CN116037111B - Bimetallic single atom catalyst and its preparation method and application - Google Patents
Bimetallic single atom catalyst and its preparation method and application Download PDFInfo
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- CN116037111B CN116037111B CN202310113954.2A CN202310113954A CN116037111B CN 116037111 B CN116037111 B CN 116037111B CN 202310113954 A CN202310113954 A CN 202310113954A CN 116037111 B CN116037111 B CN 116037111B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 107
- 229910052751 metal Inorganic materials 0.000 claims abstract description 104
- 239000002184 metal Substances 0.000 claims abstract description 104
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims description 50
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- 238000006555 catalytic reaction Methods 0.000 claims description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- 229910052702 rhenium Inorganic materials 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 239000007810 chemical reaction solvent Substances 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 7
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 7
- 239000004386 Erythritol Substances 0.000 claims description 7
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 7
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 7
- 235000019414 erythritol Nutrition 0.000 claims description 7
- 229940009714 erythritol Drugs 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229960002920 sorbitol Drugs 0.000 claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-BXKVDMCESA-N L-mannitol Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)[C@@H](O)CO FBPFZTCFMRRESA-BXKVDMCESA-N 0.000 claims description 6
- 229930182842 L-mannitol Natural products 0.000 claims description 6
- 235000010355 mannitol Nutrition 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 5
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000000811 xylitol Substances 0.000 claims description 5
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 5
- 235000010447 xylitol Nutrition 0.000 claims description 5
- 229960002675 xylitol Drugs 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 abstract description 8
- 150000002009 diols Chemical class 0.000 abstract description 5
- 238000005470 impregnation Methods 0.000 abstract description 2
- 125000004429 atom Chemical group 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 229940094933 n-dodecane Drugs 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 4
- 229910001867 inorganic solvent Inorganic materials 0.000 description 4
- 239000003049 inorganic solvent Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910001510 metal chloride Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000000952 abberration-corrected high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 230000003213 activating effect 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
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910021634 Rhenium(III) chloride Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- TYLYVJBCMQFRCB-UHFFFAOYSA-K trichlororhodium;trihydrate Chemical compound O.O.O.[Cl-].[Cl-].[Cl-].[Rh+3] TYLYVJBCMQFRCB-UHFFFAOYSA-K 0.000 description 1
- LOIHSHVELSAXQN-UHFFFAOYSA-K trirhenium nonachloride Chemical compound Cl[Re](Cl)Cl LOIHSHVELSAXQN-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
-
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6482—Vanadium
-
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
-
- 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
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
-
- 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
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
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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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开的双金属单原子催化剂，由活性组分和载体组成，活性组分由两种金属组成，两种金属以单原子结构分散于载体表面；本发明还公开了上述催化剂的制备方法，主要是通过浸渍法依次将第一金属和第二金属负载于载体表面；本发明还公开了上述催化剂的在多元醇制二醇反应中的应用。本发明的双金属单原子催化剂可有效催化多元醇制二醇的反应，且该反应可兼具高转化率与选择性，且其制备方法简单、成本较低，具有广泛的工业应用前景。
The bimetallic single-atom catalyst disclosed in the present invention is composed of an active component and a carrier, wherein the active component is composed of two metals, and the two metals are dispersed on the carrier surface in a single-atom structure; the present invention also discloses a method for preparing the above catalyst, which mainly loads the first metal and the second metal on the carrier surface in sequence by an impregnation method; the present invention also discloses the application of the above catalyst in the reaction of polyols to diols. The bimetallic single-atom catalyst of the present invention can effectively catalyze the reaction of polyols to diols, and the reaction can have both high conversion rate and selectivity, and its preparation method is simple, low cost, and has broad industrial application prospects.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a bimetallic monoatomic catalyst, a preparation method of the bimetallic monoatomic catalyst and application of the bimetallic monoatomic catalyst.
