CN112044434A - Single-atom noble metal/transition metal oxide composite material and preparation method and application thereof - Google Patents
Single-atom noble metal/transition metal oxide composite material and preparation method and application thereof Download PDFInfo
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- CN112044434A CN112044434A CN202011121258.9A CN202011121258A CN112044434A CN 112044434 A CN112044434 A CN 112044434A CN 202011121258 A CN202011121258 A CN 202011121258A CN 112044434 A CN112044434 A CN 112044434A
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- noble metal
- composite material
- acetone
- oxide
- transition metal
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 60
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 132
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 108010039918 Polylysine Proteins 0.000 claims description 11
- 239000002073 nanorod Substances 0.000 claims description 11
- 229920000656 polylysine Polymers 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 108010020346 Polyglutamic Acid Proteins 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229920002643 polyglutamic acid Polymers 0.000 claims description 4
- 150000003839 salts Chemical group 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000002107 nanodisc Substances 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 108010064470 polyaspartate Proteins 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003623 transition metal compounds Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 15
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 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 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000010949 copper Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910003112 MgO-Al2O3 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- -1 transition metal salt Chemical class 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- MBUJACWWYFPMDK-UHFFFAOYSA-N pentane-2,4-dione;platinum Chemical compound [Pt].CC(=O)CC(C)=O MBUJACWWYFPMDK-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a single-atom noble metal/transition metal oxide composite material and a preparation method and application thereof, wherein the composite material is prepared by loading noble metal on transition metal oxide in a single-atom form, and the single atom of the noble metal accounts for 0.01-1.0 wt%. When the composite material is prepared, a dispersing agent, in particular a catalyst of polyamino acid, is added, so that the noble metal is more uniformly dispersed on the carrier. The monatomic noble metal/transition metal oxide composite material obtained by the invention can be used as a monatomic catalyst for preparing isopropanol by catalytic hydrogenation of acetone, and the catalyst is simple and convenient to prepare, easy to amplify, low in preparation cost, high in low-temperature activity, high in selectivity and good in stability; in addition, the monatomic catalyst has high activity, high efficiency, good selectivity and long service life in the reaction of preparing the isopropanol by the acetone gas phase selective catalytic hydrogenation.
Description
Technical Field
The invention relates to the technical field of monatomic catalysts. More particularly, it relates to a monoatomic/transition metal oxide catalyst and its application in catalytic hydrogenation of acetone.
Technical Field
The catalytic hydrogenation of aldehydes and ketones to the corresponding alcohols is an important reaction for the production of fine chemicals. Taking acetone as an example, isopropanol which is a product of hydrogenation reaction of acetone is an important chemical and is widely applied to the fields of chemical engineering such as paint, medicine, pesticide and the like. In 2011 alone, the global usage of isopropanol reached 6.4 megatons. At present, isopropanol is obtained mainly through hydration reaction of propylene, and the process not only needs to use corrosive chemicals, but also needs to consume a lot of energy, and does not meet the requirement of green industry. In modern industry, a large amount of acetone is excessive, so that if acetone can be efficiently hydrogenated to isopropanol, the current situation of excessive acetone can be greatly relieved, and the isopropanol product with higher added value can be obtained; therefore, the method for preparing the isopropanol by efficiently hydrogenating the acetone has important social significance.
Acetone can be converted to isopropanol in liquid and vapor phase catalytic reactions. The gas phase route is more practical due to higher conversion efficiency and reaction continuity. In past research, a variety of heterogeneous catalysts have been used in acetone hydrogenation reactions. The most common catalysts are raney nickel catalysts, copper-chromium oxide composite catalysts, and the like; however, these catalysts have significant disadvantages such as low catalytic performance and selectivity; in addition, the toxicity of the used medicines and the harsh reaction conditions (high temperature and high pressure) in the reaction process are not beneficial to wide industrial popularization. In the last two decades, nanoscience and catalysis technologies have been rapidly developed, and more research has been focused on regulating and controlling the size, morphology, structure and composition of a nano catalyst, so as to improve catalytic activity, selectivity and stability. For example, Ni nanoparticles synthesized by wet chemistry have higher catalytic performance than those synthesized by conventional impregnation and precipitation methods.
