CN107649183A - 一种基于石墨烯的光催化剂制备方法 - Google Patents
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Abstract
本发明涉及石墨烯制造与石墨烯应用技术领域，具体为一种基于石墨烯的光催化剂制备方法。所述基于石墨烯的光催化剂制备包括以下步骤：s1、制备氧化石墨烯粉末；s2、制备氧化石墨烯‑TiO2复合粉末；s3、制备石墨烯‑TiO2‑酞菁铜复合粉末。本发明的石墨烯相互连通的孔结构能有效固定二氧化钛纳米颗粒和酞菁铜，极大增强了二氧化钛光催化剂与石墨烯纳米片的有效接触面积，同时也能抑制二氧化钛尺寸的增长，增强了光催化剂的吸附性能和光催化性能。传统的石墨烯‑TiO2光催化剂中引入在水中稳定性能良好的有机小分子染料酞菁铜，利用酞菁铜在可见光波段的光吸收作用，大大提高了光制氢过程中对太阳光的利用率，提高了催化剂的光催化性能。
Description
技术领域
本发明涉及石墨烯制造与石墨烯应用技术领域，具体为一种基于石墨烯的光催化剂制备方法。
背景技术
石墨烯 （ Graphene）由 Geim 等于 2004 年发现，是拥有 sp2 杂化轨道的二维碳原子晶体。石墨烯不仅有优异的电学性能 , 质量轻 , 导热性好 , 比表面积大,而且还具有一些独特的性能,如量子霍尔效应、量子隧穿效应等。 基于石墨烯的纳米复合材料在能量储存、液晶器件、电子器件、生物材料、传感材料和催化剂载体等领域展现出许多优良性能，具有广阔的应用前景。近期研究认为，石墨烯作为新型碳材料，与半导体材料复合可以有效提高半导体的光催化性能：石墨烯作为电子导线可以有效分离光生电子和空穴；作为催化剂载体，可以提高半导体的分散，增大复合物的比表面积；作为吸附剂，可以增加对污染物的吸附能力。
碳材料，尤其是碳纳米管的引入对改善复合材料光催化性能的原因有以下几个方面：1、碳材料较高的比表面积促进了复合材料中活性组分的分散程度，增加了有效反应活性位；2、碳材料较高的电子传输速率及碳材料/半导体界面异质结的形成可以促进光生电子空穴对的分离，提高光催化效率。3、碳材料以其较高的比表面积可以提高复合材料对污染物的吸附性能，从而增强污染物的光催化降解效率；4、碳材料的掺入可以作为半导体的光敏剂，使复合材料的费米能级向更正的方向偏移，进而增强了材料对可见光的吸收性能，提高了对光能的利用率。
酞菁铜一种常见而廉价的有机染料，其结构及其能级特点决定了它具有很多优良的功能特性。这些性质已经或将在很多领域中得以广泛的应用，如利用它的光电导性可以制备出性能优良的液晶光阀。利用气敏性可制备出灵敏的气体传感器。利用酞菁铜的光伏效应可制备出性能稳定、廉价的太阳能电池等等。酞菁铜作为有机物却很稳定，难溶或者不溶于很多有机溶剂，特别是其在太阳可见光波段具有良好的吸收，本发明旨在利用酞菁铜对在可见光波段的吸收作用，提高光催化剂的水制氢催化性能。
发明内容
本发明的目的在于提供石墨烯的光催化剂制备方法，以解决上述背景技术中提出的问题。
为实现上述目的，本发明提供如下技术方案：一种基于石墨烯的光催化剂制备方法，其特征在于，所述基于石墨烯的光催化剂制备包括以下步骤：
s1、制备氧化石墨烯粉末；
s2、制备氧化石墨烯-TiO2复合粉末；
s3、制备石墨烯-TiO2-酞菁铜复合粉末。
进一步的，所述步骤s1氧化石墨烯粉末的制备包括步骤：
(1)将石墨粉与98%的0℃浓硫酸和硝酸溶液缓慢混合；
(2)将混合溶液搅拌均匀，并缓慢加入高锰酸钾，45℃水浴条件下继续搅拌反应24h；
(3)将上述混合溶液冷却至室温，在冰浴下缓慢加入适量30% 双氧水和超纯水；
(4) 将上述液体过滤，用10wt% 盐酸溶液和大量去离子水清洗至中性；
(5) 对液体超声处理60 min 后，在3000rpm下离心分离20 min，去除没有剥离的 氧化石墨烯；
(6) 取上清液，过滤后在 60℃下烘干20小时，得到氧化石墨烯粉末。
进一步的，所述步骤s2氧化石墨烯-TiO2复合粉末的制备包括步骤：
(1)将钛酸异丙酯、十六胺加入到无水乙醇中并添加氯化钾水溶液，室温下搅拌混合溶液 24小时，过滤反应溶液，然后用乙醇反复洗涤，干燥后获得二氧化钛前驱体；
(2)将二氧化钛前驱体与步骤s1中制得的氧化石墨烯粉末充分混合，并研磨获得氧化石墨烯-TiO2复合粉末初品；
