CN115074771A - 一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂及其制备方法 - Google Patents
一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂及其制备方法 Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
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- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
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Abstract
本申请涉及电催化剂的技术领域,具体公开了一种氮掺杂碳纳米管包覆Ni3ZnC0.7/N异质纳米粒子电催化剂及其制备方法;制备方法包括以下步骤:取NiCl2·6H2O、Zn(OAc)2·2H2O和二聚氰胺研磨得到混合粉末;将混合粉末转至瓷舟,置于管式炉在惰性气氛下,经高温碳化还原,冷却至室温后研磨得到基础电催化剂;将基础电催化剂经碱性溶液处理后,用乙醇和水交替清洗至中性,真空干燥得到电催化剂。本申请一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂具有低成本、高活性、高稳定性的优点,其制备方法工艺简单,无需前驱体的制备便能成功合成,可行性强。
Description
技术领域
本申请涉及电催化剂的技术领域,更具体地说,它涉及一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂及其制备方法。
背景技术
面对当前不断增长的能源危机和环境污染问题,探寻一种能可持续使用且绿色环保的新能源已经迫在眉睫。氢能因其环保且能量利用率高的特性被认为是21世纪最受青睐的新能源之一。工业生产氢气的方式虽然较多,但相比较而言,电解水制氢无论从原料、工艺、环保等各方面都占巨大优势。此外,电解水生产的氢气纯度较高,因此这种制氢技术是目前实现氢能源产业化发展的最佳选择。基于电解水产氢的诸多优势,越来越多的研究者都将矛头转向这方面研究,但是到目前为止,由于电解水产氢机制的复杂电子转移过程,无论从动力学还是热力学,反应过程的能垒都比较大,因而需要高性能的催化剂来提高水裂解的效率。
目前商用的催化剂主要是贵金属基电催化剂,如铂(Pt)、铱(IrO2)等,由于这类催化剂的储量有限且成本昂贵,使其长期工业化应用受到限制,因此开发一种低成本、高活性、高稳定性的非贵金属电催化剂是大势所趋。
发明内容
为了提供一种低成本、高活性、高稳定性的非贵金属电催化剂,本申请提供一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂及其制备方法。
第一方面,本申请提供一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法。
一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法,包括以下步骤:
1)按摩尔比为(1~3):1分别取NiCl2·6H2O和Zn(OAc)2·2H2O,然后按NiCl2·6H2O和Zn(OAc)2·2H2O的质量和与二聚氰胺按质量比1:5取二聚氰胺,将三者充分研磨得到混合粉末;
2)将混合粉末转至瓷舟,置于管式炉在惰性气氛下,经500~1000℃碳化还原1~4h,冷却至室温后研磨得到基础电催化剂;
3)将基础电催化剂经碱性溶液处理24h后,用乙醇和水交替清洗至中性,在60~80℃真空干燥6~8h得到电催化剂。
进一步的,所述步骤2)中惰性气氛为Ar气或H2和Ar的混合气。
进一步的,所述步骤2)中管式炉升温速率为5~10℃/min。
进一步的,所述步骤2)中惰性气氛的气流速率为80~100mL/min。
进一步的,所述步骤3)中碱性溶液为1M KOH。
进一步的,所述Ni3ZnC0.7/Ni异质纳米粒子电催化剂的结构为碳纳米管内嵌异相Ni3ZnC0.7/Ni异质纳米粒子。
第二方面,本申请提供一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂。
一种如上述制备方法制得的氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂。
进一步的,所述Ni3ZnC0.7/Ni异质纳米粒子电催化剂的结构为碳纳米管内嵌异相Ni3ZnC0.7/Ni异质纳米粒子。
进一步的,所述催化剂在1M KOH溶液中,10mA/cm-2的电流密度下的产氢过电势为191mV;在O2饱和的0.1M KOH中,氧还原反应在1600rpm转速下的起始电位为1.015V,半波电位为0.835V。
综上所述,本申请具有以下有益效果:
1)本申请采用简单的一步固相法合成具有双功能特性的碳包覆双金属碳化物结构纳米电催化材料,实现高效的电催化析氢和氧还原反应,进一步创新性的实现了HER和ORR反应的双金属活性位点;
2)本申请通过高温碳化处理成功地设计出氮掺杂碳骨架负载双金属原子基团,金属原子与碳之间形成牢固的金属-C化学键,提高了催化剂的稳定性;与单金属相比,双金属提供了更多的活性位点供氢原子吸附,从而提高了产氢效率;此外,Ni3ZnC0.7纳米颗粒表现出一种合金特性,增强了催化剂的导电率,并确保反应过程中有效的电子传输;且Ni3ZnC0.7与Ni之间形成的异质结构可提供更多的催化反应位点及强烈的电子密度耗尽和积累,从而可降低反应过程的吸附脱附能垒,加速反应动力学;
