CN106890998A - 管状Ni‑Pt纳米合金的制备方法 - Google Patents
管状Ni‑Pt纳米合金的制备方法 Download PDFInfo
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Abstract
本发明提供一种管状Ni‑Pt纳米合金的制备方法，属于金属合金技术领域，该方法是以对苯二甲酸乙二酯聚合物为模板，经紫外照射、溶液刻蚀形成孔基底，通过SnCl2溶液敏化，PdCl2溶液活化形成以Pd金属成核中心，加入化学Ni镀液和Pt镀液混合后加入处理后的模板，随后加入水合肼还原液，在常温下反应0.5‑3 h，去除聚合物模板后，得到管状Ni‑Pt纳米合金材料。本操作工艺的主要特点为以聚合物为原料，原料丰富，节能降耗；通过简单的敏化、活化、化学镀简单的方法，在常温下形成稳定的管状Ni‑Pt纳米合金材料，拓宽金属纳米材料的形貌可控性及应用领域。
Description
技术领域
本发明涉及金属合金技术领域，具体地说是一种管状Ni-Pt纳米合金的制备方法。
背景技术
一般的，金属合金纳米材料具有一定的前瞻性和广阔的应用前景。通常是细微颗粒形成存在，由于具有较高的表面积，自由能较大，在使用过程中很容易团聚，导致催化剂失活。因此科研工作者一直在致力于金属纳米管的研究，通过不同的方法已经成功制备了不同的单一金属纳米管。理想的两种或两种以上合金取决于这几种金属的表面方向性，以及晶体表面的单一性等。同时，在制备金属材料过程中，不同金属材料所需要的还原剂、反应温度以及不同金属在还原过程中的还原速率也各不相同，因此，既要同时形成两种金属又要保持纳米管的形貌是一直具有挑战性的研究课题。
化学镀技术具有镀层结构均匀，设备简单，结合力和防腐能力强和耐腐蚀等优点；同时可以通过改变氧化还原反应的条件来调控镀层金属的结构和形貌。此外，化学镀存在废液排放少，而且成本较低，效率很高，在很多应用方面比电镀表现出更优异的性能，已成为一种新型的环保型表面处理工艺。
美国专利（US2016276280A1）介绍了一种以铜为基底超薄多层金属纳米合金材料。铜合金为其合金材料提供应力迁移阻力和介电层力制备钨/铜合金和/铜合金。此方法要求的制备条件相对比较复杂，具有一定的应用局限性。
俄罗斯专利（RU2015110737A）介绍了一种依附在钛-铝合金上形成晶体纳米多孔氧化物的方法。此方法设计到电镀技术，通过制备钛-铝合金粉末，并清洗，干燥，经阳极处理形成纳米多孔表面氧化物。电镀效果好，但耗用成本较高，且电镀不均匀，需开发一种成本低，镀法均匀且高效的方法。
美国专利（WO2016176509A1）介绍了一种铁磁性记忆合金纳米促动器，涉及到合金领域。通过弹性变形和压缩状态的磁场制备形成螺旋状金属记忆合金。一方面以磁铁为主，另一方面配上不同的金属来提供配体结合来实现癌症细胞的靶向治疗。此方法具有重要的研究意义，相对制备条件复杂，成本较高，可控性较差。
公开号为CN1926254A的中国专利介绍了一种Ni-Pt合金和Ni-Pt合金靶。以电化学方式熔化3N级别的原料Ni的工艺；以氨水中和该电解浸渍出的溶液的工序；使用活性炭过滤除去杂质的工序；通入二氧化碳气体生成碳酸镍，在还原性气氛下制造高纯度的Ni粉的工序；以酸浸渍3N级别的原料Pt的工序；通过电解浸蚀出的溶液制造高纯度电析Pt的工序；熔化如上制造出的高纯度Ni粉和高纯度电析Pt的工序。本发明提供了Ni-Pt合金锭的硬度降低而可轧制，并稳定高效地制造轧割制靶的技术。此方法操作复杂，成本高，不环保，有待于开发聚合物原料。
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公开号CN184777203A的中国专利介绍了Pt-Ni合金纳米管阵列电极的制备方法及在无酶葡萄糖传感器的应用。以Ni纳米线阵列为模板，采用电流置换法制备Pt-Ni合金纳米管阵列电极。将多孔模板的其中一面喷金处理，多孔模板包括AAO模板和PC模板通过导电银胶固定在电极表面，使用绝缘橡胶封住模板周围；在多孔模板内电沉积制备Ni纳米线，然后去除模板得到Ni纳米线阵列电极，采用电流置换法制备Pt-Ni合金纳米管阵列电极，前驱体溶液为氯铂酸或氯铂酸钾。并应用于葡萄糖传感器。此方法选用了金属为模板，不环保，有待于开发聚合物原料。