The prior art acetone hydrogenation mostly uses nickel-based or copper-based catalysts, or uses noble metals such as Pt, Pd, Ru, etc. Acetone and hydrogen are fed into a fixed bed reactor according to a certain proportion, and are hydrogenated at a proper temperature and hydrogen pressure to generate isopropanol.
CN103706377A discloses a platinum-based catalyst for acetone catalytic hydrogenation, which is prepared by uniformly mixing octadecylamine and a carrier, and injecting acetylacetone platinum dissolved in oleylamine and transition metal salt to finally obtain a supported platinum catalyst. The catalyst obtained in the patent is used for acetone hydrogenation, the selectivity of isopropanol is good, but the utilization efficiency of the catalyst is not high, the dosage of the catalyst is high, and the acetone conversion rate is greatly reduced at a high airspeed, and industrial production is not utilized.
CN101927168A discloses a nickel-based catalyst for preparing isopropanol by acetone hydrogenation, which is an alumina carrier loaded with Ni, Mo and Zn. The acetone conversion rate and the isopropanol selectivity are high, but the space velocity of the acetone liquid is 0.5/h, and the production efficiency is very low. CN103030526A discloses a method for preparing isopropanol by acetone gas phase hydrogenation, wherein the catalyst comprises 10-40 wt% of CuO,10-25 wt% of NiO and 25-70 wt% of Al2O3And an auxiliary selected from MgO, ZnO or CaO. Similarly, the space velocity is increased but still in the lower range (below 5.0/h). CN104084209A discloses a MgO-supported high-activity nickel catalyst for preparing isopropanol by acetone hydrogenation, wherein the catalyst is prepared by preparing solution A from nickel nitrate and magnesium nitrate, adding a sodium carbonate solution, stirring at a high speed, filtering the obtained green precipitate, washing, roasting, switching hydrogen atmosphere, and reducing to obtain the catalyst. The catalyst is complicated to prepare, needs two-step roasting, and also needs to be in a hydrogen atmosphere. The catalyst has high acetone conversion rate of 1 and high isopropanol selectivity at a high space velocity.
One problem with the above prior art catalysts is that the utilization efficiency of the catalyst is low, a large amount of noble metal is required, and the cost is high; on the other hand, the catalyst has a short life and the activity of the catalyst gradually decreases after a certain period of use. This is one of the reasons that such catalysts have been difficult to be industrially applied. The monoatomic catalyst with the highest metal atom utilization rate, a definite active center structure and a low coordination number has become a new research hotspot in the field of materials. With the continuous reduction of the size of the metal, the coordination number of the metal is reduced, the surface free energy of metal atoms is increased sharply, the highly unsaturated characteristic is easier to adsorb reaction substrates and even change the path of catalytic reaction, and the corresponding catalytic activity is also improved. Monatomic catalysts have been used as heterogeneous catalysts, but monatomic catalysts for vapor phase hydrogenation of acetone to produce isopropanol have not been reported.
Disclosure of Invention
The first purpose of the invention is to provide a single-atom noble metal/transition metal oxide composite material, wherein noble metal is loaded on transition metal oxide in a single-atom form, and the single atom of the noble metal accounts for 0.01-1.0 wt%.
Preferably, the noble metal is present in the monoatomic noble metal/transition metal oxide composite in an amount of 0.1 to 0.5 wt%.
Preferably, the noble metal is at least one selected from gold, silver, platinum, palladium and nickel, and the transition metal oxide is at least one selected from iron oxide, manganese oxide, nickel oxide, cuprous oxide, cobalt oxide, cerium oxide, titanium oxide, silicon oxide and aluminum oxide.
More preferably, the noble metal is platinum and the transition metal compound is cerium oxide. Among noble metal materials, platinum (Pt) is widely used in the fields of energy conversion and environmental protection due to its excellent catalytic performance, however, its large-scale commercial application is hindered by the factors of platinum resource scarcity, high cost, low use efficiency, etc. CeO (CeO)2The catalyst material has excellent chemical properties, has abundant oxygen defects on the surface, can be used for anchoring noble metal atoms, and is often applied to heterogeneous catalytic reaction; with CeO2The synthesis of the carrier is simple, and the carrier is convenient for large-scale production and provides possibility for commercial application.
