CN115672323A - Carbon shell coated metal particle loaded silicon-based catalyst, and preparation method and application thereof - Google Patents
Carbon shell coated metal particle loaded silicon-based catalyst, and preparation method and application thereof Download PDFInfo
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- CN115672323A CN115672323A CN202211308409.0A CN202211308409A CN115672323A CN 115672323 A CN115672323 A CN 115672323A CN 202211308409 A CN202211308409 A CN 202211308409A CN 115672323 A CN115672323 A CN 115672323A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 64
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 50
- 239000010703 silicon Substances 0.000 title claims abstract description 50
- 239000002923 metal particle Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 80
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052751 metal Inorganic materials 0.000 claims abstract description 59
- 239000002184 metal Substances 0.000 claims abstract description 59
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 32
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 49
- 150000003839 salts Chemical class 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- 229910052914 metal silicate Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 239000004005 microsphere Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical class [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Chemical class 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229910052707 ruthenium Chemical class 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Chemical class 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000008098 formaldehyde solution Substances 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract 2
- 239000011229 interlayer Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000011946 reduction process Methods 0.000 abstract 1
- 239000002344 surface layer Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- FMQXRRZIHURSLR-UHFFFAOYSA-N dioxido(oxo)silane;nickel(2+) Chemical compound [Ni+2].[O-][Si]([O-])=O FMQXRRZIHURSLR-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 4
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 4
- 235000012141 vanillin Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZZBBCSFCMKWYQR-UHFFFAOYSA-N copper;dioxido(oxo)silane Chemical compound [Cu+2].[O-][Si]([O-])=O ZZBBCSFCMKWYQR-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZENOXNGFMSCLLL-UHFFFAOYSA-N vanillyl alcohol Chemical compound COC1=CC(CO)=CC=C1O ZENOXNGFMSCLLL-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of catalytic materials, and particularly relates to a carbon shell coated metal particle loaded silicon-based catalyst, and a preparation method and application thereof. The catalyst takes a silicon ball as a core, silicon dioxide loaded with metal particles as an interlayer and a carbon layer as a shell. The metal particles are one or the combination of more than two of non-noble metals or noble metals. The size of the silicon spheres can be adjusted by adjusting the adding amount of tetraethyl orthosilicate in the synthesis process, and the thickness of the carbon shell can be adjusted by adjusting the adding amount of resorcinol and formaldehyde in the synthesis process. Due to the coating effect of the carbon shell, metal components of the catalyst are not easy to lose in the reaction process, the stability of the catalyst is improved, and the carbon shell is fully filled in the loose surface layer of the silicate in the forming process, so that metal particles are dispersed in the carbon shell structure after the carbothermic reduction process, the dispersibility of the metal particles is improved, and the agglomeration is reduced.
Description
Technical Field
The invention belongs to the field of catalysis, relates to synthesis and application of a nano catalyst, and particularly relates to a carbon shell coated metal particle loaded silicon-based catalyst, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Silicon-based materials are widely used in the industrial production field, especially in catalytic reactions such as hydrogenation, hydrodeoxygenation and oxidation, due to their characteristics of good hydrophilicity, easy surface modification and sintering resistance. In the reaction process, because the interaction between the silicon-based carrier and the metal is not strong, the metal particles loaded on the surface of the silicon-based material are easy to lose, deactivate and the like, so that the stability of the catalyst is poor. The research finds that the space confinement effect can effectively protect the internal active metal part and prevent the loss and the inactivation of the active metal, thereby greatly improving the stability of the supported metal catalyst.
The prior art discloses a method for improving the stability of a metal catalyst by utilizing a space confinement effect, but the method introduces carbon quantum dots as a reducing agent, and although the carbon quantum dots also play a role in coating internal precious metals, the concentration of the carbon quantum dots is difficult to accurately regulate and control, the preparation method is complex, the preparation cost is high, and the large-scale production cannot be realized.
Disclosure of Invention
In order to solve the defects of poor stability, complex preparation method, poor controllability and high cost of the supported metal catalyst in the prior art, the invention aims to provide the preparation method of the carbon shell coated metal particle supported silicon-based catalyst, and the catalyst prepared by the method has high reaction activity and stability in a low-temperature water phase.
