CN114950456A - Silicon dioxide nanotube confinement nickel-CeO 2 Nanoparticles and method for preparing same - Google Patents
Silicon dioxide nanotube confinement nickel-CeO 2 Nanoparticles and method for preparing same Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000002071 nanotube Substances 0.000 title claims abstract description 83
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 50
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 47
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 50
- FMQXRRZIHURSLR-UHFFFAOYSA-N dioxido(oxo)silane;nickel(2+) Chemical compound [Ni+2].[O-][Si]([O-])=O FMQXRRZIHURSLR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 239000012695 Ce precursor Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- WITQLILIVJASEQ-UHFFFAOYSA-N cerium nickel Chemical compound [Ni].[Ce] WITQLILIVJASEQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 238000000593 microemulsion method Methods 0.000 claims abstract description 3
- 239000012298 atmosphere Substances 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004530 micro-emulsion Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- 238000005245 sintering Methods 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 33
- 229910052684 Cerium Inorganic materials 0.000 description 22
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 22
- 239000011258 core-shell material Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 11
- 239000012046 mixed solvent Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000006057 reforming reaction Methods 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000005233 alkylalcohol group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 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 description 2
- 239000002994 raw material Substances 0.000 description 2
- 244000292604 Salvia columbariae Species 0.000 description 1
- 235000012377 Salvia columbariae var. columbariae Nutrition 0.000 description 1
- 235000001498 Salvia hispanica Nutrition 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000014167 chia Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- KEAYESYHFKHZAL-OUBTZVSYSA-N sodium-24 Chemical compound [24Na] KEAYESYHFKHZAL-OUBTZVSYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C—CHEMISTRY; METALLURGY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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Abstract
The invention discloses a silicon dioxide nanotube confinement nickel-CeO 2 Nanoparticles and a method for preparing the same. Firstly, synthesizing a multi-wall nickel silicate nanotube as a precursor of a nickel nanoparticle by a hydrothermal method under an alkaline condition with a silicon source precursor; secondly, precipitating a cerium precursor on the surface of the nickel silicate by a precipitation method under the heating condition; thirdly, hydrolyzing a silicon dioxide precursor by using a micro-emulsion method, and coating a uniform silicon dioxide nanotube shell layer on the nickel-cerium precursor; fourthly, under the high temperature and reducing atmosphere, the precursor of the nickel silicate nano tube is decomposed into nickel nano particles and CeO in situ 2 The nano particles are positioned among the nickel nano particles to form silicon dioxide nano tube limited nickel-CeO 2 And (3) nanoparticles. The preparation method can protectProves that under the condition of high load, nickel-CeO is realized 2 The nano particles are completely confined in the silicon dioxide nano tube, and have the advantages of high specific surface area, high oxygen hole concentration, high sintering resistance and the like.
Description
Technical Field
The invention belongs to the field of advanced nano composite materials and technology, and particularly relates to silicon dioxide nanotube confinement nickel-CeO 2 Nano meterGranules and a process for their preparation.
Background
In recent years, the anisotropy and large specific surface area of one-dimensional nanostructures have attracted the interest of many researchers. Confinement of the nanoparticles within the cavities of the one-dimensional nanomaterial can increase metal-support interaction and minimize metal sintering due to the confinement effect, providing an active interface between the metal and the support. However, since the outer and inner surfaces of these nanotubes are similarly hydrophilic, the active material at the outer surface sinters, resulting in higher carbon deposition. (C.E.Figueira, P.F.Moreira, R.Giudici, R.Alves, M.Schmal, appl.Catal.A 550(2018)297-307. S.Aghamamamandi, M.Haghighi, M.Maleki, N.Rahemi, mol.Catal.431(2017)39-48.) on the other hand, CeO 2 Are widely used as supports or promoters for catalysts which, due to their high oxygen storage capacity, are able to supply oxygen species in the reaction, thereby reducing the amount of carbon deposition (d.guo, y.lu, y.ruan, y.zhao, x.b.ma.appl.catal.b 277(2020), m.l.ang, u.oemr, e.t.saw, l.mo, y.kathiraser, b.h.chia, s.kawi, ACS catal.4(2014)3237-3248, e.t.saw, u.oemr, m.l.ang, k.hidajat, s.kawi, chemcatem 7(2015) 3358-3367.). However, in these studies, CeO 2 Sintering also occurs in the reaction process, reducing CeO 2 The carbon removing ability of (1). In addition, the interaction between the functional groups on the surface of the porous carrier and the nanoparticles prevents the nanoparticles from being completely confined. Especially when the nanoparticle loading is high, there is always a small amount of nanoparticles present on the outer surface of the porous support. These small amounts of nanoparticles present on the outer surface of the porous support may cause agglomeration, etc., which affects the overall properties of the material.
