CN107519875B - 一种碳基材负载钴氧化物纳米复合材料的制备方法和应用 - Google Patents
一种碳基材负载钴氧化物纳米复合材料的制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种碳基材负载钴氧化物纳米复合材料的制备方法和应用,属于纳米材料、高分子聚合物与催化剂技术领域。采用聚合‑浸渍‑热解方法,制备碳基材负载钴氧化物纳米复合材料。该材料制备所用原料成本低,制备工艺简单,反应能耗低,具有工业应用前景。该材料用于催化电解水析氧,具有良好的析氧电催化活性与电化学稳定性。
Description
技术领域
本发明涉及一种碳基材负载钴氧化物纳米复合材料的制备方法和应用,属于纳米材料、高分子聚合物与电化学析氧技术领域。
背景技术
水电解制氢已具有一百多年的发展历史,是综合各方面考量制取氢气最可行且环保的方式,目前已成为制备氢气比较常用且成熟的一种方法。该方法对设备的要求不高,其工艺过程相对简单,对环境造成的污染较小,且制得的氢纯度较为理想。
水电解形成氢气和氧气的过程可以看作是氢氧燃烧的逆过程,其理论分解电势差为 1.23V。但在真实溶液环境和实际操作中由于氧气和氢气生成过程中的产生的过电位(大于理论分解电势的外加偏压)、电解液电阻、电极接触及其它电阻等造成的损耗的存在,实际的槽工作电压常为2.0~2.2V,远远高出理论值,而整体能量转换效率一般只有40~60%。探索廉价且高效的水电解制氢工艺,无疑成为了氢能开发利用亟待解决的重要课题。
聚脲(polyurea)是由二元或多元异氰酸酯与胺或水反应生成的一种分子链中含-NH-CO-NH-(脲基)链节的有机聚合物。它由于其3D多孔高比表面积结构,有利于电解液和生成气体的质量传递和分子扩散,然而,其弱的导电性,导致其析氧电催化活性也很差,目前,基于有机高分子聚合物电催化析氧研究报道极少。因此,研究高分子聚合物不同组成和形貌与电催化析氧性能之间的关系及规律,对发展新型修饰电极对构建电化学传感器以及拓展新能源电极材料有着重要的科学意义。
发明内容
本发明的技术任务之一是为了弥补现有技术的不足,提供一种碳基材负载钴氧化物纳米复合材料的制备方法,该方法所用原料成本低,制备工艺简单,反应能耗低,具有工业应用前景。
本发明的技术任务之二是提供碳基材负载钴氧化物纳米复合材料的用途,即用该材料用于电化学催化析氧,具有良好的析氧电催化活性与电化学稳定性。
本发明的技术方案如下:
1.一种碳基材负载钴氧化物纳米复合材料的制备方法,步骤如下:
(1) 浸渍法制备多孔Co-聚脲配位聚合物材料
将0.60-1.20g的硝酸钴溶解在4-8mL乙醇中,加入0.20-0.4g聚脲粉末PU,搅拌均匀后,于120 W超声15 min后,浸渍过夜,60℃干燥,制得多孔Co-聚脲配位聚合物材料,产率为70-81%;
(2) 热解法制备碳基材负载钴氧化物纳米复合材料
将Co-聚脲配位聚合物材料置于管式炉中,空气氛下,升温速率为 3-5℃/min,加热至300-500℃,保温1.5-2.5 h,然后, 降温冷却到室温,制得碳基材负载钴氧化物纳米复合材料;
步骤(1)中所述聚苯脲粉末PU,由甲苯二异氰酸酯和双氰胺反应制得,制备步骤如下:
