CN108273524B - 一种硫属化合物与过渡金属修饰的碳复合材料及其制备方法与应用 - Google Patents
一种硫属化合物与过渡金属修饰的碳复合材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明提供了一种硫属化合物与过渡金属修饰的碳复合材料及其制备方法与应用,将碳纳米管与可溶性硫属化合物的混合物加到溶剂中,超声形成悬浊液后滴加于经预处理的玻碳电极表面,自然晾干形成均匀的碳纳米管薄层,得到碳纳米管与硫属化合物的混合物修饰的玻碳电极;在去离子水中加入过渡金属盐,支撑电解质,用硫酸调节pH为0~13,得到电镀液;将碳纳米管与硫属化合物的混合物修饰的玻碳电极置于电镀液中实施电镀,之后用水清洗并在常温下自然干燥,得到最终产品;本发明方法操作简单,制得的复合材料在催化氢析出和能量转换方面具有很大的优势,可应用于电催化水分解产氢以及光电转换领域。
Description
技术领域
本发明属于纳米复合材料研究领域,特别是通过一种溶化法、超声混合的方法来制备修饰过的碳复合材料和通过电沉积的方法得到硫属化合物与过渡金属修饰的碳复合材料。
背景技术
煤,石油等传统的化石燃料的燃烧带来了酸雨,温室效应以及雾霾等环境问题,并且化石燃料是不可再生资源,正在日益枯竭。所以,努力寻求、开发理想的清洁高效的新能源日益重要 ,这也是新世纪亟待解决的主要能源问题之一。而燃料电池就很符合上述新能源的要求。目前,商业化燃料电池中使用最成熟的阴、阳极催化剂均为贵金属及其合金,然而贵金属的价格及其昂贵,储存量稀少,致使燃料电池催化剂成本太高,阻碍了燃料电池进一步的发展。另外,在阴极的氧气环境下,贵金属铂易被一氧化碳中毒从而导致料催化寿命降低。因此,降低贵金属催化剂的用量或寻求廉价的非贵金属催化剂已成为了当前燃料电池催化剂研究的主要导向。
所以为了能使电解水可持续产氢,我们得寻求一种高催化性、高稳定性的非贵金属催化剂来代替Pt。Brewer-Engel价键理论认为,当过渡金属d轨道在半充满或者未充满状态时, 有利于电子在析氢过程中的传递,这些结构的金属会在电催化方面会产生明显的协同作用提高析氢反应的催化活性, 因此,过渡金属化合物显示了可替代铂或铂合金巨大的潜在价值。
最近关于硫化物氢析出电催化剂的发展,主要集中在以下几个方面:(1)将其与碳材料(如炭黑、碳纳米管、掺杂非金属元素后的碳纳米管、石墨烯等)耦合来改善其导电性;(2)将其设计成各种不同的纳米尺寸结构来最大限度的暴露其活性位点;(3)通过掺杂其它元素设计制备多空道结构来提高材料本身的催化活性。
为了能实现其大规模的使用,必须研究开发简便且成本较低的制备方法来得到活性较高的氧还原反应催化剂,从而提升氧还原反应催化剂的实际应用前景。
发明内容
本发明的目的是为了克服现有技术存在的缺点和不足,而提供一种硫属化合物与过渡金属修饰的碳复合材料的制备方法,合成方法简单,不涉及有毒有害物质,易于大规模生产。
本发明的第二个目的是提供一种硫属化合物与过渡金属修饰的碳复合材料,该复合材料孔径大小可控、边缘活性位多、活性高、活性成分与载体理想复合。
本发明的第三个目的是提供一种硫属化合物与过渡金属修饰的碳复合材料
作为电催化氢析出反应催化剂的应用。
为实现上述目的,本发明采用如下技术方案:
一种硫属化合物与过渡金属修饰的碳复合材料的制备方法,按照如下步骤进行:
(1)制备碳纳米管修饰的玻碳电极:将阵列碳纳米管与硫属化合物硫代硫酸钠按照1:1~5的质量比加到溶剂中,4超声2h形成悬浊液,将该悬浊液滴加于经预处理的玻碳电极表面,自然晾干形成均匀的碳纳米管薄层,得到修饰的碳纳米管的玻碳电极;
所述的溶剂为乙醇、水或乙醇/水体积比1:1~5的混合液
所述的碳纳米管(CNTs)与硫代硫酸钠的比例为1:1~5
所述溶剂的体积用量以碳纳米管的质量计为0.1~0.5mL/mg(特别优选0.25mL/mg);
