CN109414686B - 高纵横比层状双氢氧化物材料和其制备方法 - Google Patents
高纵横比层状双氢氧化物材料和其制备方法 Download PDFInfo
- Publication number
- CN109414686B CN109414686B CN201780016756.7A CN201780016756A CN109414686B CN 109414686 B CN109414686 B CN 109414686B CN 201780016756 A CN201780016756 A CN 201780016756A CN 109414686 B CN109414686 B CN 109414686B
- Authority
- CN
- China
- Prior art keywords
- adamantane
- ldh
- intercalated
- precursor
- particles
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 title claims description 15
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000002245 particle Substances 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000011541 reaction mixture Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- JIMXXGFJRDUSRO-UHFFFAOYSA-N adamantane-1-carboxylic acid Chemical compound C1C(C2)CC3CC2CC1(C(=O)O)C3 JIMXXGFJRDUSRO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 2
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 150000001450 anions Chemical class 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 150000004692 metal hydroxides Chemical class 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 adamantane ions Chemical class 0.000 description 3
- 238000005349 anion exchange Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000004922 13C solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 102000040954 LDH family Human genes 0.000 description 1
- 108091077232 LDH family Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/12—Saturated polycyclic compounds
- C07C61/125—Saturated polycyclic compounds having a carboxyl group bound to a condensed ring system
- C07C61/135—Saturated polycyclic compounds having a carboxyl group bound to a condensed ring system having three rings
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- B01J23/007—Mixed salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/407—Aluminium oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/005—General concepts, e.g. reviews, relating to methods of using catalyst systems, the concept being defined by a common method or theory, e.g. microwave heating or multiple stereoselectivity
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
- B01J2531/002—Materials
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
- B01J2531/008—Methods or theories
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/08—Intercalated structures, i.e. with atoms or molecules intercalated in their structure
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
实施例涉及插入有金刚烷的层状双氢氧化物(LDH)颗粒和制备插入有金刚烷的LDH颗粒的方法。所述方法包含向水溶液中加入第一前体和第二前体以形成初始混合物，其中所述第一前体是Al(OH)3或Al2O3，所述第二前体是氢氧化物M(OH)2或氧化物MO，其中M是氧化态为+2的金属；且所述初始混合物的M/Al摩尔比为从1至5。所述方法还包含向所述初始混合物中加入一定量的金刚烷以形成Al/金刚烷摩尔比为从0.5至2的反应混合物；和加热所述反应混合物以制备插入有金刚烷的LDH颗粒，其中所述插入有金刚烷的LDH颗粒具有大于100的纵横比。
Description
相关申请的交叉引用
本申请要求2016年3月17日提交的美国临时申请62/309,645的权益，其以全文引用的方式并入本文中。
技术领域
本公开的实施例主要涉及层状双氢氧化物材料，并且具体地涉及高纵横比层状双氢氧化物材料和制备方法。
背景技术
负载金属或金属氧化物催化剂的合成在多相催化中具有极大的工业重要性。高活性、高选择性和长催化剂寿命是任何工业催化剂的期望特性。催化剂材料可以由层状双氢氧化物(LDH)制备。LDH，也称为阴离子粘土，是广泛使用的硅铝酸盐阳离子粘土在结构和特性上的反电荷类似物。一般来说，尽管存在许多制备金属氧化物颗粒的方法，但与通过合成方法例如湿法浸渍/固态制备获得的氧化物颗粒相比，通过分解LDH获得的氧化物具有几个优点。具体来说，LDH可以提供一种简单、节省成本且在环境上适合的方式以在原子水平上实现金属离子的均匀分布。为了将LDH层用于各种应用，人们需要能够剥离或分层这些层。由于碳酸盐LDH在热力学上更稳定，因此难以将其换成其他离子或难以剥离其中碳酸盐是电荷平衡离子的LDH层。结果，这些材料的使用受到限制。已经尝试从碳酸盐LDH开始制备高纵横比的非碳酸化LDH；但是，这种方法有多个步骤，而且很麻烦。