In a preferred embodiment of the present invention,the single atom/transition metal oxide is Pt/CeO2And the XRD has the following characteristic peaks: 28.6 +/-0.3 degrees, 33.8 +/-0.3 degrees, 47.5 +/-0.3 degrees and 52.1 +/-0.3 degrees.
The inventors found that Pt/CeO having the characteristic peaks of XRD as described above2The catalyst for preparing isopropanol by catalytic hydrogenation of acetone has high catalytic activity and good selectivity.
Preferably, the metal oxide is in the shape of a nanorod, a nanodisk, a nanoparticle, a nanocube; preferably, the nano-rod has the length of 20-100nm and the diameter of 3-10 nm.
The second object of the present invention is to provide a method for preparing the above-mentioned monatomic noble metal/transition metal oxide composite material, comprising the steps of:
adding a precursor containing noble metal into an aqueous solution of nano-scale transition metal oxide, adding a dispersing agent, stirring for 20-40h, washing, centrifuging, vacuum drying, heating the obtained sample in a mixed gas of hydrogen and inert gas to the temperature of 150 ℃ and 200 ℃, and heating for 1-4h to obtain the monatomic noble metal/transition metal oxide composite material.
The dispersing agent is at least one selected from polyether polyol, long-chain alkyl sulfonate, polyamino acid, lauryl alcohol ether phosphate and potassium lauryl alcohol ether phosphate, preferably polyamino acid, and the polyamino acid is at least one selected from polyglutamic acid, polylysine and polyaspartic acid.
The inventor unexpectedly finds that the polyamino acid not only can disperse the precursor of the noble metal, but also has abundant groups on the polyamino acid, such as amino, carboxyl and carbonyl, which can play a chelating role with the noble metal to anchor the noble metal on the transition metal oxide carrier, and the obtained monoatomic noble metal/transition metal oxide composite material has the advantages of uniform distribution of the noble metal, narrow particle size distribution, stable activity and long catalytic life when used in a catalyst.
In a more preferred embodiment of the present invention, the polyamino acid is polylysine, which is more basic and facilitates the anchoring of the noble metal to the transition metal oxide support.
The precursor containing the noble metal is a salt of the noble metal, and preferably a salt of an acid group containing the noble metal. For example, when the noble metal is platinum, the precursor is at least one of chloroplatinic acid, potassium chloroplatinate, sodium chloroplatinate, chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, platinum acetylacetonate and tetraammineplatinum nitrate, and preferably at least one of chloroplatinic acid, potassium chloroplatinate, sodium chloroplatinate, chloroplatinic acid, sodium chloroplatinate and potassium chloroplatinate.
The nanometer metal oxide can be in the shapes of nanorods, nanodiscs, nanoparticles and nanocubes, and is preferably nanorods, and the nanorods have the length of 50-100nm and the diameter of 5-10 nm.
Preferably, the mass ratio of the precursor containing noble metal, the nanoscale transition metal oxide and the dispersing agent is 1-5: 50-300: 5-30, preferably 1-2: 50-200:10-20.
The concentration of the metal oxide in the aqueous solution of the nano-scale transition metal oxide is 0.3-1 g/mL.
Preferably, the hydrogen gas is present in an amount of 5-10% by volume of the mixture of hydrogen gas and an inert gas, which is well known in the art, such as helium or argon.
The washing solvent is a mixed solvent of alcohol and water, and specifically is a mixed solvent of alcohol and water according to a volume ratio of 1-2: 1-2; the alcohol is at least one of methanol, ethanol and propanol. The centrifugation speed of the centrifugation is 2000-3000 r/min.
The third purpose of the invention is to provide the application of the single-atom precious metal/transition metal oxide composite material as a catalyst for preparing isopropanol by catalytic hydrogenation of acetone.
A fourth object of the present invention is to provide a method for preparing isopropanol by catalytic hydrogenation of acetone and hydrogen, which is characterized in that the above-mentioned monatomic noble metal/transition metal oxide composite is used as a catalyst.