公开号CN105798326A的中国专利介绍了一种银-铂双金属空心纳米球，其制备方法及应用。此方法利用液相法一步合成了银-铂双金属空心纳米球，其形貌为纳米空心球状，纳米空心球形状完整，大小均一，银和铂共同作为空心球壳的成分，各组分分布均匀。此方法操作简单，周期短，合成效率高，重复性好，且对环境绿色无污染，应用在燃料电池催化剂，药物载运，气体传告和高效催化领域。然而，有待于通过简单的制备方法开发一种还原性相差较大的两种金属合金材料。
发明内容
本发明的技术任务是解决现有技术的不足，提供一种管状Ni-Pt纳米合金的制备方法。
本发明的技术方案是按以下方式实现的，该管状Ni-Pt纳米合金的制备方法是：以对苯二甲酸乙二酯聚合物为模板，经紫外照射、溶液刻蚀形成孔基底，通过敏化溶液敏化、活化溶液活化形成金属成核中心，在化学Ni镀液和Pt镀液混合后加入处理后的模板，随后加入还原液，在常温下反应0.5～3h，去除聚合物模板后，得到管状Ni-Pt纳米合金材料。
该方法具体是：以对苯二甲酸乙二酯作为模板，在30～60 ℃下1～3M摩尔浓度的氢氧化钠溶液下刻蚀10～30 min，随后分别对其正反两面进行紫外灯辐射5～30 min，再在二甲基甲酰胺DMF溶剂中浸渍5～30 min；
在由SnCl2 50～200 mg，90%-98wt%乙醇1～10 mL，标准液1.0mol/L的三氟乙酸10～100uL，去离子水1～20 mL混合而成的敏化溶液中浸渍5～30 min；
再在由PdCl2 100～500mg，去离子水 1～50mL，NaCl 10～100mg混合而成的活化溶液中浸渍5～20 min；
将处理后的薄膜模板放入：由硫酸镍40mg；亚氨基二乙酸30 mg；32 wt%的NaOH溶液30μL混合而成的 Ni镀液，以及由K2PtCl4溶液10 mg；标准液1.0mol/L的乙二胺134 μL；去离子水5 mL 混合而成的Pt镀液两者的混合化学镀液中，向放入薄膜模板的混合化学镀液中加入由40%-80wt%水合肼20 μL和去离子水1 mL混合而成的还原液，常温下反应0.5～3h，去除聚合物模板后，得到管状Ni-Pt纳米合金材料。
本发明与现有技术相比所产生的有益效果是：
该管状Ni-Pt纳米合金的制备方法选用一种常见的聚合物对苯二甲酸乙二酯薄膜为原料，经过离子刻蚀敏化活化法刻蚀出孔结构，再经不同的化学镀液，以及相同的金属还原剂，在常温下简单，高效的制备出具有管状Ni-Pt纳米合金，拓宽金属纳米材料的形貌可控性及应用领域。
金属能否高效合理的施镀到聚合物上与模板刻蚀、敏化、活化过程有很大的关系。聚合物的结晶程度是关键问题，结晶度高的聚合物可以使金属更好的附着在聚合物表面，形成稳定的合金材料。聚对苯二甲酸乙二醇酯(PET)具有抗蠕变性好，耐疲劳性强，耐摩擦性好以及尺寸稳定等优点，其内部酯键可以在强酸、强碱和水蒸汽作用下发生分解，因此选其作为模板，利用简单的方法高效的制备金属纳米合金材料有着重要的现实意义和应用价值。
该方法选用以聚合物为原料，原料丰富，产量充足有保障，原料成本低，节能降耗。
该方法改变了传统的生产工艺，使用简单的敏化、活化、化学镀方法，就可形成稳定的管状Ni-Pt纳米合金。
该方法根据不同金属的还原性能，选用相同的还原剂使金属稳定的还原出来，操作高效，可控性强。
该方法溶液用量少，反应时间短，耗时少，耗能低，在常温下就可高效制备管状Ni-Pt纳米合金。
该管状Ni-Pt纳米合金的制备方法设计合理、安全可靠、操作方便、易于掌控，具有很好的推广使用价值。
附图说明
附图1是本发明制得管状Ni-Pt纳米合金的扫描电子显微镜SEM图。
具体实施方式
