CN110787805B - 一种富勒烯纳米棒/层状双金属氢氧化物电催化剂及其制备方法 - Google Patents
一种富勒烯纳米棒/层状双金属氢氧化物电催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种富勒烯纳米棒/层状双金属氢氧化物电催化剂及其制备方法,所述制备方法具体步骤包括:1)、对富勒烯自组装纳米棒(FNR‑150)进行改性处理:2)、采用共沉淀法将过渡金属盐、富勒烯纳米棒、尿素进行加热回流,抽滤洗涤后得富勒烯纳米棒/层状双金属氢氧化物电催化剂;本发明制备方法简单易行,所采用的原料廉价易得,制备成本低,所得产物电催化活性高且稳定性高。
Description
技术领域
本发明涉及电催化剂领域,具体涉及一种富勒烯纳米棒/层状双金属氢氧化物电催化剂及其制备方法。
背景技术
电催化裂解水是一种绿色高效的新能源技术,能将水分解为氢气和氧气,不易产生有毒有害中间产物,且与其他技术兼容、协调效果很好。
层状双氢氧化物(LDH)作为一种典型的二维材料,LDH的片层结构由共边的八面体连接而成,羟基位于八面体的顶点,金属原子位于八面体中心,构成带正电荷的层板,为了使化合物呈电中性,层间充满阴离子。金属原子和阴离子的种类和性质都会影响LDH材料的性质和应用。LDH材料的这种结构使其具有比较大的比表面积,使LDH具有优异的性能,成为一种较理想的催化剂。
富勒烯(Fullerene)是最重要的碳同素异形体之一,是一大类笼状分子,每个分子由十二个五边形和几个六边形组成。由于它们的共轭结构和令人着迷的化学物理性质,富勒烯已经在化学、物理学、生物医学和材料科学中被广泛研究。富勒烯纳米棒就是富勒烯的一种聚集形态。富勒烯自组装纳米棒(FNR)作为一种光电半导体材料,因具有良好的电荷传输性质、光化学稳定性使其在技术应用上非常具有吸引力。
由于传统的铂、钌催化剂高昂的价格以及差的稳定性严重阻碍了它们在电催化方面的大规模应用,电催化裂解水技术难以大规模应用,电催化裂解水目前面临的重要挑战即寻找廉价高效的催化剂。
发明内容
本发明的目的在于提供一种廉价高效、稳定性高的富勒烯纳米棒/层状双金属氢氧化物电催化剂及其制备方法。
本发明的目的通过以下技术方案实现:
一种富勒烯纳米棒/层状双金属氢氧化物电催化剂的制备方法,具体步骤包括:
步骤一:将质量比为5:1的聚乙烯吡咯烷酮和富勒烯自组装纳米棒溶于去离子水搅拌后倒入烧瓶,于60~120 ℃下反应3~8h,反应完成后得到富勒烯自组装纳米棒的改性样品;
步骤二:将30-80mg步骤一所得改性样品与0.5-2.5mmol过渡金属盐混合后溶于乙二醇和去离子水混合溶液中并搅拌,边搅拌边加入7.5-37.5mmol尿素,搅拌完成后于100~150 ℃的条件下进行回流,再将产物抽滤,用去离子水和无水乙醇洗涤后真空干燥,得到富勒烯纳米棒/层状双金属氢氧化物电催化剂。
进一步,所述步骤一中的富勒烯自组装纳米棒制备方法为:将50~200 mg的C60溶于有机溶剂中并超声分散形成均匀的C60饱和溶液,向C60饱和溶液中加入100~300 mL醇溶液后静置,静置后离心,将离心得到的沉淀洗涤、干燥,再于150 ℃条件下进行退火处理,得到富勒烯自组装纳米棒。
进一步,所述有机溶剂为甲苯、二甲苯、均三甲苯、异丙苯中的一种或几种。
进一步,所述静置的时间为6~48 h。
进一步,所述退火处理的时间为3 h。
进一步,所述步骤一中的搅拌时间为10 min,步骤二中搅拌的时间为15 min。