电动搅拌下,将17.0 g丙酮和2.4-3.0mmol的双氰胺溶解成澄清的溶液,加入8-12g水,冰浴冷却10 min后,以300 rpm的搅拌速率,恒速滴加22-24 mmol 甲苯二异氰酸酯和8-10g丙酮的共混液,30min滴完,升温至30℃,保温聚合反应3 h,对产物抽滤分离,并用质量比为3/7的水和丙酮混合液洗涤三次,得到的固体于70℃的烘箱中烘干至恒重,即制得了聚苯脲粉末PU,产率为82-90%。
步骤(1)中所述多孔Co-聚脲配位聚合物材料,多孔由孔径尺寸为微孔、介孔和小于5um 的大孔组成;
步骤(2)中所述降温冷却到室温,速率为 2℃/ min;
步骤(2)中所述碳基材负载钴氧化物纳米复合材料,是粒径为10-40 nm的单层半导体Co3O4纳米粒子负载在多孔碳基材上的复合材料,碳基材为石墨和富勒烯C70复合材料。
2. 如上所述的碳基材负载钴氧化物纳米复合材料用于电催化析氧的应用,步骤如下:
(1)在基底电极为玻碳电极的表面构建碳基材负载钴氧化物纳米复合材料,制备碳基材负载钴氧化物纳米复合材料工作电极;
所述表面构建碳基材负载钴氧化物纳米复合材料,是将玻碳电极依次用1.0、0.3、0.05 µm的Al2O3粉末抛光,并依次在超纯水、稀硝酸、超纯水和乙醇中超声清洗,室温晾干后,在其表面滴涂6uL碳基材负载钴氧化物纳米复合材料溶液,室温晾干制得工作电极;
所述碳基材负载钴氧化物纳米复合材料溶液,是将4 mg碳基材负载钴氧化物纳米复合材料分散于250μL乙醇、720μL水以及30μL的Nafion中,室温超声15min,制得混合液;
(2)将参比电极、对电极和上述步骤(1)制备的工作电极连接在电化学工作站上,参比电极为Ag/AgCl电极(饱和KCl溶液),对电极为铂片电极, 电解液为 0.5 M KOH水溶液中测试电催化分解水性能;
(3)上述碳基材负载钴氧化物纳米复合材料工作电极电解水析氧,当电流密度J=10mA/cm2时,电位为1.52 V vs RHE;塔菲尔斜率为74mV dec-1,均说明该材料高效的析氧催化活性;循环 500 次前后,该类材料极化曲线没有发现明显的变化,表明催化剂具有良好的稳定性。
本发明的有益的技术效果:
(1)操作简便,成本低廉,易于工业化
本发明采用聚合-浸渍-热解方法,首先将高活性芳香族甲苯二异氰酸酯(TDI)与对双氰胺在水和丙酮中逐步沉淀聚合,无需任何稳定剂、致孔剂以及表面改性,一步法制备了表面富含胺基和亚胺基的多孔聚脲高分子材料,继续将其与过渡金属Co2+反应,制得了以配位键为驱动力构建的过渡金属Co(Ⅱ)-聚脲配位聚合物,将其热解后处理,获得了碳基材负载钴氧化物纳米复合材料,所用原料价格低廉,合成过程简单,易于工业化。
(2)本发明提供了一种碳基材负载钴氧化物纳米复合材料作为催化剂电解水析氧催化剂的应用。由于该材料是由Co3O4半导体纳米粒子负载在石墨和富勒烯C70上构成的纳米片,形貌规整、比表面积高,暴露了更多且不同的活性位点,发挥了Co3O4半导体纳米粒子以及石墨和富勒烯C70的协同作用,使得基于该复合材料的催化析氧,催化效率高且稳定性好。
具体实施方式
下面结合实施例对本发明作进一步描述,但本发明的保护范围不仅局限于实施例,该领域专业人员对本发明技术方案所作的改变,均应属于本发明的保护范围内。
实施例1一种碳基材负载钴氧化物纳米复合材料的制备方法
(1) 将0.60g的硝酸钴溶解在4 mL乙醇中,加入0.20g聚脲粉末PU,搅拌均匀后,于120 W超声15 min后,浸渍过夜,60℃干燥,制得多孔Co-聚脲配位聚合物材料;