Disclosure of Invention
The invention aims to provide a silicon dioxide nanotube confinement nickel-CeO 2 Nanoparticles and a method for preparing the same. The preparation method can ensure high nickel nano-particles and high CeO 2 Under the condition of nano-particle loading, the method realizes complete confinement of the nano-particles in the silicon dioxide nano-tube, and has the advantages of high specific surface area, high oxygen hole concentration, high sintering resistance and CeO 2 Controllable load capacity and the like. When the catalyst is used for catalyzing methane carbon dioxide reforming reaction, oxygen cavities in the catalyst can directly react with carbon deposition to generate other carbon species, so that the catalyst has higher carbon deposition resistance, and can also be applied to other high-temperature reforming reactions. The preparation method disclosed by the invention can realize the effects of wall thickness, specific surface area, oxygen hole concentration and CeO on the silicon dioxide nanotube 2 The control of the load can realize the control of all nickel nano particles and CeO 2 The complete confinement of the nanoparticles. The synthesis raw materials are easy to obtain, the method is simple and rapid, and large-batch synthesis can be realized.
The technical scheme of the invention is as follows: silicon dioxide nanotube confinement nickel-CeO 2 The nanoparticles and their preparation (fig. 1) are as follows: firstly, forming a nickel silicate nanotube by a silicon source and a nickel salt precursor under an alkaline condition by adopting a hydrothermal synthesis method; secondly, precipitating a cerium precursor on the surface of the nickel silicate nanotube by using a precipitating agent under the heating condition; thirdly, hydrolyzing a silicon dioxide precursor under an alkaline condition by using a micro-emulsion method, and coating a uniform silicon dioxide nanotube shell layer on the surface of the nickel-cerium precursor; finally, the silicate nanotube precursor is decomposed into nickel nanoparticle and CeO in situ by high temperature reduction method 2 The nano particles are positioned among the nickel nano particles and completely confined in the shell layer of the silicon dioxide nano tube, and the silicon dioxide nano tube confined nickel-CeO is synthesized 2 And (3) nanoparticles. Adding appropriate solvent, washing, centrifuging to remove alkaline and acidic substances, and drying.
The wall thickness of the synthesized silicon dioxide nano-tube is 3 nm-30 nm, and the synthesized silicon dioxide nano-tube is nickel-CeO 2 The specific surface area of the @ silicon dioxide nanotube core-shell structure is 300m 2 .g -1 ～500m 2 .g -1 nickel-CeO 2 The particle diameter of the nano-particles is 5 nm-8 nm, and the oxygen hole concentration (Ce) 3 + /(Ce 3+ +Ce 4+ ) In the range of (0.2-0.7).
Preferably, the silicon source used for preparing the nickel silicate nanotube is one or more of ethyl orthosilicate, methyl orthosilicate and sodium silicate.
Preferably, the nickel precursor for preparing the nickel silicate nanotube is one or more of nickel nitrate, nickel chloride, nickel acetate and nickel acetylacetonate.
Preferably, the alkali in the hydrothermal synthesis system is one or more of urea, concentrated ammonia water and sodium hydroxide. The pH value is controlled to be 8-12.
Preferably, the reaction time for preparing the nickel silicate nanotube is controlled to be 10-24 hours.
Preferably, the reaction temperature for preparing the nickel silicate nanotube is controlled to be 120-220 ℃.