所述的碳纳米管为单壁、多壁、阵列或杂原子(如N、S)掺杂的碳纳米管中的一种或多种组合的混合物;
所述玻碳电极的预处理方法为常规处理电极的方法,即:将玻碳电极依次进行抛光、水洗、于16~32KHz超声10~60s的预处理;
(2)配制电镀液:在去离子水中加入前驱体A,用氨水和盐酸调节pH为0~13,得到电镀液;
所述前驱体A在电镀液中的终浓度为≤10mol/L;
所述前驱体A为硫属化合物过渡金属可溶性盐,如四硫代钨酸铵、四硫代钼酸铵、硫酸钴。
(3)硫属化合物与过渡金属修饰的碳复合材料:将步骤(1)得到的碳纳米管修饰的玻碳电极置于步骤(2)得到的电镀液中,在扫描电位为-2.0~1.0V,扫描速度为1~100mV/s,操作温度为18~35℃的条件下实施电镀,施镀时间为1~200min,得到覆有硫属化合物与过渡金属修饰的碳复合材料的玻碳电极,将该玻碳电极用水清洗并在常温下自然干燥后,用刀片将复合材料从玻碳电极表面刮下即得到最终产品。
本发明所制备的碳化合物/碳纳米管复合材料形貌均一,大小可控,(通过对电镀时间和电镀液浓度的调控来实现),所制得的硫属化合物与过渡金属修饰的碳复合材料在电催化产氢的应用可应用于光、电催化氧还原反应。
本发明的有益效果在于:
(1)所选用的基底是具有较好导电性的CNTs(单壁、多壁、阵列或杂原子掺杂等)、石墨烯中的一种或两种以上;
(2)制备的复合材料孔径大小可控;
(3)制备的复合材料的边缘活性位很多;
(4)制备的复合材料界面结合很好,有利于实现电子的高效传输以及材料之间的协同效应,更好的发挥活性。
综上所述,一方面,本发明提供的硫属化合物与过渡金属修饰的碳复合材料并用作电催化剂研究的方法,操作简单,不涉及有毒有害物质即可完成,易于大规模生产;另一方面,通过合适的条件控制,可将CNTs与非贵金属的化合物复合,制得的复合材料在催化氢析出和能量转换方面具有很大的优势,在催化氢析出反应中,制得的复合材料的超电势较低,电流密度较大,稳定性较强,从而提高了其在燃料电池以及光电转换中的应用价值。
附图说明
图1本发明硫属化合物与过渡金属修饰的碳复合材料的流程示意图;
图2 本发明实施例1制得的硫属化合物与过渡金属修饰的碳复合材料的扫描电子显微镜图片;
图3本发明实施例1制得的硫属化合物与过渡金属修饰的碳复合材料的线性伏安曲线图。
具体实施方式
下面通过具体实施例对本发明进行进一步的说明,但本发明的保护范围并不仅限于此。
实施例1
制备硫属化合物与过渡金属钨修饰的碳复合材料(WxSy/CNTs)
(1)电极的预处理:取玻碳电极(上海辰华,CHI104,直径3mm),依次进行抛光、水洗、20KHz超声30s的预处理。
(2)制备碳纳米管与硫代硫酸钠修饰过的玻碳电极:将阵列碳纳米管(2mg)与硫代硫酸钠(2mg)混合物加到乙醇和水体积比4:1的混合液(1mL)中,于超声2h形成悬浊液,用移液枪移取一定体积的溶液滴加到步骤(1)中已处理的电极的表面,根据负载量的要求,可以多滴几次,但每两次之间一定得等材料自然晾干后再滴加,待材料干燥后,即形成一层致密的黑色薄膜后,用移液枪移取一定体积的萘酚乙醇溶液(质量分数为0.2%)滴加到附有催化剂的电极上,自然晾干电极备用。得到碳纳米管与硫代硫酸铵混合物修饰的玻碳电极;
(3)配制电镀液:在去离子水(100mL)中加入四硫代钨酸铵 ((NH4)2WS4)(1.7141g),用0.5M H2SO4调节pH为2.0,得到电镀液;
(4)制备硫属化合物与过渡金属钨修饰的碳复合材料(WxSy /CNTs):将步骤(2)得到的碳纳米管与硫代硫酸钠混合物修饰的玻碳电极置于步骤(3)得到的电镀液中,在扫描电位为-1V,扫描速度为50mV/s,操作温度为20℃的条件下采用计时电流法实施电镀,施镀时间为30min,得到覆有硫属化合物与过渡金属钨修饰的碳复合材料(WxSy /CNTs)的玻碳电极,将该玻碳电极用水清洗后,无需将复合材料从电极表面刮下,直接进行电化学测试。