(3)将上述氧化石墨烯-TiO2复合粉末初品置于管式炉中，在350℃条件下高温烧结3h，研磨后即得到氧化石墨烯-TiO2复合粉末成品，所述高温烧结过程中，管式炉的升温方式设定为5℃每分钟；
进一步的，，所述步骤s3氧化石墨烯-TiO2-酞菁铜复合粉末的制备包括步骤：
(1)将步骤s2中制得的氧化石墨烯-TiO2复合粉末与酞菁铜粉末混合均匀，然后分散于氯化钠溶液中；
(2)在上述混合溶液中加入肼还原剂，在90℃条件下超声反应12h，最后将溶液离心，水洗，40-60℃真空干燥24h后得到石墨烯-TiO2-酞菁铜复合粉末，完成光催化剂的制备。
进一步的，所述步骤s1中，混合溶液加入双氧水和超纯水后的PH为9-10。
进一步的，所述步骤s2中十六胺、去离子水、氯化钾、无水乙醇 和钛酸异丙酯的摩尔比为 0.5：6：0.005：250：1。
进一步的，所述步骤s2中二氧化钛前驱体和氧化石墨烯混合比例为按照摩尔比为1:1。
进一步的，所述步骤s3中氯化钠溶液的浓度为1M。
与现有技术相比，本发明的有益效果是：(1)石墨烯相互连通的孔结构能有效固定二氧化钛纳米颗粒和酞菁铜，极大增强了二氧化钛光催化剂与石墨烯纳米片的有效接触面积，同时也能抑制二氧化钛尺寸的增长，增强了光催化剂的吸附性能和光催化性能。(2)本发明在传统的石墨烯-TiO2光催化剂中引入在水中稳定性能良好的有机小分子染料酞菁铜，利用酞菁铜在可见光波段的光吸收作用，大大提高了光制氢过程中对太阳光的利用率，提高了催化剂的光催化性能。(3)本发明使用的原材料成本低廉，适合于大规模的工业化生产。
附图说明
图1为本发明的基于石墨烯的光催化剂制备流程示意图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
请参阅图1，本发明提供一种技术方案：一种基于石墨烯的光催化剂制备方法，其特征在于，所述基于石墨烯的光催化剂制备包括以下步骤：
s1、制备氧化石墨烯粉末:包括步骤，(1)将石墨粉与98%的0℃浓硫酸和硝酸溶液缓慢混合； (2)将混合溶液搅拌均匀，并缓慢加入高锰酸钾，45℃水浴条件下继续搅拌反应24h；(3)将上述混合溶液冷却至室温，在冰浴下缓慢加入适量30% 双氧水和超纯水，混合溶液加入双氧水和超纯水后的PH为9-10；(4) 将上述液体过滤，用10wt% 盐酸溶液和大量去离子水清洗至中性；(5) 对液体超声处理60 min 后，在3000rpm下离心分离20 min，去除没有剥离的氧化石墨烯； (6) 取上清液，过滤后在 60℃下烘干20小时，得到氧化石墨烯粉末。
s2、制备氧化石墨烯-TiO2复合粉末；包括步骤：(1)将钛酸异丙酯、十六胺加入到无水乙醇中并添加氯化钾水溶液，室温下搅拌混合溶液 24小时，过滤反应溶液，然后用乙醇反复洗涤，干燥后获得二氧化钛前驱体，其中，十六胺、去离子水、氯化钾、无水乙醇 和钛酸异丙酯的摩尔比为 0.5：6：0.005：250：1；(2)将二氧化钛前驱体与步骤s1中制得的氧化石墨烯粉末充分混合，并研磨获得氧化石墨烯-TiO2复合粉末初品，其中，二氧化钛前驱体和氧化石墨烯混合比例为按照摩尔比为1:1；(3)将上述氧化石墨烯-TiO2复合粉末初品置于管式炉中，在350℃条件下高温烧结3h，研磨后即得到氧化石墨烯-TiO2复合粉末成品，所述高温烧结过程中，管式炉的升温方式设定为5℃每分钟；
s3、制备石墨烯-TiO2-酞菁铜复合粉末；包括步骤：(1)将步骤s2中制得的氧化石墨烯-TiO2复合粉末与酞菁铜粉末混合均匀，然后分散于氯化钠溶液中，其中，氯化钠溶液的浓度为1M； (2)在上述混合溶液中加入肼还原剂，在90℃条件下超声反应12h，最后将溶液离心，水洗，40-60℃真空干燥24h后得到石墨烯-TiO2-酞菁铜复合粉末，完成光催化剂的制备。
本发明的成功是基于以下几点; (1)石墨烯相互连通的孔结构能有效固定二氧化钛纳米颗粒和酞菁铜，极大增强了二氧化钛光催化剂与石墨烯纳米片的有效接触面积，同时也能抑制二氧化钛尺寸的增长，增强了光催化剂的吸附性能和光催化性能。(2)本发明在传统的石墨烯-TiO2光催化剂中引入在水中稳定性能良好的有机小分子染料酞菁铜，利用酞菁铜在可见光波段的光吸收作用，大大提高了光制氢过程中对太阳光的利用率，提高了催化剂的光催化性能。(3)本发明使用的原材料成本低廉，适合于大规模的工业化生产。
尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (8)
1.一种基于石墨烯的光催化剂制备方法，其特征在于，所述基于石墨烯的光催化剂制备包括以下步骤：
s1、制备氧化石墨烯粉末；
s2、制备氧化石墨烯-TiO2复合粉末；
s3、制备石墨烯-TiO2-酞菁铜复合粉末。
2.根据权利要求1所述的一种基于石墨烯的光催化剂制备方法，其特征在于，所述步骤s1氧化石墨烯粉末的制备包括步骤：
(1)将石墨粉与98%的0℃浓硫酸和硝酸溶液缓慢混合；
(2)将混合溶液搅拌均匀，并缓慢加入高锰酸钾，45℃水浴条件下继续搅拌反应24h；
(3)将上述混合溶液冷却至室温，在冰浴下缓慢加入适量30% 双氧水和超纯水；
(4) 将上述液体过滤，用10wt% 盐酸溶液和大量去离子水清洗至中性；
(5) 对液体超声处理60 min 后，在3000rpm下离心分离20 min，去除没有剥离的 氧化石墨烯；
(6) 取上清液，过滤后在 60℃下烘干20小时，得到氧化石墨烯粉末。
3.根据权利要求1所述的一种基于石墨烯的光催化剂制备方法，其特征在于，所述步骤s2氧化石墨烯-TiO2复合粉末的制备包括步骤：
(1)将钛酸异丙酯、十六胺加入到无水乙醇中并添加氯化钾水溶液，室温下搅拌混合溶液 24小时，过滤反应溶液，然后用乙醇反复洗涤，干燥后获得二氧化钛前驱体；
(2)将二氧化钛前驱体与步骤s1中制得的氧化石墨烯粉末充分混合，并研磨获得氧化石墨烯-TiO2复合粉末初品；
(3)将上述氧化石墨烯-TiO2复合粉末初品置于管式炉中，在350℃条件下高温烧结3h，研磨后即得到氧化石墨烯-TiO2复合粉末成品，所述高温烧结过程中，管式炉的升温方式设定为5℃每分钟。
4.根据权利要求1所述的一种基于石墨烯的光催化剂制备方法，其特征在于，所述步骤s3氧化石墨烯-TiO2-酞菁铜复合粉末的制备包括步骤：
(1)将步骤s2中制得的氧化石墨烯-TiO2复合粉末与酞菁铜粉末混合均匀，然后分散于氯化钠溶液中；
(2)在上述混合溶液中加入肼还原剂，在90℃条件下超声反应12h，最后将溶液离心，水洗，40-60℃真空干燥24h后得到石墨烯-TiO2-酞菁铜复合粉末，完成光催化剂的制备。
5.根据权利要求1所述的一种基于石墨烯的光催化剂制备方法，其特征在于，所述步骤s1中，混合溶液加入双氧水和超纯水后的PH为9-10。
6.根据权利要求1所述的一种基于石墨烯的光催化剂制备方法，其特征在于，所述步骤s2中十六胺、去离子水、氯化钾、无水乙醇 和钛酸异丙酯的摩尔比为 0.5：6：0.005：250：1。
7.根据权利要求1所述的一种基于石墨烯的光催化剂制备方法，其特征在于，所述步骤s2中二氧化钛前驱体和氧化石墨烯混合比例为按照摩尔比为1:1。
8.根据权利要求1所述的一种基于石墨烯的光催化剂制备方法，其特征在于，所述步骤s3中氯化钠溶液的浓度为1M。
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| CN110676376A (zh) * | 2019-08-27 | 2020-01-10 | 深圳大学 | 一种基于二维MXene材料的阻变存储器及制备方法 |
| CN113477276A (zh) * | 2021-06-29 | 2021-10-08 | 衡水学院 | 负载型光催化剂及其制备方法 |
| CN113477276B (zh) * | 2021-06-29 | 2023-08-25 | 衡水学院 | 负载型光催化剂及其制备方法 |
| CN113651356A (zh) * | 2021-08-16 | 2021-11-16 | 电子科技大学 | 核壳空腔结构二氧化钛石墨烯复合体制备方法及其应用 |
| CN113651356B (zh) * | 2021-08-16 | 2022-04-29 | 电子科技大学 | 核壳空腔结构二氧化钛石墨烯复合体制备方法及其应用 |
| CN114950561A (zh) * | 2022-04-11 | 2022-08-30 | 山东大学 | 一种co2光还原催化剂的制备方法 |
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