CN112387290A - Fe3O4负载的金属纳米颗粒的制备方法及其应用 - Google Patents
Fe3O4负载的金属纳米颗粒的制备方法及其应用 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000002082 metal nanoparticle Substances 0.000 title claims description 33
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 133
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 51
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 49
- 239000001257 hydrogen Substances 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 27
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 27
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 21
- 238000005303 weighing Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000010953 base metal Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000010970 precious metal Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- 230000005291 magnetic effect Effects 0.000 abstract description 7
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 96
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 63
- 239000002105 nanoparticle Substances 0.000 description 34
- 238000003917 TEM image Methods 0.000 description 21
- 239000011259 mixed solution Substances 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 229910052697 platinum Inorganic materials 0.000 description 11
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 10
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000010948 rhodium Substances 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- -1 hydrogen Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910018979 CoPt Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910016551 CuPt Inorganic materials 0.000 description 1
- 229910005335 FePt Inorganic materials 0.000 description 1
- 229910002644 NiRh Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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Abstract
本文发明了Fe3O4载体参与的催化剂来催化产氢,以硼氢化钠为原料,然后以不同金属以及不同金属比例制得催化剂,分散到水中催化硼氢化钠产氢。本实验中由于催化剂具有磁性效果,因此回收利用较为方便,并且具有良好的产氢效果,本文采用此方法制备了十二种不同的金属配比以及不同金属催化剂来催化硼氢化钠产氢,其中Ni2Pt@Fe3O4、Ni2Pd@Fe3O4、Ni2Rh@Fe3O4具有最优越的催化产氢效果。
Description
技术领域
本发明涉及Fe3O4负载的金属纳米颗粒的制备方法及其应用,属于功能材料领域。
背景技术
近年来人口和经济的快速增长导致了世界范围内对能源的需求不断增加,不断增长的化石燃料消耗导致大量温室气体排放,特别是二氧化碳,导致全球变暖和极端气候变化。开发以可再生能源为基础的清洁替代燃料是最重要关注的问题之一。氢由于其能量密度高、可再生性好,被认为是一种有吸引力的绿色燃料,也是一种很有前途的高效能源载体,可用于应对未来的能源挑战。从环境和经济的角度来看,可再生能源系统的发展都是一个关键问题,人们对石油短缺和温室气体排放的担忧日益加剧,这激发了人们对向氢经济转型的兴趣。但是蒸汽重整、煤气化、水的高温热解、水的电解等传统制氢方法效率低、能耗高,利用大规模、低能耗,无污染氢生产技术对绿色经济社会和工业生产的发展,具有重要意义。
从文献报道来看,Fe3O4负载的NiPt金属纳米颗粒尚未报道,并且具有非常好的催化效果,具有合成方法简单、合成时间较短、纳米颗粒易负载、催化效率高等优点。在金属纳米颗粒产氢具有良好的发展前景。
发明内容
本发明的技术方案以Fe3O4负载金属纳米颗粒为催化剂催化硼氢化钠水解产氢,此方法包括以下步骤:
Fe3O4负载的金属纳米颗粒制备方法,包括以下步骤:
步骤1:将去离子水预热到60-70℃,然后加入FeCl3·6H2O及FeSO4·7H2O,搅拌;
步骤2:将氨水预热到60-70℃后滴加到步骤1的溶液中搅拌反应,产物经冷却离心洗涤,干燥即可得到Fe3O4;
步骤3:称取步骤2所制的Fe3O4分散到水中,超声分散均匀;
步骤4:向步骤3中加入金属溶液,搅拌2-3h后加如NaBH4,继续搅拌反应,产物经离心洗涤、真空干燥即可制得Fe3O4负载的金属纳米颗粒。
步骤1中FeCl3·6H2O及FeSO4·7H2O的质量比为1.6-2.0:1。
所述的氨水的体积浓度为0.01-0.05%。
步骤4中,所述的金属溶液包括贱金属溶液及贵金属溶液的混合物,其中,贱金属溶液包括氯化镍、氯化铁、氯化钴、氯化铜中的任意一种;贵金属溶液包括氯化氯化铂、氯化铑、四氯金酸、四氯钯酸钾的任意一种。其中,金属溶液的物质的量浓度为2.84×10-2 mmol/mL。
贱金属溶液及贵金属溶液的混合物中,贱金属与贵金属的元素摩尔比为0.5-3。优选为贱金属与贵金属的元素摩尔比为2。
Fe3O4、金属溶液、NaBH4的物质的量比为0.3-0.5:0.4-0.6:0.4-0.6。作为优选方案, Fe3O4、金属溶液、NaBH4的物质的量比为0.4319:0.0568:0.5551。
本发明将所述制备得到的Fe3O4负载的金属纳米颗粒作为催化剂在催化硼氢化钠产氢上的应用。
