JP2021519204A - メソポーラス材料内に閉じ込められたナノ触媒を作製する方法およびその使用 - Google Patents
メソポーラス材料内に閉じ込められたナノ触媒を作製する方法およびその使用 Download PDFInfo
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- JP2021519204A JP2021519204A JP2020551555A JP2020551555A JP2021519204A JP 2021519204 A JP2021519204 A JP 2021519204A JP 2020551555 A JP2020551555 A JP 2020551555A JP 2020551555 A JP2020551555 A JP 2020551555A JP 2021519204 A JP2021519204 A JP 2021519204A
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- Prior art keywords
- mof
- metal
- mesoporous
- mpm
- confined
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- 239000013335 mesoporous material Substances 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 77
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 58
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 141
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000446 fuel Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000000969 carrier Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims description 79
- 239000002184 metal Substances 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 71
- 239000002243 precursor Substances 0.000 claims description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000003446 ligand Substances 0.000 claims description 39
- 238000003786 synthesis reaction Methods 0.000 claims description 37
- 230000015572 biosynthetic process Effects 0.000 claims description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 32
- 238000011282 treatment Methods 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 28
- 239000013207 UiO-66 Substances 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 23
- -1 M 2 ( dobpdc) Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 150000004706 metal oxides Chemical class 0.000 claims description 20
- 229910021645 metal ion Inorganic materials 0.000 claims description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims description 19
- 150000002894 organic compounds Chemical class 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 238000006722 reduction reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 11
- 239000013291 MIL-100 Substances 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000013206 MIL-53 Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000013177 MIL-101 Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 239000013118 MOF-74-type framework Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 239000013097 PCN-222 Substances 0.000 claims description 5
- 238000006473 carboxylation reaction Methods 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 5