发明内容
根据先前提出的背景技术，对具有高纵横比的LDH材料存在持续需求。
本公开的实施例涉及用调节高纵横比片层的生长的高对称金刚烷离子制备的LDH。此外，由于其亲有机性，金刚烷可以在有机溶剂中剥离。因此，这些LDH层可用于如先前提及的各种应用中。本公开的实施例涉及高纵横比的非碳酸化LDH，其仅使用一当量的阴离子盐。此外，这些LDH提供了工艺改进，因为它们能够实现“一锅”合成，并且由于使用金属氢氧化物作为起始材料和仅使用一当量的阴离子，在反应结束时洗涤工作较少(包括不洗涤)。所形成的材料一旦煅烧也具有期望特性。
根据一个实施例，提供了一种制备插入有金刚烷的层状双氢氧化物(LDH)颗粒的方法。所述方法包含向水溶液中加入第一前体和第二前体以形成初始混合物，其中第一前体是Al(OH)3或Al2O3，且第二前体是氢氧化物M(OH)2或氧化物MO，其中M是氧化态+2的金属。以初始混合物的总重量计，初始混合物具有1至5的M/Al摩尔比或小于10重量％固体的固体负载。所述方法还包含向初始混合物中加入一定量的金刚烷以形成具有从0.5至2的Al/金刚烷摩尔比的反应混合物，并加热反应混合物以制备插入有金刚烷的LDH颗粒，其中插入有金刚烷的LDH颗粒具有大于100的纵横比。纵横比通过插入有金刚烷的LDH颗粒的宽度除以插入有金刚烷的LDH颗粒的厚度来定义。
根据另一个实施例，提供了一种呈插入有金刚烷的LDH颗粒形式的插入有金刚烷的层状双氢氧化物(LDH)材料。插入有金刚烷的LDH颗粒包含由[M1-xAlx(OH)2](A)x·mH2O定义的通式，其中x是从0.14至0.33，m是从0.33至0.50，M选自Mg、Ca、Co、Ni、Cu或Zn，且A是金刚烷羧酸盐。插入有金刚烷的LDH颗粒进一步包含大于100的纵横比。纵横比通过插入有金刚烷的LDH颗粒的宽度除以插入有金刚烷的LDH颗粒的厚度来定义。
所描述的实施例的额外特征和优点将在下文的具体实施方式中阐述，并且将部分地由所属领域的技术人员从该描述容易了解或通过实践所描述的实施例(包括下文的具体实施方式、权利要求书以及附图)而认识到。
附图说明
图1A是通过阴离子交换制备的Mg/Al-CO3LDH的扫描电子显微法(SEM)图像；
图1B是通过共沉淀制备的Mg/Al-CO3LDH的SEM图像；
图2A和2B是根据本公开的一个或多个实施例制备的Mg/Al-金刚烷酸盐LDH的不同放大倍数的SEM图像；
图3是根据本公开的一个或多个实施例的Mg/Al-金刚烷酸盐LDH的粉末X射线衍射(PXRD)图；
图4是根据本公开的一个或多个实施例的Mg/Al-金刚烷酸盐LDH的红外(IR)光谱图；
图5是根据本公开的一个或多个实施例的Mg/Al-金刚烷酸盐LDH的1H固态核磁共振(NMR)光谱图；和
图6是根据本公开的一个或多个实施例的Mg/Al-金刚烷酸盐LDH的13C固态NMR光谱图。
具体实施方式
活性还原金属或金属氧化物颗粒在稳定载体上的分散是复杂且费力的过程。为实现此目标，人们需要考虑各种参数，例如合成条件、载体的性质和在载体上分散/分布活性催化剂的适当方式。在金属/金属氧化物负载型催化剂中，负载于不同载体(氧化铝、二氧化硅和碳)上的Cu/ZnO/Al2O3系统和金属/金属氧化物(Pt、Pd、Rh和Au)系统具有很大的工业重要性。已知这些催化系统具有催化工业上重要反应的潜力，所述反应例如有甲醇的合成、水煤气变换反应、石油化学物流的脱硫、水的光化学/电化学分裂，和将二氧化碳光化学/电化学还原成有用的化学物质。
现在将详细参考具有高纵横比的插入有金刚烷的层状双氢氧化物(LDH)颗粒和其制备方法的实施例。具体来说，插入有金刚烷的LDH颗粒具有大于100的纵横比。如所定义的，纵横比由LDH颗粒的宽度除以LDH颗粒的厚度来定义。如所定义的，低于10的纵横比被认为是低的，小于100的纵横比被认为是中等的，并且100或更大的纵横比被认为是高纵横比。LDH颗粒可以从SEM图像计算。例如，参考图2B的实施例，显而易见的是，层状颗粒具有大的表面积，但缺乏厚度，从而导致高纵横比。另外，可以使用原子力显微法(AFM)来测量LDH颗粒的宽度和厚度并确定纵横比。
制备插入有金刚烷的LDH颗粒的方法可包括向水溶液中加入第一前体和第二前体以形成初始混合物的步骤。在一个实施例中，水溶液可以基本由水组成。第一前体可包含Al(OH)3或Al2O3。第二前体可包括含金属的化合物，例如氢氧化物M(OH)2或氧化物MO，其中M是氧化态+2的金属。虽然也考虑了各种其他金属，但M可选自Mg、Ca、Co、Ni、Cu、Zn或其组合。在一个或多个实施例中，第二前体可包括Mg(OH)2、Ca(OH)2、Co(OH)2、Ni(OH)2、Cu(OH)2、Zn(OH)2或其组合。在其它实施例中，第二前体是Mg(OH)2或MgO。在一个实例中，第二前体是Mg(OH)2且第一前体是Al(OH)3。
此外，在其它实施例中，初始混合物可具有1至5或1至3的M/Al摩尔比。此外，以初始混合物的总重量计，初始混合物可具有小于10重量％固体的固体负载，或小于5重量％固体的固体负载。
随后，所述方法包括向初始混合物中加入一定量的金刚烷，以形成Al/金刚烷摩尔比为从0.5至2的反应混合物。在一个或多个另外的实施例中，Al/金刚烷的摩尔比可以为从0.8至1.2，或可以为1比1。考虑了各种金刚烷源。在一个实施例中，金刚烷可以以羧酸的形式加入。任选地，反应可被搅拌。
一般来说，用无机客体阴离子制备用于转化成混合型金属氧化物催化剂的LDH，所述无机客体阴离子可以在热处理下容易地除去。当使用有机阴离子例如羧酸官能化的金刚烷时，可以实现LDH的特性的改善。金刚烷具有以高对称性(Td)为特征的结构，没有分子内应变，因此具有极高的热力学稳定性。同时，金刚烷可以被化学官能化。金刚烷的熔点为270℃，并且即使在室温下也会缓慢升华。金刚烷难溶于水，但易溶于烃。
在不受理论束缚的情况下，使用热稳定的金刚烷作为结构导向剂，这允许在c结晶轴上的a和b结晶方向上LDH的优先生长。这导致观察到高纵横比的颗粒。此外，使用水热合成和金属氢氧化物前体在pH和动力学方面小心控制生长条件。
接下来，所述方法包括加热反应混合物以产生插入有金刚烷的LDH颗粒，其中插入有金刚烷的LDH颗粒具有大于100的纵横比。如所定义的，插入有金刚烷的LDH颗粒意谓将金刚烷插入LDH颗粒基质中。在其它实施例中，插入有金刚烷的LDH颗粒的纵横比大于125，或大于150，或大于200。此外，插入有金刚烷的LDH颗粒具有2至12μm或5至10μm的粒径。加热步骤可以在110℃至180℃的反应温度下进行，反应时间为12小时至48小时，或者在130℃至170℃的反应温度下进行，反应时间为20小时至30小时。
LDH族材料的最大群组包括具有组成[MII 1-xMIII x(OH)2]x+或[MI xMIII 1-x(OH)2]x+(MI＝Li；MII＝Mg、Ca、Co、Ni、Zn；MIII＝Al、Cr、Fe；0.14≤x≤0.33)。的带正电荷的金属氢氧化物层层上的正电荷由中间层中存在的阴离子平衡。阴离子被命名为阴离子粘土。一组阴离子粘土包括具有通式[MII 1-xMIII x(OH)2](An-)x/n·mH2O或[MI xMIII 1-x(OH)2]x+(An-)x/n·mH2O(m＝0.33–0.50)的材料，其中A是阴离子，例如硝酸盐或卤素。
插入有金刚烷的LDH颗粒可具有通式[M1-xAlx(OH)2](A)x·mH2O，其中x是从0.14至0.33，m是从0.33至0.50，M选自Mg、Ca、Co、Ni、Cu或Zn，且A是金刚烷羧酸盐。