催化硼氢化钠产氢过程中Fe3O4负载的金属纳米颗粒的量是硼氢化钠的0.5-2.0%。
作为优选方案,催化硼氢化钠产氢过程中Fe3O4负载的金属纳米颗粒的量是硼氢化钠的1.0%。
Fe3O4负载的金属纳米颗粒催化硼氢化钠产氢步骤如下:
步骤1:称取磁性Fe3O4负载的金属纳米颗粒25mg于产氢反应瓶内,再用注射器打入4mL水,封口置于30℃水浴锅中搅拌;
步骤2:称取1mmol NaBH4溶于1mL水中;
步骤3:用注射器吸取步骤2中的硼氢化纳溶液,注入步骤1中的反应瓶中,立即开始计时并封好口;
步骤4:每间隔10s记录对应时间下的氢气体积。
附图说明
图1是实施例1制备的Fe3O4的TEM图。
图2是实施例1制备的Fe3O4的XRD图。
图3是本发明制备的Ni2Pt@Fe3O4的TEM图。
图4是本发明制备的Ni2Pt@Fe3O4的XRD图。
图5是本发明制备的NiPt2@Fe3O4的TEM图。
图6是本发明制备的NiPt@Fe3O4的TEM图。
图7是本发明制备的Ni3Pt@Fe3O4的TEM图。
图8是本发明制备的Pt@Fe3O4的TEM图。
图9是本发明制备的Ni@Fe3O4的TEM图。
图10是Fe3O4负载不同Pt、Ni比例以及纯Pt与纯Ni所制得的纳米颗粒催化1 mmolNaBH4水解的产氢速率图。
图11是实施例1制备的Fe3O4的磁性效果图,A为Fe3O4溶解在水中的,B为瓶外加磁铁后的效果图。
图12是ZIF-8的磁性效果图,A为ZIF-8溶解在水中的,B为瓶外加磁铁后的效果图。
图13是Ni2Pt@Fe3O4纳米颗粒五次循环后的产氢效果。
图14是ZIF-8负载的NiPt纳米颗粒两次循环后的产氢效果。
图15是本发明制备的Ni2Pd@Fe3O4的TEM图。
图16是本发明制备的Ni2Rh@Fe3O4的TEM图。
图17是本发明制备的Ni2Au@Fe3O4的TEM图。
图18是Fe3O4负载的Ni与不同贵金属所制得的纳米颗粒催化1mmol NaBH4水解的产氢速率图。
图19是本发明制备的Fe2Pt@Fe3O4的TEM图。
图20是本发明制备的Cu2Pt@Fe3O4的TEM图。
图21是本发明制备的Co2Pt@Fe3O4的TEM图。
图22是Fe3O4负载的Pt与不同贱金属所制得的纳米颗粒催化1mmol NaBH4水解的产氢速率图。
具体实施方式
实施例1
本发明采用的制备方案包括以下步骤:
步骤1:量取180mL的去离子水,预热到70℃,然后加0.17g FeCl3·6H2O和0.11gFeSO4· 7H2O,搅拌1h;
步骤2:取0.4mL氨水稀释到20mL预热到70℃,滴加到步骤1中的溶液中搅拌10min,冷却离心洗涤,60℃干燥4h,制备得到Fe3O4。
图1是制备的Fe3O4的TEM图,从图中可以看出Fe3O4是类球形颗粒,分散均匀。
图2是制备的Fe3O4的XRD图,从图中可以看Fe3O4的特征峰与标准卡片(标准卡片的编号是PDF#01-1111)相匹配,表明Fe3O4成功合成。
实施例2
步骤1、2同实施例1;
步骤3:称取步骤2所制的Fe3O4 100mg,分散到5mL水中,超声5min,搅拌30min;
步骤4:向步骤3中加2mL的氯化镍溶液与氯化铂溶液的混合溶液或氯化镍溶液或氯化铂溶液,之后搅拌2h,加(1mL,21mg)NaBH4,搅拌30min后离心洗涤干燥,60℃真空过夜,即可制得Fe3O4负载的金属纳米颗粒。
氯化镍溶液的物质的量浓度为2.84×10-2mmol/mL、氯化铂溶液的物质的量浓度为2.84×10-2mmol/mL。
吸取氯化镍溶液1ml,吸取氯化铂溶液2ml,混合得到氯化镍溶液体积:氯化铂溶液体积=1:2的溶液,吸取混合之后的溶液2ml作为制备纳米颗粒的金属溶液,因为氯化镍与氯化铂物质的量浓度相等,因此镍与铂的物质的量比为1:2,得到的产品标记为 NiPt2@Fe3O4。