Background
Biomass and its derivatives have the advantages of large storage capacity, renewable and the like, so that the biomass and its derivatives become an important part of development and utilization of new energy. The most abundant components in biomass are sugar and sugar-derived polyols, and the deoxygenation of these oxygen-rich materials can provide renewable pathways for platform chemicals and transportation fuels, thereby providing alternative resources for fossil fuels, and therefore the conversion of biomass polyols has high application value.
For the conversion of polyols to diols, compared to conventional pyrolysis, acid catalyzed dehydration, hydrogenation, etc., the deoxygenation dehydration (DODH) process between adjacent hydroxyl groups can achieve a one-step conversion of alcohols to olefins, which are then converted to the desired products, i.e., the corresponding diols, by further hydrogenation reactions. However, in the existing technology for preparing glycol from polyol, only a few metals such as rhenium, molybdenum, ruthenium, rhodium, palladium, platinum, gold and the like can effectively catalyze the reaction, but the noble metals are high in price, and the utilization rate of metal atoms of the traditional non-single-atom catalyst is low, so that the catalyst cost is high, and the catalyst is not suitable for industrial application and popularization. Therefore, for the process of preparing glycol by catalyzing polyol with catalyst, it is highly needed to provide a catalyst which has high selectivity, high conversion rate and low cost and is suitable for industrial popularization and application.
Disclosure of Invention
The invention aims to provide a bimetallic monoatomic catalyst which has high selectivity and high conversion rate in the reaction of preparing glycol from polyalcohol.
It is another object of the present invention to provide a method for preparing the above bimetallic monoatomic catalyst.
It is another object of the present invention to provide the use of the bimetallic monoatomic catalyst described above in the reaction of a polyol to make a glycol.
The technical scheme adopted by the invention is that the bimetallic single-atom catalyst consists of an active component and a carrier, wherein the active component consists of two metals, and the two metals are dispersed on the surface of the carrier in a single-atom structure.
The preparation method of the bimetallic monoatomic catalyst comprises the following steps:
step 1, preparing a first metal precursor solution and a second metal precursor solution;
Step 2, uniformly mixing the first metal precursor solution obtained in the step 1 with a carrier, stirring, drying and carrying out heat treatment to obtain a single metal single atom catalyst precursor;
And step 3, uniformly mixing the second metal precursor solution obtained in the step 1 with the single-metal single-atom catalyst precursor obtained in the step 2, stirring, drying and performing heat treatment to obtain the double-metal single-atom catalyst.
The other technical scheme adopted by the invention is the application of the bimetallic monoatomic catalyst in the glycol preparation reaction of the polyalcohol.
The present invention is also characterized in that,
The two metals comprise one of rhenium, molybdenum or vanadium, wherein the content of the first metal in the catalyst is 1-20wt% based on the corresponding simple substance, the content of the second metal in the catalyst is 0.25-20wt% based on the corresponding simple substance, and the carrier is one of aluminum oxide, silicon oxide, iron oxide, cerium oxide or titanium oxide.
The specific preparation process of the first metal precursor solution in the step 1 comprises the steps of dissolving a first metal soluble precursor in a solvent to obtain a first metal precursor solution, wherein the metal concentration in the first metal precursor solution is 0.14-3.9 mol/L, and the specific preparation process of the second metal precursor solution in the step 1 comprises the step of dissolving a second metal soluble precursor in the solvent to obtain a second metal precursor solution, and the metal concentration in the second metal precursor solution is 0.034-1.9 mol/L.
The first metal soluble precursor is one of metal chloride, ammonium salt or organic complex, the second metal soluble precursor is one of metal chloride, ammonium salt or acetate, the solvent is inorganic solvent or organic solvent, the inorganic solvent is one of deionized water, ammonia water, hydrochloric acid, oxalic acid, diethyl ether or chloroform, and the organic solvent is one or a mixture of two of absolute ethyl alcohol, acetone, aniline and ethylenediamine in any ratio.