In order to realize the purpose, the invention adopts the following technical scheme: a preparation method of a carbon shell coated metal particle loaded silicon-based catalyst comprises the following steps:
s1, dissolving metal salt in deionized water, and then mixing the metal salt with ammonia water to obtain a mixed solution; dispersing the silicon dioxide microspheres into deionized water to obtain a silicon dioxide microsphere dispersion liquid; adding the silicon dioxide microsphere dispersion liquid into the mixed liquid, uniformly dispersing, transferring into a reaction kettle, reacting at 70-150 ℃ for 1-48h, separating out green solids, washing with deionized water and ethanol for multiple times, and drying to obtain silicon dioxide wrapped by metal silicate;
s2, mixing ethanol, deionized water and ammonia water according to a volume ratio of 70; adding the silicon dioxide coated by the metal silicate prepared in the step S1 into a mixed solvent, adding resorcinol and formaldehyde aqueous solution, stirring and reacting for 1-48h at 25-50 ℃, separating out earthy yellow solid, washing with deionized water and ethanol for multiple times, and drying to obtain a precursor;
and S3, carrying out carbon thermal reduction treatment on the precursor at high temperature in the atmosphere of nitrogen or inert gas, generating metal particles in situ by using metal silicate, and generating a carbon layer by using a phenolic resin high polymer to obtain the carbon shell coated metal particle loaded silicon-based catalyst.
The preparation method of the catalyst used as the carbon shell coated metal particle loaded silicon-based catalyst is further improved:
preferably, the diameter of the silica microspheres is 600-900nm.
Preferably, the mass ratio of the silica microspheres, the metal salt and the ammonia water in step S1 is 1.
Preferably, the mass ratio of the resorcinol to the formaldehyde in the aqueous formaldehyde solution to the metal silicate-coated silica in the step S2 is 1.2 (0.5-8), and the concentration of the aqueous formaldehyde solution is 30-40%.
Preferably, the temperature of the high-temperature carbonization reduction treatment in the step S3 is 600-900 ℃, the carbonization time is 2-10h, and the temperature rise speed is 2-10 ℃/min.
Preferably, the metal salt is a combination of one or more single metal element salts containing one or more single metal element salts of iron, cobalt, nickel, copper, zinc, platinum, palladium and ruthenium, or a combination of one or more complex metal element salts containing two or more complex metal element salts of iron, cobalt, nickel, copper, zinc, platinum, palladium and ruthenium, or a combination of a single metal element salt and a complex metal element salt.
Preferably, the iron-containing metal salt is one or a combination of more than two of ferric nitrate, ferric chloride, ferric sulfate and ferric acetylacetonate; or the cobalt-containing metal salt is one or the combination of more than two of cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt acetylacetonate; or the nickel-containing metal salt is one or the combination of more than two of nickel nitrate, nickel chloride, nickel sulfate and nickel acetylacetonate; or the copper-containing metal salt is one or the combination of more than two of copper nitrate, copper chloride, copper sulfate and copper acetylacetonate; or the zinc-containing metal salt is one or the combination of more than two of zinc nitrate, zinc chloride, zinc sulfate and zinc acetylacetonate; or the platinum-containing metal salt is one or the combination of more than two of platinum chloride and chloroplatinic acid; or the palladium-containing metal salt is one or the combination of two of palladium chloride and ammonium chloropalladate; alternatively, the ruthenium-containing metal salt is ruthenium chloride.
The invention also aims to provide the carbon shell coated metal particle loaded silicon-based catalyst prepared by the preparation method.
The further technical proposal of the carbon shell coated metal particle loaded silicon-based catalyst is as follows:
preferably, the thickness of the carbon shell layer in the catalyst is 10-50nm, and the diameter of the metal particles is 5-20nm.
The invention also aims to provide the application of the carbon shell coated metal particle loaded silicon-based catalyst in catalytic hydrogenation, hydrodeoxygenation and hydrogenolysis reactions. .
