CN110479232A - 一种还原氧化石墨烯基光催化气凝胶珠的制备方法 - Google Patents
一种还原氧化石墨烯基光催化气凝胶珠的制备方法 Download PDFInfo
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Abstract
本发明公开一种还原氧化石墨烯基光催化气凝胶珠的制备方法,包括:制备氧化石墨烯水溶液;制备氧化石墨烯/光催化剂分散液;将海藻酸盐粉体缓慢加入氧化石墨烯/光催化剂分散液中,得到氧化石墨烯/光催化剂/海藻酸盐混合液;将所述混合液滴加到金属盐溶液中,得到氧化石墨烯基水凝胶珠,静置使凝胶珠交联完全;还原制备的水凝胶珠,得到还原氧化石墨烯基水凝胶珠;将制得的水凝胶珠冷冻干燥,得到还原氧化石墨烯基气凝胶珠。本发明方法流程简单,成本低成本、可快速大量生产,制成的气凝胶珠对有机染料的吸附作用和光催化降解作用优异。
Description
技术领域
本发明涉及一种光催化材料的制备方法,具体地,涉及一种还原氧化石墨烯基光催化气凝胶珠的制备方法。
背景技术
随着社会的发展,能源、环境等问题日益突出,一方面人类对石油燃料的需求越来越大,但由于其不可再生的特性,使得人类面临着严峻的能源危机;另一方面工业生产、日常生活产生的各种污染物肆意排放,不仅影响了人类的健康更对生态环境造成了极大的破坏。光催化技术作为一种利用光能来驱动各类化学反应的技术,由于其反应条件温和、能量来源清洁丰富等优点,受到越来越多科研人员的关注。但是,多数光催化材料都存在量子效率低、可见光利用率低、稳定性较差、不易回收等问题,这对光催化材料在实际领域中的应用提出了极大的挑战。
石墨烯是由碳原子按照蜂窝状结构排列而成的单原子厚度的二维晶体,被认为是构建其他维度sp2杂化碳材料的基本结构单元。石墨烯的独特结构赋予了其诸多优异性能,可以弥补现有光催化材料的不足,如其超高的室温载流子迁移速率可以加速光生电子-空穴的迁移,减少其重新复合的几率;巨大的比表面积可以将反应物快速吸附到材料表面,加速光催化氧化还原反应的进行;同时可以作为支撑载体将半导体光催化材料均匀分散,抑制其团聚;还可以作为光稳定剂抑制半导体发生光腐蚀等。
另一方面,多数光催化材料宏观上为粉末态,这在实际应用中存在许多弊端,主要是粉体不易回收,使其不能直接投放到污水河道,极大地限制了光催化材料的应用。同时,易团聚、二次污染等,都是粉体催化剂现存的主要问题。构筑光催化气凝胶材料,既提供了支撑骨架,有效避免了粉体催化剂的团聚,三维宏观尺寸还有利于催化剂的回收和再利用,其多孔结构还可进一步提高材料的吸附能力。
目前石墨烯基光催化气凝胶的制备多采用直接冷冻干燥法,即以石墨烯宏观体为三维骨架负载光催化材料。然而采用这种方法得到的气凝胶力学强度不高,经过液体的长时间浸泡后不能保持结构的持续稳定,因而在实际应用中受到了限制。
发明内容
鉴于现有技术的上述情况,本发明的目的在于提供一种用于有机染料吸附及光催化降解的还原氧化石墨烯基光催化气凝胶珠的制备方法,一方面在增大材料吸附能力、光催化效率的同时,提高材料的耐水性及分离回收效率;另一方面实现低成本、快速、大量地制备形状与体积可控的高品质光催化材料。利用该方法可为光催化材料在污水处理领域的实际应用奠定基础,具有显著的经济效益和社会效益。
本发明的上述目的是利用以下技术方案实现的:
一种还原氧化石墨烯基光催化气凝胶珠的制备方法,包括下述步骤:
1.1氧化石墨烯水溶液的制备