The drying temperature in the stirring and drying process in the step 2 is 40-120 ℃ and the drying time is 5-24 hours, the drying temperature in the stirring and drying process in the step 3 is 40-120 ℃ and the drying time is 4-24 hours, and the heat treatment process in the step 2 and the heat treatment process in the step 3 is carried out for 60-300 minutes under the condition of 200-800 ℃ in one or two mixed atmospheres of random ratio of He, ar, N 2、O2 or H 2.
Mixing a substrate with a reaction solvent to obtain a reaction solution, adding a bimetallic monoatomic catalyst, and carrying out catalytic reaction in a closed high-pressure reaction kettle, wherein the initial pressure of hydrogen in the reaction kettle is 1-5 MPa at room temperature, the reaction temperature is 50-150 ℃, and the reaction time is 5-240 min.
The initial pressure of hydrogen in the reaction kettle is 2-4 MPa at room temperature, the reaction temperature is 80-120 ℃, and the reaction time is 60-180 min.
The substrate is one or a mixture of two of erythritol, xylitol, D-sorbitol, D-mannitol or L-mannitol in any ratio, the reaction solvent is one or a mixture of two of methanol, ethanol, toluene, ethylbenzene, cyclohexane, tetrahydrofuran, isopropanol or deionized water in any ratio, the concentration of the substrate in the reaction solution is 0.11-1.32 mol/L, and the molar ratio of the active component of the catalyst to the substrate is 1.3X10 -3 -0.073.
The invention has the advantages that,
(1) The first metal and the second metal active components of the bimetallic monoatomic catalyst are dispersed on the surface of the carrier in a monoatomic structure, and compared with a non-monoatomic catalyst, the bimetallic monoatomic catalyst can realize the maximization of the utilization rate of metal atoms, and effectively reduce the consumption of noble metals, thereby reducing the cost of the catalyst.
(2) The first metal and the second metal active components in the bimetallic monoatomic catalyst respectively bear different catalytic processes, and cooperatively complete the catalytic reaction of the polyol to prepare the glycol, and the bimetallic monoatomic catalyst in the reaction has higher selectivity and conversion rate, and the preparation method is simple and suitable for industrial popularization and application.
Drawings
FIG. 1 is an AC-HAADF-STEM diagram of a Pt-Re/CeO 2 bimetallic monoatomic catalyst according to example 1 of the present invention;
FIG. 2 is an EDS-Mapping graph of a Pt-Re/CeO 2 bimetallic monoatomic catalyst in example 1 of the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The bimetallic monoatomic catalyst consists of an active component and a carrier, wherein the active component of the catalyst consists of two metals, the first metal and the second metal, the first metal is one of rhenium, molybdenum or vanadium, the catalyst plays a role of preparing glycol by using active hydrogen, the content of the first metal in the catalyst is 1-20wt% based on corresponding simple substances, the second metal is one of ruthenium, rhodium, palladium, platinum or gold, the catalyst plays a role of activating hydrogen to generate active hydrogen, the content of the second metal in the catalyst is 0.25-20wt% based on corresponding simple substances, the carrier of the catalyst is one of alumina, silica, ferric oxide, cerium oxide, titanium oxide or other metal oxides, and in addition, the two metals of the active component are dispersed on the surface of the carrier in a monoatomic structure, so that the maximum utilization rate of metal atoms can be realized, the consumption of the noble metal can be effectively reduced, and the cost of the catalyst is reduced.
The invention prepares the bimetallic monoatomic catalyst by an impregnation method, and is specifically implemented according to the following steps:
The preparation method comprises the steps of 1, preparing a first metal precursor solution and a second metal precursor solution, wherein the specific preparation process comprises the steps of dissolving a first metal soluble precursor in a solvent to obtain the first metal precursor solution with the metal concentration of 0.14-3.9 mol/L, and dissolving a second metal soluble precursor in the solvent to obtain the second metal precursor solution with the metal concentration of 0.034-1.9 mol/L.