Preferably, the cerium precursor is prepared by mixing one or more of cerium nitrate, cerium acetate and cerium chloride.
Preferably, the temperature of the precipitation method used is controlled to be 40 ℃ to 150 ℃.
Preferably, the silicon source used for preparing the shell layer of the silicon dioxide nanotube adopts one or more of tetraethoxysilane, methyl orthosilicate and sodium silicate.
Preferably, the reaction time for preparing the silicon dioxide nanotube shell is controlled to be 1-14 days.
Preferably, the silicon dioxide nanotube is limited in nickel-CeO 2 The nanometer particle and its preparation process includes mixing one or several of urea, concentrated ammonia water and sodium hydroxide as alkali in the microemulsion system. The pH value is controlled to be 8-12.
Preferably, the temperature of the high-temperature reduction method is controlled to be 500 ℃ to 900 ℃.
Preferably, the washing solvent used is a mixed solution of an alkyl alcohol and water. Wherein the alkyl alcohol is one or more of methanol, ethanol, and isopropanol. The mass ratio of the alkyl alcohol to the water is 9: 1-1: 9.
Preferably, in the nickel silicate nanotube hydrothermal synthesis system, the silicon source accounts for 0.5 wt% -5 wt%, the nickel precursor accounts for 0.5 wt% -30 wt%, the alkali accounts for 5 wt% -50 wt%, and the balance is water solvent. In a precipitation method system for synthesizing a cerium-nickel precursor, the mass percent of a silicon source is 0.5-5 wt%, the mass percent of a nickel precursor is 0.5-30 wt%, the mass percent of a precipitator is 5-50 wt%, the mass percent of a cerium precursor is 0.5-30 wt%, and the balance is an ethanol-water mixed solution. In a microemulsion system for synthesizing a shell layer of a silicon dioxide nanotube, the mass percent of a silicon source is 0.5-15 wt%, the mass percent of a nickel silicate nanotube is 0.5-50 wt%, the mass percent of a nickel precursor is 0.5-30 wt%, the mass percent of a precipitator is 5-50 wt%, the mass percent of an alkali is 0.5-10 wt%, the mass percent of a surfactant is 0.5-10 wt%, and the balance is an ethanol-water mixed solution, wherein the pH value is controlled to be 8-12.
The invention has the beneficial effects that: the invention discloses a silicon dioxide nanotube confinement nickel-CeO 2 The nano-particles and the preparation method thereof can ensure that under the conditions of high nickel loading (20 wt% -30 wt%) and high cerium loading (20 wt% -30 wt%), nickel-CeO is loaded 2 The nanoparticles are completely confined within the silica nanotubes. It is characterized in that the oxygen hole concentration, the wall thickness and the specific surface area of the silicon dioxide nanotube can be regulated and controlled (3 nm-30 nm) and 300m 2 .g -1 ～500m 2 .g -1 ) And has the advantages of high sintering resistance and the like. When the catalyst is used for catalyzing the methane carbon dioxide reforming reaction, the catalyst has high carbon deposition resistance, and can also be applied to other high-temperature reforming reactions. The preparation method disclosed by the invention has the advantages of easily available synthesis raw materials, simplicity and rapidness, and can realize large-batch synthesis.
Drawings
FIG. 1 shows a limited nickel-CeO structure of a silica nanotube 2 A flow chart for preparing nanoparticles;
FIG. 2 is a transmission electron micrograph of a 20 cerium/nickel silicate nanotube;
FIG. 3 is a transmission electron micrograph of a 20 cerium/nickel silicate nanotube @ silica core-shell structured nanotube;
FIG. 4 is an X-ray diffraction diagram;
FIG. 5 is a transmission electron micrograph of a 20 cerium/nickel silicate nanotube @ silica core-shell structured nanotube after reduction at 700 ℃ for 1 hour;
FIG. 6 is a plot of the EDS spectra for cerium, oxygen, nickel, and silicon elements for a 20 cerium/nickel silicate nanotube @ silica core-shell nanotube;
FIG. 7 is a Ce spectrum of an X-ray photoelectron spectrum of a cerium/nickel @ silica core-shell structured catalyst;
FIG. 8 is a graph of the stability of the carbon dioxide methane reforming of 20 cerium/nickel silicate nanotube @ silica at 700 ℃ for 80 hours;
FIG. 9 is a transmission electron micrograph of 20 cerium/nickel silicate nanotubes @ silica after reaction for 80 hours at 700 ℃ for carbon dioxide methane reforming;
FIG. 10 is a thermogram of 20 cerium/nickel silicate nanotubes @ silica after 80 hours of reaction at 700 ℃ for carbon dioxide methane reforming.