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 5
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 239000013208 UiO-67 Substances 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 238000000231 atomic layer deposition Methods 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-K benzene-1,3,5-tricarboxylate(3-) Chemical compound [O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-K 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 238000006735 epoxidation reaction Methods 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- CZCNMDLBCRHRRE-UHFFFAOYSA-N N1C(=CC=C1)C(=O)O.N1=CN=CC=C1 Chemical compound N1C(=CC=C1)C(=O)O.N1=CN=CC=C1 CZCNMDLBCRHRRE-UHFFFAOYSA-N 0.000 claims description 3
- 239000013522 chelant Substances 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000007792 gaseous phase Substances 0.000 claims description 2
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 20
- 239000007787 solid Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 230000009466 transformation Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002159 nanocrystal Substances 0.000 description 46
- 239000000463 material Substances 0.000 description 43
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 239000011148 porous material Substances 0.000 description 19
- 229910004298 SiO 2 Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000013459 approach Methods 0.000 description 12
- 239000013110 organic ligand Substances 0.000 description 12
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000011651 chromium Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000000197 pyrolysis Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002262 Schiff base Substances 0.000 description 6
- 150000004753 Schiff bases Chemical class 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 125000005647 linker group Chemical group 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 229910052707 ruthenium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 238000007306 functionalization reaction Methods 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000004820 halides Chemical group 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000013337 mesoporous metal-organic framework Substances 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 150000001412 amines Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 3
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 229910018967 Pt—Rh Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
