CN106191905B - 孔隙型微米管结构催化储氢协同功效材料的制备方法 - Google Patents
孔隙型微米管结构催化储氢协同功效材料的制备方法 Download PDFInfo
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Abstract
本发明涉及一种孔隙型微米管结构催化储氢协同功效材料的制备方法，该制备方法包括石墨烯表面羧基和羟基基团改性、石墨烯网状联接以及MoS2纳米颗粒在空间网状石墨烯液相沉降固定和孔隙型微米管的搭建。根据本发明方法制备的孔隙型微米管结构材料，是由石墨烯网络构建的微米管结构材料，具有中空结构，微米管壁具有连通孔隙，MoS2纳米颗粒固定于微米管壁石墨烯网络内。根据本发明方法制备的孔隙型微米管结构材料既具有对电解水制备氢气的催化效应，也具有高效吸附储氢功能。
Description
技术领域
本发明涉及电解水制备氢气催化和储氢材料领域，特别是一种孔隙型微米管结构催化储氢协同功效材料的制备方法。
背景技术
随着经济社会的发展，石油、煤炭等不可再生能源已不能满足人类的需要。氢气的燃烧热值高，燃烧产物无污染，可循环利用，因而是最有潜力的新能源。
实现氢能源大规模广泛应用的关键在于廉价而又高效的制氢技术和安全高效的储氢技术的研发。通过电解水工业化生产制备氢气是大规模获得洁净、可持续能源氢燃料的有效手段，高效制氢电极催化材料和高效储氢材料的研究是氢燃料制备和储存技术得以突破的关键所在。迄今为止，已研发的氢催化材料和储氢材料都局限于各自的氢制备领域和储氢技术领域，导致氢制备技术和储氢技术分离，难以实现氢制备和储存一体化技术的发展，从而制约了氢能源大规模广泛应用。
发明内容
为了克服现有技术的不足，本发明提供了一种孔隙型微米管结构催化储氢协同功效材料的制备方法，根据本发明方法制备的催化储氢协同功效材料，是由石墨烯网络构建的微米管结构材料，具有中空结构，微米管壁具有连通孔隙，MoS2纳米颗粒固定于微米管壁石墨烯网络内。这种孔隙型微米管结构催化储氢协同功效材料既具有对电解水制备氢气的催化效应，也具有高效吸附储氢功能。
本发明解决其技术问题所采用的技术方案是：一种孔隙型微米管结构催化储氢协同功效材料的制备方法，包括按顺序进行的如下步骤：
步骤[1]石墨烯表面羧基和羟基基团改性；
步骤[2]石墨烯网状联接；
步骤[3]MoS2纳米颗粒在空间网状石墨烯上液相沉降固定及孔隙型微米管的搭建。
所述步骤[1]具体包括：
a1.石墨烯表面羧基基团改性：将石墨烯、分析纯的正已酸酐、邻苯二甲酸酐加入到乙烯乙二醇醚中，形成羧基改性液，超声波搅拌20-40分钟，在温度为30-70℃环境下恒温反应0.5-1.5小时，冷却至室温，过滤固相物质，用丙酮洗涤，在干燥箱中40-60℃下干燥8-12小时；
a2.石墨烯表面羟基基团改性：将石墨烯、分析纯的磷酸二氢钾、氢氧化钡和乙酸亚铁加入去离子水中，形成羟基改性液，超声波搅拌30-40分钟，在室温下反应1-1.5小时，过滤固相物质，用去离子水洗涤，在干燥箱中50-60℃下干燥10-13小时。
优选的，步骤a1中所述羧基改性液中石墨烯的浓度为60g/L-110g/L、正已酸酐的浓度为160mL/L-200mL/L、邻苯二甲酸酐的浓度为40g/L-60g/L。
优选的，步骤a2中羟基改性液中的石墨烯浓度为100g/L-130g/L、磷酸二氢钾浓度为20g/L-65g/L、氢氧化钡浓度为10g/L-20g/L、乙酸亚铁浓度为30g/L-45g/L。