具有高纵横比的LDH在包装中的氧气屏障的发展中起一定作用，在纳米复合材料中作为填充剂，以及作为阻燃剂等。对于所有这些应用，可以容易地分散在聚合物基质中的高纵横比的片层是所期望的，但是不容易获得。阴离子(阴离子的电荷和对称性)在LDH晶体的成核和生长中起关键作用。碳酸盐离子在自然界中普遍存在，具有与LDH的层间对称性良好匹配的D3h对称性，并且与其他阴离子相比具有更高的电荷密度。结果，LDH优选碳酸盐离子而不是其他离子，并且这调节了层的有序堆叠。图1A和1B的SEM展示分别经由阴离子交换和共沉淀制备的Mg/Al-碳酸盐LDH。
与本发明实施例相反，LDH通常通过共沉淀技术制备，其中将金属盐的均匀混合溶液加入另一种含有氢氧化钠和待掺入的过量客体阴离子的溶液中。由于快速的多次成核和结晶事件，从该方法获得的LDH总是显示具有亚微米尺寸的微晶。共沉淀的晶体可具有约1-10或更小的纵横比。这表明晶体具有窄的宽度并且优先沿c轴生长。这反映了阴离子和阳离子的高过饱和度和在反应器的混合区中许多晶体的快速成核。
为了说明，通过共沉淀和阴离子交换方法制备的Mg/Al-CO3LDH样品的SEM图像提供于图1A和1B中。如图所示，这些颗粒是不规则的较厚团聚物。由于此厚度，Mg/Al-CO3LDH样品的纵横比很低。相反，如图2A和2B所示产生的Mg/Al-金刚烷酸盐LDH的SEM显微照片描绘了具有比Mg/Al-CO3小得多的厚度的片状层。鉴于这些低厚度，这些Mg/Al-金刚烷酸盐LDH颗粒具有高纵横比。
实例
所描述的实施例将通过以下实例进一步阐明。
实例1
层状双氢氧化物的制备
在一种典型的制备中，通过将5克(g)Mg(OH)2溶解在95g去离子水中制备5重量％的Mg(OH)2溶液。向其中加入3.36g Al(OH)3以达到Mg/Al摩尔比为2。然后，将9.31g金刚烷羧酸加入到相同的溶液中(Al/金刚烷摩尔比＝1)，并将所得反应混合物在室温下剧烈搅拌1小时。此后，将溶液转移到Teflon衬里的高压釜中并在150℃下加热24小时(h)。测量初始反应混合物和最终滤液的pH，结果分别为9.5和8.6。在另一组实验中，通过使Mg/Al摩尔比达到5重复上述工序。反应结束后，用水彻底洗涤产物并在65℃下干燥。
为了比较，通过更常规的氨沉淀法从金属硝酸盐开始合成Mg/Al-NO3LDH(Mg/Al摩尔比＝2)。
所合成的LDH的PXRD图谱示于图3中，并且显示了在
处的基础反射(001)对应于中间层中金刚烷离子的双层排列。在较高的2θ值处可以看到(001)的约数。金刚烷酸的插入进一步用IR光谱表征，如图4所示。1517cm-1和1395cm-1处的振动对应于COO-基团的反对称和对称伸展振动。2901cm-1和2847cm-1处的振动用于C-H振动。4302cm-1振动是由于层金属氢氧化物基团与中间层中的插入水分子的氢键结合。
记录Mg/Al-金刚烷酸盐LDH的1H和13C固态NMR光谱，并在图5和6中分别给出。图5的1H光谱中的在较低ppm值下的4个尖峰是由于金刚烷环中存在的氢。3.8ppm和4.8ppm的峰分别是因为插入的水和金属氢氧化物的氢。参考图6，Mg/Al-金刚烷酸盐的13C NMR光谱在29.5ppm、37.3ppm、40.6ppm和42.8ppm处显示出4个峰，这是由于金刚烷分子中存在4种不同的碳。186.98ppm处的峰是因为羧酸盐基团的碳。所合成的LDH的扫描电子显微镜(SEM)图像显示了层状材料的典型的片层形态(图2A和2B)。
本领域的技术人员将清楚，在不脱离要求保护的主题的精神和范围的情况下，可以对本文中所描述的实施例进行各种修改和变化。因此希望本说明书涵盖本文中描述的各种实施例的修改和变化，条件是此类修改和变化落在所附权利要求书和其等效物的范围内。
Claims (15)
1.一种制备插入有金刚烷的层状双氢氧化物(LDH)颗粒的方法，所述方法包含：
向水溶液加入第一前体和第二前体以形成初始混合物，其中：
所述第一前体是Al(OH)3或Al2O3；
所述第二前体是氢氧化物M(OH)2或氧化物MO，其中M是氧化态+2的金属；和
所述初始混合物具有从1至5的M/Al摩尔比；
以初始溶液的总重量计，所述初始混合物具有小于10重量％固体的固体负载；
向所述初始混合物中加入一定量的金刚烷以形成具有从0.5至2的Al/金刚烷摩尔比的反应混合物；和
加热所述反应混合物以制备所述插入有金刚烷的LDH颗粒，其中所述插入有金刚烷的LDH颗粒具有大于100的纵横比，所述纵横比通过插入有金刚烷的LDH颗粒的宽度除以所述插入有金刚烷的LDH颗粒的厚度来定义。
2.如权利要求1所述的方法，还包含搅拌所述反应混合物。
3.如权利要求1所述的方法，其中所述金刚烷以羧酸的形式加入。
4.如权利要求1所述的方法，其中所述加热步骤在从110℃至180℃的反应温度下进行，反应时间为12小时至48小时。
5.如权利要求1所述的方法，其中M选自Mg、Ca、Co、Ni、Cu或Zn。
6.如权利要求1所述的方法，其中所述第二前体是Mg(OH)2、Ca(OH)2、Co(OH)2、Ni(OH)2、Cu(OH)2或Zn(OH)2。
7.如权利要求1所述的方法，其中所述第二前体是Mg(OH)2或MgO。
8.如权利要求1所述的方法，其中所述第二前体是Mg(OH)2，且所述第一前体是Al(OH)3。
9.如权利要求1所述的方法，其中所述Al/金刚烷的摩尔比为从0.8至1.2。
10.如权利要求1所述的方法，其中所述插入有金刚烷的LDH颗粒具有通式[M1-xAlx(OH)2](A)x·mH2O，其中x是从0.14至0.33，m是从0.33至0.50，M选自Mg、Ca、Co、Ni、Cu或Zn，且A是金刚烷羧酸盐。
11.如权利要求1所述的方法，其中以所述初始混合物的总重量计，所述初始混合物具有小于5重量％固体。
12.如权利要求1所述的方法，其中所述纵横比大于125。
13.一种呈插入有金刚烷的LDH颗粒形式的插入有金刚烷的层状双氢氧化物(LDH)材料，其中所述插入有金刚烷的LDH颗粒包含：
由[M1-xAlx(OH)2](A)x·mH2O定义的通式，其中x是从0.14至0.33，m是从0.33至0.50，M选自Mg、Ca、Co、Ni、Cu或Zn，且A是金刚烷羧酸盐；和
大于100的纵横比，所述纵横比通过插入有金刚烷的LDH颗粒的宽度除以所述插入有金刚烷的LDH颗粒的厚度来定义。
14.如权利要求13所述的插入有金刚烷的LDH材料，其中所述纵横比大于125。
15.如权利要求13所述的插入有金刚烷的LDH材料，其中所述插入有金刚烷的LDH颗粒具有5至10μm的粒径。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201662309645P | 2016-03-17 | 2016-03-17 | |
| US62/309,645 | 2016-03-17 | ||
| PCT/US2017/022485 WO2017160965A1 (en) | 2016-03-17 | 2017-03-15 | High aspect ratio layered double hydroxide materials and methods for preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109414686A CN109414686A (zh) | 2019-03-01 |
