CN114950440A - 一种凹凸棒-纳米镍粉复合物的宏量室温制备方法 - Google Patents
一种凹凸棒-纳米镍粉复合物的宏量室温制备方法 Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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Abstract
本发明公开了一种凹凸棒‑纳米镍粉复合物的宏量室温制备方法,焦磷酸钠溶于去离子水,搅拌下缓慢加入凹凸棒原土,持续搅拌至分散均匀,缓慢加入酸,超声,继续搅拌,静置,抽滤分离,水洗至中性,真空干燥,研磨,得纯化凹凸棒土;镍盐溶于去离子水,缓慢加入纯化凹凸棒土,水浴中搅拌,静置,抽滤分离,水洗,真空干燥,得凹凸棒‑镍盐复合物;该复合物分散于去离子水中,缓慢加入还原剂,水浴中搅拌至反应没有气泡产生,离心分离,去离子水洗涤,真空干燥,制得凹凸棒‑纳米镍粉复合物。该制备方法以水为溶剂,原料储量丰富,设备要求低,操作步骤简单,可以实现大量合成,是一项有望实现镍及其合金复合物产业化的关键技术。
Description
技术领域
本发明涉及一种凹凸棒-纳米镍粉复合物的室温制备方法。
背景技术
比表面积大、表面活性位点多等特征促使纳米镍粉在催化剂领域发挥重要作用。此外,纳米镍粉也延续了纳米颗粒特有的表面效应、量子尺寸效应、小尺寸效应和宏观量子隧道效应等性质,使其在燃料电池、吸波材料、润滑材料、磁性材料、纳米涂层材料及硬质合金黏结剂等领域具备良好的应用前景。例如,在聚丙烯酸钠(Na-PA)存在下,用水合肼在多元醇介质中还原氯化镍合成的纳米镍粉末具有铁磁性,其饱和磁化强度和矫顽力随粒径尺寸的变化而变化。由于纳米颗粒的小体积和粉末表面氧化引起的饱和磁化强度降低,使其矫顽力明显增强。以SDS、CTAB、PEG-2000为改性剂制备的纳米镍颗粒分散性好,粒径小,能用来制备镍基导电膏,而镍基导电膏的导电率与纳米镍颗粒的wt%有关。在火箭固体推进剂中加入质量分数约1%的纳米镍粉,可使每克燃料的燃烧热增加至原来的2倍。在外磁场作用下纳米镍粉填充聚苯乙烯薄膜的透层电导率的研究进展。这一过程导致镍纳米柱的形成横跨厚度方向,同时在两者之间产生纳米颗粒贫化区,导致了光传输的方向依赖性增强,特别是在薄膜的法线方向上。在磁场的影响下,仅使用2wt% (0.22 vol%)的镍,就能够获得高的穿透厚度电导率。此外,纳米镍粉催化剂可使对硝基苯酚加氢反应的效率提高16倍。通过控制合成参数,合成表面形貌呈针状或树莓状,颗粒粒径50~200 nm的镍纳米粒子,并研究了该催化剂在空气中的热行为及其对CO甲烷化反应的催化性能等。随着纳米镍粉应用领域的不断扩展,近年来国内外对纳米镍粉的研究与日俱增,部分制备工艺已实现了产业化。