Detailed Description
Example 1:
(1) adding 1.9 g of nickel chloride, 10ml of water, 1.5 g of sodium silicate and 24 g of sodium hydroxide into a hydrothermal kettle in sequence, stirring at room temperature for 30 minutes, putting into a thermostat at 200 ℃, reacting for 10 hours, and taking out. After cooling to room temperature, washing and centrifuging for many times by using a mixed solvent of ethanol and water, and drying at room temperature to obtain the nickel silicate nanotube.
(2) 0.3 g of the nickel silicate nanotube prepared in the previous step is weighed and placed into a 200 ml flask, 120 ml of ethanol is added, and after 30 minutes of ultrasonic treatment, 0.18 g of cerium nitrate is added. Then 7 g of urotropine and 60 ml of deionized water are added into a beaker, and the mixture is transferred into the solution after ultrasonic treatment until the urotropine is dissolved. Finally, the solution was heated at 50 ℃ for 2 hours and cooled to room temperature. The sample was collected by washing with a mixed solvent of ethanol and water several times and centrifuging. As can be seen from FIG. 2, CeO 2 Successfully supported on nickel silicate nanotubes.
(3) The cerium/nickel precursor prepared in the above step was put into a 200 ml flask, and 100 ml of ethanol, 60 ml of water, 2 ml of ammonia (28 wt%) and CTAB were sequentially added and stirred uniformly. Then, 2 ml of ethyl orthosilicate was added, and after 24 hours of reaction, centrifugation was performed. Washing with mixed solvent of ethanol and water, and centrifugingAfter drying at room temperature for 12 hours, the mixture was calcined at 700 ℃ for 4 hours. The specific surface area of the obtained cerium/nickel silicate nanotube @ silicon dioxide nanotube core-shell structure is 416m 2 .g -1 . Wherein, the thickness of the shell layer of the silicon dioxide nanotube is 12.8nm (figure 3). The XRD diffractogram (fig. 4) showed a diffraction peak of silica at 23.5 °. In addition, nickel silicate has a weak diffraction peak intensity. CeO (CeO) 2 The diffraction peaks of (a) appear at 28.5 °, 33.1 °, 47.5 ° and 56.3 °. These all indicate that the cerium/nickel silicate nanotube @ silica nanotube core-shell structure was successfully synthesized.
(4) Reducing the cerium/nickel silicate nanotube @ silicon dioxide nanotube core-shell structure obtained in the last step with pure hydrogen at 700 ℃ for 1 hour to obtain the limited nickel-CeO of the silicon dioxide nanotube 2 Nanoparticles (fig. 5). The nickel particles are about 5.5nm in size. EDS elemental analysis (fig. 6), again demonstrating the presence of these elements in the encapsulated catalyst. From FIG. 7, it can be calculated that the oxygen vacancy concentration (Ce) 3+ /(Ce 3+ +Ce 4+ ) ) a ratio of 0.51, with a higher oxygen vacancy concentration.
Example 2:
(1) adding 1.9 g of nickel nitrate, 10ml of water, 10ml of ethyl orthosilicate and 24 g of urea into a hydrothermal kettle in sequence, stirring at room temperature for 30 minutes, putting into a thermostat at 200 ℃, reacting for 24 hours, and taking out. After cooling to room temperature, washing and centrifuging for many times by using a mixed solvent of ethanol and water, and drying at room temperature to obtain the nickel silicate nanotube.