The first metal soluble precursor is one of metal chloride, ammonium salt or organic complex, the second metal soluble precursor is one of metal chloride, ammonium salt or acetate, the solvent is inorganic solvent or organic solvent, wherein the inorganic solvent is one of deionized water, ammonia water, hydrochloric acid, oxalic acid, diethyl ether or trichloromethane, and the organic solvent is one of absolute ethyl alcohol, acetone, aniline or ethylenediamine or a mixture of any two of the two at any ratio.
And 2, uniformly mixing the first metal precursor solution obtained in the step 1 with a carrier, stirring and drying at 40-120 ℃ for 5-24 hours, then placing in one or two mixed atmospheres of He, ar, N 2、O2 or H 2 at any ratio, and performing heat treatment at 200-800 ℃ for 60-300 minutes to obtain the single metal single atom catalyst precursor.
And 3, uniformly mixing the second metal precursor solution obtained in the step 1 and the single metal single atom catalyst precursor obtained in the step 2, stirring and drying at 40-120 ℃ for 4-24 hours, then placing in a mixed atmosphere of one or two of He, ar, N 2、O2 or H 2 in any ratio, and performing heat treatment at 200-800 ℃ for 60-300 min to obtain the bimetallic single atom catalyst.
The invention also comprises the application of the bimetallic monoatomic catalyst in the glycol preparation reaction of the polyol, and the polyol has a unique adjacent glycol structure, so that the polyol can be efficiently converted into glycol by one-step reaction under the catalysis of the bimetallic monoatomic catalyst, and the specific reaction is as follows:
The specific process for preparing glycol by using the bimetallic monoatomic catalyst to catalyze the polyhydric alcohol comprises the steps of firstly mixing a reaction solvent and a substrate to obtain a reaction solution, wherein the reaction solvent is one or a mixture of two of methanol, ethanol, toluene, ethylbenzene, cyclohexane, tetrahydrofuran, isopropanol or deionized water in any ratio, the substrate is one or a mixture of two of erythritol, xylitol, D-sorbitol, D-mannitol, L-mannitol or other polyhydric alcohols in any ratio, the concentration of the substrate in the reaction solution is 0.11-1.32 mol/L, and then adding the bimetallic monoatomic catalyst into the reaction solution and carrying out catalytic reaction in a closed high-pressure reaction kettle, wherein the molar ratio of the active component of the bimetallic monoatomic catalyst to the substrate is 1.3X10 -3 -0.073. The catalytic reaction condition is that the initial pressure of hydrogen in the reaction kettle is 1-5 MPa at room temperature, the reaction temperature is 50-150 ℃, the reaction time is 5-240 min, preferably, the initial pressure of hydrogen in the reaction kettle is 2-4 MPa at room temperature, the reaction temperature is 80-120 ℃, and the reaction time is 60-180 min.
Example 1
The bimetallic monoatomic catalyst takes Pt-Re/CeO 2 as an example, and is specifically prepared according to the following steps:
Step 1, 0.27g of tetrabutylammonium perrhenate is dissolved in 3g of absolute ethanol to obtain a first metal precursor solution with Re concentration of 0.14mol/L, and 0.07g of chloroplatinic acid hexahydrate is dissolved in 10g of aniline to obtain a second metal precursor solution with Pt concentration of 3.41 multiplied by 10 - 2 mol/L.
And 2, uniformly mixing the first metal precursor solution obtained in the step 1 with 10g of cerium oxide carrier, stirring and drying at 60 ℃ for 18 hours, placing in an N 2 atmosphere, and performing heat treatment at 550 ℃ for 120 minutes to obtain the single metal single atom catalyst precursor.
And 3, uniformly mixing the second metal precursor solution obtained in the step 1 and the single metal single-atom catalyst precursor obtained in the step 2, stirring and drying at 50 ℃ for 4 hours, then placing in an N 2 atmosphere, and performing heat treatment at 400 ℃ for 200 minutes to obtain the Pt-Re/CeO 2 bimetallic single-atom catalyst, wherein the content of Pt and Re in the catalyst is 0.25 weight percent and 1.0 weight percent respectively based on corresponding simple substances.