| CN109414686B true CN109414686B (zh) | 2021-09-28 |
Family
ID=58464633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780016756.7A Active CN109414686B (zh) | 2016-03-17 | 2017-03-15 | 高纵横比层状双氢氧化物材料和其制备方法 |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US10138199B2 (zh) |
| EP (1) | EP3429749B1 (zh) |
| JP (1) | JP6914282B2 (zh) |
| KR (1) | KR102164758B1 (zh) |
| CN (1) | CN109414686B (zh) |
| SA (1) | SA518392386B1 (zh) |
| SG (1) | SG11201807817SA (zh) |
| WO (1) | WO2017160965A1 (zh) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476505B (zh) * | 2016-03-17 | 2021-06-01 | 沙特阿拉伯石油公司 | 过渡金属金刚烷盐和氧化物纳米复合材料的合成 |
| US10106482B2 (en) * | 2016-03-17 | 2018-10-23 | Saudi Arabian Oil Company | Synthesis of magnesium adamantane salts and magnesium oxide nanocomposites, and systems and methods including the salts or the nanocomposites |
| US10252245B2 (en) | 2016-03-17 | 2019-04-09 | Saudi Arabian Oil Company | High temperature layered mixed-metal oxide materials with enhanced stability |
| US10087355B2 (en) | 2016-03-17 | 2018-10-02 | Saudi Arabian Oil Company | Oil-based drilling fluids containing an alkaline-earth diamondoid compound as rheology modifier |
| US10138199B2 (en) | 2016-03-17 | 2018-11-27 | Saudi Arabian Oil Company | High aspect ratio layered double hydroxide materials and methods for preparation thereof |
| US10875092B2 (en) * | 2017-05-19 | 2020-12-29 | Saudi Arabian Oil Company | Methods for preparing mixed-metal oxide diamondoid nanocomposites and catalytic systems including the nanocomposites |
| WO2018213007A1 (en) | 2017-05-19 | 2018-11-22 | Saudi Arabian Oil Company | Synthesis of transition-metal adamantane salts and oxide nanocomposites |
| EP3527536A1 (en) * | 2018-02-15 | 2019-08-21 | Scg Chemicals Co. Ltd. | Method for preparing a camgal mixed oxide, a camgal mixed oxide obtainable this way and the use thereof for oligomerization of glycerol |
| CN108963277B (zh) * | 2018-07-02 | 2021-03-23 | 河南师范大学 | 一种可充式锌空电池双功能催化剂的制备方法及其应用 |
| CN109133200B (zh) * | 2018-08-31 | 2021-11-05 | 哈尔滨理工大学 | 一种花状Ni-Co水滑石电极材料的制备 |
| CN114507534B (zh) * | 2022-04-02 | 2023-05-12 | 陕西科技大学 | 一种氢氧化镍改性镁铝水滑石/蒙脱土纳米材料的制备方法 |
| CN114950547B (zh) * | 2022-06-01 | 2024-04-02 | 常州大学 | 酚钠盐改性水滑石的制备方法及其在制备酚醚类香料中的应用 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5326891A (en) * | 1990-10-29 | 1994-07-05 | Henkel Kommanditgesellschaft Auf Aktien | Hydrophobicized double layer hydroxide compounds |
| US5399329A (en) * | 1993-07-06 | 1995-03-21 | Aristech Chemical Corporation | Hydrotalcite-like materials having a sheet-like morphology and process for production thereof |
| US5414080A (en) * | 1992-11-25 | 1995-05-09 | Board Of Trustees Operating Michigan State University | Porphyrin-metallic complex intercalated layered double hydroxides |
| CN102730646A (zh) * | 2012-06-04 | 2012-10-17 | 上海大学 | 层状双氢氧化物纳米带的制备方法 |
| CN103596671A (zh) * | 2011-04-11 | 2014-02-19 | 沙特阿拉伯石油公司 | 金属负载的二氧化硅基催化膜反应器组件 |
| CN103965661A (zh) * | 2014-05-15 | 2014-08-06 | 南京林业大学 | 一种二次改性层状双氢氧化物的制备方法和应用 |
| CN104220161A (zh) * | 2011-04-11 | 2014-12-17 | 沙特阿拉伯石油公司 | 用于烃的自热蒸汽重整(atr)的催化剂结构体 |
| CN104310449A (zh) * | 2014-10-15 | 2015-01-28 | 上海应用技术学院 | 一种层状双氢氧化物纳米棒的制备方法 |