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, silicon dioxide is used as a precursor for synthesizing metal silicate by a step-by-step synthesis method, and different metal salts and ammonia water are utilized to react on the surface of the silicon dioxide to form the metal silicate, so that the structure of the silicon dioxide wrapped by the metal silicate is obtained. And then taking the structure as a precursor, without additional modification on the surface of silicon dioxide, and generating a layer of phenolic resin high polymer precursor on the surface of the metal silicate by utilizing the polycondensation reaction between resorcinol and formaldehyde aqueous solution. And then carrying out carbon thermal reduction treatment on the precursor at the high temperature of 700 ℃, wherein the metal silicate coated inside can directly generate metal particles in situ due to the reducibility of carbon, so that the problem of uneven metal loading is avoided, and the phenolic resin polymer on the surface of the silicate is carbonized at high temperature to generate a carbon layer, so that the carbon shell coated metal particle loaded silicon-based catalyst is obtained.
The coated carbon layer prepared by the method is thin, so that the full contact between reactants and active metal is not influenced, and the internal active metal can be protected by utilizing the space confinement effect of the carbon layer, so that the problems of loss, agglomeration and the like do not occur in the catalytic reaction process, and the problem of the stability of the heterogeneous catalyst in a liquid phase environment is solved. In addition, in a catalysis experiment for preparing vanillyl alcohol by low-temperature aqueous phase hydrogenation of vanillin, the performance of the silicon-based catalyst which is coated with nickel and loaded by a carbon shell is hardly reduced after 5 times of reaction, and the conversion rate of reactants is close to 100% at 40 ℃, so that the problem that the catalytic activity and the stability are reduced due to the fact that active metal of the catalyst is easy to lose or inactivate in aqueous phase reaction is solved.
The metal salt added in the step is various single metal salts or salts of more than two composite metals, different metal silicates are synthesized firstly, and then the carbon shell coated silicon-based catalyst loaded with different metals is prepared.
The thickness of the coating carbon layer in the catalyst can be regulated and controlled by simply regulating the addition of resorcinol, so that the optimal catalytic performance is achieved.
Drawings
Fig. 1 is an image of a scanning electron microscope of the carbon shell coated nickel supported silicon based catalyst of example 1.
Fig. 2 is a transmission electron microscope image of a carbon shell coated nickel metal particle supported silicon based catalyst synthesized with 0.2g resorcinol added as in example 1.
Fig. 3 is a transmission electron microscope image of a carbon shell coated nickel metal particle supported silicon based catalyst synthesized with the addition of 0.1g resorcinol in example 1.
Fig. 4 is a transmission electron microscope image of a carbon shell coated nickel metal particle supported silicon based catalyst synthesized with the addition of 0.05g resorcinol in example 1.
FIG. 5 is a graph comparing the aqueous hydrogenation performance of vanillin by carbon shell-coated nickel metal particles supported on silicon-based catalysts formed from resorcinol and formaldehyde in different qualities in example 1 (reaction conditions: 40 deg.C, 2 MPa of hydrogen, 2 hours).
FIG. 6 is a comparison of the aqueous phase hydrogenation stability of a carbon shell coated nickel metal particle supported silicon based catalyst formed from 0.1g resorcinol and 0.05g resorcinol in example 1: the cycle performance of a silicon-based catalyst which is formed by resorcinol in an amount of 0.1g and is coated with a carbon shell and loaded with nickel; b.0.05g resorcinol forms a carbon shell coating nickel-loaded silicon-based catalyst cycle performance (reaction conditions: 40 ℃,2 mpa hydrogen, 2 hours).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative effort based on the embodiments of the present invention belong to the protection scope of the present invention.
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The embodiment provides a preparation method of a silicon-based catalyst loaded with nickel metal particles coated with a carbon shell, which specifically comprises the following steps:
a silicon-based catalyst with high stability and nickel-carried carbon shell is prepared from carbon shell and nickel silicate through proportional mixing. The preparation method of the silicon spheres and the nickel silicate and the coating method of the carbon shell are as follows:
s1, 64g of absolute ethanol and 25ml of aqueous ammonia are mixed, followed by the rapid addition of 4.2ml of tetraethyl silicate with vigorous stirring. Stirring for a while to form a white suspension, continuously stirring for 2h, centrifugally separating the obtained white solid, washing with deionized water and ethanol for multiple times, and drying in an oven to obtain the silica microspheres, wherein the diameter of the microspheres is 600-900nm through testing.