The Pt-Re/CeO 2 bimetallic monoatomic catalyst prepared by the above steps, the AC-HAADF-STEM diagram and EDS-Mapping diagram of which are respectively shown in fig. 1 and 2, and the existence of any nano metal particles and the distribution of the bright spots of the elements of the catalyst shown in fig. 1 can not be observed, which can be seen from fig. 1, in this example, the Pt-Re/CeO 2 bimetallic monoatomic catalyst was successfully prepared, and Pt and Re were dispersed on the surface of the CeO 2 carrier in a monoatomic structure.
The Pt-Re/CeO 2 bimetallic monoatomic catalyst is applied to the butanediol preparation reaction of erythritol, firstly, 100mg of erythritol substrate and 5g of cyclohexane reaction solvent are mixed to obtain a reaction solution, wherein the substrate concentration in the reaction solution is 0.13mol/L, then 20mg of Pt-Re/CeO 2 catalyst is added into the reaction solution, and the reaction solution is subjected to catalytic reaction in a closed high-pressure reaction kettle, wherein the molar ratio of the active component of the catalyst to the substrate is 1.3X10. 10 -3. The catalytic reaction condition is that the initial pressure of hydrogen in the reaction kettle is 2MPa at room temperature, the reaction temperature is 100 ℃, and the reaction time is 120min. The reaction selectivity is 98% and the conversion is 80% as shown by using n-dodecane as an internal standard and analyzing the result by using gas chromatography after the reaction.
In addition, since the second metal and the first metal in the bimetallic monoatomic catalyst respectively play roles in activating hydrogen to generate active hydrogen species and utilizing the active hydrogen species to realize glycol preparation from the polyol, in order to improve the conversion rate of the catalyst to glycol preparation from the polyol, the catalyst needs to ensure that enough active hydrogen species can be generated in the reaction process, so that the subsequent conversion reaction is ensured. For this reason, in this example, under the precondition of ensuring that other conditions are not changed, catalysts with different loadings of the second metal were prepared and applied to the erythritol butanediol production reaction, and the reaction results are shown in table 1:
| Catalyst | Time(min) | Conversion(%) | Selectivity(%) |
| 0.25%Pt-1%Re/CeO2 | 120 | 99.9 | 92.2 |
| 0.20%Pt-1%Re/CeO2 | 120 | 91.0 | 99.9 |
| 0.15%Pt-1%Re/CeO2 | 120 | 88.5 | 92.5 |
| 0.10%Pt-1%Re/CeO2 | 120 | 76.4 | 90.3 |
the result shows that when the loading of the second metal in the Pt-Re/CeO 2 bimetallic monoatomic catalyst is increased, the conversion rate of the catalyst for catalyzing the erythritol to prepare the butanediol is correspondingly increased, but at the same time, the selectivity of the catalyst shows a trend of increasing first and then decreasing second, which indicates that the conversion rate and the selectivity of the catalyst are mutually restricted, and in the polyol to prepare the diol process, the loading of the second metal of the catalyst is determined according to the requirements of practical application on the conversion rate and the selectivity.
Example 2
The bimetallic monoatomic catalyst takes Ru-Re/SiO 2 as an example, and is specifically prepared according to the following steps:
Step 1, 0.79g of rhenium trichloride is dissolved in 10ml of deionized water to obtain a first metal precursor solution with Re concentration of 0.27mol/L, and 0.0138g of ruthenium acetate is dissolved in 5ml of acetone to obtain a second metal precursor solution with Ru concentration of 0.099 mol/L.
And 2, uniformly mixing the first metal precursor solution obtained in the step 1 with 10g of silicon oxide carrier, stirring and drying at 40 ℃ for 24 hours, and then placing in a mixed atmosphere (volume ratio of O 2 to Ar is 1:99) for heat treatment at 200 ℃ for 60 minutes to obtain the single metal single atom catalyst precursor.