3)本申请中的制备方法工艺简单,无需前驱体的制备便能成功合成,可行性强。
附图说明
图1为本申请实例1制备的氮掺杂碳包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的XRD图谱。
图2为本申请调节NiCl2·6H2O与Zn(OAc)2·2H2O摩尔比分别制备的氮掺杂碳包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的XRD图谱。
图3为本申请实例1制备的氮掺杂碳包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的TEM及HRTEM图谱。
图4为本申请实例1制备的氮掺杂碳包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的LSV产氢性能曲线。
图5为本申请实例1制备的氮掺杂碳包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的氧还原性能曲线。
图6为本申请对比例1两步法制备的氮掺杂碳包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的SEM图。
图7为本申请对比例1两步法制备的氮掺杂碳包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的XRD图谱。
图8为本申请对比例1两步法制备的氮掺杂碳包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂与实例1一步法制备催化剂的LSV产氢性能曲线。
具体实施方式
以下结合实施例对本发明的具体内容做进一步详细解释说明,予以特别说明的是:以下实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行,以下实施例中所用原料除特殊说明外均可来源于普通市售。
实施例
实施例1
一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法,包括以下步骤:
1)取0.357g的NiCl2·6H2O、0.165g的二水乙酸锌Zn(OAc)2·2H2O和2.61g二聚氰胺研磨30min得到混合粉末;
2)将混合粉末转至瓷舟,置于管式炉在惰性气氛下,以10℃/min的升温速率一步升温至800℃保温2h后,冷却至室温后研磨得到基础电催化剂;
3)将基础电催化剂经0.1M的KOH溶液处理24h后,用乙醇和水交替清洗至中性,在60℃真空干燥8h得到电催化剂。
从图1中可以看出在44.4°、51.7°、76.3°为Ni单质的特征峰;在42.9°、50.0°、73.3°显示出Ni3ZnC0.7的特征峰;在26.5°显示出C的特征峰,以上结果证明了复合产物的成功合成。
图2为调控Ni源与Zn源的摩尔比合成的不同催化剂的XRD图谱,从图2中可以看出实施案例中采用的任意一种比例均可以得到本专利中氮掺杂碳包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂。
从图3中可以清楚地看到该样品的形貌是Ni3ZnC0.7和Ni纳米粒子异质嵌入到氮掺杂的碳骨架中,该结构可以抑制纳米粒子的团聚以及在电解液中反应。
由图4可以看出10mA/cm2的电流密度下,其产氢过电势约为191mV,具有优异的电化学产氢活性。
由图5可以看出在O2饱和的0.1MKOH电解液中,其1600rmp下的氧还原反应半波电位E1/2=0.81V,具有较好的氧还原催化活性。
实施例2
一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法,包括以下步骤:
1)取0.237g的NiCl2·6H2O、0.109g的Zn(OAc)2·2H2O和1.73g二聚氰胺研磨30min得到混合粉末;
2)将混合粉末转至瓷舟,置于管式炉在H2和Ar的混合气气氛下,以10℃/min的升温速率一步升温至800℃并煅烧2h,冷却至室温后研磨得到基础电催化剂;
3)将基础电催化剂经0.1M的KOH溶液处理24h后,用乙醇和水交替清洗至中性,在60℃真空干燥8h得到电催化剂。
实施例3
一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法,按照实施例2中方法进行,不同之处在于,步骤2)中管式炉中氩气气氛中下以10℃/min的升温速率一步升温至800℃并煅烧2h得到黑色产物,将得到的黑色产物用乙醇和水交替清洗至中性再干燥得到基础电催化剂。
实施例4
一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法,按照实施例1中方法进行,不同之处在于,原料中NiCl2·6H2O的添加量为0.474g,Zn(OAc)2·2H2O的添加量为0.438g,二聚氰胺的添加量为4.56g。
步骤2)中管式炉中氩气气氛中下以5℃/min的升温速率一步升温至500℃并煅烧4h得到黑色产物,将得到的黑色产物用乙醇和水交替清洗至中性再干燥得到基础电催化剂。
实施例5
一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法,按照实施例1中方法进行,不同之处在于,原料中NiCl2·6H2O的添加量为0.355g,Zn(OAc)2·2H2O的添加量为0.109g,二聚氰胺的添加量为2.32g。