纳米镍粉的制备方法有很多,如激光沉积法、蒸发冷却法、热分解法、气相还原法、液相还原法、水热法、反相微乳液法、电解法、射线辐照还原法、微波辅助水热法等。例如以水为介质,采用液相还原法合成纳米镍。以聚乙二醇-2000 (PEG-2000)、十二烷基硫酸钠(SDS)、十六烷基三甲基溴化铵(CTAB)为改性剂,制备平均粒径100~200nm的纳米镍。通过金属丝电爆炸法合成纳米镍粉,并对其结构表征得出镍纳米团簇呈球形,平均直径50 nm。x射线衍射图分析表明,电爆炸纳米粉体的晶格参数大于标准参数。以双分散的NaCl为致孔粉,通过烧结-溶解法制备了多孔镍粉。在管式炉中240~280℃温度下,用氢气还原NiO纳米粉得到平均粒径60~120 nm的镍纳米粉,每个纳米镍粒子通过颈部与相邻的几个粒子相连。此外还有在碱性溶液中,以肼为原料,用化学还原法制备形貌为球形、花状、球形或线状的纳米镍粉体。X射线衍射(XRD)表明,所制得的镍粉呈立方晶状,平均粒径在几十纳米到几百纳米之间等。
在这些制备方法中,等离子体法制备纳米镍粉具有产物纯度高、平均粒径小、尺寸分布均匀、形状与尺寸可控及制备过程对环境友好等优点。但由于对生产设备的要求高,目前使用此方法生产纳米镍粉的企业较少。电火花放电腐蚀法具有设备简单、产物纯度高等优点。但其合成的纳米镍粉粒径较大,且表面容易发生氧化而形成氧化镍薄膜。高能球磨法具有操作简单、成本低廉、产量高等优点,且可以通过改变球磨时间对合成的纳米镍粉的粒径加以控制。但该方法在操作过程中容易引入杂质,产物的纯度较低且粒径分布不均匀,容易发生团聚。
发明内容
本发明的目的是提供一种凹凸棒-纳米镍粉复合物的宏量室温制备方法,能够实现尺寸小、不易氧化纳米镍粉复合物的大量制备。
为实现上述目的,本发明所采用的技术方案是:一种凹凸棒-纳米镍粉复合物的宏量室温制备方法,具体按以下步骤进行:
1)凹凸棒土(ATP)的纯化:
5~10 mmol焦磷酸钠加入1000~2000 mL去离子水中,室温下搅拌至焦磷酸钠完全溶解,然后在搅拌下加入50~100 g凹凸棒原土,室温下持续搅拌30 min,分散均匀后,缓慢加入4~7 mL酸,超声30 min,继续搅拌3 h,静置12 h,抽滤分离,蒸馏水洗涤,至洗涤后水呈中性,110℃温度下真空干燥12 h,研磨,过200目筛,得纯化凹凸棒土;
酸采用摩尔浓度10 mol/L的盐酸、摩尔浓度5 mol/L的硫酸或摩尔浓度10 mol/L的硝酸。
)制备凹凸棒-镍盐复合物:
将10~30 mmol镍盐溶解于1000~3000 mL去离子水中,缓慢加入10~30 g纯化凹凸棒土,于30 ℃水浴中搅拌24 h,静置,抽滤分离,水洗除去未配位的镍盐,60 ℃温度下真空干燥12 h,得凹凸棒-镍盐复合物;
镍盐采用硫酸镍、六水合氯化镍、乙酸镍或六水合硝酸镍
3)制备凹凸棒-纳米镍粉复合物:
将5~20 g凹凸棒-镍盐复合物分散于1000~4000 mL去离子水中,然后缓慢加入7.5~50 mmol 还原剂,30 ℃水浴中搅拌至反应没有气泡产生,离心分离,去离子水洗涤,60 ℃真空干燥,制得凹凸棒-纳米镍粉复合物。
还原剂采用硼氢化钠、抗坏血酸、水合肼或草酸。
凹凸棒是一种天然存在的镁(铝)-氧(氢-氧)插层两个硅氧四面体的八面体(即2:1粘土矿物)水镁铝硅酸盐粘土矿物。特殊的链层状晶体结构赋予其独特的流变特性、阳离子交换能力、吸附性以及载体性。因其较大的比表面积和多孔结构,常被用作分散和稳定纳米颗粒的机械载体。经过酸化处理的凹凸棒土,溶解孔道的部分杂质,增加比表面积。镍离子与凹凸棒的硅羟基配位络合稳定镍离子后,在硼氢化钠、抗坏血酸、水合肼或草酸等还原剂作用下得到凹凸棒-纳米镍粉复合物,凹凸棒特有的多孔结构有效分散了镍纳米颗粒并缓解了镍纳米颗粒的氧化。