S2, mixing a nickel nitrate solution (0.54 g of nickel nitrate hexahydrate dissolved in 30ml of deionized water) with ammonia water (4 ml, about 3.6 g) to obtain a mixed solution; weighing 0.36g of silica microspheres and dispersing the silica microspheres into 40ml of deionized water to obtain a silica microsphere dispersion (wherein the mass ratio of the silica microspheres to the metal salt to the ammonia water is 1: 1.5; adding the silicon dioxide microsphere dispersion liquid into the mixed liquid, carrying out ultrasonic treatment for 30 minutes, transferring the mixture into a 100ml polytetrafluoroethylene liner, and putting the liner into an oven to react for 12 hours at 90 ℃ to form metal silicate on the surface of the silicon dioxide microsphere. And (3) centrifugally separating the green solid obtained after the reaction, washing the green solid for multiple times by using deionized water and ethanol, drying the green solid for hours at the temperature of 60 ℃ in an oven, and collecting the green solid to obtain the silicon dioxide coated by the nickel silicate.
S3, mixing 70ml of ethanol, 10ml of deionized water and 1ml of ammonia water to obtain a mixed solvent; and (3) adding 0.2g of the silicon dioxide wrapped by the nickel silicate prepared in the step (S1) into the mixed solvent, and repeating the operation to prepare 5 parts of the same solution with the number of 1-5.
Then, the following resorcinol and formaldehyde aqueous solution (with the concentration of 30-40%) are respectively added into 5 parts of the solution, wherein the addition amount of each number is as follows:
no. 1, adding 0.4g of resorcinol and 0.5g of formaldehyde in the formalin, wherein the mass ratio of the resorcinol to the formaldehyde in the formalin to the silicon dioxide coated by the metal silicate is 1.2;
adding 0.2g of resorcinol and 0.24g of formalin into No. 2, wherein the mass ratio of resorcinol to formaldehyde in the formalin to silicon dioxide wrapped by metal silicate is 1.2;
adding 0.1g of resorcinol and 0.12g of formalin into No. 3, wherein the mass ratio of resorcinol to formaldehyde in the formalin to silicon dioxide wrapped by metal silicate is 1.2;
no. 4, adding 0.05g of resorcinol and 0.06g of formalin, wherein the mass ratio of resorcinol to formaldehyde in the formalin to silicon dioxide coated by metal silicate is 1;
adding 0.025g of resorcinol and 0.03g of formalin into No. 5, wherein the mass ratio of the resorcinol to the formaldehyde in the formalin to the silicon dioxide wrapped by the metal silicate is 1.2;
continuing stirring for 24 hours at normal temperature to generate a layer of phenolic resin high polymer on the surface of the metal silicate, separating out earthy yellow solids, and centrifugally washing with deionized water and ethanol for multiple times to obtain a precursor;
and S4, raising the temperature of the precursor to 700 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, and keeping for 5 hours to fully carbonize the phenolic resin on the surface to form the No. 1-5 nickel metal particle-loaded silicon-based catalyst coated with different carbon shell thicknesses.
FIG. 1 is a scanning electron micrograph of a carbon shell coated nickel-loaded silicon-based catalyst prepared by adding 0.4g of resorcinol, which shows that the catalyst has a spherical structure with a rough surface and is covered with a plurality of flaky nickel silicates. FIGS. 2, 3 and 4 are transmission electron microscope pictures of silicon-based catalysts loaded with nickel coated with carbon shells formed by adding 0.2g, 0.1g and 0.05g of resorcinol and formalin, respectively, and it can be seen that the nickel silicate is coated with a layer of carbon shells with different thicknesses, and the shell thickness is about 10-15nm. The carbon shell thickness is thicker in fig. 2 than in fig. 4, and thus it can be seen that the carbon shell thickness becomes thicker as the input amount of resorcinol and formalin increases.