And 3, uniformly mixing the second metal precursor solution obtained in the step 1 and the single metal single atom catalyst precursor obtained in the step 2, stirring and drying at 40 ℃ for 24 hours, then placing in a mixed atmosphere (volume ratio of O 2 to Ar is 1:99), and performing heat treatment at 200 ℃ for 60 minutes to obtain the Ru-Re/SiO 2 bimetallic single atom catalyst, wherein the content of Ru and Re in the catalyst is respectively 0.05 weight percent and 5 weight percent based on the corresponding simple substance.
The Ru-Re/SiO 2 bimetallic monoatomic catalyst is applied to the reaction of preparing hexanediol from D-mannitol and L-mannitol, firstly, 100mg of mixed substrate of D-mannitol and L-mannitol (the mass ratio is 1:1) is added into 5ml of mixed reaction solvent of methanol and toluene (the volume ratio is 1:1) to obtain a reaction solution, wherein the substrate concentration in the reaction solution is 0.11mol/L, and then, 100mg of Ru-Re/SiO 2 catalyst is added into the reaction solution and is subjected to catalytic reaction in a closed high-pressure reaction kettle, wherein the molar ratio of active components of the catalyst to the substrate is 0.049. The catalytic reaction is carried out under the conditions that the initial pressure of hydrogen in a reaction kettle is 1MPa at room temperature, the reaction temperature is 50 ℃ and the reaction time is 5min. The reaction selectivity is 98% and the conversion is 90% as shown by using n-dodecane as an internal standard and analyzing the result by using gas chromatography after the reaction.
In addition, since the cycling stability of the catalyst is one of the key indexes of practical application, the Ru-Re/SiO 2 bimetallic single-atom catalyst is adopted to carry out multiple cycling reactions on the D-mannitol and the hexanediol prepared from the L-mannitol under the premise of ensuring that other conditions are unchanged, and the reaction results are shown in Table 2:
The result shows that the Ru-Re/SiO 2 bimetallic monoatomic catalyst still maintains higher selectivity and conversion rate after multiple cycle reactions, which proves that the catalyst has higher stability.
Example 3
The bimetallic monoatomic catalyst takes Rh-Mo/Al 2O3 as an example, and is specifically prepared according to the following steps:
Step 1, 2.04g of ammonium molybdate is dissolved in 10ml of ammonia water to obtain a first metal precursor solution with Mo concentration of 1mol/L, and 0.26g of rhodium chloride trihydrate is dissolved in 2ml of ethylenediamine to obtain a second metal precursor solution with Rh concentration of 0.49 mol/L.
And 2, uniformly mixing the first metal precursor solution obtained in the step 1 with 10g of alumina carrier, stirring and drying at 120 ℃ for 18 hours, placing in He atmosphere, and performing heat treatment at 800 ℃ for 300 minutes to obtain the single metal single atom catalyst precursor.
And 3, uniformly mixing the second metal precursor solution obtained in the step 1 with the single metal single atom catalyst precursor obtained in the step 2, stirring and drying at 120 ℃ for 20 hours, then placing in He atmosphere, and performing heat treatment at 800 ℃ for 300 minutes to obtain the Rh-Mo/Al 2O3 bimetallic single atom catalyst, wherein the content of Rh and Mo in the catalyst is 1wt% and 10wt% respectively according to corresponding simple substances.
The Rh-Mo/Al 2O3 bimetallic monoatomic catalyst is applied to the reaction of preparing hexanediol from D-sorbitol, firstly, 100mg of D-sorbitol substrate and 5g of deionized water are mixed to obtain a reaction solution, wherein the substrate concentration in the reaction solution is 0.11mol/L, then, 40mg of Au-Mo/TiO 2 catalyst is added into the reaction solution and the reaction solution is subjected to catalytic reaction in a closed high-pressure reaction kettle, and the molar ratio of the active component of the catalyst to the substrate is 0.073. The catalytic reaction is carried out under the conditions that the initial pressure of hydrogen in a reaction kettle is 5MPa at room temperature, the reaction temperature is 80 ℃ and the reaction time is 60min. The reaction selectivity is 90% and the conversion is 99% as shown by using n-dodecane as an internal standard and analyzing the result by using gas chromatography after the reaction.
