EP1998890A1 - Process for preparing colloidal nanocatalysts - Google Patents
Process for preparing colloidal nanocatalystsInfo
- Publication number
- EP1998890A1 EP1998890A1 EP07723437A EP07723437A EP1998890A1 EP 1998890 A1 EP1998890 A1 EP 1998890A1 EP 07723437 A EP07723437 A EP 07723437A EP 07723437 A EP07723437 A EP 07723437A EP 1998890 A1 EP1998890 A1 EP 1998890A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalytically active
- colloidal
- active metal
- ligand
- promoter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000007669 thermal treatment Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000003125 aqueous solvent Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical group 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000010949 copper Substances 0.000 description 27
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000011701 zinc Substances 0.000 description 10
- 239000000084 colloidal system Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 9
- 229940032094 squalane Drugs 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 5
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 239000002082 metal nanoparticle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010415 colloidal nanoparticle Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- -1 high-chain alkanes Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000271897 Viperidae Species 0.000 description 1
- 238000004998 X ray absorption near edge structure spectroscopy Methods 0.000 description 1
- 238000002056 X-ray absorption spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005741 alkyl alkenyl group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000003926 complexometric titration Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 238000004917 polyol method Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a process for the preparation of colloidal nanocatalysts which comprise nanoparticles of a catalytically active metal and the surface of which is occupied in regions with a promoter compound, and a colloidal nanocatalyst obtainable by the process and its use.
- Colloidal catalysts consisting of individual nanoparticles and having their specific surfaces modified ("decorated") to modify their stability, solubility, and functionality represent a growing field of nanochemistry (J.Greenes et al., Chem. Commun 2003, 2257-2260).
- colloids are typically carried out by the reduction of a metal salt in the presence of surface-active compounds, for example by the so-called polyol process (CB Murray et al., Ann Rev. Mater., 2000, 30, 545-610) or by electrochemical Method.
- polyol process CB Murray et al., Ann Rev. Mater., 2000, 30, 545-610
- electrochemical Method electrochemical Method
- the present invention therefore provides a process for the preparation of colloidal nanocatalysts which comprise nanoparticles of a catalytically active metal and whose surface area is occupied in regions with a promoter compound, wherein a ligand-stabilized complex of an ion of the catalytically active metal which is soluble in an inert, non-aqueous solvent in the inert non-aqueous solvent is subjected to a thermal treatment at ⁇ 220 ° C., very particularly preferably at ⁇ 200 ° C. over a period of 1 to 10 minutes and, after completion of the thermal treatment. A precursor compound of the promoter compound is added.
- the process according to the invention makes it possible to provide specific, in particular monomodally distributed, highly active catalyst nanoparticles which are soluble in organic media.
- partially occupied means that a spherical or globular catalytically active metal nanoparticle is completely or partially covered or covered by the promoter compound This also applies to aggregates of catalytically active metal nanoparticles, however, it is preferred that not all of them Surface is covered or covered.
- the process according to the invention can be described as so-called kinetic trapping of growing metal particles by surface deposition of the promoter compound.
- An essential aspect of the process according to the invention consists in the sequential addition of the precursor compound of the promoter compound after a defined period of time during which the ligand-stabilized complex of an ion of the catalytically active metal has already partially decomposed under thermally mild conditions, ie has partially reacted to the catalytically active metal.
- This period is preferably 1 to 8 minutes, very particularly preferably 1 to 5 minutes, and in still more preferred embodiments of the process according to the invention 1 to 2 minutes.
- the addition of the precursor compound of the promoter compound at the temperature of the previous thermal treatment, so that their decomposition (pyrolysis) under gentle conditions can be continued directly and the deposition of the promoter compound on the catalytically active metal nanoparticles without delay, so that they immediately in -situ be stabilized.
- the inert, non-aqueous solvent is an organic solvent and is preferably selected from pure, high-boiling hydrocarbons, such as high-chain alkanes, for example octane, decane, undecane, substituted and unsubstituted aromatics, such as benzene, toluene, mesitylene, polyethers, and squalane. which only boil at the temperatures used in the process according to the invention, but do not evaporate to substantial proportions.
- substantially proportion is intended to express that after completion of the reaction, more than 50% of the original volume of the solution fraction is present.
- the inert nonaqueous solvent is heated to the temperature for the thermal treatment and then the ligand-stabilized complex of the ion of the catalytically active metal in the form of a solution in the same or a different inert non-aqueous solvent is added, preferably in one easily evaporable solvent.
- the ligand-stabilized complex of the catalytically active metal ion may also be added just prior to heating and a suitable temperature program applied to produce the desired particles.
