CN115090293A - 一种核壳型二氧化铈纳米棒负载镍催化剂及其制备方法 - Google Patents
一种核壳型二氧化铈纳米棒负载镍催化剂及其制备方法 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 88
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000002073 nanorod Substances 0.000 title claims abstract description 52
- 239000011258 core-shell material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 15
- FMQXRRZIHURSLR-UHFFFAOYSA-N dioxido(oxo)silane;nickel(2+) Chemical compound [Ni+2].[O-][Si]([O-])=O FMQXRRZIHURSLR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 6
- 238000000593 microemulsion method Methods 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 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 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 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 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- 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 4
- 239000004530 micro-emulsion Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000002563 ionic surfactant Substances 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 16
- 239000001301 oxygen Substances 0.000 abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 abstract description 16
- 238000011068 loading method Methods 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 125000005233 alkylalcohol group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-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
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- WEOYIFRDQDXVKP-UHFFFAOYSA-M O=[Si]=O.[O-2].[OH-].[Ce+3] Chemical group O=[Si]=O.[O-2].[OH-].[Ce+3] WEOYIFRDQDXVKP-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- -1 cerium dioxide-nickel Chemical compound 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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Abstract
本发明公开了一种核壳型二氧化铈纳米棒负载镍催化剂制备方法,首先采用水热法,在碱性条件下合成二氧化铈纳米棒;再采用微乳液法,将二氧化硅前驱体在碱性条件下水解,在二氧化铈纳米棒表面包覆一层均匀的二氧化硅,形成二氧化铈纳米棒‑二氧化硅核壳结构;然后利用水热法,将二氧化铈纳米棒‑二氧化硅核壳结构和镍的前驱体在碱性条件下处理,得到二氧化铈纳米棒‑镍硅酸盐核壳结构;最后用高温还原法,将镍硅酸盐前驱体原位分解为粒径小且高度分散的镍纳米颗粒负载在二氧化铈纳米棒上。所述的催化剂具有氧空穴浓度高、抗烧结能力强、镍负载量可调、镍硅酸盐壳层厚度可控等优点。
Description
技术领域
本发明属于先进纳米复合材料与技术领域,具体涉及一种核壳型二氧化铈纳米棒负载镍催化剂及其制备方法。
背景技术
二氧化铈具有显著的储氧能力,并能通过Ce4+/Ce3+的氧化还原来不断释放填充氧空穴中的氧,因此常用于甲烷二氧化碳重整反应中催化剂的设计,以提高催化剂的抗积碳能力。理论研究证明,氧空穴在二氧化铈不同晶面上的形成能不同,这其中以(110)晶面的氧空穴形成能最低,这说明二氧化铈的(110)晶面上更容易形成氧空位(R.Si,M.Flytzani-Stephanopoulos,Angew.Chem.Int.Ed.47(15)(2008)2884-2887.A.D.Mayernick,M.J.Janik,J.Phys.Chem.C 112(38)(2008)14955-14964.)。因此,相比于其它形状的二氧化铈,如立方体、多面体,二氧化铈纳米棒具有更高的氧空穴浓度,因为它拥有四个(110)晶面,更有利于提高催化剂性能。然而,使用传统浸渍法制备的镍/二氧化铈负载型催化剂始终遭受着高温下载体烧结和结构坍塌的问题,进而导致反应中氧空穴浓度和抗积碳能力的降低。在这一点上,二氧化硅作为一种惰性材料,常被用作核壳型催化剂的壳层,以提高催化剂的热稳定性(Z.Li,Z.Wang,B.Jiang,S.Kawi,Catal.Sci.Technol.8(13)(2018)3363-3371.)。此外,二氧化硅层还能在碱性水热条件下与镍源反应生成镍硅酸盐,这种前驱体在还原后能分解成尺寸较小的镍纳米颗粒,同时,镍与镍硅酸盐之间的相互作用也有利于催化剂在甲烷二氧化碳重整中性能的提高(Z.Li,L.Mo,Y.Kathiraser,S.Kawi,ACS Catal.4(5)(2014)1526-1536.)。
发明内容
本发明要解决的技术问题是:提供一种核壳型二氧化铈纳米棒负载镍催化剂及其制备方法。该制备方法能够同时防止二氧化铈纳米棒和镍纳米颗粒的烧结,具有高氧空穴浓度、高的抗烧结能力、镍负载量可调、镍硅酸盐壳层厚度可控等优点。当该催化剂用于催化甲烷二氧化碳重整反应时,具有高的抗积碳能力,在其它催化领域也有重要的应用前景。本发明所报道的制备方法,能够实现对镍硅酸盐壳层厚度、比表面积、氧空穴浓度、镍负载量的控制,能够同时防止二氧化铈纳米棒和镍纳米颗粒的烧结。合成原料易得、方法简单迅速,能够实现大批量的合成。
本发明的技术方案是:一种核壳型二氧化铈纳米棒负载镍催化剂的制备方法,首先,采用水热合成法,把铈源在碱性条件下,形成二氧化铈纳米棒;第二,利用水/乙醇/表面活性剂微乳液法,将硅源在碱性条件下水解,在二氧化铈纳米棒表面包覆一层均匀的二氧化硅壳层,形成二氧化铈纳米棒-二氧化硅核壳结构;第三,利用水热法,将二氧化铈纳米棒-二氧化硅核壳结构和镍前驱体在碱性条件下处理,得到二氧化铈纳米棒-镍硅酸盐前驱体核壳结构,加入溶剂洗涤、离心分离除去碱性、酸性物质,干燥、煅烧即可;第四,在高温、还原气氛下,将镍硅酸盐前驱体原位分解为镍纳米颗粒负载在二氧化铈纳米棒表面。