(2) 将Co-聚脲配位聚合物材料置于管式炉中,空气氛下,升温速率为 3℃/min,加热至300℃,保温1.5 h,然后,以速率为 2℃/ min,降温冷却到室温,制得碳基材负载钴氧化物纳米复合材料。
实施例2一种碳基材负载钴氧化物纳米复合材料的制备方法
(1) 将0.90g的硝酸钴溶解在6 mL乙醇中,加入0.30g聚脲粉末PU,搅拌均匀后,于120 W超声15 min后,浸渍过夜,60℃干燥,制得多孔Co-聚脲配位聚合物材料;
(2) 将Co-聚脲配位聚合物材料置于管式炉中,空气氛下,升温速率为 4℃/min,加热至500℃,保温2 h,然后,以速率为 2℃/ min,降温冷却到室温,制得碳基材负载钴氧化物纳米复合材料。
实施例3一种碳基材负载钴氧化物纳米复合材料的制备方法
(1) 将1.20g的硝酸钴溶解在8 mL乙醇中,加入0.40g聚脲粉末PU,搅拌均匀后,于120 W超声15 min后,浸渍过夜,60℃干燥,制得多孔Co-聚脲配位聚合物材料;
(2) 将Co-聚脲配位聚合物材料置于管式炉中,空气氛下,升温速率为 5℃/min,加热至400℃,保温2.5 h,然后,以速率为 2℃/ min,降温冷却到室温,制得碳基材负载钴氧化物纳米复合材料。
实施例4 实施例1和2使用的聚脲粉末的制备方法
电动搅拌下,将17.0g丙酮和2.6mmol的双氰胺溶解成澄清的溶液,加入10g水,冰浴冷却10 min后,以300 rpm的搅拌速率,恒速滴加23mmol 甲苯二异氰酸酯和8g丙酮的共混液,30min滴完,升温至30℃,保温聚合反应3 h,对产物抽滤分离,并用质量比为3/7的水和丙酮混合液洗涤三次,得到的固体于70℃的烘箱中烘干至恒重,即制得了聚苯脲粉末PU,产率为90%。
实施例5 实施例3使用的聚苯脲粉末PU的制备方法
电动搅拌下,将17.0 g丙酮和3.0mmol的双氰胺溶解成澄清的溶液,加入12g水,冰浴冷却10 min后,以300 rpm的搅拌速率,恒速滴加24 mmol 甲苯二异氰酸酯和10g丙酮的共混液,30min滴完,升温至30℃,保温聚合反应3 h,对产物抽滤分离,并用质量比为3/7的水和丙酮混合液洗涤三次,得到的固体于70℃的烘箱中烘干至恒重,即制得了聚苯脲粉末PU,产率为82 %。
实施例6 实施例1-3所述的多孔Co-聚脲配位聚合物材料,其多孔由孔径尺寸为微孔、介孔和小于5um 的大孔组成。
实施例1-3所述的碳基材负载钴氧化物纳米复合材料,是粒径为10-40 nm的单层半导体Co3O4纳米粒子负载在多孔碳基材上的复合材料,碳基材为石墨和富勒烯C70复合材料。
实施例7 实施例1所述的碳基材负载钴氧化物纳米复合材料作为催化剂用于电催化析氧的应用
(1)在基底电极为玻碳电极的表面构建碳基材负载钴氧化物纳米复合材料,制备碳基材负载钴氧化物纳米复合材料工作电极;
所述表面构建碳基材负载钴氧化物纳米复合材料,是将玻碳电极依次用1.0、0.3、0.05 µm的Al2O3粉末抛光,并依次在超纯水、稀硝酸、超纯水和乙醇中超声清洗,室温晾干后,在其表面滴涂6uL碳基材负载钴氧化物纳米复合材料溶液,室温晾干制得工作电极;
所述碳基材负载钴氧化物纳米复合材料溶液,是将4 mg碳基材负载钴氧化物纳米复合材料分散于250μL乙醇、720μL水以及30μL的Nafion中,室温超声15min,制得混合液;