(2) 0.3 g of the nickel silicate nanotube prepared in the previous step is weighed and put into a 200 ml flask, 120 ml of ethanol is added, and after 30 minutes of ultrasonic treatment, 0.3 g of cerium acetate is added. Then 7 g of urea and 60 ml of deionized water are added into a beaker, and the mixture is transferred into the solution after ultrasonic treatment until the urea is dissolved. Finally, the solution was heated at 100 ℃ for 2 hours and cooled to room temperature. The sample was collected by washing with a mixed solvent of ethanol and water several times and centrifuging.
(3) The cerium/nickel precursor prepared in the above step is put into a 200 ml flask, and 100 ml ethanol, 50 ml water, 2 g sodium hydroxide and CTAB are sequentially added and uniformly stirred. Then, 2 ml of n-hexane was addedMethyl silicate, after 7 days of reaction, centrifuged. Washing with a mixed solvent of ethanol and water for several times, centrifuging, drying at room temperature for 12 hours, and calcining at 700 deg.C for 4 hours. The specific surface area of the obtained cerium/nickel silicate nanotube @ silicon dioxide nanotube core-shell structure is 450m 2 .g -1 . Wherein, the thickness of the shell layer of the silicon dioxide nanotube is 15 nm.
(4) Reducing the cerium/nickel silicate nanotube @ silicon dioxide nanotube core-shell structure obtained in the last step by pure hydrogen at 500 ℃ for 5 hours to obtain silicon dioxide nanotube confinement nickel-CeO 2 And (3) nanoparticles.
Example 3:
(1) adding 1.9 g of nickel acetylacetonate, 10ml of water, 5 ml of ethyl orthosilicate and 10ml of strong ammonia water into a hydrothermal kettle in sequence, stirring for 10 minutes at room temperature, putting into a thermostat at 200 ℃, reacting for 36 hours, and taking out. After cooling to room temperature, washing and centrifuging for many times by using a mixed solvent of ethanol and water, and drying at room temperature to obtain the nickel silicate nanotube.
(2) 0.3 g of the nickel silicate nanotube prepared in the previous step is weighed and put into a 200 ml flask, 120 ml of ethanol is added, and 0.5 g of cerium chloride is added after 30 minutes of ultrasonic treatment. Then 7 g of sodium hydroxide and 60 ml of deionized water are added into a beaker, and the mixture is transferred into the solution after ultrasonic treatment until the mixture is dissolved. Finally, the solution was heated at 120 ℃ for 2 hours and cooled to room temperature. The sample was collected by washing with a mixed solvent of ethanol and water several times and centrifuging.
(3) The cerium/nickel precursor prepared in the above step is put into a 200 ml flask, and 100 ml of ethanol, 50 ml of water, 2 g of urea and CTAB are sequentially added and uniformly stirred. Then, 30 ml of methyl orthosilicate was added, and after 14 days of reaction, it was centrifuged. Washing with a mixed solvent of ethanol and water for several times, centrifuging, drying at room temperature for 12 hours, and calcining at 700 deg.C for 4 hours. The specific surface area of the obtained cerium/nickel silicate nanotube @ silicon dioxide nanotube core-shell structure is 480m 2 .g -1 . Wherein the thickness of the shell layer of the silicon dioxide nanotube is 23 nm.
(4) The nickel silicate nanotube @ silicon dioxide nano-scale obtained in the last stepReducing the core-shell structure of the tube by pure hydrogen for 5 hours at 800 ℃ to obtain the silicon dioxide nanotube confinement nickel-CeO 2 And (3) nanoparticles.