Further, the method for preparing isopropanol by catalytic hydrogenation of acetone and hydrogen comprises the following steps: the method comprises the steps of placing a single-atom noble metal/transition metal oxide composite material serving as a catalyst in a fixed bed reactor, and preparing isopropanol by taking acetone and hydrogen as raw materials through catalytic reaction.
The reaction pressure is 0.1-1MPa, the reaction temperature is 50-100 ℃, the flow rate ratio of acetone to hydrogen is 1:2-10, and the liquid space velocity of acetone is 10-100h-1。
Preferably, the reaction pressure is 0.1-0.2MPa, the reaction temperature is 60-70 ℃, the flow rate ratio of acetone to hydrogen is 1:4-6, and the liquid space velocity of acetone is 50-65h-1。
By controlling the reaction conditions within the above range, the conversion of acetone and the selectivity of isopropanol can be both satisfactory. In the preferred technical scheme of the invention, the acetone conversion rate and the isopropanol selectivity are both more than 99 percent; in addition, the catalyst provided by the invention has the advantages that the noble metal active component is stably and lowly loaded on the transition metal oxide in a monoatomic state, the stability is good, the catalyst can be kept for 100 hours without being replaced, the acetone conversion rate is over 98 percent, and the isopropanol selectivity is over 99 percent.
The method for preparing isopropanol by catalytic hydrogenation of acetone provided by the invention has three main advantages: 1) the problem that noble metals in noble metal/transition metal oxide carrier materials are dispersed in the form of nano particles, the size of the nano particles is consistent, and the catalytic activity is high is solved; 2) because the noble metal is dispersed in atomic level, the utilization efficiency of the metal is improved to the maximum extent, and the use cost of the catalyst is reduced; 3) the method has the advantages of improving the interaction between the catalyst and the carrier, solving the problem of poor material stability, prolonging the service life of the catalyst and solving the problem of high cost of the noble metal catalyst.
The invention has the advantages of
1) The noble metal in the composite material provided by the invention is dispersed in atomic level, and the composite material shows excellent catalytic activity and stability in the reaction of preparing isopropanol by acetone hydrogenation, so that the problem of obtaining isopropanol with higher added value while solving the problem of excess acetone is solved.
2) The method provided by the invention has wider modulation space, and the content of the noble metal and the content of the transition metal can be correspondingly increased or reduced (ensuring that the noble metal and the transition metal are monoatomic) within a certain range. Solves the problems of large size range, irregular shape and the like of the product prepared by the prior art.
3) The method provided by the invention can prepare noble metal/transition metal oxide composite materials with dispersed atomic level on a large scale; the catalytic material with a definite structure lays a foundation for the correlation of the catalyst structure and the performance.
4) The invention creatively uses the polyamino acid as a stabilizer, so that the monoatomic acid is more uniformly and stably loaded on the transition metal oxide carrier. The prepared catalyst has more stable activity and longer service life.
Drawings
FIG. 1 shows Pt/CeO obtained in example 1 of the present invention2Electron micrographs of (A).
FIG. 2 shows Pt/CeO obtained in comparative example 1 of the present invention2X-ray diffraction pattern of (a).
FIG. 3 shows Pt/CeO obtained in example 1 of the present invention2Electron micrograph of (a).
FIG. 4 shows Pt/CeO obtained in example 1 of the present invention2The dark field pattern of (a).
FIG. 5 shows Pt/CeO obtained in example 1 of the present invention2Pt element distribution diagram of (a).
FIG. 6 shows Pt/CeO obtained in example 1 of the present invention2Distribution diagram of Ce element.
FIG. 7 shows Pt/CeO obtained in example 1 of the present invention2Distribution diagram of the O element.
FIG. 8 shows Pt/CeO obtained in example 1 of the present invention2The conversion rate and selectivity of the catalytic hydrogenation of acetone at different temperatures.
FIG. 9 shows Pt/CeO obtained in example 1 of the present invention2Stability profile of (d).
FIG. 10 shows Pt/CeO obtained in example 1 of the present invention2Comparison of acetone hydrogenation catalytic performance with other materials.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the present invention, the production method is a conventional method unless otherwise specified, and the raw materials used are commercially available from public or produced according to the prior art without specifically specified, and the percentages are mass percentages without specifically specified.