(2)将参比电极、对电极和上述步骤(1)制备的工作电极连接在电化学工作站上,参比电极为Ag/AgCl电极(饱和KCl溶液),对电极为铂片电极, 电解液为 0.5 M KOH水溶液中测试电催化分解水性能;
(3)上述碳基材负载钴氧化物纳米复合材料电解水析氧,当电流密度J=10 mA/cm2时,电位为1.56 V (vs RHE);塔菲尔斜率为111 mV dec-1,均说明该材料高效的析氧催化活性;循环 500 次前后,该类材料极化曲线没有发现明显的变化,表明催化剂具有良好的稳定性。
实施例8
方法同实施例7,仅将实施例7中使用的碳基材负载钴氧化物纳米复合材料替换为实施例2制得的碳基材负载钴氧化物纳米复合材料;当电流密度J=10mA/cm2时,电位为1.52V (vs RHE);塔菲尔斜率为74 mV dec-1,均说明该材料高效的析氧催化活性;循环 500 次前后,该类材料极化曲线没有发现明显的变化,表明催化剂具有良好的稳定性。
实施例9
方法同实施例7,仅将实施例7中使用的碳基材负载钴氧化物纳米复合材料替换为实施例3制得的碳基材负载钴氧化物纳米复合材料;当电流密度J=10 mA/cm2时,电位为1.52 V (vs RHE);塔菲尔斜率为74 mV dec-1,均说明该材料高效的析氧催化活性;循环500 次前后,该类材料极化曲线没有发现明显的变化,表明催化剂具有良好的稳定性。
Claims (4)
1.一种碳基材负载钴氧化物纳米复合材料的制备方法,其特征在于,步骤如下:
(1)将0.60-1.20g的硝酸钴溶解在4-8mL乙醇中,加入0.20-0.40g聚脲粉末PU,搅拌均匀后,于120W超声15min后,浸渍过夜,60℃干燥,制得多孔Co-聚脲配位聚合物材料,
产率为70-81%;
(2)将Co-聚脲配位聚合物材料置于管式炉中,空气氛下,升温速率为3-5℃/min,加热至300-500℃,保温1.5-2.5h,然后,降温冷却到室温,制得碳基材负载钴氧化物纳米复合材料;
所述聚脲粉末PU,由甲苯二异氰酸酯和双氰胺反应制得,制备步骤如下:
电动搅拌下,将17.0g丙酮和2.4-3.0mmol的双氰胺溶解成澄清的溶液,加入8-12g水,冰浴冷却10min后,以300rpm的搅拌速率,恒速滴加22-24mmol甲苯二异氰酸酯和8-10g丙酮的共混液,30min滴完,升温至30℃,保温聚合反应3h,对产物抽滤分离,并用质量比为3/7的水和丙酮混合液洗涤三次,得到的固体于70℃的烘箱中烘干至恒重,即制得了聚脲粉末PU,产率为82-90%;
所述多孔Co-聚脲配位聚合物材料,其孔径由微孔、介孔和小于5μm的大孔组成。
2.如权利要求1所述的碳基材负载钴氧化物纳米复合材料的制备方法,其特征在于,步骤(2)中所述降温冷却到室温,速率为2℃/min。
3.如权利要求1所述的碳基材负载钴氧化物纳米复合材料的制备方法,其特征在于,步骤(2)中所述碳基材负载钴氧化物纳米复合材料,是粒径为10-40nm的单层半导体Co3O4纳米粒子负载在多孔碳基材上的复合材料,碳基材为石墨和富勒烯C70复合材料。
4.如权利要求1所述的制备方法制备的碳基材负载钴氧化物纳米复合材料用于电催化析氧的应用。
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