Example 4:
preheating methane (10mL/min), carbon dioxide (10mL/min) and nitrogen (10mL/min) by a preheater at normal pressure, introducing into a 20 cerium/nickel @ silicon dioxide core-shell structure nanotube catalyst fixed bed reactor (700 ℃) and reacting for 80 hours. For this catalyst, the conversion of methane and carbon dioxide stabilized at 76.3% and 80.1%, respectively (fig. 8). The size of the nickel crystal grain of the 20 cerium/nickel @ silica core-shell structure nanotube catalyst can be calculated to be 7.5nm (fig. 9) through a transmission electron microscope, and compared with a fresh catalyst (5.5nm), the size of the nickel crystal grain before and after the reaction is not changed greatly, which indicates that sintering does not occur in the reaction process. From thermogravimetric analysis, the carbon deposition of the 20 cerium/nickel @ silica core-shell structure nanotube catalyst was 17.9% (fig. 10).
Claims (10)
1. Silicon dioxide nanotube confinement nickel-CeO 2 The preparation method of the nano-particles is characterized by comprising the following steps: comprises the following steps: firstly, forming a precursor of a nickel silicate nanotube by a silicon source precursor under an alkaline condition by adopting a hydrothermal synthesis method; secondly, precipitating a cerium precursor on the surface of the nickel silicate by using a precipitating agent under the heating condition; thirdly, hydrolyzing a silicon dioxide precursor under an alkaline condition by using a micro-emulsion method, and coating a uniform silicon dioxide nanotube shell layer on the nickel-cerium precursor; fourthly, under the high temperature and reducing atmosphere, the precursor of the silicate nano tube is decomposed into nickel nano particles and CeO in situ 2 The nano particles are positioned among the nickel nano particles and completely confined in the shell layer of the silicon dioxide nano tube to form silicon dioxide nano tube confined nickel-CeO 2 And (3) nanoparticles.
2. The silica nanotube confined nickel-CeO of claim 1 2 The preparation method of the nano-particles is characterized by comprising the following steps: the silicon source for preparing the nickel silicate nanotube adopts one or more of ethyl orthosilicate, methyl orthosilicate and sodium silicateAnd (4) mixing.
3. The silica nanotube confined nickel-CeO of claim 1 2 The preparation method of the nano-particles is characterized by comprising the following steps: the nickel precursor for preparing the nickel silicate nanotube is one or more of nickel nitrate, nickel chloride, nickel acetate and nickel acetylacetonate.
4. The silica nanotube confined nickel-CeO of claim 1 2 The preparation method of the nano-particles is characterized by comprising the following steps: the reaction temperature of the hydrothermal method is 120-220 ℃, and the reaction time is 10-36 hours.
5. The silica nanotube confined nickel-CeO of claim 1 2 The preparation method of the nano-particles is characterized by comprising the following steps: the precipitator in the precipitation synthesis system is one or more of urotropine, urea, concentrated ammonia water and sodium hydroxide; the cerium precursor in the precipitation synthesis system is one or more of cerium nitrate, cerium acetate and cerium chloride.
6. The silica nanotube-confined nickel-CeO of claim 1 2 The preparation method of the nano-particles is characterized by comprising the following steps: the temperature of the precipitation method is controlled to be 40-150 ℃.
7. The silica nanotube confined nickel-CeO of claim 1 2 The preparation method of the nano-particles is characterized by comprising the following steps: the silicon source used for preparing the silicon dioxide nanotube shell layer is one or more of tetraethoxysilane, methyl orthosilicate and sodium silicate; the reaction time for preparing the silicon dioxide nanotube shell is 1-14 days.
8. The silica nanotube confined nickel-CeO of claim 1 2 A method for producing nanoparticles, characterized in thatThe method comprises the following steps: the alkali in the microemulsion system is one or more of urea, concentrated ammonia water and sodium hydroxide; the pH value is 8-12.
9. The silica nanotube confined nickel-CeO of claim 1 2 The preparation method of the nano-particles is characterized by comprising the following steps: the high temperature and the reduction temperature are 500-900 ℃.