(5)电化学测试:在三电极体系(步骤(4)制备的覆有硫属化合物与过渡金属钨修饰的碳复合材料(WxSy /CNTs)的电极作为工作电极,银/氯化银电极作为参比电极,铂片电极作为辅助电极中,测量WS/CNTs的线性扫描伏安曲线。测试所用的电解质溶液为0.5M的H2SO4溶液。图3为其线性伏安曲线图,图a)、图b)为在酸性条件下,可以看出:相比于纯碳纳米管和硫代硫酸钠可以发现起始电位更小,因此可以看出本实施例制得的WxSy /CNTs对于氢析出有优异的催化活性。
将制得的复合材料(WxSy /CNTs)进行形貌测试,图2(a)为所述复合材料的扫描电子显微镜图片照片。
实施例2
硫属化合物与过渡金属钼修饰的碳复合材料(MoxSy/CNTs)
(1)电极的预处理:取玻碳电极(上海辰华,CHI104,直径3mm),依次进行抛光、水洗、20KHz超声30s的预处理。
(2)制备碳纳米管与硫代硫酸钠修饰过的玻碳电极:将阵列碳纳米管(2mg)与硫代硫酸钠(2mg)混合物加到乙醇和水体积比4:1的混合液(1mL)中,于超声2h形成悬浊液,用移液枪移取一定体积的溶液滴加到步骤(1)中已处理的电极的表面,根据负载量的要求,可以多滴几次,但每两次之间一定得等材料自然晾干后再滴加,待材料干燥后,即形成一层致密的黑色薄膜后,用移液枪移取一定体积的萘酚乙醇溶液(质量分数为0.2%)滴加到附有催化剂的电极上,自然晾干电极备用。得到碳纳米管与硫代硫酸铵混合物修饰的玻碳电极;
(3)配制电镀液:在去离子水(100mL)中加入四硫代钼酸铵 ((NH4)2MS4)(1.301g),用0.5M H2SO4调节pH为2.0,得到电镀液;
(4)制备硫属化合物与过渡金属钼修饰的碳复合材料(MoxSy /CNTs):将步骤(2)得到的碳纳米管与硫代硫酸钠混合物修饰的玻碳电极置于步骤(3)得到的电镀液中,在扫描电位为-0.2~0.8V,扫描速度为50mV/s,操作温度为20℃的条件下采用循环伏安法实施电镀,施镀时间为30min,得到覆有硫属化合物与过渡金属钼修饰的碳复合材料(MoxSy /CNTs)的玻碳电极,将该玻碳电极用水清洗后,无需将复合材料从电极表面刮下,直接进行电化学测试。
(5)电化学测试:在三电极体系(步骤(4)制备的覆有硫属化合物与过渡金属钼修饰的碳复合材料(MoxSy /CNTs)的电极作为工作电极,银/氯化银电极作为参比电极,铂片电极作为辅助电极中,测量MoxSy/CNTs的线性扫描伏安曲线。测试所用的电解质溶液为0.5M的H2SO4溶液。图3为其线性伏安曲线图,图a)、图b)为在酸性条件下,可以看出:相比于纯碳纳米管和无硫代硫酸钠修饰,可以发现起始电位更小,因此可以看出本实施例制得的MoxSy /CNTs对于氢析出有优异的催化活性。
将制得的复合材料(MoxSy /CNTs)进行形貌测试,图2(b)为所述复合材料的扫描电子显微镜图片照片。
实施例3
硫属化合物与过渡金属钴修饰的碳复合材料(CoxSy/CNTs)
(1)电极的预处理:取玻碳电极(上海辰华,CHI104,直径3mm),依次进行抛光、水洗、20KHz超声30s的预处理。
(2)制备碳纳米管与硫代硫酸钠修饰过的玻碳电极:将阵列碳纳米管(2mg)与硫代硫酸钠(2mg)混合物加到乙醇和水体积比4:1的混合液(1mL)中,于超声2h形成悬浊液,用移液枪移取一定体积的溶液滴加到步骤(1)中已处理的电极的表面,根据负载量的要求,可以多滴几次,但每两次之间一定得等材料自然晾干后再滴加,待材料干燥后,即形成一层致密的黑色薄膜后,用移液枪移取一定体积的萘酚乙醇溶液(质量分数为0.2%)滴加到附有催化剂的电极上,自然晾干电极备用。得到碳纳米管与硫代硫酸铵混合物修饰的玻碳电极;
(3)配制电镀液:在去离子水(100mL)中加入硫酸钴 (CoSO4•7H2O)(8.433g)、次磷酸钠(2.639g),支撑电解质硼酸(4.946g),用0.5M H2SO4调节pH为2.0,得到电镀液;