氯化镍溶液吸取1ml,氯化铂溶液吸取1ml,制备混合溶液,镍与铂的物质的量比为1:1,得到的产品标记为NiPt@Fe3O4。
氯化镍溶液吸取2ml,氯化铂溶液吸取1ml,制备混合溶液,镍与铂的物质的量比为2:1时,得到的产品标记为Ni2Pt@Fe3O4。
氯化镍溶液吸取3ml,氯化铂溶液吸取1ml,制备混合溶液,镍与铂的物质的量比为3:1时,得到的产品标记为Ni3Pt@Fe3O4。
仅添加物质的量浓度为2.84×10-2mmol/mL的氯化铂溶液时,得到的产品标记为Pt@Fe3O4。
仅添加物质的量浓度为2.84×10-2mmol/mL的氯化镍溶液时,得到的产品标记为Ni@Fe3O4。
图3是本发明制备的Ni2Pt@Fe3O4的TEM图,从图中可以看出Ni2Pt@Fe3O4中的金属纳米颗粒分散较为均匀,没有明显的团聚现象,类球形为Fe3O4,黑色斑点为NiPt纳米颗粒。
图4是本发明制备的Ni2Pt@Fe3O4的XRD图,从图中可以看出Ni2Pt@Fe3O4的衍射峰与Fe3O4可以很好的匹配。
图5是本发明制备的NiPt2@Fe3O4的TEM图,从图中可以看出类似球形的是 Fe3O4,黑色斑点是NiPt纳米颗粒。
图6是本发明制备的NiPt@Fe3O4的TEM图,其中球形的是Fe3O4,上面的黑点是 NiPt纳米颗粒,可以看出纳米颗粒没有发生团聚现象。
图7是本发明制备的Ni3Pt@Fe3O4的TEM图,图中黑色小点是NiPt纳米颗粒,大的球形是Fe3O4。
图8是本发明制备的Pt@Fe3O4的TEM图,图中黑色点是Pt纳米颗粒,大的球形是Fe3O4。
图9是本发明制备的Ni@Fe3O4的TEM图,Fe3O4是图中类球形的物质,Ni纳米颗粒是黑色斑点,可以看出这些黑色斑点没有发生团聚现象。
采用NiPt2@Fe3O4、NiPt@Fe3O4、Ni2Pt@Fe3O4、Ni3Pt@Fe3O4、Pt@Fe3O4、 Ni@Fe3O4催化剂催化硼氢化钠水解产氢,具体步骤如下:
步骤1:分别称取NiPt2@Fe3O4、NiPt@Fe3O4、Ni2Pt@Fe3O4、Ni3Pt@Fe3O4、Pt@Fe3O4、 Ni@Fe3O4 25mg于产氢反应瓶内,再用注射器打入4mL水,封口置于30℃水浴锅中搅拌;
步骤2:称取1mmol NaBH4溶于1mL水中;
步骤3:用注射器吸取步骤2中的硼氢化纳溶液,注入步骤1中的反应瓶中,立即开始计时并封好口;
步骤4:每间隔10s记录对应时间下的氢气体积。
图10是NiPt2@Fe3O4、NiPt@Fe3O4、Ni2Pt@Fe3O4、Ni3Pt@Fe3O4、Pt@Fe3O4、 Ni@Fe3O4所制得的纳米颗粒催化1mmol NaBH4水解的产氢速率图,从图中可以看出, 1min内,Ni2Pt@Fe3O4产生了75.5mL气体,反应速度是最快的,而Ni@Fe3O4只产生7.5 mL气体,反应速度是最慢的。
图11是Fe3O4的磁性效果,A瓶内是把其溶解在水中,是黑色浑浊溶液,B瓶外是磁铁,可以看出黑色物质被吸附在磁铁上。
本实施例以Ni2Pt@Fe3O4纳米颗粒以催化硼氢化钠水解产氢的步骤进行5次循环,即在步骤4完成后收集Ni2Pt@Fe3O4纳米颗粒再次实施步骤1-4,循环5次,其效果如图13。从图13中可以看出循环5次后Ni2Pt@Fe3O4依然保持良好的催化活性,是因为图3所表示的Fe3O4的磁性效果,才能使Ni2Pt@Fe3O4纳米颗粒方便回收,损失较少,且活性维持较好。
本发明以不具有任何磁性的ZIF-8作为对比案例,其中,ZIF-8为沸石咪唑酯骨架材料。其制备方法参考北京交通大学硕士专业学位论文《金属有机骨架材料ZIF-8的制备及吸附性能研究》,李耀,2015年。