取氧化石墨烯粉体超声分散于蒸馏水中,得到氧化石墨烯水溶液,所述氧化石墨烯粉体的质量与蒸馏水的体积的比例为1:1g/L~10:1g/L。
1.2氧化石墨烯/光催化剂分散液的制备
搅拌下,取光催化剂分散至步骤1.1制备的氧化石墨烯水溶液中,超声使其分散均匀,光催化剂与氧化石墨烯粉体的质量比为10:1~10:10。其中所述光催化剂可以为TiO2纳米颗粒、TiO2纳米线、MoS2纳米片、ZnO纳米颗粒中的一种。
1.3氧化石墨烯/光催化剂/海藻酸盐混合液的制备
搅拌下,将海藻酸盐粉体缓慢加入步骤1.2制备的氧化石墨烯/光催化剂分散液中,继续搅拌直至体系均匀,所述海藻酸盐粉体与氧化石墨烯粉体的质量比为1:1~20:1。其中所述海藻酸盐粉体可以为海藻酸钠或海藻酸钾粉体。
1.4氧化石墨烯基水凝胶珠的制备
将步骤1.3得到的混合液滴加到浓度为2~30mg/mL的金属盐溶液中,得到氧化石墨烯基水凝胶珠,静置使凝胶珠交联完全。其中所述金属盐为Ag+、Ca2+、Ni2+、La3+、Zr4+盐溶液中的一种或者它们的组合。
1.5还原氧化石墨烯基水凝胶珠的制备
将步骤1.4制备的水凝胶珠还原,得到还原氧化石墨烯基水凝胶珠;其中还原方法可以采用紫外光照还原、微波还原、水合肼蒸汽还原中的一种。其中紫外光照还原法使用300W氙灯为光源,激发波长为254~365nm,工作电流为11~18A,照射时间为20~120min。其中在水合肼蒸汽还原法中,水合肼溶液的体积浓度为25~85%,反应温度为30~100℃,反应时间2~10h。
1.6还原氧化石墨烯基气凝胶珠的制备
将步骤1.5制得的水凝胶珠冷冻干燥,得到还原氧化石墨烯基气凝胶珠。其中冷冻干燥为真空冷冻干燥,温度为-50℃~-15℃,真空度<10Pa,冷冻干燥时间为3~5天。
与最接近的现有技术比,本发明具有以下有益效果:
(1)该还原氧化石墨烯基光催化气凝胶珠制备流程简单,具备了低成本、可快速大量生产的工艺优势;
(2)该还原氧化石墨烯基光催化气凝胶珠通过还原氧化石墨烯和海藻酸钠二者间的协同作用,实现了对光催化剂的均匀分散,促进了光生载流子的有效分离和传输,增大了对有机染料的吸附作用和光催化降解作用;
(3)制成的还原氧化石墨烯基光催化气凝胶珠具有质轻、耐水、易回收等优点,在液相环境中可以长时间维持其结构的稳定,为光催化材料在污水处理领域的实际应用奠定了基础。
附图说明
图1为按照实施例1制备的还原氧化石墨烯基光催化气凝胶珠剖面的SEM照片;
图2为按照实施例1制备的还原氧化石墨烯基光催化气凝胶珠剖面局部放大的SEM照片;
图3为按照实施例1、实施例4、实施例5和实施例6制备的还原氧化石墨烯基光催化气凝胶珠对有机染料亚甲基蓝的吸附及光催化降解曲线。
具体实施方式
为了更清楚地理解本发明的目的、技术方案及优点,下面结合附图及实施例,对本发明进行进一步详细说明。
本发明的还原氧化石墨烯基光催化气凝胶珠的制备方法,包括下述步骤:
1.1氧化石墨烯水溶液的制备
称取氧化石墨烯粉体置于烧杯中,加入蒸馏水,在超声细胞粉碎仪中超声处理,得到氧化石墨烯的水溶液。所述氧化石墨烯粉体的质量与蒸馏水的体积的比例为1:1~10:1,氧化石墨烯粉体质量的单位为g,蒸馏水体积的单位为L;所述超声细胞粉碎仪的工作频率为20~25kHz;所述超声处理的时间为0.5~2h;
1.2氧化石墨烯/光催化剂分散液的制备