Family Cites Families (65)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3342880A (en) | 1963-03-14 | 1967-09-19 | Du Pont | Adamantane derivatives |
| US3671432A (en) | 1969-10-23 | 1972-06-20 | Standard Oil Co | Preparation of supported transition metal oxide polymerization catalysts |
| HU169494B (zh) | 1974-11-29 | 1976-12-28 | ||
| US4419222A (en) | 1978-07-25 | 1983-12-06 | Exxon Research And Engineering Co. | Hydrocarbon conversion processes using improved transition metal oxide catalysts |
| US4774212A (en) | 1987-12-22 | 1988-09-27 | Amoco Corporation | Pillared hydrotalcites |
| DE3803122C1 (zh) | 1988-02-03 | 1989-07-13 | Degussa Ag, 6000 Frankfurt, De | |
| US4956481A (en) | 1988-10-21 | 1990-09-11 | International Flavors & Fragrances Inc. | Adamantane derivatives, compositions of matter containing same, processes for preparing said adamantane derivatives and said compositions, and organoleptic and deodorancy uses of said adamantane derivatives and said compositions |
| US5021184A (en) | 1988-10-21 | 1991-06-04 | International Flavors & Fragrances Inc. | Adamantane derivatives, compositions of matter containing same, processes for preparing said adamantane derivatives and said compositions, and organoleptic and deodorancy uses of said adamantane derivatives and said compositions |
| US4952748A (en) | 1989-05-26 | 1990-08-28 | Mobil Oil Corp. | Purification of hydrocarbonaceous fractions |
| US5260495A (en) | 1991-08-23 | 1993-11-09 | Union Carbide Chemicals & Plastics Technology Corporation | Monoalkylene glycol production using highly selective monoalkylene glycol catalysts |
| US5507980A (en) * | 1993-07-06 | 1996-04-16 | Aristech Chemical Corporation | Basic inorganic binders |
| US5635457A (en) | 1995-04-17 | 1997-06-03 | Union Oil Company Of California | Non-toxic, inexpensive synthetic drilling fluid |
| WO1997034963A1 (en) | 1996-03-22 | 1997-09-25 | Exxon Research And Engineering Company | High performance environmentally friendly drilling fluids |
| US5883041A (en) | 1996-07-08 | 1999-03-16 | Connolly International Ltd. | Composite catalyst for purifying exhaust gases from carbon monoxide and organic compounds |
| JPH10124131A (ja) | 1996-10-22 | 1998-05-15 | Fanuc Ltd | 制御装置に接続される機器の管理方法 |
| JP4626896B2 (ja) | 1998-02-13 | 2011-02-09 | ダイセル化学工業株式会社 | アシル化剤とそれを用いたアシル化法、及びアダマンタン誘導体 |
| US6323270B1 (en) | 1998-11-16 | 2001-11-27 | Case Western Reserve University | Polybenzoxazine nanocomposites of clay and method for making same |
| US6410635B1 (en) | 1999-02-22 | 2002-06-25 | Ppg Industries Ohio, Inc. | Curable coating compositions containing high aspect ratio clays |
| JP3278631B2 (ja) * | 1999-04-06 | 2002-04-30 | 科学技術振興事業団 | アニオン−層状複水酸化物層間化合物の製法及びその製造物 |
| CA2389013A1 (en) | 1999-12-08 | 2001-06-14 | The Procter & Gamble Company | Compositions including ether-capped poly(oxyalkylated) alcohol wetting agents |
| AU2001291024B2 (en) | 2000-09-21 | 2006-11-23 | Rohm And Haas Company | Hydrophobically modified clay polymer nanocomposites |
| DK1358128T3 (da) | 2001-02-09 | 2005-11-28 | Akzo Nobel Nv | Fremgangsmåde til fremstilling af anionisk ler |
| ATE452107T1 (de) | 2001-07-20 | 2010-01-15 | Harvard College | Übergangsmetalloxid-nanodrähte und diese enthaltende vorrichtungen |