下面结合附图对本发明的管状Ni-Pt纳米合金的制备方法作以下详细说明。
该管状Ni-Pt纳米合金的制备方法是：选用对苯二甲酸乙二酯作为模板，在45-60℃下1-3 M 氢氧化钠溶液下刻蚀10-30 min，随后分别对其正反两面进行紫外灯辐射5-20min，再在DMF溶剂中浸渍5-20 min。经敏化溶液（SnCl2 90 mg，90%-98wt%乙醇3.3 mL，标准液1.0mol/L的三氟乙酸 46 uL，去离子水6.7 mL混合而成）浸渍5-20 min，再经活化溶液（PdCl2 218 mg，去离子水 10 mL，NaCl 47 mg）浸渍5-20 min。将处理后的薄膜放入Ni镀液（硫酸镍40mg； 亚氨基二乙酸30 mg；32 wt%的NaOH溶液30 μL）和Pt镀液（K2PtCl4溶液10mg；标准液1.0mol/L的乙二胺134 μL；去离子水5 mL）的混合液中，加入还原液（40%-80wt%的水合肼20 μL和去离子水1 mL），反应0.5-3 h，得到管状Ni-Pt纳米合金材料。
实施例1：
选用对苯二甲酸乙二酯作为模板，在45 ℃下1 M 氢氧化钠溶液下刻蚀10 min，随后分别对其正反两面进行紫外灯辐射5 min，再在DMF溶剂中浸渍5 min。经敏化溶液（SnCl2 90mg，90wt%乙醇3.3 mL，标准液1.0mol/L的三氟乙酸 46 uL，去离子水6.7 mL混合而成）浸渍5 min，再经活化溶液（PdCl2 218 mg，去离子水 10 mL，NaCl 47 mg）浸渍5 min。将处理后的薄膜放入Ni镀液（硫酸镍40mg； 亚氨基二乙酸30 mg；32 wt%的NaOH溶液30 μL）和Pt镀液（K2PtCl4溶液10 mg；标准液1.0mol/L的乙二胺134 μL；去离子水5 mL）的混合液中，加入还原液（80wt%水合肼20 μL和去离子水1 mL），反应0.5 h，得到管状Ni-Pt纳米合金材料。
实施例2：
选用对苯二甲酸乙二酯作为模板，在50 ℃下2 M 氢氧化钠溶液下刻蚀15 min，随后分别对其正反两面进行紫外灯辐射10 min，再在DMF溶剂中浸渍10 min。经敏化溶液（SnCl290 mg，98wt%乙醇3.3 mL，标准液1.0mol/L的三氟乙酸 46 uL，去离子水6.7 mL混合而成）浸渍15 min，再经活化溶液（PdCl2 218 mg，去离子水 10 mL，NaCl 47 mg）浸渍15 min。将处理后的薄膜放入Ni镀液（硫酸镍40mg； 亚氨基二乙酸30 mg；32 wt%的NaOH溶液30 μL）和Pt镀液（K2PtCl4溶液10 mg；标准液1.0mol/L的乙二胺134 μL；去离子水5 mL）的混合液中，加入还原液（40wt%水合肼20 μL和去离子水1 mL），反应1 h，得到管状Ni-Pt纳米合金材料。
实施例3：
选用对苯二甲酸乙二酯作为模板，在55 ℃下3 M 氢氧化钠溶液下刻蚀20 min，随后分别对其正反两面进行紫外灯辐射15 min，再在DMF溶剂中浸渍15 min。经敏化溶液（SnCl290 mg，90%-98wt%乙醇3.3 mL，标准液1.0mol/L的三氟乙酸 46 uL，去离子水6.7 mL混合而成）浸渍10 min，再经活化溶液（PdCl2 218 mg，去离子水 10 mL，NaCl 47 mg）浸渍10 min。将处理后的薄膜放入Ni镀液（硫酸镍40mg； 亚氨基二乙酸30 mg；32 wt%的NaOH溶液30 μL）和Pt镀液（K2PtCl4溶液10 mg；标准液1.0mol/L的乙二胺134 μL；去离子水5 mL）的混合液中，加入还原液（40%-80wt%水合肼20 μL和去离子水1 mL），反应1.5 h，得到管状Ni-Pt纳米合金材料。
实施例4：