磁力搅拌下,取光催化剂分散至步骤1.1配制的氧化石墨烯水溶液中,超声使其分散均匀。所述光催化剂为TiO2纳米颗粒、TiO2纳米线、MoS2纳米片、ZnO纳米颗粒中的一种;光催化剂与氧化石墨烯粉体的质量比为10:1~10:10。
1.3氧化石墨烯/光催化剂/海藻酸钠混合液的制备
称取海藻酸盐粉体,磁力搅拌下缓慢加入步骤1.2的分散液中,继续搅拌直至体系均匀。所述海藻酸盐粉体与氧化石墨烯粉体的质量比为1:1~20:1,所述海藻酸盐粉体可以为海藻酸钠或海藻酸钾粉体。利用氧化石墨烯对光催化剂进行改性,石墨烯的独特结构赋予了其诸多优异性能,可以弥补现有光催化材料的不足,如其超高的室温载流子迁移速率可以加速光生电子-空穴的迁移,减少其重新复合的几率;巨大的比表面积可以将反应物快速吸附到材料表面,加速光催化氧化还原反应的进行;同时可以作为支撑载体将半导体光催化材料均匀分散,抑制其团聚;还可以作为光稳定剂抑制半导体发生光腐蚀等。
1.4氧化石墨烯基水凝胶珠的制备
将步骤1.3得到的混合液用注射器滴加到金属盐溶液中,得到氧化石墨烯基水凝胶珠,静置使凝胶珠交联完全。所述金属盐为Ag+、Ca2+、Ni2+、La3+、Zr4+盐溶液中的一种;金属盐溶液的浓度为2~30mg/mL;静置时间为4小时~2天。另外,通过改变注射器针头孔径及滴加速度,可以实现不同形状与体积的凝胶珠的可控制备。
1.5还原氧化石墨烯基水凝胶珠的制备
将步骤1.4制备的水凝胶珠还原,得到还原氧化石墨烯基水凝胶珠。所述还原方法可以为紫外光照还原、微波还原、水合肼蒸汽还原中的一种;紫外光照还原法使用300W氙灯为光源,激发波长为254~365nm,工作电流为11~18A,照射时间为20~120min;水合肼蒸汽还原法中,水合肼溶液的体积浓度为25~85%,反应温度为30~100℃,反应时间2~10h。通过还原处理,可提高石墨烯的导电性,促进光生电子-空穴的分离,减少其重新复合的几率。
1.6还原氧化石墨烯基气凝胶珠的制备
将步骤1.5中的水凝胶珠冷冻干燥,得到还原氧化石墨烯基气凝胶珠。所述的冷冻干燥为真空冷冻干燥,温度为-50℃~-15℃,真空度<10Pa,冷冻干燥时间为3~5天。
制备的还原氧化石墨烯基光催化气凝胶珠可用于有机染料的吸附及光催化降解。
实施例1
1)称取氧化石墨烯粉体0.1g于100mL蒸馏水中,20kHz超声处理0.5h;
2)磁力搅拌下,取TiO2纳米颗粒1g分散至步骤1)配制的氧化石墨烯水溶液中,超声使其分散均匀;
3)称取海藻酸钠粉体1g,磁力搅拌下缓慢加入步骤2)的分散液中,继续搅拌直至体系均匀;
4)将步骤3)得到的混合液用注射器滴加到5mg/mL的Zr4+溶液中,得到氧化石墨烯基水凝胶珠,静置1.5天使凝胶珠交联完全;
5)将步骤4)制备的水凝胶珠置于300W氙灯光源下进行还原处理,激发波长为254nm,工作电流11A,照射时间60min;
6)将步骤5)中的水凝胶珠冷冻干燥,得到还原氧化石墨烯基气凝胶珠,冷冻干燥的温度为-45℃,真空度<10Pa,冷冻干燥时间为3天。
取制备的还原氧化石墨烯基气凝胶珠在可见光照下对亚甲基蓝进行光催化降解实验。
图1是按照本实施例制备的还原氧化石墨烯基光催化气凝胶珠剖面的SEM照片,图2是按照本实施例制备的还原氧化石墨烯基光催化气凝胶珠剖面局部放大的SEM照片,易见片层上均匀分布着TiO2颗粒。
实施例2
1)称取氧化石墨烯粉体0.4g于100mL蒸馏水中,25kHz超声处理1.5h;
2)磁力搅拌下,取TiO2纳米线0.4g分散至步骤1)配制的氧化石墨烯水溶液中,超声使其分散均匀;