10. The silica nanotube-confined nickel-CeO of claim 1 2 The preparation method of the nano-particles is characterized by comprising the following steps: in a nickel silicate nanotube hydrothermal synthesis system, the mass percent of a silicon source is 0.5-5 wt%, the mass percent of a nickel precursor is 0.5-30 wt%, the mass percent of an alkali is 5-50 wt%, and the balance is a water solvent; in a precipitation method system for synthesizing a cerium-nickel precursor, the mass percent of a silicon source is 0.5-5 wt%, the mass percent of a nickel precursor is 0.5-30 wt%, the mass percent of a precipitator is 5-50 wt%, the mass percent of a cerium precursor is 0.5-30 wt%, and the balance is an ethanol-water mixed solution; in a microemulsion system for synthesizing a shell layer of a silicon dioxide nanotube, the mass percent of a silicon source is 0.5-15 wt%, the mass percent of a nickel silicate nanotube is 0.5-50 wt%, the mass percent of a nickel precursor is 0.5-30 wt%, the mass percent of a precipitator is 5-50 wt%, the mass percent of an alkali is 0.5-10 wt%, the mass percent of a surfactant is 0.5-10 wt%, and the other components are ethanol-water mixed solution, and the pH value is controlled to be 8-12.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140144803A (en) * | 2013-06-11 | 2014-12-22 | 연세대학교 산학협력단 | Silica-coated Ni supported catalyst, method for manufacturing therof and production method of synthesis gas using the catalyst |
| CN106076347A (en) * | 2016-05-31 | 2016-11-09 | 贵州理工学院 | A kind of hollow core shell mould metal silicate/cerium oxide nanoparticles and preparation method thereof |
| CN108453265A (en) * | 2018-04-24 | 2018-08-28 | 贵州理工学院 | A kind of Silica Nanotube confinement nano nickel particles and preparation method thereof |
| CN108525669A (en) * | 2018-05-04 | 2018-09-14 | 贵州理工学院 | A kind of high degree of dispersion Silica Nanotube supported nickel catalyst and preparation method thereof |
| CN108786822A (en) * | 2018-02-08 | 2018-11-13 | 贵州理工学院 | A kind of methane reforming multinuclear shell hollow type nickel-nisiloy hydrochlorate-CeO2Preparation method |
| CN109529857A (en) * | 2018-12-10 | 2019-03-29 | 江苏大学 | Ni@SiO2@CeO2The preparation method of nucleocapsid catalyst and its application in methane carbon dioxide reformation |
-
2022
- 2022-06-16 CN CN202210687654.0A patent/CN114950456A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140144803A (en) * | 2013-06-11 | 2014-12-22 | 연세대학교 산학협력단 | Silica-coated Ni supported catalyst, method for manufacturing therof and production method of synthesis gas using the catalyst |
| CN106076347A (en) * | 2016-05-31 | 2016-11-09 | 贵州理工学院 | A kind of hollow core shell mould metal silicate/cerium oxide nanoparticles and preparation method thereof |
| CN108786822A (en) * | 2018-02-08 | 2018-11-13 | 贵州理工学院 | A kind of methane reforming multinuclear shell hollow type nickel-nisiloy hydrochlorate-CeO2Preparation method |
| CN108453265A (en) * | 2018-04-24 | 2018-08-28 | 贵州理工学院 | A kind of Silica Nanotube confinement nano nickel particles and preparation method thereof |
| CN108525669A (en) * | 2018-05-04 | 2018-09-14 | 贵州理工学院 | A kind of high degree of dispersion Silica Nanotube supported nickel catalyst and preparation method thereof |
| CN109529857A (en) * | 2018-12-10 | 2019-03-29 | 江苏大学 | Ni@SiO2@CeO2The preparation method of nucleocapsid catalyst and its application in methane carbon dioxide reformation |
Non-Patent Citations (2)
| Title |
|---|
| SIXUE LIN ET AL.: "Trifunctional strategy for the design and synthesis of a Ni-CeO2@SiO2 Catalyst with remarkable low-temperature sintering and coking resistance for methane dry reforming", CHINESE JOURNAL OF CATALYSIS, vol. 42, no. 10, pages 2 * |
| 李琳等: "催化剂Ni-CeO2的制备及其在甲烷二氧化碳重整反应中的催化性能", 中南民族大学学报（自然科学版）, vol. 37, no. 4, pages 1 * |
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