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- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
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- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
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- 150000002500 ions Chemical group 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000013336 microporous metal-organic framework Substances 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 150000003515 testosterones Chemical class 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- YNIWBQWSPPNHRN-UHFFFAOYSA-N 2,6-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C(O)=C1 YNIWBQWSPPNHRN-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
この出願は、2018年3月26日に出願された“METHOD OF MAKING CONFINED NANOCATALYSTS WITHIN MESOPOROUS MATERIALS AND USES THEREOF,”と題する米国仮特許出願第62/647,949号に関して優先権を主張し、その出願全体が参照により本明細書に援用される。
本開示は、メソポーラス材料(MPM)内に閉じ込められたナノ触媒を作製する方法を提供する。この方法は、ナノ結晶金属有機構造体(MOF)の固体成長と、それに続く制御された変換を利用して、メソポーラス材料内にその場でナノ触媒を生成する。本開示はまた、液体有機水素担体、合成液体燃料の調製、および窒素の固定を含むがこれらに限定されない、多種多様な分野へのナノ触媒の適用を提供する。
(2.1.序文)
本明細書で提供される「背景」の説明は、本開示の文脈を一般的に提示することを目的としている。この背景セクションに記載されている限りにおいて、現在発明者として記載されている者の研究、同様に出願時に先行技術として適格とならない可能性のある説明の態様は、明示的にも暗示的にも本開示に対する先行技術として認められない。
本開示は、(a)少なくとも1つの金属イオンと配位結合を形成することが可能である1つ以上の多座配位子[Ax(L−x)]を備える、少なくとも1つ以上の有機化合物をメソポーラス材料に含浸させて、第1の中間体[(Ax(L−x)/MPM)]を形成するステップと、(b)第1の中間体[(Ax(L−x)/MPM)]を気相の酸に曝して、第2の中間体[(Hx(L−x)/MPM)]を形成するステップと、(c)第2の中間体[(Hx(L−x)/MPM)]に、1つ以上の金属イオン(M1 +y,M2 +y,M3 +y)の溶媒溶液を添加して、メソポーラス材料[MOF/MPM]内に閉じ込められた金属有機構造体(MOF)前駆体を形成する1つ以上の多座配位子と配位結合を形成するステップと、(d)ステップ(c)[MOF/MPM]の前駆体を制御された変換条件下で処理して、メソポーラス材料内に閉じ込められた金属ナノ触媒を形成するステップと、を含む、メソポーラス材料(MPM)内に閉じ込められた金属ナノ触媒を調製する方法を提供する。
(4.図面の簡単な説明)
この開示は、MOFナノ結晶の制御された変換を介してナノサイズの触媒を調製するための新しい方針を提供する。これらの触媒は、以前または以後にメソポーラス材料内に閉じ込められた追加の有機金属系金属錯体または金属塩で必要に応じて装飾され得、およびまたは必要に応じて、ポリマー、有機金属配位子前駆体、窒素含有有機化合物、リン含有有機化合物、硫黄含有有機化合物、ホウ素含有有機化合物、ハロゲン化物塩、有機ハロゲン化物、原子層堆積または化学蒸気堆積を介して添加された金属原子、またはメソポーラス材料内に以前または以後に閉じ込められた他の化合物で装飾され得る。この一般的な方法は、分散、ナノサイズの寸法、および元の担体前駆体のメソポーラスマトリックスに沿った3D分布を得られた触媒に保存し、こうしてナノメートルおよびサブナノメートルの活性種(金属、金属酸化物、Nドープ炭素、Pドープ炭素、Sドープ炭素、Bドープ炭素、ハロゲン化物ドープ炭素、およびそれらの組み合わせなど)の形成を、ハイブリッド前駆体(すなわち、有機金属系金属錯体、金属塩、ポリマー、有機金属配位子前駆体、窒素含有有機物、リン含有有機物、硫黄含有有機物、ホウ素含有有機物、ハロゲン化物塩、有機ハロゲン化物、MOFおよびメソポーラス足場)の適切な選択を用いることにより、高精度で促進する。
(6.1.材料および方法)