| US7098366B2 (en) | 2001-12-06 | 2006-08-29 | Basf Aktiengesellschaft | Supported metal oxides as catalysts for aldol condensations |
| US8158843B2 (en) | 2002-02-12 | 2012-04-17 | The Penn State Research Foundation | Deep desulfurization of hydrocarbon fuels |
| US7129287B1 (en) | 2002-04-29 | 2006-10-31 | The Ohio State University | Clay nanocomposites prepared by in-situ polymerization |
| US7001866B2 (en) | 2002-11-13 | 2006-02-21 | Conocophillips Company | Modification of the pore structure of metal oxide and mixed metal oxide supports for catalysts synthesis |
| CA2675742A1 (en) | 2002-12-20 | 2004-07-15 | Honda Giken Kogyo Kabushiki Kaisha | Noble metal-free nickel catalyst formulations for hydrogen generation |
| WO2004071653A1 (en) | 2003-02-13 | 2004-08-26 | Akzo Nobel N.V. | Composition comprising a metal hydroxy salt, its preparation and use as catalyst or sorbent |
| CA2594060A1 (en) | 2004-12-23 | 2006-06-29 | Minh-Tan Ton-That | Compatibilization of polymer clay nanocomposites |
| ES2277545B1 (es) | 2005-11-18 | 2008-06-16 | Consejo Superior Investig. Cientificas | Procedimiento simplificado para la preparacion de catalizadores de metales u oxidos metalicos soportados sobre materiales porosos. |
| WO2007065859A1 (en) * | 2005-12-06 | 2007-06-14 | Akzo Nobel N.V. | Process for preparing organically modified layered double hydroxide |
| US7711337B2 (en) | 2006-01-14 | 2010-05-04 | Paratek Microwave, Inc. | Adaptive impedance matching module (AIMM) control architectures |
| WO2008043750A1 (en) | 2006-10-11 | 2008-04-17 | Universidad De Chile | Hybrid clays for obtaining nanocomposites and the preparation process of these clays and polyolefin / clay nanocomposites |
| CN1944264A (zh) | 2006-11-07 | 2007-04-11 | 北京化工大学 | 一种均匀致密的取向性多元金属氧化物纳米薄膜的制备方法 |
| CN1994888B (zh) | 2007-01-12 | 2010-05-19 | 北京化工大学 | 一种层状复合金属氢氧化物的清洁制备方法 |
| EP2164925A2 (en) * | 2007-07-05 | 2010-03-24 | University Of North Texas | Nickel incorporation into ldh chlorobenzenesulfonate |
| JP5317293B2 (ja) | 2007-12-05 | 2013-10-16 | 独立行政法人物質・材料研究機構 | 陰イオン交換性層状複水酸化物の製造方法 |
| CN101402039B (zh) | 2008-11-13 | 2010-12-08 | 北京化工大学 | 一种负载型金属钯催化剂的制备方法 |
| JP4877381B2 (ja) | 2008-12-16 | 2012-02-15 | 横浜ゴム株式会社 | シラノール縮合触媒、加熱硬化性光半導体封止用シリコーン樹脂組成物およびこれを用いる光半導体封止体 |
| EP2263976A1 (en) | 2009-06-03 | 2010-12-22 | Akzo Nobel Chemicals International B.V. | Layered double hydroxide with a specific morphology, its preparation and use |
| US8613900B2 (en) | 2010-01-27 | 2013-12-24 | The Regents Of The University Of California | Nanostructured transition metal oxides useful for water oxidation catalysis |
| EP2363378A1 (en) | 2010-02-23 | 2011-09-07 | Corning Incorporated | Process for synthesizing layered oxides |
| EP2366664A1 (en) | 2010-03-09 | 2011-09-21 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Palladium-modified hydrotalcites and their use as catalyst precursors |
| US8652994B2 (en) | 2010-05-27 | 2014-02-18 | Beijing University Of Chemical Technology | Supported noble metal catalyst and process for preparing the same in situ |
| US20120322694A1 (en) | 2010-06-28 | 2012-12-20 | Baker Hughes Incorporated | Electrically Conductive Oil-Base Fluids for Oil and Gas Applications |
| JP5517808B2 (ja) | 2010-07-22 | 2014-06-11 | 三菱電機株式会社 | フィルタ装置 |