Polylysine used in the invention is purchased from Thermo Fisher and has a molecular weight of about 5300; polyglutamic acid used was purchased from Thermo Fisher and has a molecular weight of about 6800.
CeO for use in the invention2The nano-rod is self-made, and the specific method is that the hydrothermal process and the calcination process are combined, and Ce (NO) is used3)2·6H2O is cerium source, and Ce (NO) is slowly injected into NaOH solution3)2·6H2Stirring O solution, transferring into a high-pressure reaction kettle, reacting at 100 deg.C for 24 hr, washing the obtained product with deionized water and anhydrous ethanol, drying, calcining at 400 deg.C for 2 hr in air atmosphere to obtain CeO2The nanometer size is about 50-100nm in length and 5-10nm in diameter.
Preparation example 1
0.30g of CeO2Dispersing the nano-rods in 50mL of aqueous solution, performing ultrasonic treatment to obtain a uniform solution, adding 3mg of potassium tetrachloroplatinate into the solution, adding 30mg of polylysine, stirring for 12 hours, centrifuging, washing for 3 times by using a mixed solution (1:1, v/v) of water and ethanol, removing unadsorbed metal precursors, and putting the material in a vacuum drying oven for standing overnight at 70 ℃. The dried material is placed in a tube furnace at H2And reacting for 2-3 h at 180 ℃ in an Ar (volume ratio of 5: 95) atmosphere. After the reaction is finished, taking out the product to prepare Pt/CeO2. The loading capacity of the catalyst is 0.18 percent by a method for measuring the content of the catalyst by an inductively coupled plasma emission spectrometer.
For the prepared Pt/CeO2The characteristics are carried out by a spherical aberration electron microscope and a synchrotron radiation technology, and the result proves that the noble metal Pt is dispersed in CeO in a monoatomic form2In a carrier. FIG. 1 shows Pt/CeO obtained in this example2A Transmission Electron Microscope (TEM) photograph of (a). It can be observed that Pt/CeO2With CeO to which no noble metal precursor is added2Has the same appearance and the like, and has the advantages of simple structure,is a nano rod. The obtained Pt/CeO2The X-ray diffraction of (2) is shown in FIG. 2.
Furthermore, the invention is also applicable to the prepared Pt/CeO2The electron microscope sample is observed at multiple angles and is not observed in CeO2Pt or other nanoparticles were observed on the support surface. To further determine the Pt in Pt/CeO2Distribution in the material, the invention is used for preparing Pt/CeO2Performing electron microscopy characterization for spherical aberration correction, as shown in FIG. 3, there are numerous "dots" with brighter colors dispersed in CeO2On the nanorods, it was demonstrated that Pt was dispersed in CeO in the form of a single atom2In a carrier material.
The element distribution characterization charts of FIGS. 4-7 further show that the Pt, Ce and O are uniformly dispersed in the Pt/CeO2The above shows that the noble metal can be dispersed on the carrier at an atomic level by this method.
Preparation example 2
The other conditions and procedures were the same as in preparation example 1 except that polylysine was replaced with polyglutamic acid of equal mass.
Preparation example 3
The other conditions and procedures were the same as in preparation example 1 except that polylysine was replaced with sodium dodecylsulfate of equal mass.
Preparation example 4
The other conditions and procedure were the same as in preparation example 1 except that the amount of polylysine was changed to 15 mg.
Preparation example 5
The other conditions and procedure were the same as in preparation example 1 except that the amount of polylysine was changed to 60 mg.
Preparation example 6
The other conditions and procedure were the same as in preparation example 1 except that the amount of polylysine was changed to 10 mg.
Preparation example 7
The other conditions and procedure were the same as in preparation example 1 except that the amount of polylysine was changed to 100 mg.
Comparative preparation example 1
The other conditions and procedures were the same as in preparation example 1 except that lysine was not added.
Application example 1
The catalytic hydrogenation of acetone involved in the present invention occurs in a continuous flow system. The catalyst can be directly tested without any pretreatment, 0.2g of the catalyst of preparation example 1 is packed in a quartz fixed bed reactor, and the mass ratio of hydrogen to acetone is 4: 1, the reaction is carried out at 0.1 MPa.