化学物質。すべての化学物質は、さらに精製することなく、シグマアルドリッチから受領したままで使用した。Cr(NO3)3・9H2O、CrCl3・6H2O、Al(NO3)3・9H2O、AlCl3xH2O、Co(NO3)2・6H2O、Ni(NO3)2・6H2O、ZrOCl2・8H2O、RuCl3・xH2O、Zn(NO3)3・9H2O、1,4−ベンゼンジカルボン酸(H2BDC)、1,3,5−ベンゼントリカルボン酸(H3BTC)、2−アミノテレフタル酸(H2BDC(NH2))、2−スルホテレフタレート一ナトリウム(H2BDC(SO3Na))、2,5−ジヒドロキシテレフタル酸(H4DOBDC)、2,2´−ビピリジン−5,5´−ジカルボン酸(H2BpyDC)、2−メチルイミダゾール(HMeIM)、テトラキス(4−カルボキシ−フェニル)−ポルフィリン(H4TCPP)。1,3,6,8−テトラキス(p−安息香酸)ピレン(H4TBAPy)は、公開されている手順に従って合成された。Deria,P.;Bury,W.;Hupp,J.T.;Farha,O.K.:Versatile functionalization of the NU−1000 platform by solvent−assisted ligand incorporation. Chem. Commun. 2014,50,1965−1968.を参照されたい。トリエチルアミン(TEA)、N,N−ジメチルホルムアミド(DMF)、テトラヒドロフラン(THF)、およびメタノール(MeOH)は、分析グレード(シグマアルドリッチ)であった。
(Cr)MIL−101(Ferey,G.;Mellot−Draznieks,C.;Serre,C.;Millange,F.;Dutour,J.;Surble,S.;Margiolaki,I.:A chromium terephthalate−based solid with unusually large pore volumes and surface area. Science 2005,309,2040−2042およびSerre,C.;Millange,F.;Thouvenot,C.;Nogues,M.;Marsolier,G.;Loue:r,D.;Ferey,G.:Very Large Breathing Effect in the First Nanoporous Chromium(III)−Based Solids:MIL−53 or CrIII(OH)・{O2C-C6H4-CO2} {HO2C-C6H4-CO2H}x・H2Oy.J.Am.Chem.Soc.2002,124,13519−13526)、
(Cr)MIL−100(Long,P.P.;Wu,H.W.;Zhao,Q.;Wang,Y.X.;Dong,J.X.;Li,J.P.:Solvent effect on the synthesis of MIL−96(Cr) and MIL−100(Cr).Microporous Mesoporous Mater.2011,142,489−493)、
(Cr)MIL−101(SO3H)(Juan−Alcaniz,J.;Gielisse,R.;Lago,A.B.;Ramos−Fernan−dez,E.V.;Serra−Crespo,P.;Devic,T.;Guillou,N.;Serre,C.;Kapteijn,F.;Gascon,J.:Towards acid MOFs−catalytic performance of sulfonic acid functionalized architectures.Catal.Sci.Technol.2013,3,2311−2318)、
(Al)MIL−100(Volkringer,C.;Popov,D.;Loiseau,T.;Ferey,G.;Burghammer,M.;Riekel,C.;Haouas,M.;Taulelle,F.:Synthesis,Single−Crystal X−ray Microdiffraction, and NMR Characterizations of the Giant Pore Metal−Organic Framework Aluminum Trimesate MIL−100.Chem.Mater.2009,21,5695−5697)、
(Al)MIL−53(NH2)(Couck,S.;Denayer,J.F.M.;Baron,G.V.;Remy,T.;Gas−con,J.;Kapteijn,F.:An Amine−Functionalized MIL−53 Metal−Organic Framework with Large Separation Power for CO2 and CH4.J.Am.Chem.Soc.2009,131,6326−+)、
(Co,Ni)MOF−74(Dietzel,P.D.C.;Morita,Y.;Blom,R.;Fjellva&g,H.:An In Situ High−Temperature Single−Crystal Investigation of a Dehydrated Metal−Organic Framework Compound and Field−Induced Magnetization of One−Dimensional Metal−Oxygen Chains.Angew.Chem.,Int.Ed.2005,44,6354−6358およびDietzel,P.D.C.;Panella,B.;Hirscher,M.;Blom,R.;Fjell−vag,H.:Hydrogen adsorption in a nickel based coordination polymer with open metal sites in the cylindrical cavities of the desolvated frame−work.Chem.Commun.2006,959−961)、
(Zr)UiO−66(H,NH2)(Kandiah,M.;Nilsen,M.H.;Usseglio,S.;Jakobsen,S.;Ols−bye,U.;Tilset,M.;Larabi,C.;Quadrelli,E.A.;Bonino,F.;Lillerud,K.P.:Synthesis and Stability of Tagged UiO−66 Zr−MOFs.Chem.Ma−ter.2010,22,6632−6640)、