| AU2011298030A1 (en) | 2010-09-01 | 2013-03-21 | Basf Se | Process for producing carbon-comprising composite |
| WO2013002728A1 (en) | 2011-06-27 | 2013-01-03 | National University Of Singapore | Synthesis of mesoporous transition metal oxides as anode materials |
| GB201111781D0 (en) | 2011-07-08 | 2011-08-24 | Isis Innovation | Stream reforming of methanol |
| US8916491B2 (en) | 2011-11-08 | 2014-12-23 | Basf Se | Process for producing a methanation catalyst and a process for the methanation of synthesis gas |
| DE102011086451A1 (de) | 2011-11-16 | 2013-05-16 | Süd-Chemie Ip Gmbh & Co. Kg | Methanolsynthesekatalysator auf basis von kupfer, zink und aluminium |
| US8840803B2 (en) | 2012-02-02 | 2014-09-23 | Baker Hughes Incorporated | Thermally conductive nanocomposition and method of making the same |
| KR102064551B1 (ko) | 2012-03-28 | 2020-01-09 | 삼성전자주식회사 | 이산화탄소 흡착제, 그 제조 방법 및 이를 포함하는 이산화탄소 포집 모듈 |
| US20140072505A1 (en) | 2012-09-07 | 2014-03-13 | Antonio Fonseca | Layered multiphase catalyst supports and carbon nanotubes produced thereon |
| US9133385B2 (en) | 2012-09-30 | 2015-09-15 | Halliburton Energy Services, Inc. | Method for improving high temperature rheology in drilling fluids |
| WO2014080428A1 (en) | 2012-11-23 | 2014-05-30 | Council Of Scientific And Industrial Research | Mixed metal oxidic nano sheets coated monolithic catalysts useful for the decomposition of toxic n2o and a process for the preparation thereof |
| US9587469B2 (en) | 2013-07-23 | 2017-03-07 | Halliburton Energy Services, Inc. | Poly(alkyenylamide)-polysaccharide hydrogels for treatment of subterranean formations |
| WO2015086428A1 (en) | 2013-12-09 | 2015-06-18 | Unilever Plc | Process of making adamantanamides |
| CN105017485A (zh) | 2015-08-25 | 2015-11-04 | 中国石油化工股份有限公司 | 一种含金刚烷基的疏水缔合两性离子黄原胶及其制备方法 |
| US10087355B2 (en) | 2016-03-17 | 2018-10-02 | Saudi Arabian Oil Company | Oil-based drilling fluids containing an alkaline-earth diamondoid compound as rheology modifier |
| US10252245B2 (en) | 2016-03-17 | 2019-04-09 | Saudi Arabian Oil Company | High temperature layered mixed-metal oxide materials with enhanced stability |
| US10106482B2 (en) | 2016-03-17 | 2018-10-23 | Saudi Arabian Oil Company | Synthesis of magnesium adamantane salts and magnesium oxide nanocomposites, and systems and methods including the salts or the nanocomposites |
| CN109476505B (zh) | 2016-03-17 | 2021-06-01 | 沙特阿拉伯石油公司 | 过渡金属金刚烷盐和氧化物纳米复合材料的合成 |
| US10138199B2 (en) | 2016-03-17 | 2018-11-27 | Saudi Arabian Oil Company | High aspect ratio layered double hydroxide materials and methods for preparation thereof |
-
2017
- 2017-03-03 US US15/449,207 patent/US10138199B2/en active Active
- 2017-03-15 SG SG11201807817SA patent/SG11201807817SA/en unknown
- 2017-03-15 CN CN201780016756.7A patent/CN109414686B/zh active Active
- 2017-03-15 WO PCT/US2017/022485 patent/WO2017160965A1/en active Application Filing
- 2017-03-15 JP JP2018568161A patent/JP6914282B2/ja active Active
- 2017-03-15 KR KR1020187029910A patent/KR102164758B1/ko active IP Right Grant
- 2017-03-15 EP EP17715303.8A patent/EP3429749B1/en active Active
-
2018
- 2018-09-10 SA SA518392386A patent/SA518392386B1/ar unknown