步骤2)中管式炉中氩气气氛中下以8℃/min的升温速率一步升温至1000℃并煅烧1h得到黑色产物,将得到的黑色产物用乙醇和水交替清洗至中性再干燥得到基础电催化剂。
对比例
对比例1
一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法,包括以下步骤:
1)取0.237g的NiCl2·6H2O、0.109g的Zn(OAc)2·2H2O和0.180g的尿素溶解于24ml超纯水和36ml甲醇的混合液中,室温下磁力搅拌得到均匀溶液A;
2)将溶液A倒入水热釜中,密封,置于烘箱中在170℃水热反应17h;待反应完成后冷却至室温,所得产物用乙醇和水交替清洗干净并在60℃真空干燥8h后得到NiZn-LDH粉末;
3)取0.1gNiZn-LDH粉末,另取0.5gDCD,一同放入研钵中充分研磨30min得到粉末样品;
4)将粉末样品转移至瓷舟,然后在管式炉中氩气气氛下以10℃/min的升温速率升温至800℃并煅烧2h得到电催化剂。
从图6可以看出,相同摩尔比下采用先水热再热处理合成的电催化剂纳米粒子团聚严重,纳米管结构几乎不可见,这种结构不利于催化活性位点的暴露。
从图7可以看出,两步法也可合成类似于一步固相反应的复合相Ni3ZnC0.7和Ni纳米电催化剂。
从图8可以看出,对比例1两步法合成纳米电催化剂HER性能明显不如本申请实施例1,具体表现为对比例1驱动10mA/cm2的电流密度,需要的过电势为329mV,而本申请实施例1仅为191mV,说明本申请的工艺简单,而且可达到优于对比例的HER活性。
对比例2
一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法,包括以下步骤:
1)取0.237g的NiCl2·6H2O、0.07g的Zn(OAc)2·2H2O和0.180g的尿素溶解于50ml的超纯水中,室温下磁力搅拌得到均匀溶液A;
2)将溶液A倒入水热釜中,密封,置于烘箱中在170℃水热反应17h;待反应完成后冷却至室温,所得产物用乙醇和水交替清洗干净并在60℃真空干燥8h后得到NiZn-LDH粉末;
3)取0.1gNiZn-LDH粉末,另取0.5gDCD,一同放入研钵中充分研磨30min得到粉末样品;
4)将粉末样品转移至瓷舟,然后在管式炉中氩气气氛下以10℃/min的升温速率升温至800℃并煅烧2h得到电催化剂。
对比例3
1)取0.237g的NiCl2·6H2O、0.219g的Zn(OAc)2·2H2O和0.180g的尿素溶解于50ml的超纯水中,室温下磁力搅拌得到均匀溶液A;
2)将溶液A倒入水热釜中,密封,置于烘箱中在170℃水热反应17h;待反应完成后冷却至室温,所得产物用乙醇和水交替清洗干净并在60℃真空干燥8h后得到NiZn-LDH粉末;
3)取0.1gNiZn-LDH粉末,另取0.5gDCD,一同放入研钵中充分研磨30min得到粉末样品;
4)将粉末样品转移至瓷舟,然后在管式炉中氩气气氛下以10℃/min的升温速率升温至800℃并煅烧2h得到电催化剂。
Claims (8)
1.一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法,其特征在于,包括以下步骤:
1)按摩尔比为(1~3):1分别取NiCl2·6H2O和Zn(OAc)2·2H2O,然后按NiCl2·6H2O和Zn(OAc)2·2H2O的质量和与二聚氰胺按质量比1:5取二聚氰胺,将三者充分研磨得到混合粉末;
2)将混合粉末转至瓷舟,置于管式炉在惰性气氛下,经500~1000℃碳化还原1~4h,冷却至室温后研磨得到基础电催化剂;
3)将基础电催化剂经碱性溶液处理24h后,用乙醇和水交替清洗至中性,在60~80℃真空干燥6~8h得到电催化剂。
2.根据权利要求1所述的一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法,其特征在于:所述步骤2)中惰性气氛为Ar气或H2和Ar的混合气。
3.根据权利要求1所述的一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法,其特征在于:所述步骤2)中管式炉升温速率为5~10℃/min。
4.根据权利要求1所述的一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法,其特征在于:所述步骤2)中惰性气氛的气流速率为80~100mL/min。
5.根据权利要求1所述的一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂的制备方法,其特征在于:所述步骤3)中碱性溶液为1M KOH。
6.一种如权利要求1-5中任意一项所述制备方法制得的氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂。
7.根据权利要求6所述的一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂,其特征在于:所述Ni3ZnC0.7/Ni异质纳米粒子电催化剂的结构为碳纳米管内嵌异相Ni3ZnC0.7/Ni异质纳米粒子。
8.根据权利要求6所述的一种氮掺杂碳纳米管包覆Ni3ZnC0.7/Ni异质纳米粒子电催化剂,其特征在于:所述催化剂在1M KOH溶液中,10mA/cm-2的电流密度下的产氢过电势为191mV;在O2饱和的0.1M KOH中,氧还原反应在1600rpm转速下的起始电位为1.015V,半波电位为0.835V。
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