(Zr)UiO−67(Bpy)(Fei,H.;Cohen,S.M.:A robust, catalytic metal−organic framework with open 2,2−bipyridine sites.Chem.Commun.2014,50,4810−4812)、
(Ru)HKUST−1(Kozachuk,O.;Luz,I.;Llabres i Xamena,F.X.;Noei,H.;Kauer,M.;Albada,H.B.;Bloch,E.D.;Marler,B.;Wang,Y.;Muhler,M.;Fischer,R.A.:Multifunctional, Defect−Engineered Metal−Organic Frameworks with Ruthenium Centers:Sorption and Catalytic Properties.Angew.Chem.,Int.Ed.2014,53,7058−7062)、
(Zn)ZIF−8(Cravillon,J.;Mu:nzer,S.;Lohmeier,S.−J.;Feldhoff,A.;Huber,K.;Wiebcke,M.:Rapid Room−Temperature Synthesis and Characterization of Nanocrystals of a Prototypical Zeolitic Imidazolate Framework.Chem.Mater.2009,21,1410−1412)、
(Zr)PCN−222(Dawei Feng;Zhi−Yuan Gu;Jian−Rong Li;Hai−Long Jiang;ZhangwenWei;Zhou,H.−C.:Zirconium−Metalloporphyrin PCN−222: Mesoporous Metal−Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts.Angew.Chem.,Int.Ed.2012,51,10307−10310)、
(Zr)NU−1000(Deria et al.2014)およびCo2(dobpdc)(McDonald et al. Cooperative insertion of CO2 in diamine−appended metal−organic frameworks.Nature 2015,519,303−+)。
これらのMOFのFTIRスペクトルは、MOF/MPMハイブリッド材料の参照として使用された。図には、(Cr)MIL−101(SO3H)のN2等温線と細孔分布とが含まれていた。
本明細書に開示されるアプローチの範囲の例として、単一の金属および金属酸化物ナノ結晶は、前駆体としてメソポーラスシリカ上に選択された支持されたMOFナノ結晶を使用することによって制御された変換手順によって調製された。さらに、バイメタル金属酸化物ナノ結晶は、気相官能基化を含む、制御された変換の前に実行されるMOFハイブリッド前駆体の追加の多段階合成後修飾(PSM)によっても調製されており(表1および図1および2を参照)(Servalli,M.;Ranocchiari,M.;VanBokhoven,J.A.:Fast and high yield post−synthetic modification of metal−organic frameworks by vapor diffusion.Chemical Communications 2012,48,1904−1906)、続いて選択的にメタル化される(Zhang, X.;Llabres i Xamena,F.X.;Corma,A.:Gold(III)−Metal Organic Framework Bridges the Gap between Homogeneous and Heterogeneous Gold Catalysts.Journal of Catalysis 2009,265,155−160)。
バイメタル[PdCl−SI−(Zr)UiO−66(NH2)/SBA−15]前駆体は、(1)MOF前駆体溶液のSBA−15への多段階初期湿潤含浸、(2)特定の条件での処理、(3)一般的な洗浄処理、(4)合成後の気相官能基化(固体)、および(5)合成後の液相メタル化、の一般的な手順に従って、固相合成によって調製された。すべてのバイメタル[M2−Z−(M1)MOF/MPM]前駆体は、以前に記述されたように(Cirujanoetalら、2017およびPCT特許出願PCT/US2017/046231)前述の一般的な手順(ステップ1〜5)によって調製され得る。モノメタル[(M1)MOF/MPM]前駆体は、最初の3つのステップ(1〜3)のみに従って調製される。
金属ナノ結晶は、窒素または他の不活性ガス下で300〜1000oCの範囲の温度で変換を行うと得られる。いくつかの実施形態では、この処理は、MOFナノ結晶の有機組成物を炭素質種に変換する。それにもかかわらず、TGAおよび元素分析データは、600〜700°Cを超える熱分解温度で炭素またはグラフェンを含まないバイメタルナノ触媒をもたらすMOFナノ結晶の完全な「脱炭素化」を明らかにしている。これは、処理時に微孔性炭素質構造が残っているバルクMOF(100nmを超える)(図5のTGA FTIR比較を参照されたい)とは対照的である。