制备二氧化铈纳米棒所用的铈源为硝酸铈、醋酸铈和氯化铈中的一种或一种以上混合。
使用水热法制备二氧化铈纳米棒的反应温80℃~120℃;反应时间20~36小时。
硅源为正硅酸乙酯、正硅酸甲酯和硅酸钠中的一种或一种以上混合。
所述的制备二氧化铈纳米棒-二氧化硅壳层结构的反应时间控制在1~7天。
所述的制备二氧化铈纳米棒-二氧化硅壳层结构微乳液法中表面活性剂为非离子型表面活性剂或离子型表面活性剂。
所述的制备二氧化铈纳米棒-二氧化硅壳层结构微乳液法中的碱采用浓氨水、尿素和氢氧化钠中的一种或一种以上混合,pH值8~12。
所述的镍前驱体为硝酸镍、氯化镍和乙酰丙酮镍中的一种或一种以上混合。
所述的水热合成体系中的碱为浓氨水、尿素和氢氧化钠中的一种或一种以上混合,pH值8~12。
所述的第(3)步骤中所述的水热合成体系中,反应温度控制在120℃~200℃;反应时间控制在0.5~48小时。
所使用的洗涤溶剂采用烷基醇与水的混合溶液。其中烷基醇是甲醇、乙醇和异丙醇中的一种或一种以上混合。烷基醇和水的质量比为9:1~1:9。
高温还原法的温度控制在600℃~900℃。高温还原法的还原气体为5%氢气和氮气的混合气、99.99%氢气、5%一氧化碳和氮气的混合气、99.99%一氧化碳中的一种或一种以上混合。
在合成二氧化铈纳米棒的水热合成体系中,铈源的质量百分比为0.5wt%~5wt%,氢氧化钠的质量百分比为10wt%~20wt%,其它为水溶液。在合成二氧化铈纳米棒-二氧化硅核壳结构的微乳液体系中,二氧化铈纳米棒的质量百分比为0.1wt%~5wt%,二氧化硅前驱体的质量百分比为0.5wt%~10wt%,碱的质量百分比为0.5wt%~10wt%,其它为乙醇、水混合溶液,pH值控制在8~12。在合成二氧化铈-镍硅酸盐前驱体核壳结构的水热合成体系中,镍源前驱体的质量百分比为0.5wt%~10wt%,二氧化铈-二氧化硅核壳结构的质量百分比为1wt%~20wt%,其它为乙醇和水混合溶液,pH值控制在8~12。。
本发明的有益效果:本发明所合成的一种核壳型二氧化铈纳米棒负载镍催化剂及其制备方法,能够同时防止二氧化铈纳米棒和镍纳米颗粒的烧结。镍硅酸盐壳层厚度可调控(5nm~20nm)、比表面积可调控(80m2.g-1~200m2.g-1),氧空穴浓度可调控(0.20~0.40)、镍颗粒高度分散(粒径4nm~7nm)等优点。当用于催化甲烷二氧化有重整反应时,具有高的抗烧结和抗积碳能力,在其它催化领域也有重要的应用前景。本发明所报道的制备方法,合成原料易得、方法简单迅速,能够实现大批量的合成。
附图说明
图1为核壳型二氧化铈纳米棒负载镍催化剂的制备方法示意图;
图2为二氧化铈纳米棒的透射电镜图;
图3为二氧化铈纳米棒@二氧化硅核壳结构的透射电镜图;
图4为二氧化铈纳米棒@镍硅酸盐核壳结构的透射电镜图;
图5为还原后核壳型二氧化铈纳米棒负载镍催化剂的透射电镜图;
图6为还原后催化剂的X射线衍射图;
图7为还原后催化剂的X射线光电子能谱Ce谱图;
图8为还原后浸渍法制备镍/二氧化铈的透射电镜图;
图9为甲烷二氧化碳重整在700℃反应24小时的性能对比试验;
图10为甲烷二氧化碳重整在700℃反应24小时后的透射电镜图;
图11为甲烷二氧化碳重整在700℃反应24小时后的热重图。
具体实施方式
实例1:
(1)将4.35克硝酸铈和48克氢氧化钠分别溶于25毫升和175毫升去离子水中。待氢氧化钠溶液冷却后,将硝酸铈溶液缓慢倒入氢氧化钠溶液中,在室温下充分搅拌30分钟后,将浆液转移到有特氟隆内衬的高压水热反应釜内,在100℃下反应24小时。所得沉淀物用去离子水和无水乙醇交替洗涤、离心后于60℃下干燥12小时,得到二氧化铈纳米棒(图2)。
(2)将0.8克二氧化铈纳米棒溶解在60毫升去离子水和240毫升无水乙醇混合液中,并在超声辅助下进行分散。然后加入0.32克十六烷基三甲基溴化铵和2毫升浓氨水,室温下继续搅拌30分钟,随后缓慢滴加2毫升正硅酸乙酯,室温搅拌48小时。最后,用去离子水离心洗涤得到二氧化铈@二氧化硅(图3)。