进一步,所述过渡金属盐中的金属为铁、钴、镍、锰、铜、锌中的几种,过渡金属盐为硝酸盐、硫酸盐、乙酸盐、氯化物中的一种或几种。
进一步,所述步骤二中回流的时间为3~15 h。
与现有技术相比,本发明具有以下有益效果:
本发明采用富勒烯自组装纳米棒、过渡金属盐、尿素作为原料进行制备,相比于传统的铂、钌催化剂,本发明的制备成本低;经过步骤1)改性后的富勒烯纳米棒亲水性增加,有利于层状双氢氧化物在其表面稳定生长,提高了产物的稳定性;本发明采用的制备方法使反应受热均匀,易控制,易得到目标产物,操作简单易行。
本发明制备的富勒烯纳米棒具有较大的比表面积,较好的电子传输性能,作为导电基底,在其表面生长层状双氢氧化物,增加了层状双氢氧化物的催化活性位点,同时增强了其电荷传输速率,从而增强催化性能,具有高效的电催化性能。
附图说明
图1为实施例1制备得到的FNR-150-PVP/CoNi-LDH复合物与CoNi-LDH的XRD图;
图2a为实施例1制备得到的FNR的SEM表征图;
图2b为实施例1制备得到的FNR-150的SEM表征图;
图2c为实施例1制备得到的FNR-150-PVP的SEM表征图;
图3为实施例1制备得到的FNR-150-PVP/CoNi-LDH样品在100 nm放大倍数下的TEM表征图;
具体实施方式
以下结合附图和具体实施例对本发明作进一步详细的描述:
实施例1:
1)、采用液-液界面沉淀法合成富勒烯自组装纳米棒(FNR):将100 mg的C60溶于100mL的均三甲苯中,并超声分散形成均匀的C60饱和溶液,向上述C60饱和溶液中加入50mL醇溶液后静置12 h,静置后离心,将离心得到的沉淀洗涤、干燥,再于150 ℃条件下在管式炉中进行3 h退火处理,得到富勒烯自组装纳米棒(标记为FNR-150);
2)、对所得富勒烯自组装纳米棒(FNR-150)进行改性处理:称取1 g聚乙烯吡咯烷酮(PVP)和200 mg的富勒烯自组装纳米棒(FNR-150),将两者溶于100mL去离子水中并搅拌10 min之后倒入圆底烧瓶,于60 ℃下反应6 h,反应完成后得到改性样品(标记为FNR-150-PVP);
3)、采用共沉淀法将两种过渡金属盐、富勒烯纳米棒、尿素进行加热回流:将40 mg的改性样品(FNR-150-PVP)与73 mg硝酸镍、146 mg硝酸钴混合后溶于乙二醇和去离子水中并搅拌,边搅拌边加入2250 mg尿素,搅拌15 min后于110 ℃的条件下进行回流3 h,再将产物抽滤,用去离子水和无水乙醇洗涤后真空干燥,得到富勒烯纳米棒/层状双金属氢氧化物电催化剂(标记为FNR-150-PVP/LDH)。
图1为实施例1制备得到的FNR-150-PVP/CoNi-LDH复合物与CoNi-LDH的XRD图;。CoNi-LDH和CoNi-LDH/CQD样品在约11.59,23.14,34.59和60.85分别显示衍射峰,分别对应于CoNi-LDH的(003),(006),(012)和(110)面,表明CoNi-LDH的形成。复合之后峰产生了偏移,是由于FNR-150-PVP和CoNi-LDH之间产生了电荷转移而引起的。
图2a、2b、2c分别是FNR、FNR-150、FNR-150-PVP样品的SEM表征图,可以看出所合成的FNR成光滑的纳米棒状,退火之后FNR-150表面的有机溶剂分子脱出,表面出现空隙,变得粗糙。经过表面改性,纳米棒表面包裹上一层PVP分子,这改变了纳米棒的亲水性,有利于LDH在其表面生长。