- the catalytically active metal is selected from the group consisting of Cu, Ni, Pd, Pt, Ir, Ru, Rh, Os, Au, Ag, Fe, Co, Mn, of which there are easily prepared ligand-stabilized complexes such that a plurality of catalysts or multinary catalyst systems for different catalytic processes can be obtained by means of the method according to the invention.
- the ligand for the ligand-stabilized complex of the ion of the catalytically active metal are preferred are selected which are unstable above 200 0 C from the group consisting of homoleptic and heteroleptic rule complexes with pure or mixed N-, 0-, S- donor ligand.
- organometallic compounds or complex compounds such as alcoholates, polyethers, phosphines, acetylacetonates, carboxylates and homo- and heteroleptic organometallic compounds, such as metal alkyl-alkenyls, or aryls (with covalent metal-C bond) are suitable according to the invention, have the following property: a) in the temperature range of the invention ⁇ 22O 0 C autoreductively and selectively to disintegrate elemental metal and / or
- b) are selectively reducible to the metal by reducing agents such as hydrogen.
- the promoter is a metal oxide.
- all metal oxides which can be derived or produced from corresponding organometallic or complex precursor compounds can be used.
- the metal oxide is selected from the group of metal oxides consisting of the oxides of Ti, Zr, Zn, Al, Sn, Ca, Mg, Ba, and the rare earths.
- the precursor compound of the promoter compounds selected from the corresponding alkyl, alkoxide, carboxy lat, Betadiketonat-, Betaketiminat- mixed alcoholate Betadiketonat-, guanidinate, aryl and alkyl aryl compounds of the metals mentioned above, the light at ⁇ 220 0 C, in particular be decomposed at less than 200 0 C.
- a plurality of different ligand-stabilized complexes of ions of catalytically active metals are used, so that it is also possible to obtain binary, ternary, quaternary, generally multinary, catalyst systems.
- the type of protonator eg binary, ternary, multinary oxides
- An essential advantage of the method according to the invention is that the reaction mixture is free of additional stabilizers.
- the resulting nanocolloids or nanoparticles thus also contain no additional stabilizers, as required in the prior art, so that a reduction in the activity of the colloidal metal nanoparticles by an "inert" stabilizer layer is avoided.
- An essential advantage of the colloidal nanocatalysts according to the invention is that the catalyst particles have a monomodal size distribution.
- the particle size is in the range of 1 to 3 nm.
- the surface of the individual nanoparticles of the catalytically active metal is only partially occupied by the promoter compound, so that the colloidal nanoparticles according to the invention are both thermally and kinetically very stable and agglomeration of the particles is avoided among themselves.
- colloidal nanoparticles means agglomeration of individual separate metal atoms, as shown for example in FIG.
- a colloidal nanocatalyst according to the invention consisting of copper particles partially coated with ZnO (promoter) (hereinafter referred to as ZnO @ Cu), wherein this notation is also applied to other systems)
- ZnO @ Cu ZnO @ Cu
- the inventive colloidal nanocatalysts can also be supported on conventional supports (MOTräger), such as on aluminum, titanium or zirconium oxide.
- FIG. 1 shows a synthesis scheme for the preparation of the nanocatalysts according to the invention
- FIG. 1 shows the general synthesis of nanocatalysts of the prior art (I) as well as nanocatalysts according to the invention (II). In the following embodiments, reference is made to this. All syntheses were carried out in dry solvents under a protective gas atmosphere.
- the Cu particles also referred to as nanoparticles or nanocolloids
- These wine-red colloids immediately changed color to blue after being exposed to air, which was caused by the formation of Cu 2 O / Cu particles.
- Example 1 was first carried out as Comparative Example 1, but according to the invention an equimolar amount of diethylzinc was added after the addition of (1).
- ZnEt 2 (0.077 g, 0.6 mmol or 0.22 g, 1.8 mmol) was dissolved in 2 ml of mesitylene and approximately 60 seconds (in general, the addition was carried out after 1 to 2 minutes) after the injection of 1 added in pure hot squalane.
- Significantly smaller nanocolloidal catalyst particles of the invention were formed consisting of ZnOOCu particles with a size of 1 to 3 nm. Stable deep red colored colloid was formed without the addition of further stabilizing additives such as HDA.
- novel catalysts were further characterized by means of transmission electron microscopy, the samples being prepared under Ar by placing a drop of the colloidal solution or nanocatalysts of the invention on a carbon-coated gold wire (Hitachi H-8100, 200 kV, LaB 6 filament) were.