(3)将上一步得到的二氧化铈@二氧化硅溶解在15毫升去离子水和80毫升无水乙醇的混合溶液中,并在超声辅助下充分分散。然后加入0.5克硝酸镍,室温下充分搅拌30分钟。接着加入3毫升浓氨水,继续搅拌30分钟后,将混合溶液转移到水热反应釜中,在180℃下反应3小时。待反应釜自然冷却至室温后,倒去上层清液,将沉淀物用去离子水清洗和离心,直到pH值呈中性。最后,产品在60℃下干燥过夜,并在700℃下空气煅烧4小时,得到二氧化铈@镍硅酸盐。如图4所示,出现针状的镍硅酸盐物种。
(4)将二氧化铈@镍硅酸盐核壳结构复合物在纯氢气气氛下,700℃还原1小时后,即得高度分散的镍纳米颗粒(图5)。所得核壳型二氧化铈负载镍催化剂的镍硅酸盐层厚度为9nm,比表面积为84m2·g-1,镍负载量为8wt%。在X射线衍射图6中,与传统浸渍法制备的镍/二氧化铈催化剂相比,二氧化铈@镍硅酸盐的二氧化铈衍射峰强度较弱,表明核壳结构的成功合成。镍纳米颗粒粒径从图5中估计为4.5nm,从图6中计算的晶粒大小为7.4nm,从图7中计算得到氧空穴浓度(Ce3+/(Ce3++Ce4+))比值为0.33,具有较高的氧空穴浓度。
(5)对比样品的制备:用超声辅助浸渍法制备镍/二氧化铈纳米棒催化剂,镍的负载量为8wt%。步骤为称取一定量的硝酸镍和二氧化铈纳米棒,溶于30毫升无水乙醇中,超声2小时后,在60℃水浴中搅拌蒸干,然后于60℃烘箱中干燥12小时,700℃煅烧4小时,再在氢气气氛下700℃还原1小时。如图8所示,镍的粒径为7.9nm,同时二氧化铈纳米棒上可观察到孔洞形成。
实例2:
(1)将4.35克醋酸铈和48克氢氧化钠分别溶于25毫升和175毫升去离子水中。待氢氧化钠溶液冷却后,将醋酸铈溶液缓慢倒入氢氧化钠溶液中,在室温下充分搅拌30分钟后,将浆液转移到有特氟隆内衬的高压水热反应釜内,在100℃下反应30小时。所得沉淀物用去离子水和绝对乙醇交替洗涤、离心后于60℃下干燥12小时,得到二氧化铈纳米棒。
(2)将0.8克二氧化铈纳米棒溶解在60毫升去离子水和240毫升无水乙醇混合液中,并在超声辅助下进行分散。然后加入0.32克十六烷基三甲基溴化铵和2毫升浓氨水,室温下继续搅拌30分钟,缓慢滴加2毫升正硅酸甲酯,室温搅拌54小时。最后,用去离子水离心洗涤得到二氧化铈@二氧化硅。
(3)将上一步得到二氧化铈@二氧化硅溶解在15毫升去离子水和80毫升无水乙醇的混合溶液中,并在超声辅助下充分分散。然后加入1克氯化镍,室温下充分搅拌30分钟。接着加入3毫升浓氨水,继续搅拌30分钟后,将混合溶液转移到水热反应釜中,在150℃下反应6小时。待反应釜自然冷却至室温后,倒去上层清液,将沉淀物用去离子水清洗和离心,直到pH值呈中性。最后,产品在60℃下干燥过夜,并在700℃下空气煅烧4小时,700℃下氢气还原1小时。所得核壳型二氧化铈负载镍催化剂的镍硅酸盐层厚度为7nm,比表面积为93m2·g-1,镍负载量为13wt%,氧空穴浓度为0.29。
实例3:
(1)将4.35克氯化铈和48克氢氧化钠分别溶于25毫升和175毫升去离子水中。待氢氧化钠溶液冷却后,将氯化铈溶液缓慢倒入氢氧化钠溶液中,在室温下充分搅拌30分钟后,将浆液转移到有特氟隆内衬的高压水热反应釜内,在120℃下反应20小时。所得沉淀物用去离子水和绝对乙醇交替洗涤、离心后于60℃下干燥12小时,得到二氧化铈纳米棒。
(2)将0.4克二氧化铈纳米棒溶解在60毫升去离子水和240毫升无水乙醇混合液中,并在超声辅助下进行分散。然后加入0.32克十六烷基三甲基溴化铵和2克尿素,室温下继续搅拌30分钟,随后缓慢滴加2毫升正硅酸甲酯,室温搅拌36小时。最后,用去离子水离心洗涤得到二氧化铈@二氧化硅。