3)称取海藻酸钠粉体2g,磁力搅拌下缓慢加入步骤2)的分散液中,继续搅拌直至体系均匀;
4)将步骤3)得到的混合液用注射器滴加到20mg/mL的Ca2+溶液中,得到氧化石墨烯基水凝胶珠,静置8h使凝胶珠交联完全;
5)将步骤4)制备的水凝胶珠置于300W氙灯光源下进行还原处理,激发波长为365nm,工作电流18A,照射时间120min;
6)将步骤5)中的水凝胶珠冷冻干燥,得到还原氧化石墨烯基气凝胶珠,冷冻干燥的温度为-30℃,真空度<10Pa,冷冻干燥时间为4天。
取制备的还原氧化石墨烯基气凝胶珠在可见光照下对亚甲基蓝进行光催化降解实验。
实施例3
1)称取氧化石墨烯粉体0.1g于100mL蒸馏水中,20kHz超声处理1h;
2)磁力搅拌下,取MoS2纳米片0.5g分散至步骤1)配制的氧化石墨烯水溶液中,超声使其分散均匀;
3)称取海藻酸钠粉体2g,磁力搅拌下缓慢加入步骤2)的分散液中,继续搅拌直至体系均匀;
4)将步骤3)得到的混合液用注射器滴加到2mg/mL的Ag+溶液中,得到氧化石墨烯基水凝胶珠,静置2天使凝胶珠交联完全;
5)将步骤4)制备的水凝胶珠置于300W氙灯光源下进行还原处理,激发波长为254nm,工作电流18A,照射时间20min;
6)将步骤5)中的水凝胶珠冷冻干燥,得到还原氧化石墨烯基气凝胶珠,冷冻干燥的温度为-15℃,真空度<10Pa,冷冻干燥时间为5天。
取制备的还原氧化石墨烯基气凝胶珠在可见光照下对亚甲基蓝进行光催化降解实验。
实施例4
1)称取氧化石墨烯粉体1g于100mL蒸馏水中,25kHz超声处理2h;
2)磁力搅拌下,取ZnO纳米颗粒2g分散至步骤1)配制的氧化石墨烯水溶液中,超声使其分散均匀;
3)称取海藻酸钠粉体1g,磁力搅拌下缓慢加入步骤2)的分散液中,继续搅拌直至体系均匀;
4)将步骤3)得到的混合液用注射器滴加到30mg/mL的Zr4+溶液中,得到氧化石墨烯基水凝胶珠,静置4h使凝胶珠交联完全;
5)取体积浓度85%的水合肼溶液置于高压反应釜中,取步骤4)制备的水凝胶珠置于液面以上,于烘箱中100℃加热处理10h;
6)将步骤5)中的水凝胶珠用蒸馏水清洗后冷冻干燥,得到还原氧化石墨烯基气凝胶珠,冷冻干燥的温度为-15℃,真空度<10Pa,冷冻干燥时间为5天。
取制备的还原氧化石墨烯基气凝胶珠在可见光照下对亚甲基蓝进行光催化降解实验。
实施例5
1)称取氧化石墨烯粉体0.1g于100mL蒸馏水中,20kHz超声处理0.5h;
2)磁力搅拌下,取TiO2纳米颗粒1g分散至步骤1)配制的氧化石墨烯水溶液中,超声使其分散均匀;
3)称取海藻酸钠粉体1g,磁力搅拌下缓慢加入步骤2)的分散液中,继续搅拌直至体系均匀;
4)将步骤3)得到的混合液用注射器滴加到5mg/mL的Zr4+溶液中,得到氧化石墨烯基水凝胶珠,静置1.5天使凝胶珠交联完全;
5)取体积浓度25%的水合肼溶液置于高压反应釜中,取步骤4)制备的水凝胶珠置于液面以上,于烘箱中30℃加热处理2h;
6)将步骤5)中的水凝胶珠用蒸馏水清洗后冷冻干燥,得到还原氧化石墨烯基气凝胶珠,冷冻干燥的温度为-45℃,真空度<10Pa,冷冻干燥时间为3天。
取制备的还原氧化石墨烯基气凝胶珠在可见光照下对亚甲基蓝进行光催化降解实验。
实施例6
1)称取氧化石墨烯粉体0.1g于100mL蒸馏水中,20kHz超声处理0.5h;
2)磁力搅拌下,取TiO2纳米颗粒1g分散至步骤1)配制的氧化石墨烯水溶液中,超声使其分散均匀;