采用本发明制备方法制备的凹凸棒-镍粉复合物具有形貌均一、平均粒径为1.0nm的小尺寸、能够实现大量制备等优点,将镍纳米颗粒限域在凹凸棒结构中能有效地阻碍镍纳米颗粒的氧化,使其有望表现良好的催化活性。
图1是本发明制备方法制得凹凸棒-镍粉复合物的透射电镜图,从图中可以看到镍纳米颗粒分布在凹凸棒结构中,呈分散的球形颗粒,形貌均一。
该凹凸棒-镍粉复合物的粒径分布图,如图2,图中显示,该复合物的平均粒径为1.0 nm。
图3是该凹凸棒-镍粉复合物的XRD图,从图中可以看到所制备的样品在44.50°、51.85°和76.37°处并未明显表现出镍的(111)、(200)以及(220)特征晶面,说明凹凸棒起到明显的限域作用,将镍纳米颗粒完全封装到凹凸棒结构中,这种包覆不仅有效防止了镍纳米的氧化,也将其粒径控制在1.0 nm。
将镍纳米封装在一维纳米矿物凹凸棒中,由于其结构的限制,镍纳米颗粒的平均粒径约为1 nm,小尺寸颗粒为催化反应提供更多的活性位点。层链状晶体结构和纳米孔道有效防止纳米颗粒的氧化。
本发明制备方法制得的凹凸棒-镍粉复合物的可应用于催化、电容器、能源等领域。
本发明制备方法以水为溶剂,无污染物产生,低耗环保,符合绿色生产要求。制得的纳米颗粒平均粒径为1nm、形貌均一、抗氧化、适用范围广。该制备方法原料储量丰富,设备要求低,操作步骤简单,选用更环保的原材料,可以实现大量合成,具备可观的经济效益,是一项有望实现镍及其合金复合物产业化的关键技术,具有重要的理论和现实意义。
附图说明
图1是本发明制备方法制得凹凸棒-纳米镍粉复合物的表征透射(TEM)图。
图2是本发明制备方法制得凹凸棒-纳米镍粉复合物的粒径分布图。
图3是本发明制备方法制得凹凸棒-纳米镍粉复合物的X-射线衍射(XRD)图。
具体实施方式
下面结合具体实施方式对本发明做进一步详细说明。
实施例1
5 mmol焦磷酸钠加入1000 mL去离子水中,室温下搅拌至焦磷酸钠完全溶解,室温搅拌下加入50g凹凸棒原土,持续搅拌30 min,分散均匀,缓慢加入6mL摩尔浓度10 mol/L的盐酸,超声30 min,继续搅拌3 h,静置12 h,抽滤分离,蒸馏水洗涤,至洗涤后水呈中性,110℃温度下真空干燥12 h,研磨过200目筛,得纯化凹凸棒土;将20 mmol硫酸镍溶解于2000mL去离子水中,缓慢加入20 g纯化凹凸棒土,于30℃水浴中搅拌24 h,静置,抽滤分离,水洗除去未配位的硫酸镍,60℃真空干燥12 h,得凹凸棒-镍盐复合物。将10 g凹凸棒-镍盐复合物分散于2000 mL去离子水中,然后缓慢加入30 mmol抗坏血酸,30℃水浴中搅拌至反应没有气泡产生,离心分离,去离子水洗涤,60℃真空干燥,制得凹凸棒-纳米镍粉复合物。
实施例2