选用对苯二甲酸乙二酯作为模板，在60 ℃下2 M 氢氧化钠溶液下刻蚀25 min，随后分别对其正反两面进行紫外灯辐射20 min，再在DMF溶剂中浸渍20 min。经敏化溶液（SnCl290 mg，90%-98wt%乙醇3.3 mL，标准液1.0mol/L的三氟乙酸 46 uL，去离子水6.7 mL混合而成）浸渍10 min，再经活化溶液（PdCl2 218 mg，去离子水 10 mL，NaCl 47 mg）浸渍10 min。将处理后的薄膜放入Ni镀液（硫酸镍40mg； 亚氨基二乙酸30 mg；32 wt%的NaOH溶液30 μL）和Pt镀液（K2PtCl4溶液10 mg；标准液1.0mol/L的乙二胺134 μL；去离子水5 mL）的混合液中，加入还原液（40%-80wt%水合肼20 μL和去离子水1 mL），反应2 h，得到管状Ni-Pt纳米合金材料。
实施例5：
选用对苯二甲酸乙二酯作为模板，在45 ℃下3 M 氢氧化钠溶液下刻蚀30 min，随后分别对其正反两面进行紫外灯辐射20 min，再在DMF溶剂中浸渍10 min。经敏化溶液（SnCl290 mg，90%-98wt%乙醇3.3 mL，标准液1.0mol/L的三氟乙酸 46 uL，去离子水6.7 mL混合而成）浸渍20 min，再经活化溶液（PdCl2 218 mg，去离子水 10 mL，NaCl 47 mg）浸渍20 min。将处理后的薄膜放入Ni镀液（硫酸镍40mg； 亚氨基二乙酸30 mg；32 wt%的NaOH溶液30 μL）和Pt镀液（K2PtCl4溶液10 mg；标准液1.0mol/L的乙二胺134 μL；去离子水5 mL）的混合液中，加入还原液（40%-80wt%水合肼20 μL和去离子水1 mL），反应3 h，得到管状Ni-Pt纳米合金材料。见附图1。
Claims (9)
1.管状Ni-Pt纳米合金的制备方法，其特征在于该方法包括：
以对苯二甲酸乙二酯聚合物为模板，经紫外照射、溶液刻蚀形成孔基底，通过敏化溶液敏化、活化溶液活化形成金属成核中心，在化学Ni镀液和Pt镀液混合后加入处理后的模板，随后加入还原液，在常温下反应0.5～3h，去除聚合物模板后，得到管状Ni-Pt纳米合金材料。
2.管状Ni-Pt纳米合金的制备方法，其特征在于该方法包括：
以对苯二甲酸乙二酯聚合物为模板，经紫外照射、溶液刻蚀形成孔基底，通过SnCl2溶液敏化，PdCl2溶液活化形成以Pd金属成核中心，在化学Ni镀液和Pt镀液混合后加入处理后的模板，随后加入水合肼还原液，在常温下反应0.5～3 h，去除聚合物模板后，得到管状Ni-Pt纳米合金材料。
3.管状Ni-Pt纳米合金的制备方法，其特征在于该方法是：
以对苯二甲酸乙二酯作为模板，在30～60 ℃下1～3M摩尔浓度的氢氧化钠溶液下刻蚀10～30 min，随后分别对其正反两面进行紫外灯辐射5～30 min，再在二甲基甲酰胺DMF溶剂中浸渍5～30 min；
在由SnCl2 50～200 mg，90%-98wt%的乙醇1～10 mL，标准液1.0mol/L的三氟乙酸10～100uL，去离子水1～20 mL混合而成的敏化溶液中浸渍5～30 min；
再在由PdCl2 100～500mg，去离子水 1～50mL，NaCl 10～100mg混合而成的活化溶液中浸渍5～20 min；
将处理后的薄膜模板放入：由硫酸镍40mg；亚氨基二乙酸30 mg；32 wt%的NaOH溶液30μL混合而成的 Ni镀液，以及由K2PtCl4溶液10 mg；标准液1.0mol/L的乙二胺134 μL；去离子水5 mL 混合而成的Pt镀液两者的混合化学镀液中，向放入薄膜模板的混合化学镀液中加入由40%-80wt%的水合肼20 μL和去离子水1 mL混合而成的还原液，常温下反应0.5～3h，去除聚合物模板后，得到管状Ni-Pt纳米合金材料。
4.根据权利要求3所述的管状Ni-Pt纳米合金的制备方法，其特征在于该方法是：
以对苯二甲酸乙二酯作为模板，在45～60 ℃下1～3M摩尔浓度的氢氧化钠溶液下刻蚀10～30 min，随后分别对其正反两面进行紫外灯辐射5～20 min，再在二甲基甲酰胺DMF溶剂中浸渍5～20 min；