图12是ZIF-8的磁性效果,A瓶内是把其溶解在水中,是黑色浑浊溶液,B瓶外是磁铁,可以看出磁铁并不能吸附黑色物质,ZIF-8是没有磁性的。
图14是ZIF-8负载的NiPt纳米颗粒的两次循环,从图中可以看出循环2次后,活性就下降很多,是因为此催化剂没有磁性,再回收的时候有部分损失。
实施例3
步骤1、2同实施例1;
步骤3:称取步骤2所制的Fe3O4 100mg,分散到5mL水中,超声5min,搅拌30min;
步骤4:向步骤3中加2mL氯化镍溶液与四氯钯酸钾溶液的混合溶液,其中氯化镍溶液的物质的量浓度为2.84×10-2mmol/mL、四氯钯酸钾溶液的物质的量浓度为2.84×10-2 mmol/mL,氯化镍溶液吸取2ml,四氯钯酸钾溶液吸取1ml,混合之后,得到氯化镍溶液体积:四氯钯酸钾溶液体积=2:1的溶液,吸取混合之后的溶液2ml作为制备纳米颗粒的金属溶液,因为氯化镍与四氯钯酸钾物质的量浓度相等,因此镍与钯的物质的量比为2:1,之后搅拌2h,加(1mL,21mg)NaBH4,搅拌30min后离心洗涤干燥,60℃真空过夜,即可制得 Fe3O4负载的金属纳米颗粒,得到的产品标记为Ni2Pd@Fe3O4。
图15是本发明制备的Ni2Pd@Fe3O4的TEM图,其目的是显示Ni2Pd@Fe3O4中的黑色斑点即金属纳米颗粒分散较为均匀,没有明显的团聚现象。
实施例4
步骤1、2同实施例1;
步骤3:称取步骤2所制的Fe3O4 100mg,分散到5mL水中,超声5min,搅拌30min;
步骤4:向步骤3中加2mL的氯化镍溶液与氯化铑溶液的混合溶液,其中氯化镍溶液的物质的量浓度为2.84*10-2mmol/mL、氯化铑溶液的物质的量浓度为2.84*10-2mmol/mL,氯化镍溶液吸取2ml,氯化铑溶液吸取1ml,混合之后,得到氯化镍溶液体积:氯化铑溶液体积=2:1的溶液,吸取混合之后的溶液2ml作为制备纳米颗粒的金属溶液,因为氯化镍与氯化铑物质的量浓度相等,因此镍与铑的物质的量比为2:1,之后搅拌2h,加(1mL,21 mg)NaBH4,搅拌30min后离心洗涤干燥,60℃真空过夜,即可制得Fe3O4负载的金属纳米颗粒,得到的产品标记为Ni2Rh@Fe3O4。
图16是本发明制备的Ni2Rh@Fe3O4的TEM图,图中类球形的物质是Fe3O4,黑色物质是NiRh纳米颗粒,可以看出纳米颗粒分散性较好。
实施例5
步骤1、2同实施例1;
步骤3:称取步骤2所制的Fe3O4 100mg,分散到5mL水中,超声5min,搅拌30min;
步骤4:向步骤3中加2mL氯化镍与四氯金酸的混合溶液,其中氯化镍溶液的物质的量浓度为2.84*10-2mmol/mL、四氯金酸溶液的物质的量浓度为2.84*10-2mmol/mL,氯化镍溶液吸取2ml,四氯金酸溶液吸取1ml,混合之后,得到氯化镍溶液体积:四氯金酸溶液体积=2:1的溶液,吸取混合之后的溶液2ml作为制备纳米颗粒的金属溶液,因为氯化镍与四氯金酸物质的量浓度相等,因此镍与金的物质的量比为2:1,之后搅拌2h,加(1mL,21 mg)NaBH4,搅拌30min后离心洗涤干燥,60℃真空过夜,即可制得Fe3O4负载的金属纳米颗粒,得到的产品标记为Ni2Au@Fe3O4。图17是本发明制备的Ni2Au@Fe3O4的TEM图,从图中可以看出,黑色斑点是NiAu纳米颗粒,分散较为均匀,没有明显的团聚现象,类球形是Fe3O4。
采用Ni2Pd@Fe3O4、Ni2Rh@Fe3O4、Ni2Au@Fe3O4纳米颗粒催化硼氢化钠水解产氢,具体步骤如下:
步骤1:分别称取Ni2Pd@Fe3O4、Ni2Rh@Fe3O4、Ni2Au@Fe3O4 25mg于3个产氢反应瓶内,再分别用注射器打入4mL水,封口置于30℃水浴锅中搅拌;
