated inside the structure. By heating the partly dissolved structure to an elevated temperature, the surfactant is removed.
The method according to the first aspect of the invention further comprises the steps of c) impregnating the zeolite, zeolite-like or zeotype structure with the additional porosity situated inside the structure with a solution comprising at least one transition metal precursor thereby obtaining a transition metal precursor containing zeolite, zeolite-like or zeotype structure; and d) obtaining the zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure by either i) subjecting the transition metal precursor containing zeolite, zeolite-like or zeotype structure to a reactive atmosphere at an elevated temperature, or ii) decomposing the transition metal precursor containing zeolite, zeolite-like or zeotype structure by thermal treatment, wherein the transition metal, metal oxide or metal sulphide nanoparticle particles are selectively positioned inside the transition metal, metal oxide or metal sulphide nanoparticle containing zeolite, zeolite-like or zeotype structure.
By the above method is obtained a zeolite structure where the nanoparticles/clusters are evenly distributed inside the crystalline zeolite structure. The zeolite framework keeps the individual nanoparticle/cluster separated and slows down migration and coalescence, which is highly advantageous since it increases the thermal stability.
Due to the position on the internal surface of the zeolite, the metal nanoparticles/clusters remain accessible through the porous structure of the zeolites, however, but are thus protected from sintering with other nanoparticles at elevated temperatures due to the physical separation. Furthermore, the zeolite micropores ensure that the substrate has access to the encaptured nanoparticles/clusters.
The transition metal, metal oxide or metal sulphide nanoparticles/clusters inside the zeolite, zeolite-like or zeotype is refrained from sintering, thereby preserving the nanoparticles high surface area required for the effective catalytic activity. This novel approach for preparation of sintering stable nanoparticle/cluster catalysts is rather simple and can be used to e.g. develop novel automotive exhaust catalyst.
Disclosed herein in a second aspect of the invention is a zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure obtained by the method according to the first aspect of the invention.
Disclosed herein in a third aspect of the invention is a zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure.
The zeolite, zeolite-like or zeotype structure in a third aspect of the invention may have micropores with a pore size between 0-2 nm, or mesopores with a pore size between 2-50 nm, or macropores with a pore size between 50-100 nm.
The transition metal, metal oxide or metal sulphide nanoparticles/clusters in a third aspect of the invention may have a particle size between 0-40 nm, or between 1-30 nm, or between 1-20 nm, or between 1-10 nm, or between 1-5 nm, or between 2-3 nm.
The transition metal, metal oxide or metal sulphide nanoparticles in a third aspect of the invention may be distributed selectively on internal surfaces of the zeolite zeolite, zeolite-like or zeotype.
Any two consecutive transition metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype according to the third aspect of the invention may have an internal distance d between them, wherein the nearest neighbour index between any different two consecutive transition metal, metal oxide or metal sulphide nanoparticles inside the zeolite, zeolite-like or zeotype is at least 1
Also, disclosed herein in a fourth aspect of the invention is the use of a zeolite, zeolite-like or zeotype structure according to the second or third aspect of the invention as catalytic material for chemical reactions, for hydroisomerization, cracking and reforming of petrochemicals, for the synthesis of liquid hydrocarbons from synthesis gas by means of the Fisher-Tropsch process or Mobile process, for production of substitute natural gas from synthesis gas by methanation, for in-situ generation of hydrogen peroxide (H2O2) from hydrogen (H2) and oxygen (O2), for epoxidation of propylene, for selective oxidations and hydrogenations, for catalytic exhaust and/or flue-gas cleaning, for conversion of ammonia to N2O, NOx and N2, for the synthesis of olefins in methanol to olefins reactions (MTO), for the synthesis of methanol to hydrocarbons reactions (MTH), or for the synthesis of methanol to gasoline reactions (MTG).
a-d show bio-ethanol oxidation to acetaldehyde/acetic acid/CO2 using the four zeolites shown in
In
In the following detailed description of the invention, reference is made to the examples, including tables and figures.
Throughout the description, when zeolites are mentioned this is meant to comprise zeolites, zeolite-like materials and zeotypes unless otherwise specifically mentioned.
By zeolite, zeolite-like and zeotype particle is meant zeolite, zeolite-like and zeotype crystal or zeolite, zeolite-like and zeotype material.
By the term zeolite-like is meant non-silicon comprising material. Examples of zeolite-like materials are non-silicon comprising materials such as aluminum phosphate (AIPO4) molecular sieves, known as AIPO's. The phosphorous compound can be selected from the group consisting of phosphoric acid, phosphate salts and mixtures thereof. By the term “phosphate salts” is meant salts of phosphates, monohydrogen phosphates and dihydrogen phosphates.
In this application a new method for producing zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure is presented according to a first aspect of the invention.
The method according to the first aspect of the invention comprises a number of steps including a first step of treating a zeolite, zeolite-like or zeotype structure with an alkaline solution in the presence of a surfactant thereby obtaining a zeolite, zeolite-like or zeotype structure having a partly dissolved structure.
In one or more embodiments, the alkaline solution is selected from bicarbonates, carbonates, ammonia hydroxide, sodium hydroxide, and potassium hydroxide.
In one or more embodiments, the surfactant is selected from anionic, cationic, zwitterionic and nonionic surfactants. These surfactants may include C8-C18 alkyltrimethylammonium bromides, phencyclidine hydrochloride (P123), polyoxyethylene 20 cetyl ether (Brij-58), and polyoxypropylene-polyoxyethylene block polymer polyglycol (F127).
In one or more embodiments, the surfactant is cetyl trimethylammonium bromide (CTAB).
The method according to the first aspect of the invention further comprises the step of heating the partly dissolved zeolite, zeolite-like or zeotype structure to an elevated temperature between 110-200° C. thereby obtaining a zeolite, zeolite-like or zeotype structure with an additional porosity situated inside the structure. By heating the structure, the surfactant is removed.
In one or more embodiments, heating the partly dissolved zeolite, zeolite-like or zeotype structure to an elevated temperature is done in an autoclave.
In one or more embodiments, the elevated temperature is between 110-190° C.
In one or more embodiments, the elevated temperature is between 110-180° C.
In one or more embodiments, the elevated temperature is between 120-170° C.
In one or more embodiments, the elevated temperature is between 120-160° C.
In one or more embodiments, the elevated temperature is between 130-150° C.
In one or more embodiments, the elevated temperature is between 135-145° C.
The method according to the first aspect of the invention further comprises the step of impregnating the zeolite, zeolite-like or zeotype structure with the additional porosity situated inside the structure with a solution comprising at least one transition metal precursor thereby obtaining a transition metal precursor containing zeolite, zeolite-like or zeotype structure.
In one or more embodiments, the transition metal precursor comprises one or more metal precursors selected from nitrates, carbonates, acetates, sulphates, chlorides, carbonyls or formates.
In one or more embodiments, the transition metal precursor comprises one or more metal(s) selected from the group consisting of group 4 elements, group 6 elements, group 7 elements, group 8 elements, group 9 elements, group 10 elements, group 11 elements or group 12 elements or mixtures thereof. The group elements are defined by the new IUPAC numbering.
In one or more embodiments, the transition metal precursor comprises one or more metal(s) selected from the group of manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, cadmium, molybdenum, zinc, vanadium, chrome, titanium or mixtures thereof.
In one embodiment or more embodiments, the metal is selected from the group of manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold.
In one embodiment or more embodiments, the metal is selected from the group of iron, cobalt, nickel, palladium, platinum, copper, silver and gold.
In one embodiment or more embodiments, the metal is gold.
In one or more embodiments, the transition metal precursor comprises one or more metal alloys(s) selected from the group of molybdenum-cobalt, molybdenum-nickel, molybdenum-platinum, iron-ruthenium, iron-cobalt, iron-nickel, ruthenium-cobalt, ruthenium-copper, ruthenium-platinum, cobalt-palladium, cobalt-platinum, cobalt-gold, nickel-platinum, iridium-platinum, palladium-platinum, palladium-copper, palladium-gold, platinum-gold, or silver-gold. One of the metals in the metal alloy may be present in an amount of from 1 to 50%. The optimal weight ratio between the metals in the alloy depends on the metal alloy.
The metal or mixture of metal precursors might form into the respective oxides or nitrates. This can happen either during the manufacturing process or in the end product.
The method according to the invention may prior to impregnation of the zeolite, zeolite-like or zeotype structure with an additional porosity situated inside the structure be dried. The drying is performed in order to improve the impregnation of the recrystallized material. The drying can be achieved by keeping the calcined materials in a dry atmosphere or by separately drying the material prior to the impregnation by other means. The drying may be performed at elevated temperatures, preferably under reduced pressure or in a flow of dry gas.
The method according to the first aspect of the invention subsequently comprises the step of obtaining the zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure by either: i) reducing the transition metal precursor containing zeolite, zeolite-like or zeotype structure in a reactive atmosphere, or ii) decomposing the transition metal precursor containing zeolite, zeolite-like or zeotype structure by thermal treatment.
This causes the transition metal, metal oxide or metal sulphide nanoparticle particles to be selectively positioned inside the zeolite, zeolite-like or zeotype structure.
In one or more embodiments, the reactive atmosphere in alternative i) is a stream of hydrogen gas (H2), a stream of oxygen gas (O2), a stream of hydrogen sulfide gas (H2S), a stream of methane gas (CH4), or a stream of ammonia gas (NH3).
In one or more embodiments, the reactive atmosphere in alternative i) is a stream of hydrogen gas (H2) and the transition metal precursor forms metal nanoparticles.
The term “metal nanoparticles” used throughout this application also includes mixtures of metals nanoparticles. By metal nanoparticles is also meant metal oxide nanoparticles and metal sulfide nanoparticles.
In one or more embodiments, the reactive atmosphere in alternative i) is a stream of oxygen gas (O2) and the transition metal precursor forms metal oxides.
In one or more embodiments, the reactive atmosphere in alternative i) is a stream of hydrogen sulfide gas (H2S) and the transition metal precursor forms metal sulfides.
In one or more embodiments, the reactive atmosphere in alternative i) is a stream of methane gas (CH4) and the transition metal precursor forms metal carbides.
In one or more embodiments, the reactive atmosphere in alternative i) is a stream of ammonia gas (NH3) and the transition metal precursor forms metal nitrides.
In one embodiment the flow of the stream of gas is applied for around 1-7 hours, 4-6 hours, or 2-3 hours. This holds true for all of the above mentioned examples of gaseous compounds, but depends on the metal type.
In one or more embodiments, the thermal treatment in alternative ii) is performed in the temperature range from 200 to 800° C.
In one or more embodiments, the thermal treatment in alternative ii) is performed in the temperature range from 200 to 600° C.
In one or more embodiments, the thermal treatment in alternative ii) is performed in the temperature range from 200 to 500° C.
The method according to the first aspect of the invention is illustrated schematically in
After obtaining the zeolite structure 104 with the additional porosity 106, the zeolite structure 104 is impregnated with a solution comprising at least one transition metal precursor 108 thereby obtaining a transition metal impregnated zeolite, zeolite-like or zeotype structure. The transition metal impregnated zeolite, zeolite-like or zeotype structure is either reduced or decomposed to yield the final transition metal, metal oxide or metal sulphide nanoparticle containing zeolite, zeolite-like or zeotype structure 110 as depicted as the last structure in
As is illustrated in
When the steps involved in the recrystallization of the zeolite structure (steps a and b) are omitted, transition metal, metal oxide or metal sulphide particles/clusters are also observed on the outside of the zeolite, zeolite-like or zeotype structure as is discussed in connection with
Independently of what mechanism/combination of processes or chemical substances that ensures the selective positioning of the transition metal particles inside of the zeolite structure, the selectivity has a number of advantages.
The encapsulation of metal nanoparticles within the zeolite structure inhibits sintering, thereby preserving their high surface area required for the effective catalytic activity. The increase in catalytic properties of the transition metal, metal oxide or metal sulphide nanoparticle containing zeolite, zeolite-like or zeotype is clearly seen and discussed in connection with
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has a framework type selected from BEA, FAU, MFI, MEL MOR, CHA or MTW. Alternative frameworks can also be imagined.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure is silica based. Possible silica sources for zeolites may be bulk silica of different quality and alumina contamination, including pure silica, fumed silica, sodium silicate or other soluble silicate salts, precipitated silica, tetraethyl orthosilicate and other alkoxy-silicates, silicic acid, etc.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure is aluminium based. Possible aluminium sources for zeolites may be aluminium nitrate, aluminium sulphate, aluminium phosphate, sodium aluminate and more.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has micropores with a pore size between 0-2 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has micropores with a pore size between 0.5-2 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has micropores with a pore size between 1-2 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has mesopores with a pore size between 2-50 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has mesopores with a pore size between 10-40 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has mesopores with a pore size between 15-30 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has mesopores with a pore size between 20-30 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has mesopores with a pore size between 40-50 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has mesopores with a pore size between 2-15 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has macropores with a pore size between 50-100 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has macropores with a pore size between 60-90 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has macropores with a pore size between 70-80 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has macropores with a pore size between 50-60 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has macropores with a pore size between 50-70 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has macropores with a pore size between 70-100 nm.
In one or more embodiments, the zeolite, zeolite-like or zeotype structure has macropores with a pore size between 80-90 nm.
Depending on the application, the transition metal, metal oxide or metal sulphide nanoparticles may vary in size quit significantly. Thus, in one or more embodiments, the transition metal, metal oxide or metal sulphide nanoparticles may have a particle size between 0-40 nm.
In one or more embodiments, the transition metal, metal oxide or metal sulphide nanoparticles may have a particle size between 1-30 nm.
In one or more embodiments, the transition metal, metal oxide or metal sulphide nanoparticles may have a particle size between 1-20 nm.
In one or more embodiments, the transition metal, metal oxide or metal sulphide nanoparticles may have a particle size between 1-10 nm.
In one or more embodiments, the transition metal, metal oxide or metal sulphide nanoparticles may have a particle size between 1-5 nm.
In one or more embodiments, the transition metal, metal oxide or metal sulphide nanoparticles may have a particle size between 2-3 nm.
The transition metal, metal oxide or metal sulphide nanoparticles may be distributed selectively inside the zeolite zeolite, zeolite-like or zeotype.
In one or more embodiments, the transition metal, metal oxide or metal sulphide nanoparticles may be evenly distributed inside the zeolite zeolite, zeolite-like or zeotype such that any two consecutive transition metal, metal oxide or metal sulphide nanoparticles inside the zeolite, zeolite-like or zeotype has an internal distance d between them, wherein the nearest neighbour index between any different two consecutive transition metal, metal oxide or metal sulphide nanoparticles inside the zeolite, zeolite-like or zeotype is at least 1.
By nearest neighbour index is meant the ratio of the observed distance between any two different nanoparticles divided by the expected distance, where the expected distance is the average distance between neighbours in a hypothetical random distribution.
In one or more embodiments, the wherein the nearest neighbour index between any different two consecutive transition metal, metal oxide or metal sulphide nanoparticles inside the zeolite, zeolite-like or zeotype is between 1-10, or between 2-5.
The transition metal, metal oxide or metal sulphide nanoparticle containing zeolite, zeolite-like or zeotype have increased thermal stability and resistance against sintering.
By impregnating transition metal, metal oxide or metal sulphide nanoparticle in a zeolite, zeolite-like or zeotype zeolite matrix, shape selective catalysis is possible as described in the introduction.
In one embodiment the size of the zeolite crystals are in the range of 0.1 to 5 micrometer, or 0.1 to 2 micrometer, or 0.1 to 0.5 micrometer.
In one or more embodiments the amount of transition metal, metal oxide or metal sulphide nanoparticles are in the range of 0.1-25 wt %, 0.5-20 wt %, 0.5-10 wt %, 0.5-5%, 1.0-5 wt %, 1-2 wt %, or around 1 wt %.
In one embodiment the zeolite, zeolite-like or zeotype particle has a Vp value in the range of 0.1 to 0.4 cm3/g, or 0.2 to 0.4 cm3/g.
In one embodiment the zeolite, zeolite-like or zeotype particle has a BET surface area of 200 to 500 m2/g or 350 to 400 m2/g or around 375 m2/g.
As can be seen in
The Au/APS-S1 structure shown in
a-d shows the measurement of the bio-ethanol oxidation to acetaldehyde/acetic acid/CO2 using the four zeolites shown and described in
As can be seen in
The Au/S1 catalyst shown in
The Au/Meso-S1 catalyst shown in
The surface-functionalized Au/APS-S1 catalyst shown in
The Au/recryst-S1 catalyst according to the invention and shown in
In conclusion,
In
The results from the N2 physisorption measurements are summarized in table 1 below.
[a]Calculated by the BET method.
[b]Calculated by the t-plot method.
[c]Determined from the isotherm adsorption branch at around P/P0 = 0.95.
[d]Hierarchy factor calculated by HF = (Sext/SBET)(Vmicro/Vtot).
In
In
Large Pd nanoparticles of sizes about 25 nm due to sintering seem to have been avoided by the implementation of mesopores through the recrystallization according to the invention.
The invention also relates to the use of a zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure according to the invention as catalytic material for chemical reactions.
The invention further relates to the use of a zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure as defined above for the synthesis of liquid hydrocarbons from synthesis gas by means of the Fisher-Tropsch process or Mobile process.
The invention additionally relates to the use of a zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure as defined above for in-situ generation of hydrogen peroxide (H2O2) from hydrogen (H2) and oxygen (O2) for epoxidation of propylene.
The invention further relates to the use of a zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure as defined above for catalytic exhaust and/or flue-gas cleaning.
The invention further relates to the use of a zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure as defined above for synthesis of olefins in methanol to olefins reactions (MTO).
The invention further relates to the use of a zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure as defined above for synthesis of methanol to hydrocarbons reactions (MTH).
The invention further relates to the use of a zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure as defined above for the synthesis of methanol to gasoline reactions (MTG).
The invention further relates to the use of a zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure as defined above for conversion of ammonia to N2O, NOx and N2.
Additional use applications of the zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure may include fluid catalytic cracking, hydrocracking, hydroconversion, paraffin isomerisation, paraffin aromatisation, olefin oligomerisation, aromatic alkylation, aromatic disproportionation, aromatic isomerisation, hydration, hydrogenation, benzene hydroxylation, phenol hydroxylation, DeNOx stationary sources, and synthesis of fine chemicals.
The zeolite, zeolite-like or zeotype structure with selective formation of metal, metal oxide or metal sulphide nanoparticles and/or clusters inside the zeolite, zeolite-like or zeotype structure of the present invention may also be used in shape-selective catalysis. The different shape-selective catalysis options described in the introduction part are for example reactant shape selectivity, product shape selectivity, and restricted transition-state shape selectivity.
Commercial carbon black particles (Black Pearls 2000, Carbot Corporation) with an average particle diameter of around 12 nm were used as carbon-template for the synthesis of mesoporous silicalite-1. The carbon black particles were dried at 110° C. for 24 h prior to use. All other reagents were of reagent grade and used without further purification or pretreatment: HAuCl4 (Sigma-Aldrich), tetraethylorthosilicate (TEOS, Sigma-Aldrich), tetrapropylammonium hydroxide (TPAOH, 1M aqueous solution, Sigma-Aldrich), (3-aminopropyl)trimethoxysilane (APS, Sigma-Aldrich), toluene (Sigma-Aldrich), cetyl trimethylammonium bromide (CTAB, Sigma-Aldrich), ethanol (absolute, Sigma-Aldrich), deionized water and Formier gas (10% H2 in N2, Air Liquide).
Synthesis
The zeolites discussed in this application may be prepared by the following methods:
Silicalite-1 (S1)
TEOS (4.465 ml) was added dropwise to TPAOH (7.265 ml) under stirring in a Teflon beaker. The mixture was stirred for 1 hour and then transferred to a Teflon-lined stainless steel autoclave (130 ml). The autoclave was heated to 180° C. for 24 h under autogeneous pressure. The product was thoroughly washed with water, collected by filtration and washed again several times (until neutral pH). The product was dried at room temperature overnight and then calcined for 20 hours at 550° C. (heating 5° C./min) to give a fine white powder.
Au/S1
Silicalite-1 (0.9900 g) was impregnated with an aqueous solution of HAuCl4.3H2O (0.0199 g) to incipient wetness. The material was dried at room temperature overnight at then reduced in Formier gas for 2 h at 350° C. (heating 5° C./min) to give the final gold nanoparticle catalyst.
Au/Meso-S1
Pre-dried carbon black (2 g) was put in a Teflon beaker, impregnated with TPAOH (7.265 ml) and dried at room temperature overnight. The material was then impregnated with TEOS (4.465 ml) and dried at room temperature overnight once more. The Teflon beaker was placed inside a Teflon-lined stainless steel autoclave (130 ml) containing enough water to produce saturated steal (15 ml) and heated to 180° C. for 72 hours. The product was thoroughly washed with water, collected by filtration and washed again several times (until neutral pH). The product was dried at room temperature overnight and then calcined for 20 hours at 550° C. (heating 5° C./min) to give a fine white powder. The mesoporous zeolite was impregnated and reduced according to the general synthetic procedure described for the synthesis of Au/S1.
Au/APS-S1
Silicalite-1 (1 g) and toluene (100 ml) was added to a round-bottom flask equipped with a Liebig condenser. APS (1 ml) was added dropwise under stirring and the mixture was heated to 111° C. and refluxed for 4 hours. After cooling to room temperature, the product was precipitated by addition of ethanol and collected by filtration. The surface functioinalized zeolite was dried overnight and then impregnated and reduced according to the general synthetic procedure described for the synthesis of Au/S1.
Au/Recryst-S1
CTAB (0.7 g) was dissolved in an aqueous ammonia solution (100 ml, 2.5 wt %). Silicalite-1 (1 g) was added and the suspension was stirred for 3 hours at room temperature. The mixture was then transferred to a Teflon-lined stainless steel autoclave and heated to 140° C. for 24 hours. The product was collected by filtration, dried overnight and calcined at 550° C. for 5 hours to remove the surfactant. The obtained material was then impregnated and reduced according to the general synthetic procedure described for the synthesis of Au/S1.
Pd/Recryst-S1
The recryst-S1 zeolite was impregnated with the palladium precursor by incipient wetness impregnation. For this 0.99 g of the recrystallized zeolite S1 was first pre-dried under vacuum at 50° C. A solution of 0.0250 g (0.094 mmol) palladium(II)nitrate dihydrate (aq) in 0.30 mL of H2O was added to the recrystallized S1. It was dried at 25° C. and then reduced with 10% hydrogen/90% nitrogen by gradual heating at a rate of 5° C./min to the set temperature of 350° C. for 120 min to give the final palladium nanoparticle catalyst.
Ni/Recryst-S1
The recryst-S1 zeolite was impregnated with the nickel precursor by incipient wetness impregnation. For this 0.99 g of the recrystallized zeolite S1 was first pre-dried under vacuum at 50° C. A solution of 0.0495 g (0.170 mol) nickel(II)nitrate hexahydrate (aq) in 0.30 mL of H2O was added to the recrystallized S1. It was dried at 25° C. and then reduced with 10% hydrogen/90% nitrogen by gradual heating at a rate of 5° C./min to the set temperature of 350° C. for 120 min to give the final nickel nanoparticle catalyst.
Methods for Characterisation—Transmission Electron Microscopy (TEM)
TEM was performed on a FEI Tecnai microscope operated at 200 kV with the samples dispersed directly on holey carbon grids. The mean diameter and standard deviation of the nanoparticles was calculated by measurements of ˜250 particles.
Methods for Characterisation—Physisorption Analysis
Argon gas physisorption analysis was performed at 77 K on a Micromeritics ASAP 2020. The samples were outgassed in vacuum at 300° C., 16 h prior to measurement. The (apparent) total surface areas were calculated according to the BET method. Pore size distributions were calculated by the BJH method. External surface area, micropore area and micropore volume were determined by t-plot methods using the desorption branch of the isotherm.
Number | Date | Country | Kind |
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14164188.6 | Apr 2014 | EP | regional |
Filing Document | Filing Date | Country | Kind |
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PCT/EP2015/057585 | 4/8/2015 | WO | 00 |