在由SnCl2 90 mg，90%-98wt%乙醇3.3 mL，标准液1.0mol/L的三氟乙酸 46 uL，去离子水6.7 mL混合而成的敏化溶液中浸渍5～20 min；
再在由PdCl2 218 mg，去离子水 10 mL，NaCl 47 mg混合而成的活化溶液中浸渍5～20min；
将处理后的薄膜模板放入：由硫酸镍40mg；亚氨基二乙酸30 mg；32 wt%的NaOH溶液30μL混合而成的 Ni镀液，以及由K2PtCl4溶液10 mg；标准液1.0mol/L的乙二胺134 μL；去离子水5 mL 混合而成的Pt镀液两者的混合化学镀液中，向放入薄膜模板的混合化学镀液中加入由40%-80wt%水合肼20 μL和去离子水1 mL混合而成的还原液，常温下反应0.5～3h，去除聚合物模板后，得到管状Ni-Pt纳米合金材料。
5.一种根据权利要求1所述的管状Ni-Pt纳米合金的制备方法所使用的敏化溶液，其特征在于：该敏化溶液由SnCl2 50～200 mg，90%-98wt%乙醇1～10 mL，标准液1.0mol/L的三氟乙酸10～100uL，去离子水1～20 mL混合而成。
6.一种根据权利要求1所述的管状Ni-Pt纳米合金的制备方法所使用的活化溶液，其特征在于：该活化溶液由PdCl2 100～500mg，去离子水 1～50mL，NaCl 10～100mg混合而成。
7.一种根据权利要求1所述的管状Ni-Pt纳米合金的制备方法所使用的Ni镀液，其特征在于：该Ni镀液由硫酸镍40mg；亚氨基二乙酸30 mg； 32 wt%的NaOH溶液30 μL混合而成。
8.一种根据权利要求1所述的管状Ni-Pt纳米合金的制备方法所使用的Pt镀液，其特征在于：该Pt镀液由K2PtCl4溶液10 mg；标准液1.0mol/L的乙二胺134 μL；去离子水5 mL 混合而成。
9.一种根据权利要求1所述的管状Ni-Pt纳米合金的制备方法所使用的还原液，其特征在于：该还原液由40%-80wt%水合肼20 μL和去离子水1 mL混合而成。
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| CN1843673A (zh) * | 2006-05-12 | 2006-10-11 | 天津大学 | 金属纳米镍管及制备方法 |
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| CN102502573A (zh) * | 2011-10-19 | 2012-06-20 | 沈阳建筑大学 | 一种碳基纳米管同轴异质结及其模板法组装工艺 |
| CN103194772A (zh) * | 2013-04-11 | 2013-07-10 | 佛山市中国地质大学研究院 | 一种制备镍金属管状纳米阵列的电化学方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1843673A (zh) * | 2006-05-12 | 2006-10-11 | 天津大学 | 金属纳米镍管及制备方法 |
| CN102174709A (zh) * | 2011-03-08 | 2011-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | 三维金属镍纳米渐变体阵列结构及其制备方法 |
| CN102502573A (zh) * | 2011-10-19 | 2012-06-20 | 沈阳建筑大学 | 一种碳基纳米管同轴异质结及其模板法组装工艺 |
| CN103194772A (zh) * | 2013-04-11 | 2013-07-10 | 佛山市中国地质大学研究院 | 一种制备镍金属管状纳米阵列的电化学方法 |
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