The silicon-based catalyst which is formed by resorcinol and formaldehyde aqueous solution with different qualities and is coated by carbon shells and loaded with nickel is respectively applied to a vanillin water-phase hydrodeoxygenation experiment, and the experimental conditions are as follows: 2 MPa of hydrogen at 40 ℃ for 2 hours. Figure 5 shows a study of the activity of carbon shell coated nickel loaded silicon based catalysts formed from different masses of resorcinol and formaldehyde in hydrodeoxygenation of vanillin, from which it can be seen that carbon shell coated nickel loaded silicon based catalysts formed from 0.1g resorcinol and 0.05g resorcinol are more active than the others. Fig. 6 shows an investigation of the aqueous phase hydrogenation stability of a nickel loaded silicon based catalyst coated with a carbon shell formed from 0.1g resorcinol and 0.05g resorcinol. It can be seen that the two catalysts with different carbon layer thicknesses still maintain nearly 100% of activity after 5 cycles, which fully shows that the carbon shell coated nickel-loaded silicon-based catalyst structure has good aqueous phase hydrogenation activity and cycle stability.
Example 2
The embodiment provides a preparation method of a carbon shell coated copper supported silicon-based catalyst, which specifically comprises the following steps:
s1, 64g of absolute ethanol and 25ml of aqueous ammonia are mixed, followed by the rapid addition of 4.2ml of tetraethyl silicate with vigorous stirring. Stirring for a while to form a white suspension, continuously stirring for 2h, centrifugally separating the obtained white solid, washing with deionized water and ethanol for multiple times, and drying in an oven to obtain the silica microspheres with the diameter of 600-900nm.
S2, mixing a copper nitrate solution (0.195 g of copper nitrate trihydrate is dissolved in 30ml of deionized water) with ammonia water (1.5 ml, about 1.3 g) to obtain a mixed solution; adding 0.13g of silica microspheres into 20ml of deionized water (wherein the mass ratio of the silica microspheres to the metal salt to the ammonia water is 1; adding the silicon dioxide microsphere dispersion liquid into the mixed liquid, ultrasonically dispersing for 30 minutes, transferring the solution into a 100ml polytetrafluoroethylene liner, and putting the liner into an oven to react for 12 hours at the temperature of 140 ℃ to form metal silicate on the surface of the silicon dioxide microsphere. And centrifugally separating a light blue solid obtained after the reaction, washing the light blue solid with deionized water and ethanol for multiple times, drying the light blue solid in a drying oven at the temperature of 60 ℃ for several hours, and collecting the light blue solid to obtain the silicon dioxide coated with the copper silicate.
S3, mixing 0ml of ethanol, 10ml of deionized water and 1ml of ammonia water to obtain a mixed solvent; to the mixed solvent was added 0.2g of copper silicate-coated silica, followed by adding 0.05g of resorcinol and 62.5. Mu.l of an aqueous formaldehyde solution (concentration 30 to 40%), wherein the ratio of resorcinol: formaldehyde: the mass ratio of the silicate is 1:1.2: continuously stirring for 24 hours at normal temperature to generate a layer of phenolic resin high polymer on the surface of the metal silicate, separating out earthy yellow solid, and centrifugally washing with deionized water and ethanol for multiple times to obtain a precursor;
and S4, heating the precursor to 700 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, and keeping for 5 hours to fully carbonize phenolic resin on the surface, thereby preparing the carbon shell coated copper-loaded silicon-based catalyst.
The performance test of the hydrogenolysis reaction stability of the catalyst proves that the catalyst still maintains nearly 100% of activity after 5 times of circulation, which fully shows that the carbon shell coated copper supported silicon-based catalyst structure has good hydrogenolysis reaction activity and circulation stability.
It should be understood by those skilled in the art that the foregoing is only illustrative of several embodiments of the invention, and is not an exhaustive list. It should be noted that many variations and modifications are possible to those skilled in the art, and all variations and modifications that do not depart from the scope of the invention as set forth in the claims should be deemed to be a part of the present invention.