所述步骤[2]具体为：
将表面羧基基团和羟基基团改性的石墨烯各100-120g、分析纯的三苯基磷-多卤代甲烷20-40g和二环已基碳二亚胺5-10g加入600-800mL的乙二醇单甲醚中，超声波搅拌5-7分钟，在室温下反应20-35分钟，过滤固相物质，用丙酮洗涤后再以去离子水清洗，在干燥箱中40-60℃下干燥16-18小时，得网状连接石墨烯。
所述步骤[3]具体包括：
b1.MoS2纳米颗粒在空间网状石墨烯上沉降固定：将网状联接石墨烯、MoS2纳米颗粒、氧化锌微米棒、分析纯的葡萄糖、钼酸钠和磷酸二氢铵加入去离子水形成沉降液；超声波搅拌1-1.5小时，待沉降液固体沉淀后，过滤得沉积物。
b2.孔隙型微米管的搭建：将上述沉积物放入电炉中加热至200-240℃保温2-3小时，使沉积物中石墨烯与氧化锌微米棒界面分离，然后将沉积物浸入质量浓度为15-20％的氢氧化钠溶液中40-60分钟，将沉积物中的ZnO微米棒溶解去除；过滤后用去离子水洗涤，在干燥箱中40-60℃下烘干9-12小时。
优选的，步骤b1中所述沉降液中网状联接石墨烯的浓度为150g/L-170g/L、氧化锌微米棒的浓度为240g/L-280g/L、MoS2纳米颗粒的浓度为90g/L-130g/L、葡萄糖的浓度为1.5g/L-4g/L、钼酸钠的浓度为10g/L-20g/L、磷酸二氢铵的浓度为40g/L-50g/L。
本发明的积极效果：根据本发明方法制备的孔隙型微米管结构催化储氢协同功效材料，其由表面改性石墨烯形成的网络联接构建的微米管结构显著地提高了石墨烯和MoS2纳米颗粒的表面积，增大了氢气的吸附区域。这种微米管结构材料具有中空结构，微米管壁具有连通孔隙，利于氢气在微米管中的流动。MoS2纳米颗粒固定于微米管壁石墨烯网络内，可促使水分子在MoS2空位处分解成氧和氢原子，氢原子即被石墨烯吸附。因而本发明方法制备的孔隙型微米管结构材料既具有对电解水制备氢气的催化效应，也具有高效吸附储氢功能。
附图说明
图1是本发明所述催化储氢协同功效材料制备方法的流程示意图；
图2是本发明所述催化储氢协同功效材料的结构示意图。
具体实施方式
下面结合附图对本发明的优选实施例进行详细说明。
参照图1和图2，本发明优选实施例提供一种孔隙型微米管结构催化储氢协同功效材料的制备方法，按下列步骤顺序进行：
①石墨烯表面羧基基团改性：将石墨烯、分析纯的正已酸酐、邻苯二甲酸酐加入乙烯乙二醇醚中，形成石墨烯浓度为60g/L-110g/L、正已酸酐浓度为160mL/L-200mL/L和邻苯二甲酸酐浓度为40g/L-60g/L的羧基改性液，超声波搅拌20-40分钟，在温度为30-70℃环境下恒温反应0.5-1.5小时，冷却至室温，过滤固相物质，用丙酮洗涤，在干燥箱中40-60℃下干燥8-12小时。
②石墨烯表面羟基基团改性：将石墨烯、分析纯的磷酸二氢钾、氢氧化钡和乙酸亚铁加入去离子水获得羟基改性液，羟基改性液中的石墨烯浓度为1000g/L-130g/L、磷酸二氢钾浓度为20g/L-65g/L、氢氧化钡浓度为10g/L-20g/L、乙酸亚铁浓度为30g/L-45g/L，超声波搅拌30-40分钟，在室温反应1-1.5小时，过滤固相物质，用去离子水洗涤，在干燥箱中50-60℃下干燥10-13小时。