Example 4
The bimetallic monoatomic catalyst takes Pd-V/Fe 2O3 as an example, and is specifically prepared according to the following steps:
Step 1, dissolving 4.59g of ammonium metavanadate in 10ml of absolute ethyl alcohol to obtain a first metal precursor solution with the V concentration of 3.9mol/L, and dissolving 5.34g of ammonium chloropalladate in 10ml of dilute hydrochloric acid with the concentration of 4mol/L to obtain a second metal precursor solution with the Pd concentration of 1.9 mol/L.
And 2, uniformly mixing the first metal precursor solution obtained in the step 1 with 10g of ferric oxide carrier, stirring and drying at 100 ℃ for 5 hours, placing in a mixed atmosphere (volume ratio of 1:99) of O 2 and N 2, and performing heat treatment at 400 ℃ for 200 minutes to obtain the single metal single atom catalyst precursor.
And 3, uniformly mixing the second metal precursor solution obtained in the step 1 and the single metal single-atom catalyst precursor obtained in the step 2, stirring and drying at 100 ℃ for 20 hours, then placing in a mixed atmosphere (volume ratio of 1:99) of O 2 and N 2, and performing heat treatment at 600 ℃ for 200 minutes to obtain the Pd-V/Fe 2O3 double-metal single-atom catalyst, wherein the content of Pd and V in the catalyst is 20wt% and 20wt% respectively based on the corresponding simple substance.
The Pd-V/Fe 2O3 bimetallic monoatomic catalyst is applied to the reaction of preparing pentanediol from xylitol, firstly, 1g of xylitol substrate is added into 5ml of mixed reaction solvent of tetrahydrofuran and isopropanol (volume ratio is 1:1) to obtain a reaction solution, wherein the substrate concentration in the reaction solution is 1.32mol/L, then 100mg of Pd-V/Fe 2O3 catalyst is added into the reaction solution and the reaction is catalyzed in a closed high-pressure reaction kettle, wherein the molar ratio of the active component of the catalyst to the substrate is 0.06. The catalytic reaction condition is that the initial pressure of hydrogen in the reaction kettle is 4MPa at room temperature, the reaction temperature is 120 ℃, and the reaction time is 180min. The reaction selectivity is 98% and the conversion is 98% as shown by using n-dodecane as an internal standard and analyzing the result by using gas chromatography after the reaction.
Example 5
The bimetallic monoatomic catalyst takes Au-Mo/TiO 2 as an example, and is specifically prepared according to the following steps:
Step 1, dissolving 4.08g of ammonium molybdate in 10ml of ammonia water to obtain a first metal precursor solution with Mo concentration of 2mol/L, and dissolving 4.2g of chloroauric acid tetrahydrate in a mixed solvent of 10ml of diethyl ether and chloroform (volume ratio of 1:1) to obtain a second metal precursor solution with Au concentration of 1 mol/L.
And 2, uniformly mixing the first metal precursor solution obtained in the step 1 with 10g of titanium oxide carrier, stirring and drying at 80 ℃ for 15H, placing in an H 2 atmosphere, and performing heat treatment at 200 ℃ for 60min to obtain the single metal single atom catalyst precursor.
And 3, uniformly mixing the second metal precursor solution obtained in the step 1 and the single metal single atom catalyst precursor obtained in the step 2, stirring and drying at 100 ℃ for 15 hours, then placing in an H 2 atmosphere, and performing heat treatment at 200 ℃ for 60 minutes to obtain the Au-Mo/TiO 2 bimetallic single atom catalyst, wherein the content of Au and Mo in the catalyst is 20wt% and 20wt% respectively based on corresponding simple substances.
The Au-Mo/TiO 2 bimetallic monoatomic catalyst is applied to the reaction of preparing hexanediol from D-sorbitol, firstly, 0.64g of D-sorbitol substrate and 5g of deionized water are mixed to obtain a reaction solution, wherein the substrate concentration in the reaction solution is 0.7mol/L, and then 40mg of Au-Mo/TiO 2 catalyst is added into the reaction solution and is subjected to catalytic reaction in a closed high-pressure reaction kettle, wherein the molar ratio of the active component of the catalyst to the substrate is 0.24. The catalytic reaction is carried out under the conditions that the initial pressure of hydrogen in a reaction kettle is 3MPa at room temperature, the reaction temperature is 150 ℃ and the reaction time is 240min. The reaction selectivity is 88% and the conversion is 99% as shown by analysis of the results after the reaction using n-dodecane as an internal standard.
Claims (3)
1. The application of the bimetallic monoatomic catalyst in the glycol preparation reaction of the polyalcohol is characterized in that the bimetallic monoatomic catalyst is added into a closed high-pressure reaction kettle for catalytic reaction after a substrate and a reaction solvent are mixed to obtain a reaction solution, the initial pressure of hydrogen in the reaction kettle is 1-5 MPa at room temperature, the reaction temperature is 50-150 ℃, and the reaction time is 5-240 min;
The bimetallic monoatomic catalyst is specifically a Pt-Re/CeO 2 catalyst, the active component is composed of Pt-Re, and the Pt-Re is dispersed on the surface of a CeO 2 carrier in a monoatomic structure;
the preparation method of the bimetallic monoatomic catalyst specifically comprises the following steps:
step 1, preparing a first metal precursor solution and a second metal precursor solution;
Dissolving tetrabutylammonium perrhenate in absolute ethyl alcohol to obtain a first metal precursor solution with Re concentration of 0.14-3.9 mol/L, dissolving hexa-hydrated chloroplatinic acid in aniline to obtain a second metal precursor solution with Pt concentration of 0.034-1.9 mol/L;
Step 2, uniformly mixing the first metal precursor solution obtained in the step 1 with a carrier, stirring, drying and carrying out heat treatment to obtain a single metal single atom catalyst precursor;
the drying temperature in the stirring and drying process is 40-120 ℃ and the drying time is 5-24 h;
The heat treatment process is to heat treat for 60-300 min at 200-800 ℃ in one or two mixed atmospheres of He, ar, N 2 or H 2 in any ratio;
Step 3, uniformly mixing the second metal precursor solution obtained in the step 1 with the single-metal single-atom catalyst precursor obtained in the step 2, stirring, drying and performing heat treatment to obtain a double-metal single-atom catalyst to obtain the Pt-Re/CeO 2 double-metal single-atom catalyst, wherein the content of Pt and Re in the catalyst is 0.25-20wt% and 1-20wt% respectively based on the corresponding simple substances;
the drying temperature in the stirring and drying process is 40-120 ℃ and the drying time is 4-24 h;
The heat treatment process is to heat treat the mixture for 60-300 min at 200-800 ℃ in one or two mixed atmospheres of He, ar, N 2 or H 2.
2. The application of the bimetallic monoatomic catalyst in the glycol preparation reaction of the polyalcohol according to claim 1, wherein the initial pressure of hydrogen in the reaction kettle is 2-4 MPa under the condition of room temperature, the reaction temperature is 80-120 ℃, and the reaction time is 60-180 min.
3. The application of the bimetallic monoatomic catalyst according to claim 1 or 2 in a glycol preparation reaction of a polyol, wherein the substrate is one or two of erythritol, xylitol, D-sorbitol, D-mannitol or L-mannitol, the reaction solvent is one or two of methanol, ethanol, toluene, ethylbenzene, cyclohexane, tetrahydrofuran, isopropanol or deionized water, the concentration of the substrate in the reaction solution is 0.11-1.32 mol/L, and the molar ratio of the active component of the catalyst to the substrate is 1.3X10 -3 -0.073.
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