步骤2:称取1mmol NaBH4溶于1mL水中;
步骤3:用注射器吸取步骤2中的硼氢化纳溶液,注入步骤1中的3个反应瓶中,立即开始计时并封好口;
步骤4:每间隔10s记录对应时间下的氢气体积。
图18是Fe3O4负载的Ni与不同贵金属所制得的纳米颗粒催化1mmol NaBH4水解的产氢速率图,可以看出,在1min内,Ni2Pd@Fe3O4与Ni2Rh@Fe3O4
分别产生85.5mL和86.5mL气体,反应速率较快,而Ni2Au@Fe3O4只有54mL气体,反应速率最慢。
实施例6
步骤1、2同实施例1;
步骤3:称取步骤2所制的Fe3O4 100mg,分散到5mL水中,超声5min,搅拌30min;
步骤4:其中氯化铁溶液的物质的量浓度为2.84*10-2mmol/mL、氯化铂溶液的物质的量浓度为2.84*10-2mmol/mL,氯化铁溶液吸取2ml,氯化铂溶液吸取1ml,混合之后,得到氯化铁溶液体积:氯化铂溶液体积=2:1的溶液,吸取混合之后的溶液2ml来作为制备纳米颗粒的金属溶液,因为氯化铁与氯化铂物质的量浓度相等,因此铁与铂的物质的量比为2:1,之后搅拌2h,加(1mL,21mg)NaBH4,搅拌30min后离心洗涤干燥,60℃真空过夜,即可制得 Fe3O4负载的金属纳米颗粒,得到的产品标记为Fe2Pt@Fe3O4。
采用Fe2Pt@Fe3O4催化剂催化硼氢化钠水解产氢,具体步骤如下:
步骤1:称取Fe2Pt@Fe3O4 25mg于产氢反应瓶内,再用注射器打入4mL水,封口置于 30℃水浴锅中搅拌;
步骤2:称取1mmol NaBH4溶于1mL水中;
步骤3:用注射器吸取步骤2中的硼氢化纳溶液,注入步骤1中的反应瓶中,立即开始计时并封好口;
步骤4:每间隔10s记录对应时间下的氢气体积。
图19是本发明制备的Fe2Pt@Fe3O4的TEM图,可看出Fe2Pt@Fe3O4中的黑色小的FePt纳米颗粒分散较为均匀,没有明显的团聚现象。图中的类球形的物质是Fe3O4。
实施例7
步骤1、2同实施例1;
步骤3:称取步骤2所制的Fe3O4 100mg,分散到5mL水中,超声5min,搅拌30min;
步骤4:其中氯化铜溶液的物质的量浓度为2.84*10-2mmol/mL、氯化铂溶液的物质的量浓度为2.84*10-2mmol/mL,氯化铜溶液吸取2ml,氯化铂溶液吸取1ml,混合之后,得到氯化铜溶液体积:氯化铂溶液体积=2:1的溶液,吸取混合之后的溶液2ml来作为制备纳米颗粒的金属溶液,因为氯化铜与氯化铂物质的量浓度相等,因此铜与铂的物质的量比为2:1,之后搅拌2h,加(1mL,21mg)NaBH4,搅拌30min后离心洗涤干燥,60℃真空过夜,即可制得 Fe3O4负载的金属纳米颗粒,得到的产品标记为Cu2Pt@Fe3O4。
采用Cu2Pt@Fe3O4催化剂催化硼氢化钠水解产氢,具体步骤如下:
步骤1:称取Cu2Pt@Fe3O4 25mg于产氢反应瓶内,再用注射器打入4mL水,封口置于 30℃水浴锅中搅拌;
步骤2:称取1mmol NaBH4溶于1mL水中;
步骤3:用注射器吸取步骤2中的硼氢化纳溶液,注入步骤1中的反应瓶中,立即开始计时并封好口;
步骤4:每间隔10s记录对应时间下的氢气体积。
图20是本发明制备的Cu2Pt@Fe3O4的TEM图,图中球形物质是Fe3O4,黑色的小的物质是CuPt纳米颗粒,可看出纳米颗粒无明显聚集现象。
实施例8
步骤1、2同实施例1;
步骤3:称取步骤2所制的Fe3O4 100mg,分散到5mL水中,超声5min,搅拌30min;