Tang,J.;Salunkhe,R.R.;Zhang,H.;Malgras,V.;Ahamad,T.;Alshehri,S.M.;Kobayashi,N.;Tominaka,S.;Ide,Y.;Kim,J.H.;Yamauchi,Y.:Bimetallic Metal−Organic Frameworks for Controlled Catalytic Graphitization of Nanoporous Carbons.Scientific Reports 2016,6,30295;Masoomi,M.Y.;Morsali,A.:Applications of metal−organic coordination polymers as precursors for preparation of nano−materials.Coordination Chemistry Reviews 2012,256,2921−2943;Wezendonk,T.A.;Santos,V.P.;Nasalevich,M.A.;Warringa,Q.S.E.;Dugulan,A.I.;Chojecki,A.;Koeken,A.C.J.;Ruitenbeek,M.;Meima,G.;Islam,H.U.;Sankar,G.;Makkee,M.;Kapteijn,F.;Gascon,J.:Elucidating the Nature of Fe Species during Pyrolysis of the Fe−BTC MOF into Highly Active and Stable Fischer−Tropsch Catalysts. ACS Catalysis 2016,6,3236−3247、を参照されたい。ナノ触媒からの炭素放出を回避するために、低温熱分解(<500°C)を使用し得る。図4aは、不活性雰囲気で加熱して調製したナノ触媒のSTEM画像を示している。
変換処理に酸素を使用すると、すべての有機組成物が低温で放出される。炭素を含まないバイメタルナノ触媒は、300〜600°Cを超える温度で得られる。図4bは、酸素含有雰囲気中でのか焼によって調製されたナノ触媒のSTEM画像を示している。
水素含有雰囲気を使用すると、より穏やかな温度(室温から300°C)で制御された変換が発生する。これらの条件下では、MOFナノ結晶を装飾する遷移金属カチオンが還元されて、MOFの微孔性空洞内に閉じ込められたモノメタルナノ結晶が形成されるが、MOF炭素微細構造は完全には分解されない。サブナノメートルの金属ナノ結晶の形成は、微孔性MOF内に限定される。図4cは、水素含有雰囲気での還元によって調製されたナノ触媒のSTEM画像を示している。
我々の新しいアプローチによって調製された支持ナノ結晶のいくつかの例を表1に示す。これらの材料の選択は、他の構造の調製を制限するものではない。
本発明のアンモニア合成への適用を実証する実験を以下に説明する。Ru/SiO2は高収率で合成され、2グラムの固定床マイクロリアクターでテストするための材料を提供した。ナノ触媒に変換される前に、Ru−HKUST−1の構造は、X線回折(XRD)、フーリエ変換赤外分光法(FTIR)およびBET表面積測定を照合することによって確認され、シリカ複合材料の表面積の増加はMOFの存在と相関することを示した。次に、Ru−HKUST−1は、ゆっくりとした温度上昇で900°Cの熱処理を使用してルテニウムナノ粒子に変換された。400°Cを超える温度では、有機リンカーの特定の成分がガス化されてCO2として放出されるため、MOFの高表面積と長距離構造が破壊される。単原子ルテニウムは錯化から放出され、残留有機フラグメントの中で表面に堆積する。ルテニウム原子の凝集は高温で起こり、十分に分散した小さなルテニウムナノ粒子が支持体の表面に形成される。ルテニウム触媒によるアンモニア合成を促進することが示されている硝酸バリウムおよび硝酸セシウムを使用した文献からの促進手順に従った(Bielawa,H.;Hinrichsen,O.;Birkner,A.;Muhler,M.:The ammonia−synthesis catalyst of the next generation:Barium−promoted oxide−supported ruthenium. Angewandte Chemie−International Edition 2001,40,1061−1063)。促進は、水溶液からRu/SiO2の表面への硝酸バリウムおよび硝酸セシウム塩の湿式堆積によって達成され、バリウムおよびセシウムによって促進されるRu/SiO2触媒が得られた。
独自の機能を利用して得られた触媒の幅広い用途の例を説明するために、それらは、流動化メソポーラスシリカ(ここでは、流動化ナノリアクター、FN)内で構成される、先端概念である流動化ナノリアクター水素担体(ここではFNHC)の触媒活性プラットフォームに使用される。OHCは、接触水素化反応によってH2を水素希薄分子に結合することによる化学的水素貯蔵で構成され、触媒脱水素化を介して放出することができる。結合H2は、現実的な「オフボード」の水素充填ステーションから、自動車や宇宙船などのモバイルプラットフォームでの未来的な「オンボード」の水素生成に至るまで、いくつかの用途のための燃料として使用され得る(Preuster,P.;Papp,C.;Wasserscheid,P.:Liquid Organic Hydrogen Carriers(LOHCs):Toward a Hydrogen −free Hydrogen Economy. Accounts of Chemical Research 2017,50,74−85.)。
Fe触媒は、(Fe)MIL−100/SiO2を、空気と窒素との2つの異なる変換条件を使用して直接変換し、それぞれFe3O4/SiO2とFeC/SiO2を形成することによって調製した。これら2つの触媒は、水素を使用したCO2から燃料への熱変換について評価された。320°C、30bar、4000h−1のGHSVでFeのさまざまな配合を含むこれらの触媒によって得られた結果のいくつかの例を図7と8に示す(Wei,J.;Ge,Q.;Yao,R.;Wen,Z.;Fang,C.;Guo,L.;Xu,H.;Sun,J.:Directly converting CO2 into a gasoline fuel.Nature Communications2017,8,15174−82.)。