The acetone hydrogenation catalysis is carried out under the conditions to prepare the isopropanol, the product is quantified by a gas chromatograph (SP-6890, an ion flame detector), and the following experiments are carried out on different reaction temperatures, different space velocities and the service life of the catalyst:
FIG. 8 shows that the space velocity of acetone is 50h-1Preparation of Pt/CeO obtained in example 12Conversion and selectivity to catalytic hydrogenation of acetone at different temperatures. It can be seen that Pt/CeO2The catalyst shows conversion close to thermodynamic equilibrium at 60-120 ℃, wherein at 60 ℃, the conversion rate of acetone and the selectivity of isopropanol are high and close to 100%, so that 60 ℃ is selected as the reaction temperature in the later experiment. Interestingly, even when the reaction temperature dropped to 40 deg.C, Pt/CeO was used2Still, 78% conversion of acetone was exhibited.
The reaction temperature of 60 ℃ is selected, the acetone conversion rate and the isopropanol selectivity are studied under different acetone space velocities, and the acetone conversion rate and the isopropanol selectivity are found to be even between 50 and 60 DEG C-1The high acetone space velocity can still keep high acetone conversion rate and isopropanol selectivity.
The stability of the catalytic reaction is another important factor in evaluating the performance of the material. As shown in FIG. 9, Pt/CeO obtained in example 12In continuous operation for 100h, the catalyst maintains the acetone conversion efficiency of 98-99.6% and the isopropanol selectivity of 99.9%, and has excellent circulation stability.
The above results show that the Pt/CeO of our invention2The material shows excellent catalytic activity and circulation stability in the reaction of preparing isopropanol by acetone gas phase hydrogenation, and has good application potential.
Application example 2
Application example according to1, hydrogenating acetone to prepare isopropanol under the same conditions, wherein the reaction temperature is 60 ℃, and the acetone airspeed is 55h-1The results of replacing the catalysts obtained in preparation examples 1 to 3 are shown in Table 1 below:
TABLE 1
Comparative example 1
Examination of the monatomic catalyst Pt/CeO obtained in preparation example 1 on a fixed-bed reactor2And conventional nano-catalyst Pt/Fe3O4，Ni/MgO-Al2O3，Cu/SiO2Performance for vapor phase conversion of acetone to isopropanol. The catalyst input was xxg, acetone was added to the reactor at a rate of 6g/h, the reaction temperature was 80 ℃ and the pressure was 1MPa, and the final product was quantified by gas chromatography (SP-6890, ion flame detector). As shown in FIG. 10, the conversion frequency (calculation formula: conversion frequency: acetone conversion mol number/(platinum mol number. unit time)) of each catalyst was as shown in preparation example 1, and Pt/CeO was obtained2Shows extremely high activity in the acetone hydrogenation reaction, and the conversion frequency reaches 15372h-1Is obviously higher than the conventional nano catalyst Pt/Fe3O4，Ni/MgO-Al2O3，Cu/SiO2。
The catalysts of preparation 2, preparation 3 and comparative preparation 1 each had a conversion frequency of 14791h under the same conditions-1，13837h-1，8674h-1。
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A composite material of noble metal and transition metal oxide is prepared through loading noble metal onto transition metal oxide in the form of single atom, and loading the noble metal single atom in 0.01-1.0 wt%.
2. The composite material of claim 1, wherein the noble metal is at least one selected from the group consisting of gold, silver, platinum, palladium, and nickel, and the transition metal oxide is at least one selected from the group consisting of iron oxide, manganese oxide, nickel oxide, cuprous oxide, cobalt oxide, cerium oxide, titanium oxide, silicon oxide, and aluminum oxide.
3. The composite material of claim 1, wherein the noble metal is platinum and the transition metal compound is cerium oxide.
4. The composite material of claim 3, wherein the metal oxide features are nanorods, nanodiscs, nanoparticles, nanocubes; preferably, the nano-rod has the length of 50-100nm and the diameter of 5-10 nm.