③石墨烯网状联接：将表面羧基基团和羟基基团改性的石墨烯各100-120g、分析纯的三苯基磷-多卤代甲烷20-40g和二环已基碳二亚胺5-10g加入600-800mL的乙二醇单甲醚中，超声波搅拌5-7分钟，在室温反应20-35分钟，过滤固相物质，用丙酮洗涤后再以去离子水清洗，在干燥箱中40-60℃下干燥16-18小时，获得网状连接石墨烯。
④MoS2纳米颗粒在空间网状石墨烯沉降固定：将网状联接石墨烯、MoS2纳米颗粒、氧化锌微米棒、分析纯的葡萄糖、钼酸钠和磷酸二氢铵加入去离子水形成网状联接石墨烯浓度为150g/L-170g/L、氧化锌微米棒浓度为240g/L-280g/L、MoS2纳米颗粒浓度为90g/L-130g/L、葡萄糖浓度为1.5g/L-4g/L、钼酸钠浓度为10g/L-20g/L和磷酸二氢铵浓度为40g/L-50g/L的沉降液；超声波搅拌1-1.5小时，待沉降液固体沉淀后，过滤得沉积物。
⑤孔隙型微米管的搭建：将上述沉积物放入电炉中加热至200-240℃保温2-3小时，使沉积物中石墨烯与氧化锌微米棒界面分离，将该沉积物浸入质量浓度为15-20％的氢氧化钠溶液中40-60分钟，将沉积物中的ZnO微米棒溶解去除；过滤后用去离子水洗涤，在干燥箱中40-60℃下烘干9-12小时。
下面给出具体实施例:
实施例：
①石墨烯表面羧基基团改性：将石墨烯、分析纯的正已酸酐、邻苯二甲酸酐加入乙烯乙二醇醚，形成石墨烯浓度为75g/L、正已酸酐浓度为160mL/L和邻苯二甲酸酐浓度为50g/L的羧基改性液，超声波搅拌40分钟，在温度为50℃环境下恒温反应1小时，冷却至室温，过滤固相物质，用丙酮洗涤，在干燥箱中40℃下干燥9小时。
②石墨烯表面羟基基团改性：将石墨烯、分析纯的磷酸二氢钾、氢氧化钡和乙酸亚铁加入去离子水，使羟基改性液中的石墨烯浓度为110g/L、磷酸二氢钾浓度为60g/L、氢氧化钡浓度为10g/L和乙酸亚铁浓度为35g/L，超声波搅拌40分钟，在室温反应1小时，过滤固相物质，用去离子水洗涤，在干燥箱中50℃下干燥10小时。
③石墨烯网状联接：将表面羧基基团和羟基基团改性的石墨烯各120g、分析纯的三苯基磷-多卤代甲烷30g和二环已基碳二亚胺10g加入700mL的乙二醇单甲醚中，超声波搅拌7分钟，在室温反应25分钟，过滤固相物质，用丙酮洗涤后再以去离子水清洗，在干燥箱中60℃下干燥16小时，获得网状连接石墨烯。
④MoS2纳米颗粒在空间网状石墨烯沉降固定：将网状联接石墨烯、MoS2纳米颗粒、氧化锌微米棒、分析纯的葡萄糖、钼酸钠和磷酸二氢铵加入去离子水形成网状联接石墨烯浓度为160g/L、氧化锌微米棒浓度为240g/L、MoS2纳米颗粒浓度为110g/L、葡萄糖浓度为4g/L、钼酸钠浓度为12g/L和磷酸二氢铵浓度为45g/L的沉降液；超声波搅拌1小时，待沉降液固体沉淀后，过滤得沉积物。
⑤孔隙型微米管的搭建：将上述沉积物放入电炉中加热至220℃保温2小时，使沉积物中石墨烯与氧化锌微米棒界面分离，将该沉积物浸入质量浓度为20％的氢氧化钠溶液中50分钟，将沉积物中的ZnO微米棒溶解去除；过滤后用去离子水洗涤，在干燥箱中60℃下烘干9小时。
将本实施例制备的孔隙型微米管结构催化储氢协同功效材料在常压下储氢时，其氢气吸附容量达到7.1％，明显高于储氢合金LaNi5的2.1％。在电解水实验中，孔隙型微米管结构材料作为阴极的交换电流密度比常用的镍钼合金大三倍。显然，依据本发明制备的孔隙型微米管结构催化储氢协同功效材料既具有对电解水制备氢气的催化效应，也具有高效吸附储氢功能。