- 2018-10-11 US US16/157,542 patent/US10906859B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5326891A (en) * | 1990-10-29 | 1994-07-05 | Henkel Kommanditgesellschaft Auf Aktien | Hydrophobicized double layer hydroxide compounds |
| US5414080A (en) * | 1992-11-25 | 1995-05-09 | Board Of Trustees Operating Michigan State University | Porphyrin-metallic complex intercalated layered double hydroxides |
| US5399329A (en) * | 1993-07-06 | 1995-03-21 | Aristech Chemical Corporation | Hydrotalcite-like materials having a sheet-like morphology and process for production thereof |
| CN103596671A (zh) * | 2011-04-11 | 2014-02-19 | 沙特阿拉伯石油公司 | 金属负载的二氧化硅基催化膜反应器组件 |
| CN104220161A (zh) * | 2011-04-11 | 2014-12-17 | 沙特阿拉伯石油公司 | 用于烃的自热蒸汽重整(atr)的催化剂结构体 |
| CN102730646A (zh) * | 2012-06-04 | 2012-10-17 | 上海大学 | 层状双氢氧化物纳米带的制备方法 |
| CN103965661A (zh) * | 2014-05-15 | 2014-08-06 | 南京林业大学 | 一种二次改性层状双氢氧化物的制备方法和应用 |
| CN104310449A (zh) * | 2014-10-15 | 2015-01-28 | 上海应用技术学院 | 一种层状双氢氧化物纳米棒的制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| Application of layered double hydroxides for removal of oxyanions: A review;Kok-Hui Goh et al.;《WATER RESEARCH》;20071107;第42卷;第1343-1368页 * |
| The intercalation of bicyclic and tricyclic carboxylates into layered double hydroxides;Aamir I. Khan et al.;《Journal of Solid State Chemistry》;20101001;第183卷;第2877-2885页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| SG11201807817SA (en) | 2018-10-30 |
| WO2017160965A1 (en) | 2017-09-21 |
| KR102164758B1 (ko) | 2020-10-13 |
| US10906859B2 (en) | 2021-02-02 |
| US10138199B2 (en) | 2018-11-27 |
| US20190039988A1 (en) | 2019-02-07 |
| KR20190049620A (ko) | 2019-05-09 |
| EP3429749B1 (en) | 2020-08-12 |
| JP2019512453A (ja) | 2019-05-16 |
| CN109414686A (zh) | 2019-03-01 |
| US20170267623A1 (en) | 2017-09-21 |
| EP3429749A1 (en) | 2019-01-23 |
| JP6914282B2 (ja) | 2021-08-04 |
| SA518392386B1 (ar) | 2021-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109414686B (zh) | 高纵横比层状双氢氧化物材料和其制备方法 | |
| US9126189B2 (en) | Method of making pyrochlores | |
| JP6936847B2 (ja) | 安定性の向上した高温層状混合金属酸化物材料 | |
| KR20190042489A (ko) | 마그네슘 아다만탄 카복실산염 및 산화물 나노복합체의 합성 | |
| KR102146239B1 (ko) | 전이금속 아다만탄 카복실레이트염 및 산화물 나노복합체의 합성 | |
| CN109847756B (zh) | 一种中空结构的镍基纳米催化剂及其制备方法与应用 | |
| CN107635661B (zh) | 铁基催化剂的制备方法和用该方法制备的铁基催化剂制备烃类的方法 | |
| do Carmo et al. | Synthesis of tailored alumina supported Cu-based solids obtained from nanocomposites: Catalytic application for valuable aldehyde and ketones production | |
| US11351604B2 (en) | Methods for preparing mixed-metal oxide diamondoid nanocomposites and catalytic systems including the nanocomposites | |
| US20220203341A1 (en) | Steam reforming catalysts for sustainable hydrogen production from biobased materials | |
| CN108786902B (zh) | 一种重质芳烃转化催化剂及其制备方法 | |
| Trujillo | Part I. Synthesis and applications of molecular sieves. Part II. The effect of temperature and support in reduction of cobalt oxide: An in situ XRD study | |
| KR20200010372A (ko) | 전이 금속 아다만탄 염 및 산화물 나노복합체의 합성 | |
| IGNAT et al. | NOVEL Ni-ZnCoFeAlLDH HETEROSTRUCTURES AND THEIR DERIVED MIXED OXIDES: STUDIES ON THE STRUCTURAL AND NANOMORPHOLOGY PROPERTIES |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |