CN108465472A - A kind of hydrotalcite supported palladium based alloy catalyst and preparation method thereof - Google Patents
A kind of hydrotalcite supported palladium based alloy catalyst and preparation method thereof Download PDFInfo
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- CN108465472A CN108465472A CN201810257336.4A CN201810257336A CN108465472A CN 108465472 A CN108465472 A CN 108465472A CN 201810257336 A CN201810257336 A CN 201810257336A CN 108465472 A CN108465472 A CN 108465472A
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- ldh
- catalyst
- hydrotalcite
- pdt
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 36
- 239000000956 alloy Substances 0.000 title claims abstract description 36
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 36
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 35
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 35
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 55
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 239000003643 water by type Substances 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 22
- 229910002651 NO3 Inorganic materials 0.000 claims description 20
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000969 carrier Substances 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 17
- 239000011591 potassium Substances 0.000 claims description 17
- 229910052700 potassium Inorganic materials 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- -1 iodo aromatic hydrocarbon Chemical class 0.000 claims description 16
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 10
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000009938 salting Methods 0.000 claims description 8
- 238000001338 self-assembly Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 241000894007 species Species 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 5
- 229920005862 polyol Polymers 0.000 abstract description 3
- 150000003077 polyols Chemical class 0.000 abstract description 3
- 239000011943 nanocatalyst Substances 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 30
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 29
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 29
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 239000010949 copper Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 229910021118 PdCo Inorganic materials 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- HDWLUGYOLUHEMN-UHFFFAOYSA-N Dinobuton Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1OC(=O)OC(C)C HDWLUGYOLUHEMN-UHFFFAOYSA-N 0.000 description 8
- 241000425573 Talanes Species 0.000 description 8
- 229910002669 PdNi Inorganic materials 0.000 description 7
- 235000013339 cereals Nutrition 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 150000008424 iodobenzenes Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910000905 alloy phase Inorganic materials 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 238000007341 Heck reaction Methods 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000001239 high-resolution electron microscopy Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229920000333 poly(propyleneimine) Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000001608 tolans Chemical class 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- NSJVYHOPHZMZPN-UHFFFAOYSA-N (2-methylphenyl)boronic acid Chemical class CC1=CC=CC=C1B(O)O NSJVYHOPHZMZPN-UHFFFAOYSA-N 0.000 description 1
- SYSZENVIJHPFNL-UHFFFAOYSA-N (alpha-D-mannosyl)7-beta-D-mannosyl-diacetylchitobiosyl-L-asparagine, isoform B (protein) Chemical class COC1=CC=C(I)C=C1 SYSZENVIJHPFNL-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L PdCl2(PPh3)2 Substances [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B01J35/393—
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- B01J35/394—
-
- B01J35/396—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Abstract
A kind of hydrotalcite supported palladium based alloy catalyst and preparation method thereof, belongs to catalyst technical field.The expression formula of catalyst is PdTx/ MAl LDH, wherein PdTxFor Pd radicel duplex metal alloy nano particle, T represents cheap transition metal Co, Ni, Fe or Cu, and x represents the molar ratio of transition metal T and Pd, and the mass percentage for being 0.1~2.2, Pd is 0.01wt%~1.0wt%, and MAl LDH are hydrotalcite, M Mg2+、Ni2+、Co2+And Cu2+Any one in bivalent metal ion or two kinds.The catalyst on Multilevel-structure hydrotalcite carrier by obtaining palladium-base alloy nano-particle made from polyol reduction method is immobilized, the PdT of size about 1.48nm~2.22nmxAlloy nano particle high dispersive is on the flower-shaped hydrotalcite of Desert Rose.The palladium-base alloy nanocatalyst of the high dispersive small size has excellent Heck reactivities, and substrate applicability is wide, and catalyst structure is stablized, and preparation process is easy.
Description
Technical field
The invention belongs to catalyst technical fields, more particularly to a kind of hydrotalcite supported palladium based alloy catalyst and its system
Preparation Method, the hydrotalcite supported palladium based alloy catalyst for Heck reactions.
Background technology
The halogenated aryl hydrocarbon of palladium chtalyst and the Heck coupling reactions of alkene have become the important organic synthesis of synthesis carbon-carbon bond
One of method is widely used in the commercial synthesis field of natural products, luminescent material, medicine and fine chemicals.However,
Phase Pd base catalyst, such as Pd (PPh3)4And PdCl2(PPh3)2, Pd- carbene complexes and ring Pd compounds etc., exist and detach back
The problems such as receiving difficult, easy inactivation, expensive and environmental pollution, greatly limits its extensive use industrially.Therefore,
By by Pd nanometer particle loads in various carriers such as polymer, carbon-based and silica-based materials, metal oxide and neatly
Shi Shang, prepare with the heterogeneous palladium catalyst that easily recycles be solve the above problems preferred embodiment (Liu Hongfei, Jia Zhigang,
Ji Shengfu catalysis journals, 2012,757-767).
Studies have shown that compared with monometallic palladium catalyst, the addition of second of metal in bimetallic palladium based alloy catalyst
The electronics and geometry that can adjust and change Metal Palladium, to improve the activity of catalyst.2015, this seminar was in water
A kind of high dispersive magnetic loading type rhotanium is made in talcum coated ferroferric oxide supported on carriers rhotanium nano-particle
Catalyst is applied to the Heck coupling reactions of iodobenzene and styrene in the mixed solution of n,N-Dimethylformamide and water,
With K2CO3For exogenously added alkali, reaction 3h iodobenzene conversion ratios are 100% (Chinese invention patent ZL 2,015 1 at 120 DEG C
0145564.9).Importantly, the bimetallic palladium based alloy catalyst that palladium is formed with cheap transition metal is because of base metal (example
Such as：Cobalt, nickel, iron and copper) incorporation can reduce the dosage of precious metal palladium to reduce cost, and get more and more people's extensive concerning.
Singh etc. is with K2PdCl4And NiCl2·6H2O is source metal, using PVP as protective agent, using NaBH4Reduction method is prepared for having height
Ni/Pd atomic ratios (99:1 and 95:5) bimetallic Ni-Pd alloy nano particles, average-size about 10nm are applied to
4- iodanisols are reacted with the Suzuki-Miyaura of 2- methylphenylboronic acids in water-ethanol solution, with K2CO3For exogenously added alkali, room temperature
The TOF of lower reaction 5h is about 250 and 200h-1, catalytic activity is substantially better than monometallic Ni, and (TOF of 5h is 0h-1) and Pd catalysis
(TOF of 5h is about 13h for agent-1)(R.K.Rai,K.Gupta,D.Tyagi,A.Mahata,S.Behrens,X.C.Yang,Q.Xu,
B.Pathak,S.K.Singh.Catal.Sci.Technol.,2016,6,5567–5579.).Shaabani etc. is with polypropylene Asia
Amine cladodification graphene hybrid is carrier, with PdCl2And CoCl2·6H2O is source metal, using total complexometry and follow-up NaBH4
Graphene-supported PdCo alloy nanoparticles (2~3nm) catalyst of polypropyleneimine cladodification has been made in reduction method, is applied to nothing
The Sonogashira coupling reactions of iodobenzene and phenylacetylene under solvent condition, with K2CO3For exogenously added alkali, ultrasonic reaction 1h bis- at room temperature
Phenylacetylene yield is 99%, and catalytic activity is substantially better than monometallic Pd catalyst (17h tolans yields are 99%) and list
Metal Co catalyst (30h tolans yields are 10%), the Strong synergy being attributed in catalyst between metal Pd and Co.
It is worth noting that the catalyst remains to reach relatively high activity (1h, 70%) under the conditions of alkali-free, it may be due to poly- third
Alkene imines cladodification graphene hybrid for need alkali reaction provide alkaline environment (A.Shaabani,
M.Mahyari.J.Mater.Chem.A,2013,1,9303-9311.).However, polypropyleneimine cladodification graphene hybrid
Prepare it is cumbersome take, strongly limit its practical application.Typical inorganic laminated hydrotalcite material, can because being formed with laminate
The features such as tune, easy intrinsic alkalinity and preparation, becomes preferred vector then.And so far, not yet honest and clean in relation to hydrotalcite supported palladium-
The report of valence transition metal alloy (PdCo, PdNi, PdFe and PdCu) catalyst.
Therefore, the present invention is quasi- prepares palladium-base alloy (PdCo, PdNi, PdFe and PdCu) nanoparticle using polyol reduction method
Son and be carried on Multilevel-structure hydrotalcite carrier to prepare load type palladium based alloy (PdCo, PdNi, PdFe and
PdCu) catalyst.Wherein, grain size is the palladium-base alloy nano-particle high dispersive of 1.48nm~2.22nm in hydrotalcite supports.
The catalyst shows excellent catalytic activity in Heck coupling reactions.
Invention content
The purpose of the present invention is to provide a kind of hydrotalcite supported palladium based alloy catalysts and preparation method thereof, solve and adopt
With traditional NaBH4The larger problem of the cheap transition metal alloy nano particle diameter of palladium-prepared by reduction method or infusion process.It should
The feature that grain size is small and particle diameter distribution is narrow is presented in hydrotalcite supports in the palladium-base alloy nano-particle high dispersive of catalyst.
The catalyst shows excellent catalytic activity in Heck reactions, and substrate applicability is wide, and catalyst structure is stable and prepares work
Skill is easy.
The catalyst of the present invention be by the palladium-base alloy of small size made from polyol reduction method (PdCo, PdNi, PdFe and
PdCu) nanometer particle load is catalyzed in the load type palladium based alloy on Multilevel-structure hydrotalcite carrier, obtaining high dispersive small size
Agent.Catalyst expression formula is PdTx/ MAl-LDH, wherein PdTxFor Pd radicel duplex metal alloy nano particle, T represents cheap transition gold
Belong to Co, Ni, Fe or Cu, x represents the molar ratio of transition metal T and Pd, is for the mass percentage of 0.1~2.2, Pd
0.01wt%~1.0wt%, particle size about 1.48nm~2.22nm；MAl-LDH is hydrotalcite supports, M Mg2+、Ni2+、Co2 +And Cu2+Any one in bivalent metal ion or two kinds, hydrotalcite supports are presented the flower-shaped multilevel hierarchy of Desert Rose, are
It is that the nanometer sheet self assembly that 100~240nm thickness is 10.0~20.0nm forms by size.
The hydrotalcite supported palladium based alloy catalyst of the present invention shows in iodo aromatic hydrocarbon and the Heck coupling reactions of alkene
Go out excellent catalytic performance, reaction condition：1mmol iodo aromatic hydrocarbons, 1.5mmol alkene, a certain amount of catalyst activity species Pd
The molar percentage for accounting for substrate iodo aromatic hydrocarbon is 0.30mol%, and 3mmol potassium carbonate, solvent is 12mL n,N-Dimethylformamide
With the mixed solution of 4mL water, 120 DEG C, react 1h after iodo aromatic hydrocarbon conversion ratio up to 99.1%~100%, target product is trans-
The yield of styrene derivative is up to 97.4%~99.4%.
Steps are as follows for present invention process：
(1) preparation of hydrotalcite supports
It weighs the nitrate of 0.009~0.015mol M and 0.003~0.005mol ANN aluminium nitrate nonahydrates is dissolved in 100mL and goes
In ionized water, mixing salt solution is made；Weigh 0.02~0.04mol NaOH and 0.006~0.012mol Na2CO3It is dissolved in
In 100mL deionized waters, mixed ammonium/alkali solutions are made；100mL deionized waters are added in 500mL four-hole boiling flasks, then slowly drip
In addition it is 10 ± 0.1 to state mixed ammonium/alkali solutions to pH, above-mentioned mixing salt solution is added dropwise simultaneously after stablizing 5min and mixed ammonium/alkali solutions begin
It is 10 ± 0.1 to keep pH eventually, until mixing salt solution is added dropwise, by gained slurries in 65 DEG C of water-baths crystallization 4h, be cooled to
With deionized water centrifuge washing to supernatant be pH after room temperature it is about 7, gained is deposited in drying at 60 DEG C obtains hydrotalcite for 24 hours
Carrier MAl-LDH, M Mg2+、Ni2+、Co2+And Cu2+Any one in bivalent metal ion or two kinds；
(2)PdTxThe preparation of-PVP nano-particles
Weigh 5.64mmol PdCl2It is dissolved in deionized water with 11.3mmol KCl, being configured to molar concentration is
The 100mL tetrachloro-palladium acid potassium solutions of 0.056mol/L；The chlorate for weighing 5.00mmol T is dissolved in deionized water, is made mole
The chlorination salting liquid of the 100mL T of a concentration of 0.050mol/L；The polyvinylpyrrolidone (PVP) of 0.82g~2.46g is dissolved in
In 150mL deionized waters, it is charged with the chlorination salting liquid of 2.5mL above-mentioned tetrachloro-palladium acid potassium solution and 0.85~8.5mL T,
50mL ethylene glycol is added, 1mol/L NaOH solutions, which are added dropwise, makes system pH be 12~13, and then flow back in 140 DEG C of oil baths 2h,
Cooled to room temperature obtains dark-brown colloidal sol, i.e. PdTx- PVP nanoparticle sols, appointing in T Co, Ni, Fe and Cu element
Meaning is a kind of；
(3) hydrotalcite supported palladium based alloy catalyst PdTxThe preparation of/MAl-LDH
Take above-mentioned PdTx0.5g~7.5g MAl-LDH carriers are added in-PVP nanoparticle sol 100mL, mechanical at room temperature
2h is stirred, is alternately washed twice with acetone and deionized water, is centrifuged, be dried in vacuo at 60 DEG C and obtain catalyst for 24 hours
PdTx/MAl-LDH。
The nitrate of M used in step (1) is Mg (NO3)2·6H2O、Ni(NO3)2·6H2O、Co(NO3)2·6H2O and Cu
(NO3)2·3H2Any one or two kinds of O.
The chlorate of T used in step (2) is CoCl2·6H2O、NiCl2·6H2O、FeCl3·6H2O and CuCl2·2H2O
Any one.
It is an advantage of the invention that：
(1) a kind of hydrotalcite supported palladium based alloy catalyst of novel high dispersive small size and preparation method thereof is provided.
It is based particularly on the double gold of palladium base of small size made from cheap mild reducing agent ethylene glycol and stabilizer polyvinylpyrrolidone
Belong to alloy nano particle to be carried on Desert Rose style Multilevel-structure hydrotalcite, obtains palladium-base alloy catalyst PdTx/MAl-
LDH.Its active component palladium-base alloy nano particle diameter narrowly distributing (0.70~4.50nm), average grain diameter (1.48~2.22nm)
Significantly lower than cheap transition metal alloy particle of the Pd- of most of document reports, and the preparation process of catalyst is easy.
(2) catalyst made from includes the hydrotalcite supports of intrinsic alkalinity and the cheap transient metal doped palladium of small size
Based alloy nano-particle.In the palladium-base alloy catalyst PdT of hydrotalcite loadxIn/MAl-LDH, using cheap transition metal Co
(or Ni, Fe, Cu) modifies precious metals pd catalytic active component, improves the catalytic activity at the centers Pd, reduces precious metals pd work
The dosage of property component, can substantially reduce the cost of Heck catalysts.
(3) catalyst structure made from is stablized, and centrifugation means point are used after reaction in the Heck of iodobenzene and styrene
From catalyst, recycle 12 times, iodobenzene conversion ratio is only reduced to 94.7% by 100%.The cyclical stability of catalyst improves
The service efficiency of the catalyst of Heck liquid-phase catalysis reaction, reduces the separation costs of liquid-phase catalysis reaction.The catalyst is more
Excellent activity is shown in the Heck of kind iodo aromatic hydrocarbon and alkene reactions, there is important industrial application value.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of sample MgAl-LDH carriers in embodiment 1.
Fig. 2 is sample P dCo in embodiment 10.28The X-ray diffractogram of-PVP.
Fig. 3 is sample P dCo in embodiment 10.28The high-resolution-ration transmission electric-lens figure of/MgAl-LDH.
Fig. 4 is sample P dCo in embodiment 10.28The grain size distribution of/MgAl-LDH.
Fig. 5 is sample P dNi in embodiment 20.10The X-ray diffractogram of-PVP.
Fig. 6 is sample P dCu in embodiment 42.2The X-ray diffractogram of-PVP.
Fig. 7 is sample P dCu in embodiment 42.2The high-resolution-ration transmission electric-lens figure of/CoAl-LDH.
Fig. 8 is sample P dCu in embodiment 42.2The grain size distribution of/CoAl-LDH.
Specific implementation mode
With reference to specific embodiment, the invention will be further described, but the present invention is not limited thereto.
Embodiment 1
(1) preparation of MgAl-LDH carriers
Weigh 0.009mol Mg (NO3)2·6H2O and 0.003mol Al (NO3)3·9H2O is dissolved in 100mL deionized waters
In, it is configured to mixing salt solution；Weigh 0.02mol NaOH and 0.006mol Na2CO3It is dissolved in 100mL deionized waters, prepares
At mixed ammonium/alkali solutions；100mL deionized waters are added in 500mL four-hole boiling flasks, above-mentioned mixed ammonium/alkali solutions are then slowly added dropwise extremely
PH is 10 ± 0.1, and mixing salt solution is added dropwise simultaneously after stablizing 5min and aqueous slkali remains that pH is 10 ± 0.1, until mixing
Salting liquid is added dropwise, by gained slurries in 65 DEG C of water-baths crystallization 4h, after being cooled to room temperature with deionized water centrifuge washing extremely
The pH of supernatant is about 7, and gained, which is deposited in drying at 60 DEG C, for 24 hours, to be obtained white powder, be denoted as MgAl-LDH.From sample
SEM schemes visible MgAl-LDH carriers in (see attached drawing 1) and the flower-shaped multilevel hierarchy of Desert Rose is presented, be by size be 190~
200nm thickness is that the nanometer sheet self assembly of 15.0~20.0nm forms.
(2)PdCo0.28The preparation of-PVP nanoparticle sols
Weigh 5.64mmol PdCl2It is dissolved in deionized water with 11.3mmol KCl, being configured to molar concentration is
The 100mL tetrachloro-palladium acid potassium solutions of 0.056mol/L；Weigh 5.00mmol CoCl2·6H2O is dissolved in deionized water, is made and is rubbed
The 100mL cobalt chloride solutions of your a concentration of 0.050mol/L；By 1.23g polyvinylpyrrolidones (PVP) be dissolved in 150mL go from
In sub- water, it is charged with 2.5mL tetrachloro-palladium acids potassium solution and 1.4mL cobalt chloride solutions, adds 50mL ethylene glycol.It is added dropwise
1mol/L NaOH solutions make system pH~13, and then flow back in 140 DEG C of oil baths 2h, and cooled to room temperature obtains dark-brown
Colloidal sol, i.e. PdCo0.28- PVP nanoparticle sols.
Take the PdCo of 100mL0.28- PVP nanoparticle sols are dried in vacuo at 90 DEG C obtains black PdCo afterwards for 24 hours0.28-
PVP nano-particles, the XRD spectra (see attached drawing 2) of the sample is 41.04oThe sharp diffraction maximum occurred, the peak is between metal Pd
(111) feature crystallographic plane diffraction peak (JCPDS 46-1043,40.12o) and metal Co (111) feature crystallographic plane diffraction peak (JCPDS
15-0806,44.22o) between, show PdCo0.28- PVP nano-particles are alloy phase.
(3) catalyst PdCo0.28The preparation of/MgAl-LDH
Take the PdCo of above-mentioned preparation0.280.75g MgAl-LDH carriers, room temperature is added in-PVP nanoparticle sol 100mL
Lower mechanical agitation 2h.It is washed twice with acetone and deionized water alternating centrifugal, gained, which is deposited in vacuum drying 12h at 60 DEG C, to be obtained
To grayish powder, it is denoted as PdCo0.28/ MgAl-LDH is through Co and Pd molar ratios in catalyst obtained by ICP elemental analyses
0.28, Pd mass content is 0.86wt%.The high resolution electron microscopy image of catalyst shows its PdCo0.28Alloy nano particle is high
It is scattered on Multilevel-structure hydrotalcite carrier (see attached drawing 3), average grain diameter is 2.22 ± 0.42nm (see attached drawing 4).
In the Heck of iodobenzene and styrene reactions, reaction condition is：1mmol iodobenzenes, 1.5mmol styrene, 37mg's
Catalyst PdCo0.28/ CoAl-LDH (molar percentage that active specy Pd accounts for substrate iodobenzene is 0.30mol%), 3mmol carbonic acid
Potassium, solvent be 12mL n,N-Dimethylformamide and 4mL water mixed solution, 120 DEG C；The conversion ratio of iodobenzene reaches after reaction 1h
100%, target product is trans--and the yield of talan is up to 98.0%；Catalyst is centrifuged and recycles and reuses, 12 secondary responses
The conversion ratio of iodobenzene still reaches 95.6%, and target product is trans--and the yield of talan is up to 94.7%.Catalyst is in same reaction
Under the conditions of iodobenzene and ethyl acrylate reaction in, react the conversion ratio of iodobenzene after 1h up to 99.8%, target product is trans--meat
The yield of ethyl cinnamate is up to 99.2%；In the reaction of the 4- nitros iodobenzene and styrene of catalyst under the same reaction conditions, instead
Answer the conversion ratio of iodobenzene after 1.0h up to 100%, the yields of the trans- -4- nitro diphenyl ethylenes of target product is up to 99.0%；Catalyst
In the reaction of 4- acetyl group iodobenzene and styrene under the same reaction conditions, after reacting 1.0h, the conversion ratio of iodobenzene reaches
100%, the yield of the trans- -4- acetyl group talan of target product is up to 98.9%.
Embodiment 2
(1) preparation of CoAl-LDH carriers
Weigh 0.009mol Co (NO3)2·6H2O and 0.003mol Al (NO3)3·9H2O is dissolved in 100mL deionized waters
In, it is configured to mixing salt solution；Weigh 0.02mol NaOH and 0.006mol Na2CO3It is dissolved in 100mL deionized waters, prepares
At mixed ammonium/alkali solutions；100mL deionized waters are added in 500mL four-hole boiling flasks, above-mentioned mixed ammonium/alkali solutions are then slowly added dropwise extremely
PH is 10 ± 0.1, and mixing salt solution is added dropwise simultaneously after stablizing 5min and aqueous slkali remains that pH is 10 ± 0.1, until mixing
Salting liquid is added dropwise, by gained suspension in 65 DEG C of water-baths crystallization 4h, after being cooled to room temperature use deionized water centrifuge washing
PH to supernatant is about 7, and gained, which is deposited in drying at 60 DEG C, for 24 hours, to be obtained purple powder, be denoted as CoAl-LDH.CoAl-
The flower-shaped multilevel hierarchy of Desert Rose is presented in LDH carriers, be by size be 200~240nm thickness is receiving for 13.0~15.0nm
Rice piece self assembly forms.
(2)PdNi0.10The preparation of-PVP colloidal sols
Weigh 5.64mmol PdCl2It is dissolved in deionized water with 11.3mmol KCl, being configured to molar concentration is
The 100mL tetrachloro-palladium acid potassium solutions of 0.056mol/L；Weigh 5.00mmol NiCl2·6H2O is dissolved in deionized water, is configured to
Molar concentration is the 100mL nickel chloride solutions of 0.050mol/L；It weighs 0.82g polyvinylpyrrolidones (PVP) and is dissolved in 150mL
In deionized water, it is charged with the above-mentioned tetrachloro-palladium acid potassium solutions of 2.5mL and 0.85mL nickel chloride solutions, adds 50mL second two
Alcohol.1mol/L NaOH solutions, which are added dropwise, makes system pH be about 12, and then flow back in 140 DEG C of oil baths 2h, and cooled to room temperature obtains
To dark-brown colloidal sol, i.e. PdNi0.10- PVP nanoparticle sols.
Take the PdNi of 100mL0.10- PVP nanoparticle sols are dried in vacuo at 90 DEG C and obtain black solid afterwards for 24 hours, should
The XRD spectra (see attached drawing 5) of sample is 40.57oThe sharp diffraction maximum occurred, the peak is between metal Pd (111) feature crystal face
Diffraction maximum (JCPDS 46-1043,40.12o) and W metal (111) feature crystallographic plane diffraction peak (JCPDS04-0580,44.51o) it
Between, show that PdNi-PVP nano-particles are alloy phase.
(3) catalyst PdNi0.10The preparation of/CoAl-LDH
Take the PdNi of above-mentioned preparation0.100.75g CoAl-LDH carriers, room temperature is added in-PVP nanoparticle sol 100mL
Lower mechanical agitation 2h.It is washed twice with acetone and deionized water alternating centrifugal, gained is deposited at 60 DEG C and is dried in vacuum overnight
Khaki powder is obtained, PdNi is denoted as0.10/ CoAl-LDH obtains Ni and Pd molar ratios in gained catalyst through ICP elemental analyses
Mass content for 0.10, Pd is 0.83wt%.
In the Heck of iodobenzene and styrene reactions, reaction condition is：1mmol iodobenzenes, 1.5mmol styrene, 38mg are urged
Agent PdNi0.10/ CoAl-LDH (molar percentage that active specy Pd accounts for substrate iodo aromatic hydrocarbon is 0.30mol%), 3mmol carbon
Sour potassium, solvent be 12mL n,N-Dimethylformamide and 4mL water mixed solution, 120 DEG C；The conversion ratio of iodobenzene after reaction 1h
Up to 99.1%, target product is trans--and the yield of talan is up to 97.4%.
Embodiment 3
(1)Cu1Ni2The preparation of Al-LDH carriers
Weigh 0.003mol Cu (NO3)2·3H2O、0.006mol Ni(NO3)2·6H2O and 0.003mol Al (NO3)3·
9H2O is dissolved in 100mL deionized waters, is configured to mixing salt solution；Weigh 0.02mol NaOH and 0.006mol Na2CO3It is dissolved in
In 100mL deionized waters, it is configured to mixed ammonium/alkali solutions.100mL deionized waters are added in 500mL four-hole boiling flasks, then slowly
It is 10 ± 0.1 that above-mentioned mixed ammonium/alkali solutions, which are added dropwise, to pH, and above-mentioned mixing salt solution and mixed ammonium/alkali solutions are added dropwise simultaneously after stablizing 5min
Remain that pH is 10 ± 0.1, until mixing salt solution is added dropwise, crystallization 4h, cooling in 65 DEG C of water-baths by gained slurries
With the pH of deionized water centrifuge washing to supernatant it is about 7 after to room temperature, gained is deposited in drying at 60 DEG C obtains neatly for 24 hours
Stone support C u1Ni2Al-LDH。Cu1Ni2The flower-shaped multilevel hierarchy of Desert Rose is presented in Al-LDH hydrotalcite supports, is to be by size
110~150nm thickness is that the nanometer sheet self assembly of 10.0~14.0nm forms.
(2)PdFe0.30The preparation of-PVP
Weigh 5.64mmol PdCl2It is dissolved in deionized water with 11.3mmol KCl, being configured to molar concentration is
The 100mL tetrachloro-palladium acid potassium solutions of 0.056mol/L；Weigh 5.00mmol FeCl3·6H2O is dissolved in deionized water, is configured to
Molar concentration is the 100mL ferric chloride solutions of 0.050mol/L；By 0.82g polyvinylpyrrolidones (PVP) be dissolved in 150mL go from
In sub- water, it is charged with the above-mentioned tetrachloro-palladium acid potassium solutions of 2.5mL and 1.4mL ferric chloride solutions, adds 50mL ethylene glycol.Drop
Add 1mol/L NaOH solutions that system pH is made to be about 12, then flow back in 140 DEG C of oil baths 2h, and cooled to room temperature obtains depth
Brown colloidal sol, is denoted as PdFe0.30- PVP nanoparticle sols.
(3) catalyst PdFe0.30/Cu1Ni2The preparation of Al-LDH
Take the PdFe of above-mentioned preparation0.300.75g Cu are added in-PVP nanoparticle sol 100mL1Ni2Al-LDH carriers, room
The lower mechanical agitation 2h of temperature.It is alternately washed twice with acetone and deionized water, centrifuges, be dried in vacuo at 60 DEG C and obtain for 24 hours
Shallow green powder is denoted as PdFe0.30/Cu1Ni2Al-LDH obtains Fe and Pd molar ratios in gained catalyst through ICP elemental analyses
Mass percentage for 0.30, Pd is 1.0wt%.
In the Heck of iodobenzene and styrene reactions, reaction condition is：1mmol iodobenzenes, 1.5mmol alkene, 32mg catalysis
Agent PdFe0.30/Cu1Ni2Al-LDH (molar percentage that active specy Pd accounts for substrate iodobenzene is 0.30mol%), 3mmol carbonic acid
Potassium, solvent be 12mL n,N-Dimethylformamide and 4mL water mixed solution, 120 DEG C；The conversion ratio of iodobenzene reaches after reaction 1h
99.4%, target product is trans--and the yield of talan is up to 97.6%.
Embodiment 4
(1) preparation of CoAl-LDH carriers
Weigh 0.009mol Co (NO3)2·6H2O and 0.003mol Al (NO3)3·9H2O is dissolved in 100mL deionized waters
In, it is configured to mixing salt solution；Weigh 0.02mol NaOH and 0.006mol Na2CO3It is dissolved in 100mL deionized waters, prepares
At mixed ammonium/alkali solutions；100mL deionized waters are added in 500mL four-hole boiling flasks, above-mentioned mixed ammonium/alkali solutions are then slowly added dropwise extremely
PH is 10 ± 0.1, and mixing salt solution is added dropwise simultaneously after stablizing 5min and aqueous slkali remains that pH is 10 ± 0.1, until mixing
Salting liquid is added dropwise, by gained suspension in 65 DEG C of water-baths crystallization 4h, after being cooled to room temperature use deionized water centrifuge washing
PH to supernatant is about 7, and gained, which is deposited in drying at 60 DEG C, for 24 hours, to be obtained purple powder, be denoted as CoAl-LDH.CoAl-
The flower-shaped multilevel hierarchy of Desert Rose is presented in LDH carriers, be by size be 200~240nm thickness is receiving for 13.0~15.0nm
Rice piece self assembly forms.
(2)PdCu2.2The preparation of-PVP
Weigh 5.64mmol PdCl2It is dissolved in deionized water with 11.3mmol KCl, being configured to molar concentration is
The 100mL tetrachloro-palladium acid potassium solutions of 0.056mol/L；Weigh 5.00mmol CuCl2·2H2O is dissolved in deionized water, is made and is rubbed
The 100mL copper chloride solutions of your a concentration of 0.050mol/L；By 2.45g polyvinylpyrrolidones (PVP) be dissolved in 150mL go from
In sub- water, it is charged with the above-mentioned tetrachloro-palladium acid potassium solutions of 2.5mL and 5.6mL copper chloride solutions, adds 50mL ethylene glycol.Drop
Add 1mol/L NaOH solutions that system pH is made to be about 13, then flow back in 140 DEG C of oil baths 2h, and cooled to room temperature obtains depth
Brown colloidal sol, i.e. PdCu2.2- PVP nanoparticle sols.
Take the above-mentioned PdCu of 100mL2.2- PVP nanoparticle sols are dried in vacuo at 90 DEG C and obtain black solid afterwards for 24 hours, should
The XRD spectra (see attached drawing 6) of sample is 42.30oThe sharp diffraction maximum occurred, the peak is between metal Pd (111) feature crystal face
Diffraction maximum (JCPDS 46-1043,40.12o) and Ni metal (111) feature crystallographic plane diffraction peak (JCPDS 04-0836,43.30o)
Between, show PdCu2.2- PVP nano-particles are alloy phase.
(3) catalyst PdCu2.2The preparation of/CoAl-LDH
Take the PdCu of above-mentioned preparation2.20.75g CoAl-LDH carriers are added, at room temperature in-PVP nanoparticle sol 100mL
Mechanical agitation 2h.It is alternately washed twice with acetone and deionized water, centrifuges, be dried overnight to obtain powdered sample at 60 DEG C
Product are denoted as PdCu2.2/ CoAl-LDH obtains Cu and the matter that Pd molar ratios are 2.2, Pd in gained catalyst through ICP elemental analyses
Amount content is 0.96wt%.Catalyst PdCu2.2The high resolution electron microscopy image of/CoAl-LDH shows its PdCu2.2Alloy nanoparticle
Sub- high dispersive is in, (see attached drawing 7), average grain diameter is 1.48 ± 0.30nm on Multilevel-structure hydrotalcite carrier (see attached drawing 8).
In the Heck of iodobenzene and styrene reactions, reaction condition is：1mmol iodobenzenes, 1.5mmol styrene, 33mg are urged
Agent PdCu2.2/ CoAl-LDH (molar percentage that active specy Pd accounts for substrate iodobenzene is 0.30mol%), 3mmol potassium carbonate,
Solvent be 12mL n,N-Dimethylformamide and 4mL water mixed solution, 120 DEG C；The conversion ratio of iodobenzene reaches after reaction 1h
100%, target product is trans--and the yield of talan is up to 99.4%.
Embodiment 5
(1) preparation of CoAl-LDH carriers
Weigh 0.015mol Co (NO3)2·6H2O and 0.005mol Al (NO3)3·9H2O is dissolved in 100mL deionized waters
In, it is configured to mixing salt solution；Weigh 0.04mol NaOH and 0.012mol Na2CO3It is dissolved in 100mL deionized waters, prepares
At mixed ammonium/alkali solutions；100mL deionized waters are added in 500mL four-hole boiling flasks, above-mentioned mixed ammonium/alkali solutions are then slowly added dropwise extremely
PH is 10 ± 0.1, and mixing salt solution is added dropwise simultaneously after stablizing 5min and aqueous slkali remains that pH is 10 ± 0.1, until mixing
Salting liquid is added dropwise, by gained slurries in 65 DEG C of water-baths crystallization 4h, after being cooled to room temperature with deionized water centrifuge washing extremely
The pH of supernatant is about 7, and gained, which is deposited in drying at 60 DEG C, for 24 hours, to be obtained purple powder, be denoted as CoAl-LDH.CoAl-LDH
The flower-shaped multilevel hierarchy of Desert Rose is presented in carrier, be by size is nanometer sheet that 200~240nm thickness is 13.0~15.0nm
Self assembly forms.
(2)PdCo0.28The preparation of-PVP colloidal sols
Weigh 5.64mmol PdCl2It is dissolved in deionized water with 11.3mmol KCl, being configured to molar concentration is
The 100mL tetrachloro-palladium acid potassium solutions of 0.056mol/L；Weigh 5.00mmol CoCl2·6H2O is dissolved in deionized water, is configured to
Molar concentration is the 100mL cobalt chloride solutions of 0.050mol/L；By 1.23g polyvinylpyrrolidones (PVP) be dissolved in 150mL go from
In sub- water, it is charged with the above-mentioned tetrachloro-palladium acid potassium solutions of 2.5mL and 1.4mL cobalt chloride solutions, adds 50mL ethylene glycol.Drop
Add 1mol/L NaOH solutions that system pH is made to be about 13, then flow back in 140 DEG C of oil baths 2h, and cooled to room temperature obtains depth
Brown colloidal sol, i.e. PdCo0.28- PVP nanoparticle sols.
(3) catalyst PdCo0.28The preparation of/CoAl-LDH
Take the above-mentioned PdCo of 100mL0.287.5g CoAl-LDH carriers are added in-PVP nanoparticle sols, and machinery stirs at room temperature
Mix 2h.It is washed twice with acetone and deionized water alternating centrifugal, gained is deposited in be dried in vacuo at 60 DEG C obtains khaki for 24 hours
Powder is denoted as PdCo0.28/CoAl-LDH.Obtaining the mass content of Pd in gained catalyst through ICP elemental analyses is
0.01wt%.
In the Heck of iodobenzene and styrene reactions, reaction condition is：1mmol iodobenzenes, 1.5mmol styrene, 3.1g are urged
Agent PdCo0.28/ CoAl-LDH (molar percentage that active specy Pd accounts for substrate iodobenzene is 0.30mol%), 3mmol carbonic acid
Potassium, solvent be 12mL n,N-Dimethylformamide and 4mL water mixed solution, 120 DEG C；The conversion ratio of iodobenzene reaches after reaction 1h
100%, target product is trans--and the yield of talan is up to 97.9%.
Embodiment 6
(1) preparation of NiAl-LDH carriers
Weigh 0.009mol Ni (NO3)2·6H2O and 0.003mol Al (NO3)3·9H2O is dissolved in 100mL deionized waters
In, mixing salt solution；Weigh 0.02mol NaOH and 0.006mol Na2CO3It is dissolved in 100mL deionized waters, is configured to mix
Aqueous slkali；In 500mL four-hole boiling flasks be added 100mL deionized waters, be then slowly added dropwise above-mentioned mixed ammonium/alkali solutions to pH be 10
± 0.1, mixing salt solution is added dropwise simultaneously after stablizing 5min and aqueous slkali remains that pH is 10 ± 0.1, until mixing salt solution
Be added dropwise, by gained slurries in 65 DEG C of water-baths crystallization 4h, with deionized water centrifuge washing to supernatant after being cooled to room temperature
PH be about 7, by gained be deposited at 60 DEG C it is dry for 24 hours, obtain green powder, be denoted as NiAl-LDH.NiAl-LDH hydrotalcites
The flower-shaped multilevel hierarchy of Desert Rose is presented in carrier, be by size is nanometer sheet that 100~120nm thickness is 10.0~13.0nm
Self assembly forms
(2)PdCo0.28The preparation of-PVP colloidal sols
Weigh 5.64mmol PdCl2It is dissolved in deionized water with 11.3mmol KCl, being configured to molar concentration is
The 100mL tetrachloro-palladium acid potassium solutions of 0.056mol/L；Weigh 5.00mmol CoCl2·6H2O is dissolved in deionized water, is configured to
Molar concentration is the 100mL cobalt chloride solutions of 0.050mol/L；By 1.23g polyvinylpyrrolidones (PVP) be dissolved in 150mL go from
In sub- water, it is charged with the above-mentioned tetrachloro-palladium acid potassium solutions of 2.5mL and 1.4mL cobalt chloride solutions, adds 50mL ethylene glycol.Drop
Add 1mol/L NaOH solutions that system pH is made to be about 13, then flow back in 140 DEG C of oil baths 2h, and cooled to room temperature obtains depth
Brown colloidal sol, i.e. PdCo0.28- PVP nanoparticle sols.
(3) catalyst PdCo0.28The preparation of/NiAl-LDH
Take the above-mentioned PdCo of 100mL0.280.75g NiAl-LDH carriers are added in-PVP nanoparticle sols, mechanical at room temperature
Stir 2h.It is alternately washed twice with acetone and deionized water, centrifuges, be dried in vacuo at 60 DEG C and obtain powdered sample for 24 hours
Product are denoted as PdCo0.28/ NiAl-LDH, it is 0.28, Pd's to obtain Co and Pd molar ratios in gained catalyst through ICP elemental analyses
Mass content is 0.64wt%.