(4)制备硫属化合物与过渡金属钴修饰的碳复合材料(CoxSy/CNTs):将步骤(2)得到的碳纳米管与硫代硫酸钠混合物修饰的玻碳电极置于步骤(3)得到的电镀液中,在扫描电位为-1.8~0.5V,扫描速度为50mV/s,操作温度为20℃的条件下采用循环伏安法实施电镀,施镀时间为30min,得到覆有硫属化合物与过渡金属钴修饰的碳复合材料(CoxSy /CNTs)的玻碳电极,将该玻碳电极用水清洗后,无需将复合材料从电极表面刮下,直接进行电化学测试。
(5)电化学测试:在三电极体系(步骤(4)制备的覆有硫属化合物与过渡金属钴修饰的碳复合材料(CoxSy /CNTs)的电极作为工作电极,银/氯化银电极作为参比电极,铂片电极作为辅助电极中,测量CoxSy/CNTs的线性扫描伏安曲线。测试所用的电解质溶液为0.5M的H2SO4溶液。图3为其线性伏安曲线图,图a)、图b)为在酸性条件下,可以看出:相比于纯碳纳米管和无硫代硫酸钠修饰,可以发现起始电位更小,因此可以看出本实施例制得的CoxSy /CNTs对于氢析出有优异的催化活性。
将制得的复合材料(CoxSy /CNTs)进行形貌测试,图2(c)为所述复合材料的扫描电子显微镜图片照片。本发明方法制得的复合材料,表现出良好的电催化氢析出性能,为氢析出催化剂的发展探索出一条新颖而有效的途径。显然,上述实施例仅仅是为了清楚地说明本发明技术方案所做的举例,而并非对实施方案的限定。对于所属领域的技术人员来说,在上述说明的基础上还可以做出其他不同形式的变化或变动,这里无需也无法对所有的实施方案予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明的保护范围内。
Claims (8)
1.一种硫属化合物与过渡金属修饰的碳复合材料的制备方法,其特征在于,包括以下步骤:
(1)制备碳纳米管修饰的玻碳电极:将阵列碳纳米管与硫代硫酸钠按照1:1~5的质量比加到溶剂中,超声形成悬浊液,将该悬浊液滴加于经预处理的玻碳电极表面,自然晾干形成均匀的碳纳米管薄层,得到修饰的碳纳米管的玻碳电极;
(2)配制电镀液:在去离子水中加入前驱体A,用氨水和盐酸调节pH为0~13,得到电镀液,所述前驱体A为硫属化合物过渡金属可溶性盐,所述前驱体A在电镀液中的终浓度为≤10mol/L;
(3)硫属化合物与过渡金属修饰的碳复合材料:将步骤(1)得到的碳纳米管修饰的玻碳电极置于步骤(2)得到的电镀液中,在扫描电位为-2.0~1.0V,扫描速度为1~100mV/s,操作温度为18~35℃的条件下实施电镀,施镀时间为1~200min,得到覆有硫属化合物与过渡金属修饰的碳复合材料的玻碳电极,从玻碳电极表面取下硫属化合物与过渡金属修饰的碳复合材料,即得到最终产品。
2.如权利要求1所述的制备方法,其特征在于,步骤(1)中,所述溶剂为乙醇、水或乙醇/水体积比1:1~5的混合液,所述的溶剂的体积用量以碳纳米管的质量计为0.1~0.5mL/mg。
3.如权利要求1所述的制备方法,其特征在于,步骤(1)中,所述玻碳电极的预处理方法为:将玻碳电极依次进行抛光、水洗、于16~32KHz超声10~60s的预处理。
4.如权利要求1所述的制备方法,其特征在于,步骤(1)中,所述碳纳米管为单壁、多壁、阵列、N掺杂或S掺杂的碳纳米管中的一种或多种组合的混合物。
5.如权利要求1所述的制备方法,其特征在于,步骤(1)中,所述悬浊液在所述玻碳电极表面的滴加量为50~200μL/cm2。
6.如权利要求1所述的制备方法,其特征在于,步骤(2)中,所述前驱体A为四硫代钨酸铵、四硫代钼酸铵或硫酸钴。
7.一种如权利要求1-6任一项所述的制备方法制备的硫属化合物与过渡金属修饰的碳复合材料。
8.一种如权利要求7所述的硫属化合物与过渡金属修饰的碳复合材料作为电催化氢析出反应中作为催化剂的应用。
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