5. The composite material of claim 4, wherein the XRD of the composite material has the following characteristic peaks: 28.6 +/-0.3 degrees, 33.8 +/-0.3 degrees, 47.5 +/-0.3 degrees and 52.1 +/-0.3 degrees.
6. A process for preparing a monatomic noble metal/transition metal oxide composite material according to any one of claims 1 to 5, which comprises the steps of:
adding a precursor containing noble metal into an aqueous solution of nano-scale transition metal oxide, adding a dispersing agent, stirring for 20-40h, washing, centrifuging, vacuum drying, heating the obtained sample in a mixed gas of hydrogen and inert gas to the temperature of 150 ℃ and 200 ℃, and heating for 1-4h to obtain the monatomic noble metal/transition metal oxide composite material.
7. The method according to claim 6, wherein the dispersant is at least one selected from the group consisting of polyether polyol, long-chain alkyl sulfonate, polyamino acid, lauryl alcohol ether phosphate, and potassium lauryl alcohol ether phosphate, preferably a polyamino acid selected from the group consisting of polyglutamic acid, polylysine, and polyaspartic acid.
8. The production method according to claim 6, wherein the noble metal-containing precursor is a salt of a noble metal, preferably a salt of an acid group containing a noble metal; the mass ratio of the precursor containing noble metal, the nano-scale transition metal oxide and the dispersing agent is 1-5: 50-300: 5-30, preferably 1-2: 50-200:10-20.
9. A process for the preparation of isopropanol by the catalytic hydrogenation of acetone and hydrogen, characterized in that a monatomic noble metal/transition metal oxide composite material according to any one of claims 1 to 5 is used as catalyst.
10. The method of claim 9, comprising the steps of: placing a single-atom noble metal/transition metal oxide composite material serving as a catalyst in a fixed bed reactor, and preparing isopropanol by taking acetone and hydrogen as raw materials through catalytic reaction; the reaction pressure is 0.1-1MPa, the reaction temperature is 50-100 ℃, the flow rate ratio of acetone to hydrogen is 1:2-10, and the liquid space velocity of acetone is 10-100h-1；
Preferably, the reaction pressure is 0.1-0.2MPa, the reaction temperature is 60-70 ℃, the flow rate ratio of acetone to hydrogen is 1:4-6, and the liquid space velocity of acetone is 50-65h-1。
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| CN114682253A (en) * | 2020-12-31 | 2022-07-01 | 北京单原子催化科技有限公司 | Preparation method of monatomic catalyst for purifying motor vehicle exhaust |
| CN112916023A (en) * | 2021-02-07 | 2021-06-08 | 西安交通大学 | Single-atom material stabilized by cuprous oxide phase change process and preparation method and application thereof |
| CN113941325A (en) * | 2021-09-24 | 2022-01-18 | 中国科学院大连化学物理研究所 | Noble metal catalyst with specific valence state, preparation method and application thereof |
| CN116408078A (en) * | 2021-12-29 | 2023-07-11 | 中国科学院上海硅酸盐研究所 | Supported noble metal monoatomic catalyst and preparation method and application thereof |
| CN114395769A (en) * | 2022-01-29 | 2022-04-26 | 中国科学技术大学 | Supported copper catalyst and preparation method and application thereof |
| CN114471539A (en) * | 2022-02-21 | 2022-05-13 | 南京大学 | High-performance platinum-titanium monatomic catalyst and preparation method and application thereof |
| CN114471539B (en) * | 2022-02-21 | 2024-04-09 | 南京大学 | High-performance platinum-titanium monoatomic catalyst and preparation method and application thereof |
| CN114678549A (en) * | 2022-04-11 | 2022-06-28 | 天津大学 | Fuel cell catalyst with low precious metal content, preparation method and application thereof |
| CN115814792A (en) * | 2022-11-27 | 2023-03-21 | 南京理工大学 | Method for improving activity of copper surface acetone hydrogenation for preparing isopropanol through surface modification |
| CN115770570A (en) * | 2023-01-31 | 2023-03-10 | 中国科学院金属研究所 | Cerium oxide loaded atomic-scale dispersed Pt catalyst and redispersion preparation method thereof |
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