步骤4:其中氯化钴溶液的物质的量浓度为2.84*10-2mmol/mL、氯化铂溶液的物质的量浓度为2.84*10-2mmol/mL,氯化钴溶液吸取2ml,氯化铂溶液吸取1ml,混合之后,得到氯化钴溶液体积:氯化铂溶液体积=2:1的溶液,吸取混合之后的溶液2ml来作为制备纳米颗粒的金属溶液,因为氯化钴与氯化铂物质的量浓度相等,因此钴与铂的物质的量比为2:1,之后搅拌2h,加(1mL,21mg)NaBH4,搅拌30min后离心洗涤干燥,60℃真空过夜,即可制得 Fe3O4负载的金属纳米颗粒,得到的产品标记为Co2Pt@Fe3O4。
采用Co2Pt@Fe3O4催化剂催化硼氢化钠水解产氢,具体步骤如下:
步骤1:称取Co2Pt@Fe3O4 25mg于产氢反应瓶内,再用注射器打入4mL水,封口置于 30℃水浴锅中搅拌;
步骤2:称取1mmol NaBH4溶于1mL水中;
步骤3:用注射器吸取步骤2中的硼氢化纳溶液,注入步骤1中的反应瓶中,立即开始计时并封好口;
步骤4:每间隔10s记录对应时间下的氢气体积。
图21是本发明制备的Co2Pt@Fe3O4的TEM图,黑色小的物质是CoPt纳米颗粒,且分散较为均匀,大的类球形的是Fe3O4,分散也较为均匀。
图22是Fe3O4负载的Pt与不同贱金属所制得的纳米颗粒催化1mmol NaBH4水解的产氢速率图,可以看出,在1min内,Ni2Pt@Fe3O4产生75.5mL气体,反应速率最快,而 Cu2Pt@Fe3O4和Fe2Pt@Fe3O4只产生31mL和37mL气体,反应速率较慢。
Claims (10)
1. Fe3O4负载的金属纳米颗粒制备方法,其特征在于,包括以下步骤:
步骤1:将去离子水预热到60-70℃,然后加入FeCl3•6H2O及FeSO4•7H2O,搅拌;
步骤2:将氨水预热到60-70℃后滴加到步骤1的溶液中搅拌反应,产物经冷却离心洗涤,干燥即可得到Fe3O4;
步骤3:称取步骤2所制的Fe3O4分散到水中,超声分散均匀;
步骤4:向步骤3中依次加入金属溶液,搅拌2-3h后加入NaBH4,继续搅拌反应,产物经离心洗涤、真空干燥即可制得Fe3O4负载的金属纳米颗粒。
2.根据权利要求1所述的Fe3O4负载的金属纳米颗粒制备方法,其特征在于,步骤1中所述的FeCl3•6H2O及FeSO4•7H2O的质量比为1.6-2.0:1。
3.根据权利要求1所述的Fe3O4负载的金属纳米颗粒制备方法,其特征在于,所述的氨水的体积浓度为0.01-0.05%。
4. 根据权利要求1所述的Fe3O4负载的金属纳米颗粒制备方法,其特征在于,步骤4中,所述的金属溶液包括贱金属溶液和/或贵金属溶液的混合物,其中,贱金属溶液包括氯化镍溶液、氯化铁溶液、氯化钴溶液、氯化铜溶液中的任意一种;贵金属溶液包括氯化铂溶液、氯化铑溶液、四氯金酸溶液、四氯钯酸钾溶液中的任意一种;其中,金属溶液的物质的量浓度为2.84×10-2 mmol/mL。
5.根据权利要求4所述的Fe3O4负载的金属纳米颗粒制备方法,其特征在于,贱金属溶液及贵金属溶液的混合物中,贱金属与贵金属的元素摩尔比为0.5-3。
6.根据权利要求5所述的Fe3O4负载的金属纳米颗粒制备方法,其特征在于,贱金属溶液及贵金属溶液的混合物中,贱金属与贵金属的元素摩尔比为2。
7.根据权利要求1所述的Fe3O4负载的金属纳米颗粒制备方法,其特征在于,
Fe3O4、金属溶液、NaBH4的物质的量比为0.3-0.5:0.4-0.6:0.4-0.6。
8.根据权利要求1-7任一项所述制备得到的Fe3O4负载的金属纳米颗粒作为催化剂在催化硼氢化钠产氢上的应用。
9.根据权利要求8所述的应用,催化硼氢化钠产氢过程中Fe3O4负载的金属纳米颗粒的量是硼氢化钠的0.5-2.0%。
10.根据权利要求9所述的应用,催化硼氢化钠产氢过程中Fe3O4负载的金属纳米颗粒的量是硼氢化钠的1.0%。
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