图3是FNR-150-PVP/CoNi-LDH样品在100 nm放大倍数下的TEM表征图,由图可以看出,LDH纳米片成功生长在纳米棒表面。
实施例1制备得到的FNR-150-PVP/CoNi-LDH复合物与CoNi-LDH相比,相同电流密度下所需电压越小即表明催化效果越好,FNR-150-PVP/CoNi-LDH的性能最好,在达到10mA/cm2时,仅仅需要313 mV的过电位。因为富勒烯纳米棒具有较大的比表面积,较好的电子传输性能,作为导电基底,在其表面生长LDH,增加了LDH的催化活性位点,同时增强了其电荷传输速率,从而增强催化性能。
实施例2:
1)、采用液-液界面沉淀法合成富勒烯自组装纳米棒(FNR):将50 mg的C60溶于50mL的均三甲苯中,并超声分散形成均匀的C60饱和溶液,向上述C60饱和溶液中加入50mL甲醇溶液后静置12 h,静置后离心,将离心得到的沉淀洗涤、干燥,再于150 ℃条件下在管式炉中进行3 h退火处理,得到富勒烯自组装纳米棒(标记为FNR-150);
2)、对所得富勒烯自组装纳米棒(FNR-150)进行改性处理:称取1 g聚乙烯吡咯烷酮(PVP)和200 mg的富勒烯自组装纳米棒(FNR-150),将两者溶于100mL去离子水中并搅拌10 min之后倒入圆底烧瓶,于60 ℃下反应6 h,反应完成后得到改性样品(标记为FNR-150-PVP);
3)、采用共沉淀法将两种过渡金属盐、富勒烯纳米棒、尿素进行加热回流:将60 mg的改性样品(FNR-150-PVP)与145 mg硝酸镍、291 mg硝酸钴混合后溶于乙二醇和去离子水中并搅拌,边搅拌边加入450 mg尿素,搅拌15 min后于130 ℃的条件下进行回流3 h,再将产物抽滤,用去离子水和无水乙醇洗涤后真空干燥,得到富勒烯纳米棒/层状双金属氢氧化物电催化剂(标记为FNR-150-PVP/LDH)。
实施例3:
1)、采用液-液界面沉淀法合成富勒烯自组装纳米棒(FNR):将50 mg的C60溶于50mL的均三甲苯中,并超声分散形成均匀的C60饱和溶液,向上述C60饱和溶液中加入50mL乙醇溶液后静置20 h,静置后离心,将离心得到的沉淀洗涤、干燥,再于150 ℃条件下在管式炉中进行3 h退火处理,得到富勒烯自组装纳米棒(标记为FNR-150);
2)、对所得富勒烯自组装纳米棒(FNR-150)进行改性处理:称取1 g聚乙烯吡咯烷酮(PVP)和200 mg的富勒烯自组装纳米棒(FNR-150),将两者溶于100mL去离子水中并搅拌10 min之后倒入圆底烧瓶,于60 ℃下反应6 h,反应完成后得到改性样品(标记为FNR-150-PVP);
3)、采用共沉淀法将两种过渡金属盐、富勒烯纳米棒、尿素进行加热回流:将80 mg的改性样品(FNR-150-PVP)、291 mg硝酸镍、582 mg硝酸钴混合后溶于乙二醇和去离子水中并搅拌,边搅拌边加入900 mg尿素,搅拌15 min后于100 ℃的条件下进行回流3 h,再将产物抽滤,用去离子水和无水乙醇洗涤后真空干燥,得到富勒烯纳米棒/层状双金属氢氧化物电催化剂(标记为FNR-150-PVP/LDH)。
实施例4:
1)、采用液-液界面沉淀法合成富勒烯自组装纳米棒(FNR):将50 mg的C60溶于12.5mL的异丙苯中,并超声分散形成均匀的C60饱和溶液,向上述C60饱和溶液中加入50mL甲醇溶液后静置12 h,静置后离心,将离心得到的沉淀洗涤、干燥,再于150 ℃条件下在管式炉中进行3 h退火处理,得到富勒烯自组装纳米棒(标记为FNR-150);