(3)将上一步得到二氧化铈@二氧化硅溶解在15毫升去离子水和80毫升无水乙醇的混合溶液中,并在超声辅助下充分分散。然后加入1克乙酰丙酮镍,室温下充分搅拌30分钟。接着加入3毫升浓氨水,继续搅拌30分钟后,将混合溶液转移到水热反应釜中,在180℃下反应1小时。待反应釜自然冷却至室温后,倒去上层清液,将沉淀物用去离子水清洗和离心,直到pH值呈中性。最后,产品在60℃下干燥过夜,并在700℃下空气煅烧4小时,700℃氢气还原1小时。所得核壳型二氧化铈负载镍催化剂的镍硅酸盐层厚度为18nm,比表面积为131m2·g-1,镍负载量为21wt%,氧空穴浓度为0.26。
性能测试:
将催化剂装入固定床反应器,在常压下,将CH4、CO2和N2以1:1:1的方式(反应空速为36L·g-1 cat·h-1),通入反应器(700℃),反应24小时(图9)。可以看出,与使用传统浸渍法制备的镍/二氧化铈催化剂相比,核壳型二氧化铈负载镍催化剂均表现出更好的催化性能。从反应后催化剂的透射电镜表征中(图10)可以看出,核壳型二氧化铈负载镍催化剂具有更好的抗烧结能力,仍旧保持了原本的二氧化铈纳米棒形貌(图10a-c),而浸渍法制备的镍/二氧化铈催化剂发生了严重的烧结,纳米棒形貌改变(图10d)。同时,镍硅酸盐厚度为9nm的核壳型二氧化铈负载镍催化剂上的镍纳米颗粒的烧结程度最低,生成的碳纳米管量最少(图10b)。另外,从图11热重分析还可以看出,硅酸盐壳层厚度为9nm的核壳型二氧化铈负载镍催化剂具有最低的重量损失,抗积碳能力强。
Claims (10)
1.一种核壳型二氧化铈纳米棒负载镍催化剂的制备方法,其特征在于:首先,采用水热合成法,把铈源在碱性条件下,形成二氧化铈纳米棒;第二,利用水/乙醇/表面活性剂微乳液法,将硅源在碱性条件下水解,在二氧化铈纳米棒表面包覆一层均匀的二氧化硅壳层,形成二氧化铈纳米棒-二氧化硅核壳结构;第三,利用水热法,将二氧化铈纳米棒-二氧化硅核壳结构和镍前驱体在碱性条件下处理,得到二氧化铈纳米棒-镍硅酸盐前驱体核壳结构,加入溶剂洗涤、离心分离除去碱性、酸性物质,干燥、煅烧即可;第四,在高温、还原气氛下,将镍硅酸盐前驱体原位分解为镍纳米颗粒负载在二氧化铈纳米棒表面。
2.根据权利要求1所述的一种核壳型二氧化铈纳米棒负载镍催化剂的制备方法,其特征在于:制备二氧化铈纳米棒所用的铈源为硝酸铈、醋酸铈和氯化铈中的一种或一种以上混合。
3.根据权利要求1所述的一种核壳型二氧化铈纳米棒负载镍催化剂的制备方法,其特征在于:使用水热法制备二氧化铈纳米棒的反应温80℃~120℃;反应时间20~36小时。
4.根据权利要求1所述的一种核壳型二氧化铈纳米棒负载镍催化剂的制备方法,其特征在于:硅源为正硅酸乙酯、正硅酸甲酯和硅酸钠中的一种或一种以上混合。
5.根据权利要求1所述的一种核壳型二氧化铈纳米棒负载镍催化剂的制备方法,其特征在于:所述的制备二氧化铈纳米棒-二氧化硅壳层结构的反应时间控制在1~7天。
6.根据权利要求1所述的一种核壳型二氧化铈纳米棒负载镍催化剂的制备方法,其特征在于:所述的制备二氧化铈纳米棒-二氧化硅壳层结构微乳液法中表面活性剂为非离子型表面活性剂或离子型表面活性剂。
7.根据权利要求1所述的一种核壳型二氧化铈纳米棒负载镍催化剂的制备方法,其特征在于::所述的制备二氧化铈纳米棒-二氧化硅壳层结构微乳液法中的碱采用浓氨水、尿素和氢氧化钠中的一种或一种以上混合,pH值8~12。
8.根据权利要求1所述的一种核壳型二氧化铈纳米棒负载镍催化剂的制备方法,其特征在于:所述的镍前驱体为硝酸镍、氯化镍和乙酰丙酮镍中的一种或一种以上混合。
9.根据权利要求1所述的一种核壳型二氧化铈纳米棒负载镍催化剂的制备方法,其特征在于:所述的水热合成体系中的碱为浓氨水、尿素和氢氧化钠中的一种或一种以上混合,pH值8~12。
10.根据权利要求1所述的一种核壳型二氧化铈纳米棒负载镍催化剂的制备方法,其特征在于:所述的第(3)步骤中所述的水热合成体系中,反应温度控制在120℃~200℃;反应时间控制在0.5~48小时。
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