In the Heck of iodobenzene and styrene reactions, reaction condition is：1mmol iodobenzenes, 1.5mmol styrene, 50mg are urged
Agent PdCo0.28/ NiAl-LDH (molar percentage that active specy Pd accounts for substrate iodobenzene is 0.30mol%), 3mmol carbonic acid
Potassium, solvent be 12mL n,N-Dimethylformamide and 4mL water mixed solution, 120 DEG C；The conversion ratio of iodobenzene reaches after reaction 1h
99.1%, target product is trans--and the yield of talan is up to 97.9%.
Claims (5)
1. a kind of hydrotalcite supported palladium based alloy catalyst, which is characterized in that expression formula PdTx/ MAl-LDH, wherein PdTxFor
Pd radicel duplex metal alloy nano particle, T represent cheap transition metal Co, Ni, Fe or Cu, and x represents mole of transition metal T and Pd
Than the mass percentage for being 0.1~2.2, Pd is 0.01wt%~1.0wt%, particle size about 1.48nm~2.22nm；
MAl-LDH is hydrotalcite supports, M Mg2+、Ni2+、Co2+And Cu2+Any one in bivalent metal ion or two kinds, hydrotalcite
The flower-shaped multilevel hierarchy of Desert Rose is presented in carrier, be by size is nanometer sheet that 100~240nm thickness is 10.0~20.0nm
Self assembly forms.
2. hydrotalcite supported palladium based alloy catalyst described in accordance with the claim 1, which is characterized in that the hydrotalcite loads palladium base
Alloy catalyst shows excellent catalytic performance, reaction condition in iodo aromatic hydrocarbon and the Heck coupling reactions of alkene：1mmol
Iodo aromatic hydrocarbon, 1.5mmol alkene, the molar percentage that a certain amount of catalyst activity species Pd accounts for substrate iodo aromatic hydrocarbon are
0.30mol%, 3mmol potassium carbonate, solvent are the mixed solution of 12mL n,N-Dimethylformamide and 4mL water, 120 DEG C, are reacted
The conversion ratio of iodo aromatic hydrocarbon is up to 99.1%~100% after 1h, the yield of target product trans-styryl derivative up to 97.4%~
99.4%.
3. a kind of preparation method of hydrotalcite supported palladium based alloy catalyst described in claim 1, which is characterized in that including with
Lower step：
(1) preparation of hydrotalcite supports
Weigh 0.009~0.015 (nitrate and 0.003~0.005mol ANN aluminium nitrate nonahydrates of mol M be dissolved in 100mL go from
In sub- water, it is configured to mixing salt solution；Weigh 0.02~0.04mol NaOH and 0.006~0.012molmol Na2CO3It is dissolved in
In 100mL deionized waters, it is configured to mixed ammonium/alkali solutions；100mL deionized waters are added in 500mL four-hole boiling flasks, then slowly
It is 10 ± 0.1 that above-mentioned mixed ammonium/alkali solutions, which are added dropwise, to pH, and above-mentioned mixing salt solution and mixed ammonium/alkali solutions are added dropwise simultaneously after stablizing 5min
Remain that pH is 10 ± 0.1, until mixing salt solution is added dropwise, crystallization 4h, cooling in 65 DEG C of water-baths by gained slurries
With the pH of deionized water centrifuge washing to supernatant it is about 7 after to room temperature, gained is deposited in drying at 60 DEG C obtains neatly for 24 hours
Stone carrier MAl-LDH, M Mg2+、Ni2+、Co2+And Cu2+Any one in bivalent metal ion or two kinds；
(2)PdTxThe preparation of-PVP nanoparticle sols
Weigh 5.64mmol PdCl2It is dissolved in deionized water with 11.3mmol KCl, it is 0.056mol/L to be configured to molar concentration
100mL tetrachloro-palladium acid potassium solutions；The chlorate for weighing 5.00mmol T is dissolved in deionized water, is configured to molar concentration and is
The chlorination salting liquid of the 100mL T of 0.050mol/L；By 0.82g~2.46g polyvinylpyrrolidones PVP be dissolved in 150mL go from
In sub- water, it is charged with the chlorination salting liquid of 2.5mL above-mentioned tetrachloro-palladium acid potassium solution and 0.85~8.5mL T, is added
50mL ethylene glycol, 1mol/L NaOH solutions, which are added dropwise, makes system pH be 12~13, and then flow back in 140 DEG C of oil baths 2h, naturally cold
But dark-brown colloidal sol, i.e. PdT are obtained to room temperaturex- PVP nanoparticle sols, it is any one in T Co, Ni, Fe and Cu element
Kind；
(3) hydrotalcite supported palladium based alloy catalyst PdTxThe preparation of/MAl-LDH
Take the above-mentioned PdT of 100mLx0.5g~7.5g MAl-LDH carriers are added, at room temperature mechanical agitation in-PVP nanoparticle sols
2h is washed twice with acetone and deionized water alternating centrifugal, gained is deposited in be dried in vacuo at 60 DEG C obtains catalyst for 24 hours
PdTx/MAl-LDH。
4. according to the method for claim 3, which is characterized in that the nitrate of the M used in step (1) is Mg (NO3)2·
6H2O、Ni(NO3)2·6H2O、Co(NO3)2·6H2O and Cu (NO3)2·3H2Any one in O or two kinds.
5. according to the method for claim 3, which is characterized in that the chlorate of the T used in step (2) is CoCl2·6H2O、
NiCl2·6H2O、FeCl3·6H2O and CuCl2·2H2Any one in O.
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