2)、对所得富勒烯自组装纳米棒(FNR-150)进行改性处理:称取1 g聚乙烯吡咯烷酮(PVP)和200 mg的富勒烯自组装纳米棒(FNR-150),将两者溶于100mL去离子水中并搅拌10 min之后倒入圆底烧瓶,于60 ℃下反应6 h,反应完成后得到改性样品(标记为FNR-150-PVP);
3)、采用共沉淀法将两种过渡金属盐、富勒烯纳米棒、尿素进行加热回流:将60 mg的改性样品(FNR-150-PVP)与54.81mg硝酸镍、58.2 mg硝酸钴混合后溶于乙二醇和去离子水中并搅拌,边搅拌边加入900 mg尿素,搅拌15 min后于130 ℃的条件下进行回流3 h,再将产物抽滤,用去离子水和无水乙醇洗涤后真空干燥,得到富勒烯纳米棒/层状双金属氢氧化物电催化剂(标记为FNR-150-PVP/LDH)。
实施例5:
1)、采用液-液界面沉淀法合成富勒烯自组装纳米棒(FNR):将50 mg的C60溶于10mL的二甲苯中,并超声分散形成均匀的C60饱和溶液,向上述C60饱和溶液中加入100mL无水乙醇溶液后静置36 h,静置后离心,将离心得到的沉淀洗涤、干燥,再于150 ℃条件下在管式炉中进行3 h退火处理,得到富勒烯自组装纳米棒(标记为FNR-150);
2)、对所得富勒烯自组装纳米棒(FNR-150)进行改性处理:称取1 g聚乙烯吡咯烷酮(PVP)和200 mg的富勒烯自组装纳米棒(FNR-150),将两者溶于100mL去离子水中并搅拌10 min之后倒入圆底烧瓶,于60 ℃下反应6 h,反应完成后得到改性样品(标记为FNR-150-PVP);
3)、采用共沉淀法将两种过渡金属盐、富勒烯纳米棒、尿素进行加热回流:将60 mg的改性样品(FNR-150-PVP)与274mg硝酸镍、291 mg硝酸钴混合后溶于乙二醇和去离子水中并搅拌,边搅拌边加入450 mg尿素,搅拌15 min后于130 ℃的条件下进行回流8 h,再将产物抽滤,用去离子水和无水乙醇洗涤后真空干燥,得到富勒烯纳米棒/层状双金属氢氧化物电催化剂(标记为FNR-150-PVP/LDH)。
实施例6:
1)、采用液-液界面沉淀法合成富勒烯自组装纳米棒(FNR):将200 mg的C60溶于200mL的均三甲苯中,并超声分散形成均匀的C60饱和溶液,向上述C60饱和溶液中加入300mL无水乙醇溶液后静置48 h,静置后离心,将离心得到的沉淀洗涤、干燥,再于150 ℃条件下在管式炉中进行3 h退火处理,得到富勒烯自组装纳米棒(标记为FNR-150);
2)、对所得富勒烯自组装纳米棒(FNR-150)进行改性处理:称取1 g聚乙烯吡咯烷酮(PVP)和200 mg的富勒烯自组装纳米棒(FNR-150),将两者溶于100mL去离子水中并搅拌10 min之后倒入圆底烧瓶,于120 ℃下反应3 h,反应完成后得到改性样品(标记为FNR-150-PVP);
3)、采用共沉淀法将两种过渡金属盐、富勒烯纳米棒、尿素进行加热回流:将60 mg的改性样品(FNR-150-PVP)与278mg硫酸亚铁、346 mg乙酸锰、混合后溶于乙二醇和去离子水中并搅拌,边搅拌边加入450 mg尿素,搅拌15 min后于150 ℃的条件下进行回流15 h,再将产物抽滤,用去离子水和无水乙醇洗涤后真空干燥,得到富勒烯纳米棒/层状双金属氢氧化物电催化剂(标记为FNR-150-PVP/LDH)。
实施例7:
1)、采用液-液界面沉淀法合成富勒烯自组装纳米棒(FNR):将150 mg的C60溶于50mL的甲苯中,并超声分散形成均匀的C60饱和溶液,向上述C60饱和溶液中加入300mL无水乙醇溶液后静置6 h,静置后离心,将离心得到的沉淀洗涤、干燥,再于150 ℃条件下在管式炉中进行3 h退火处理,得到富勒烯自组装纳米棒(标记为FNR-150);
2)、对所得富勒烯自组装纳米棒(FNR-150)进行改性处理:称取1 g聚乙烯吡咯烷酮(PVP)和200 mg的富勒烯自组装纳米棒(FNR-150),将两者溶于100mL去离子水中并搅拌10 min之后倒入圆底烧瓶,于100 ℃下反应8 h,反应完成后得到改性样品(标记为FNR-150-PVP);
3)、采用共沉淀法将两种过渡金属盐、富勒烯纳米棒、尿素进行加热回流:将30 mg的改性样品(FNR-150-PVP)与135 mg氯化铜、273 mg氯化锌混合后溶于乙二醇和去离子水中并搅拌,边搅拌边加入900 mg尿素,搅拌15 min后于150 ℃的条件下进行回流12 h,再将产物抽滤,用去离子水和无水乙醇洗涤后真空干燥,得到富勒烯纳米棒/层状双金属氢氧化物电催化剂(标记为FNR-150-PVP/LDH)。
Claims (8)
1.一种富勒烯纳米棒/层状双金属氢氧化物电催化剂的制备方法,其特征在于,具体步骤包括:
步骤一:将质量比为5:1的聚乙烯吡咯烷酮和富勒烯自组装纳米棒溶于去离子水搅拌后倒入烧瓶,于60~120 ℃下反应3~8h,反应完成后得到富勒烯自组装纳米棒的改性样品;
步骤二:将30-80mg步骤一所得改性样品与0.5-2.5mmol过渡金属盐混合后溶于乙二醇和去离子水混合溶液中并搅拌,边搅拌边加入7.5-37.5mmol尿素,搅拌完成后于100~150℃的条件下进行回流,再将产物抽滤,用去离子水和无水乙醇洗涤后真空干燥,得到富勒烯纳米棒/层状双金属氢氧化物电催化剂;
所述过渡金属盐中的金属为铁、钴、镍、锰、铜和锌中的几种,过渡金属盐为硝酸盐、硫酸盐、乙酸盐和氯化物中的一种或几种。
2.如权利要求1所述的一种富勒烯纳米棒/层状双金属氢氧化物电催化剂的制备方法,其特征在于:所述步骤一中的富勒烯自组装纳米棒制备方法为:将50~200 mg的C60溶于有机溶剂中并超声分散形成均匀的C60饱和溶液,向C60饱和溶液中加入100~300 mL醇溶液后静置,静置后离心,将离心得到的沉淀洗涤、干燥,再于150 ℃条件下进行退火处理,得到富勒烯自组装纳米棒。
3.如权利要求2所述的一种富勒烯纳米棒/层状双金属氢氧化物电催化剂的制备方法,其特征在于:所述有机溶剂为甲苯、二甲苯、均三甲苯、异丙苯中的一种或几种。
4.如权利要求2所述的一种富勒烯纳米棒/层状双金属氢氧化物电催化剂的制备方法,其特征在于:所述静置的时间为6~48 h。
5.如权利要求2所述的一种富勒烯纳米棒/层状双金属氢氧化物电催化剂的制备方法,其特征在于:所述退火处理的时间为3 h。
6.如权利要求1所述的一种富勒烯纳米棒/层状双金属氢氧化物电催化剂的制备方法,其特征在于:所述步骤一中的搅拌时间为10 min,步骤二中搅拌的时间为15 min。
7.如权利要求1所述的一种富勒烯纳米棒/层状双金属氢氧化物电催化剂的制备方法,其特征在于:所述步骤二中回流的时间为3~15 h。
8.基于权利要求1~7任意一项所述制备方法得到的富勒烯纳米棒/层状双金属氢氧化物电催化剂。
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