10 mmol焦磷酸钠加入2000mL去离子水中,室温下搅拌至焦磷酸钠完全溶解,室温搅拌下加入100g凹凸棒原土,持续搅拌30 min后,缓慢加入4mL摩尔浓度5 mol/L的硫酸,超声30 min,继续搅拌3 h,静置12 h,抽滤分离,蒸馏水洗涤,至洗涤后水呈中性,110℃温度下真空干燥12 h,研磨过200目筛,得纯化凹凸棒土。将10mmol六水合氯化镍溶解于1000 mL去离子水中,缓慢加入10g纯化凹凸棒土,于30℃水浴中搅拌24 h,静置,抽滤分离,水洗除去未配位的六水合氯化镍,60℃真空干燥12 h,得凹凸棒-镍盐复合物。将5g凹凸棒-镍盐复合物分散于1000 mL去离子水中,然后缓慢加入7.5 mmol草酸,30℃水浴中搅拌至反应没有气泡产生,离心分离,去离子水洗涤,60℃真空干燥,制得凹凸棒-纳米镍粉复合物。
实施例3
7.5mmol焦磷酸钠加入1500mL去离子水中,室温下搅拌至焦磷酸钠完全溶解,室温搅拌下加入75g凹凸棒原土,持续搅拌30 min,分散均匀,缓慢加入7 mL摩尔浓度10 mol/L的硝酸,超声30 min,继续搅拌3 h,静置12 h,抽滤分离,蒸馏水洗涤,至洗涤后水呈中性,110℃温度下真空干燥12 h,研磨,过200目筛,得纯化凹凸棒土。将30 mmol乙酸镍溶解于3000 mL去离子水中,然后缓慢加入30 g纯化凹凸棒土,于30℃水浴中搅拌24 h,静置,抽滤分离,水洗除去未配位的乙酸镍,60℃真空干燥12 h,得凹凸棒-镍盐复合物。将20 g凹凸棒-镍盐复合物分散于4000 mL去离子水中,缓慢加入50 mmol水合肼,30℃水浴中搅拌至反应没有气泡产生,离心分离,去离子水洗涤,60℃真空干燥,制得凹凸棒-纳米镍粉复合物。
Claims (5)
1.一种凹凸棒-纳米镍粉复合物的宏量室温制备方法,其特征在于,具体按以下步骤进行:
1)5~10 mmol焦磷酸钠加入1000~2000 mL去离子水中,室温下搅拌至焦磷酸钠完全溶解后,搅拌下缓慢加入50~100 g凹凸棒原土,室温下持续搅拌至分散均匀,缓慢加入4~7mL酸,超声,继续搅拌,静置,抽滤分离,洗涤,110℃温度下真空干燥,研磨,得纯化凹凸棒土;
2)将10~30mmol镍盐溶解于1000~3000 mL去离子水,缓慢加入10~30g纯化凹凸棒土,于30℃水浴中搅拌24h,静置,抽滤分离,水洗,60℃温度下真空干燥,得凹凸棒-镍盐复合物;
3)将5~20 g凹凸棒-镍盐复合物分散于1000~4000mL去离子水中,然后缓慢加入7.5~50 mmol还原剂,30℃水浴中搅拌至反应没有气泡产生,离心分离,去离子水洗涤,60℃真空干燥,制得凹凸棒-纳米镍粉复合物。
2.如权利要求1所述的凹凸棒-纳米镍粉复合物的宏量室温制备方法,其特征在于,所述步骤1)中,酸采用摩尔浓度10 mol/L的盐酸、摩尔浓度5 mol/L的硫酸或摩尔浓度10mol/L的硝酸。
3.如权利要求1所述的凹凸棒-纳米镍粉复合物的宏量室温制备方法,其特征在于,所述步骤1)中,蒸馏水洗涤酸化后的凹凸棒土时,洗涤至洗涤后水呈中性。
4.如权利要求1所述的凹凸棒-纳米镍粉复合物的室温宏量制备方法,所述步骤2)中,镍盐采用硫酸镍、六水合氯化镍、乙酸镍或六水合硝酸镍。
5.如权利要求1所述的凹凸棒-纳米镍粉复合物的室温宏量制备方法,其特征在于,所述步骤3)中,还原剂采用硼氢化钠、抗坏血酸、水合肼或草酸。
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