以下の番号付きの記述は、開示の一般的な説明を提供し、添付の特許請求の範囲を制限することを意図するものではない。
Claims (23)
- メソポーラス材料(MPM)内に閉じ込められた金属ナノ触媒を調製する方法であって、(a)少なくとも1つの金属イオンと配位結合を形成することが可能な1つ以上の多座配位子[Ax(L−x)]を備える、少なくとも1つ以上の有機化合物を含浸させて、メソポーラス材料に第1の中間体[(Ax(L−x)/MPM)]を形成するステップと、(b)前記第1の中間体[(Ax(L−x)/MPM)]を気相の酸に曝して、第2の中間体[(Hx(L−x)/MPM)]を形成するステップと、(c)前記第2の中間体[(Hx(L−x)/MPM)]に1つ以上の金属イオン(M1 +y、M2 +y、M3 +y)の溶媒溶液を添加して、1つ以上のメソポーラス材料内に閉じ込められた金属有機構造体(MOF)前駆体[MOF/MPM]を形成する1つ以上の多座配位子と配位結合を形成するステップと、(d)ステップ(c)の前記前駆体[MOF/MPM]を制御された変換条件下で処理して、前記メソポーラス材料内に閉じ込められた前記金属ナノ触媒を形成するステップと、を含む、方法。
- ステップ(d)は、ステップ(d)の前記前駆体[MOF/MPM]を1つ以上の有機化合物(Z)と接触させて、配位結合[Z/MOF/MPM]を形成することが可能である第2の多座配位子を作ることを含むステップ(d)(1)と、1つ以上の追加の金属イオンの溶媒溶液を添加して、メソポーラス材料内に閉じ込められた追加の金属を有する修飾MOF前駆体[MOF/MPM]を形成するステップ(d)(2)と、をさらに含む、請求項1に記載の方法。
- ステップ(d)(1)のキレート配位子(Z)は、第2の金属イオンを錯化するための金属結合部位を備える、請求項2に記載の方法。
- 前記制御された変換条件により、前記MOF中の炭素の90%を超える炭素が前記MOF/MPMから放出される、請求項1に記載の方法。
- 前記制御された変換条件により、前記MOF中の炭素の50%±10%が前記MOF/MPMから放出される、請求項1に記載の方法。
- 制御された変換条件下での処理は、不活性ガス雰囲気中での約300°C〜約1000°Cの温度での熱分解である、請求項1に記載の方法。
- 前記制御された変換条件下での処理は、酸素ガスを含有する雰囲気中における約300°C〜約600°Cの温度でのか焼である、請求項1に記載の方法。
- 前記制御された変換条件下での処理は、約25°C〜約300°Cの温度での水素による還元である、請求項1に記載の方法。
- 前記閉じ込められたナノ触媒は、モノメタル(M1)である、請求項1に記載の方法。
- 前記閉じ込められたナノ触媒は、バイメタル(M1+M2)である、請求項1に記載の方法。
- 前記閉じ込められたナノ触媒は、3つ以上の金属を有する、請求項1に記載の方法。
- 前記メソポーラス材料内に閉じ込められたナノ触媒は、10nm未満の直径を有する、請求項1に記載の方法。
- 前記メソポーラス材料は、メソポーラス金属酸化物、メソポーラスシリカ、メソポーラスカーボン、メソポーラスポリマー、メソポーラスシリコアルミナ(ゼオライト)、メソポーラス有機シリカ、またはメソポーラスアルミノリン酸アルミニウムである、請求項1に記載の方法。
- 前記メソポーラス金属酸化物は、酸化アルミニウム、酸化セリウム、酸化チタン、酸化ジルコニウム、または酸化マグネシウムである、請求項13に記載の方法。
- メソポーラス材料が約100m2/g〜約1000m2/gの表面積を有する、請求項1に記載の方法。
- 前記金属イオン(M1 +y、M2 +y、M3 +y)は、Al、Au、Ce、Co、Fe、Ir、Mo、Ni、Pd、Rh、Ru、Ti、V、Zrまたはそれらの組み合わせからなる群から選択される、請求項1に記載の方法。
- 前記MOFの前記多座配位子は、テレフタレート、ベンゼン−1,3,5−トリカルボキシレート、2,5−ジオキシベンゼンジカルボキシレート、ビフェニル−4,4´−ジカルボキシレート、イミダゾレート、ピリミジン−アゾレート、トリアゾレート、テトラゾレート、それらの誘導体または組み合わせからなる群から選択される、請求項1に記載の方法。
- 前記MOFは、HKUST−1、M2(dobpdc)、MIL−100、MIL−101、MIL−53、MOF−74、NU−1000、PCN−222、PCN−224、UiO−66、UiO−67、ZIF−8、ZIFs、またはそれらの誘導体から選択される、請求項1に記載の方法。
- 前記メソポーラス材料は、MCM-41、SBA-15、または市販のシリカからなる群から選択される、請求項1に記載の方法。
- 前記メソポーラス材料内に閉じ込められた、閉じ込められたナノ触媒は、ポリマー、有機金属配位子前駆体、窒素含有有機化合物、リン含有有機化合物、硫黄含有有機化合物、ホウ素含有有機化合物、ハロゲン化物塩、有機ハロゲン化物、または原子層堆積または化学蒸気堆積によって追加された金属原子を有する追加の有機金属系金属錯体または金属塩とさらに反応する、請求項1に記載の方法。
- 請求項1に記載の方法により製造された触媒。
- 追加の金属促進剤をさらに備える、請求項21に記載の触媒。
- アルケンのアンモ酸化反応、アルケンのエポキシ化、アンモニア合成、カルボキシル化反応、CO2メタン化反応、CO2の燃料への変換、メタンからの直接メタノール合成、ドライメタン改質、電気触媒アンモニア酸化、電気触媒酸素還元反応、Fischer−Tropsch合成、液体有機水素担体の水素化/脱水素化、水素化処理および水素化処理エステル化反応、合成ガスからのメタノール合成、逆水性ガスシフト反応、または水性ガスシフト反応を触媒するための、請求項21に記載の触媒の使用。
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