- a carbon-coated gold wire Hitachi H-8100, 200 kV, LaB 6 filament
- XANES, EXAFS X-ray absorption spectroscopy
- the absorption edges of Cu and zinc at 8979.0 and 9659.0 electron volts, respectively, were measured with the E4 beam line of Hasylab using a Si (IIl) double crystal monochromator, which was tuned to that he delivered only 50% maximum intensity.
- the samples were prepared in their original colloidal form using a standard EXAFS cell in which the liquid was inserted between two sheets of Kapton foil. was closed so as to avoid any contact with the ambient atmosphere.
- the spectra were recorded at room temperature. The data was evaluated using the VIPER program.
- the adsorption of CO is a good indicator of the catalytic suitability of such systems, especially in the production of methanol from CO and H 2 .
- FIG. 3A shows the ATR spectrum on a ZnOOCu nanocatalyst with a ZnO content of 25%, FIG. 3B with a ZnO content of 50% and FIG. 3C with 75%.
- the corresponding IR bands show the typical COOCu vibration bands, except in Fig. 3C.
- FIG. 2 shows an enlarged view of a nanocatalyst 200 according to the invention made of ZnOOCu with a diameter of 3 nm, in which the ZnO particles 201 occupy the surface of the copper atoms 201 in certain regions.
- the catalytic tests were carried out in a continuously operated high-pressure liquid reactor in squalane solution with freshly prepared nanocolloids according to the invention according to Example 1 carried out at 2.6 MPa with a gas mixture of 72% H 2 , 10% CO, 4% CO 2 and 14% N 2 at a flow rate of 50 mL ⁇ min -1 Squalane was chosen as the solvent for carrying out the experiments, It is of course also possible to use other suitable solvents, such as higher hydrocarbons, mesitylene, benzene, toluene etc.
- the methanol yield was measured continuously by gas chromatography with sampling every 3 hours for 14 days at 493 K. Subsequently, the colloids according to the invention (the term "colloid" is used predominantly analogous to nanodisks) were investigated once again by means of transmission electron spectroscopy and exhibited no significant changes compared with the starting state.
- Methyl formate was detected neither as a product nor in the form of a trace product, which is surprisingly contrary to the results of using the prior art "Bönnemann” colloids mentioned in the introduction, where methyl formate is a by-product (Vukojevic et al., Angew Chem. Int. Ed. 2005, 44, 7978-7981).
- the catalytic test reactor was obtained with the novel nanocatalysts obtainable according to Example 1 (300 mg) in 200 loaded with pure squalane, pressurized with the reaction gas and heated to 443 K.
- the composition of the gas phase was monitored by gas chromatography (Porapak and a molecular sieve column).
- the freshly prepared catalyst samples of the invention were dissolved in 200 ml of squalane to obtain concentrations of copper of 0.01 to 0.05, preferably 0.01 mol / 1 "-1 (verified by complexometric titration) and under inert conditions in the
- the test reactor consisted of a 150 ml stainless steel steel reactor, available from Parr Instruments The autoclave was equipped with a magnetic stirrer with two stirrers, the solution was stirred vigorously to ensure complete mixing of the liquid phase, and a The temperature of the reactor was controlled by a combination of an electric heating jacket and a cooling coil in the liquid phase, the pressure was controlled by a pressure regulator a molecular sieve column a was equipped, analyzed.
- Table 1 shows the catalytic activity of HDA / Cu nanoparticles of the prior art and ZnO / Cu nanocatalysts according to the invention of different composition in comparison with a conventional catalyst under the same conditions: Table 1
- X Zn x - - by means of the method according to the invention also so called nano nanoparticulate Bronze ZnOOCu S 1 was prepared.
- the synthesis was carried out by heating CpCuPMe3 with Zn (Cp *) 2 3 bar hydrogen in a mixture of mesitylene / squalane at 150 0 C.
- an equimolar amount of Zn (Cp *) 2 to CpCuP-Me 3 after heating to 150 ° was added first followed by Cu 1 - x Zn x particles formed, the contact with air by oxidation to nano Bronze ZnOOCu 1 - x were reacted Zn x-5 having a particle size of 3 to 6 nm.
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Abstract
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DE102006013794A DE102006013794A1 (en) | 2006-03-24 | 2006-03-24 | Preparing colloidal nano-catalyst, useful e.g. to synthesis methanol, comprises thermally treating a ligand stabilized complex of an ion of catalytically active metal in an solvent, and adding a precursor compound of an activator compound |
PCT/EP2007/002475 WO2007110176A1 (en) | 2006-03-24 | 2007-03-20 | Process for preparing colloidal nanocatalysts |
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US9295978B2 (en) | 2012-02-15 | 2016-03-29 | Basf Corporation | Catalyst and method for the direct synthesis of dimethyl ether from synthesis gas |
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