以上所述的仅为本发明的优选实施例，所应理解的是，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想，并不用于限定本发明的保护范围，凡在本发明的思想和原则之内所做的任何修改、等同替换等等，均应包含在本发明的保护范围之内。
Claims (5)
1.一种孔隙型微米管结构催化储氢协同功效材料的制备方法，其特征在于，包括按顺序进行的如下步骤：
步骤[1]石墨烯表面羧基和羟基基团改性；
步骤[2]石墨烯网状联接；
步骤[3]MoS2纳米颗粒在空间网状石墨烯上液相沉降固定及孔隙型微米管的搭建；
所述步骤[3]具体包括：
b1.MoS2纳米颗粒在空间网状石墨烯上沉降固定：将网状联接石墨烯、MoS2纳米颗粒、氧化锌微米棒、分析纯的葡萄糖、钼酸钠和磷酸二氢铵加入去离子水形成沉降液；超声波搅拌1-1.5小时，待沉降液固体沉淀后，过滤得沉积物；
b2.孔隙型微米管的搭建：将上述沉积物放入电炉中加热至200-240℃保温2-3小时，使沉积物中石墨烯与氧化锌微米棒界面分离，然后将沉积物浸入质量浓度为15-20％的氢氧化钠溶液中40-60分钟，将沉积物中的ZnO微米棒溶解去除；过滤后用去离子水洗涤，在干燥箱中40-60℃下烘干9-12小时；
步骤b1中所述沉降液中网状联接石墨烯的浓度为150g/L-170g/L、氧化锌微米棒的浓度为240g/L-280g/L、MoS2纳米颗粒的浓度为90g/L-130g/L、葡萄糖的浓度为1.5g/L-4g/L、钼酸钠的浓度为10g/L-20g/L、磷酸二氢铵的浓度为40g/L-50g/L。
2.根据权利要求1所述的一种孔隙型微米管结构催化储氢协同功效材料的制备方法，其特征在于，所述步骤[1]具体包括：
a1.石墨烯表面羧基基团改性：将石墨烯、分析纯的正已酸酐、邻苯二甲酸酐加入到乙烯乙二醇醚中，形成羧基改性液，超声波搅拌20-40分钟，在温度为30-70℃环境下恒温反应0.5-1.5小时，冷却至室温，过滤固相物质，用丙酮洗涤，在干燥箱中40-60℃下干燥8-12小时；
a2.石墨烯表面羟基基团改性：将石墨烯、分析纯的磷酸二氢钾、氢氧化钡和乙酸亚铁加入去离子水中，形成羟基改性液，超声波搅拌30-40分钟，在室温下反应1-1.5小时，过滤固相物质，用去离子水洗涤，在干燥箱中50-60℃下干燥10-13小时。
3.根据权利要求2所述的一种孔隙型微米管结构催化储氢协同功效材料的制备方法，其特征在于：步骤a1中所述羧基改性液中石墨烯的浓度为60g/L-110g/L、正已酸酐的浓度为160mL/L-200mL/L、邻苯二甲酸酐的浓度为40g/L-60g/L。
4.根据权利要求2所述的一种孔隙型微米管结构催化储氢协同功效材料的制备方法，其特征在于：步骤a2中羟基改性液中的石墨烯浓度为100g/L-130g/L、磷酸二氢钾浓度为20g/L-65g/L、氢氧化钡浓度为10g/L-20g/L、乙酸亚铁浓度为30g/L-45g/L。
5.根据权利要求1所述的一种孔隙型微米管结构催化储氢协同功效材料的制备方法，其特征在于，所述步骤[2]具体为：
将表面羧基基团和羟基基团改性的石墨烯各100-120g、分析纯的三苯基磷-多卤代甲烷20-40g和二环已基碳二亚胺5-10g加入600-800mL的乙二醇单甲醚中，超声波搅拌5-7分钟，在室温下反应20-35分钟，过滤固相物质，用丙酮洗涤后再以去离子水清洗，在干燥箱中40-60℃下干燥16-18小时，得网状连接石墨烯。
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