3)称取海藻酸钠粉体1g,磁力搅拌下缓慢加入步骤2)的分散液中,继续搅拌直至体系均匀;
4)将步骤3)得到的混合液用注射器滴加到5mg/mL的Zr4+溶液中,得到氧化石墨烯基水凝胶珠,静置1.5天使凝胶珠交联完全;
5)取体积浓度50%的水合肼溶液置于高压反应釜中,取步骤4)制备的水凝胶珠置于液面以上,于烘箱中50℃加热处理6h;
6)将步骤5)中的水凝胶珠用蒸馏水清洗后冷冻干燥,得到还原氧化石墨烯基气凝胶珠,冷冻干燥的温度为-30℃,真空度<10Pa,冷冻干燥时间为4天。
取制备的还原氧化石墨烯基气凝胶珠在可见光照下对亚甲基蓝进行光催化降解实验。
图3为按照实施例1、实施例4、实施例5和实施例6制备的还原氧化石墨烯基光催化气凝胶珠对有机染料亚甲基蓝的吸附及光催化降解曲线。其中前60min为暗环境下的吸附,后120min为可见光照下的催化剂降解,光源为300W氙灯,滤光片滤掉波长小于400nm的紫外光。曲线横坐标为时间,纵坐标为亚甲基蓝浓度与其初始浓度的比值,气凝胶珠在180min后对染料的降解率均可达到70%以上。
Claims (8)
1.一种还原氧化石墨烯基光催化气凝胶珠的制备方法,包括以下步骤:
1.1氧化石墨烯水溶液的制备
取氧化石墨烯粉体超声分散于蒸馏水中,得到氧化石墨烯水溶液,所述氧化石墨烯粉体的质量与蒸馏水的体积的比例为1:1g/L~10:1g/L;
1.2氧化石墨烯/光催化剂分散液的制备
搅拌下,取光催化剂分散至步骤1.1制备的氧化石墨烯水溶液中,超声使其分散均匀,光催化剂与氧化石墨烯粉体的质量比为10:1~10:10;
1.3氧化石墨烯/光催化剂/海藻酸盐混合液的制备
搅拌下,将海藻酸盐粉体缓慢加入步骤1.2制备的氧化石墨烯/光催化剂分散液中,继续搅拌直至体系均匀,所述海藻酸盐粉体与氧化石墨烯粉体的质量比为1:1~20:1;
1.4氧化石墨烯基水凝胶珠的制备
将步骤1.3得到的混合液滴加到浓度为2~30mg/mL的金属盐溶液中,得到氧化石墨烯基水凝胶珠,静置使凝胶珠交联完全;
1.5还原氧化石墨烯基水凝胶珠的制备
将步骤1.4制备的水凝胶珠还原,得到还原氧化石墨烯基水凝胶珠;
1.6还原氧化石墨烯基气凝胶珠的制备
将步骤1.5制得的水凝胶珠冷冻干燥,得到还原氧化石墨烯基气凝胶珠。
2.按照权利要求1所述的制备方法,其中所述光催化剂为TiO2纳米颗粒、TiO2纳米线、MoS2纳米片、ZnO纳米颗粒中的一种。
3.按照权利要求1所述的制备方法,其中所述步骤1.5中的还原方法为紫外光照还原、微波还原、水合肼蒸汽还原中的一种。
4.按照权利要求3所述的制备方法,其中所述紫外光照还原法使用300W氙灯为光源,激发波长为254~365nm,工作电流为11~18A,照射时间为20~120min。
5.按照权利要求3所述的制备方法,其中所述水合肼蒸汽还原法中,水合肼溶液的体积浓度为25~85%,反应温度为30~100℃,反应时间2~10h。
6.按照权利要求1所述的制备方法,其中所述海藻酸盐粉体为海藻酸钠或海藻酸钾粉体。
7.按照权利要求1所述的制备方法,其中所述金属盐为Ag+、Ca2+、Ni2+、La3+、Zr4+盐溶液中的一种或者它们的组合。
8.按照权利要求1所述的制备方法,其中所述步骤1.6中的冷冻干燥为真空冷冻干燥,温度为-50℃~-15℃,真空度<10Pa,冷冻干燥时间为3~5天。
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