Claims (10)
1. A preparation method of a carbon shell coated metal particle loaded silicon-based catalyst is characterized by comprising the following steps:
s1, dissolving metal salt in deionized water, and then mixing the metal salt with ammonia water to obtain a mixed solution; dispersing the silicon dioxide microspheres into deionized water to obtain silicon dioxide microsphere dispersion liquid; adding the silicon dioxide microsphere dispersion liquid into the mixed liquid, uniformly dispersing, transferring into a reaction kettle, reacting at 70-150 ℃ for 1-48h, separating out green solids, washing with deionized water and ethanol for multiple times, and drying to obtain silicon dioxide wrapped by metal silicate;
s2, mixing ethanol, deionized water and ammonia water according to a volume ratio of 70; adding the silicon dioxide coated by the metal silicate prepared in the step S1 into a mixed solvent, adding resorcinol and formaldehyde aqueous solution, stirring and reacting for 1-48h at 25-50 ℃, separating out earthy yellow solid, washing with deionized water and ethanol for multiple times, and drying to obtain a precursor;
and S3, carrying out carbon thermal reduction treatment on the precursor at high temperature in the atmosphere of nitrogen or inert gas, generating metal particles in situ by using metal silicate, and generating a carbon layer by using a phenolic resin high polymer to obtain the carbon shell coated metal particle loaded silicon-based catalyst.
2. The method for preparing the carbon-shell-coated metal particle-supported silicon-based catalyst according to claim 1, wherein the diameter of the silica microsphere is 600-900nm.
3. The method for preparing the carbon-shell-coated metal particle-supported silicon-based catalyst according to claim 1 or 2, wherein the mass ratio of the silica microspheres, the metal salt and the ammonia water in the step S1 is 1.5.
4. The preparation method of the carbon-shell-coated metal particle-supported silicon-based catalyst according to claim 1, wherein the mass ratio of the resorcinol to the formaldehyde in the aqueous formaldehyde solution to the metal silicate-coated silica in the step S2 is 1.2 (0.5-8), and the concentration of the aqueous formaldehyde solution is 30-40%.
5. The method for preparing the carbon shell coated metal particle loaded silicon-based catalyst according to claim 1, wherein the temperature of the high-temperature carbonization reduction treatment in the step S3 is 600-900 ℃, the carbonization time is 2-10h, and the temperature rise rate is 2-10 ℃/min.
6. The method for preparing a carbon shell coated metal particle supported silicon-based catalyst according to claim 1, wherein the metal salt is one or a combination of two or more single metal element salts containing one or more single metal element salts of iron, cobalt, nickel, copper, zinc, platinum, palladium and ruthenium, or one or a combination of two or more complex metal element salts containing two or more complex metal element salts of iron, cobalt, nickel, copper, zinc, platinum, palladium and ruthenium, or a combination of a single metal element salt and a complex metal element salt.
7. The method for preparing the carbon-shell-coated metal particle-supported silicon-based catalyst according to claim 6, wherein the iron-containing metal salt is one or a combination of more than two of ferric nitrate, ferric chloride, ferric sulfate and ferric acetylacetonate; or the cobalt-containing metal salt is one or the combination of more than two of cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt acetylacetonate; or the nickel-containing metal salt is one or the combination of more than two of nickel nitrate, nickel chloride, nickel sulfate and nickel acetylacetonate; or the copper-containing metal salt is one or the combination of more than two of copper nitrate, copper chloride, copper sulfate and copper acetylacetonate; or the zinc-containing metal salt is one or the combination of more than two of zinc nitrate, zinc chloride, zinc sulfate and zinc acetylacetonate; or the platinum-containing metal salt is one or the combination of more than two of platinum chloride and chloroplatinic acid; or the palladium-containing metal salt is one or the combination of two of palladium chloride and ammonium chloropalladate; alternatively, the ruthenium-containing metal salt is ruthenium chloride.
8. A silicon-based catalyst supported on carbon-shell-coated metal particles prepared by the method of any one of claims 1 to 7.
9. The carbon shell-coated metal particle-supported silicon-based catalyst according to claim 8, wherein the thickness of the carbon shell layer in the catalyst is 10 to 50nm and the diameter of the metal particle is 5 to 20nm.
10. Use of the carbon shell coated metal particle supported silicon based catalyst according to claim 8 or 9 for catalytic hydrogenation, hydrodeoxygenation, hydrogenolysis reactions.
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