CN115924896A - 一种以非均相催化剂制备石墨烯量子点的方法 - Google Patents
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Abstract
本发明公开一种以非均相催化剂制备石墨烯量子点的方法,将二氧化锰粒子分散于水中并剧烈搅拌;保持搅拌,煮沸所得分散液,停止加热并加入双氧水;立即向所得反应液中加入中性氧化石墨烯溶液并继续搅拌,保持微沸适当补加双氧水;停止加热,继续搅拌,加入盐酸和双氧水使二氧化锰全部转化为锰(II)离子;过滤所得反应液,透析所得液体获得石墨烯量子点。本发明的优点反应无需紫外光照射,装置简单。产物易于处理,不会引入新的杂质。
Description
技术领域
本发明涉及碳纳米材料领域,更具体地,涉及石墨烯量子点,尤其是指一种以非均相催化剂制备石墨烯量子点的方法。
背景技术
芬顿反应(Fenton reaction)是以铁离子为催化剂、双氧水为氧化剂的强氧化反应,常用于氧化处理有机废水。石墨烯量子点是侧向尺寸小于100 nm的石墨烯小片层。紫外光诱导的光芬顿反应可将氧化石墨烯切割为石墨烯量子点(Zhou X, Zhang Y, Wang C,et al. Photo-Fenton reaction of graphene oxide: a new strategy to preparegraphene quantum dots for DNA cleavage[J]. ACS nano, 2012, 6(8): 6592-6599.),反应进程受紫外光照射强度、时间控制,可随时停止照射,反应很快停止。但是,无需紫外光照射而通过加热引发的芬顿反应不能用于生产石墨烯量子点,因为作为产物的石墨烯量子点可和铁离子复合生成具有更高催化活性的复合物,使反应不断加速,即产生所谓的自催化现象。因此,热引发的芬顿反应一般不能停留在产生石墨烯量子点的阶段,而会继续反应生成二氧化碳和水。锰的一些氧化物也能在双氧水溶液中引发强烈的氧化反应,称作类芬顿反应(Ma Z , Wei X , Xing S , et al. Hydrothermal synthesis andcharacterization of surface-modified δ-MnO2 with high Fenton-like catalyticactivity[J]. Catalysis Communications, 2015, 67:68-71.),石墨烯量子点也能加速此类非均相类芬顿反应(Wu X , Zhang Y , Han T , et al. Composite of graphenequantum dots and Fe3O4 nanoparticles: peroxidase activity and application inphenolic compound removal[J]. Rsc Advances, 2013, 4(7):3299-3305.),但当石墨烯量子点含量增多时,也可屏蔽金属氧化物表面的活性位点使反应减速,这就为反应提供了天然的终止机理,而不必等待某个反应物耗尽。
发明内容
针对以热引发的芬顿反应难以控制的问题,本发明目的在于提供一种以非均相催化剂制备石墨烯量子点的方法。
本发明通过以下方案实现:一种以非均相催化剂制备石墨烯量子点的方法,包括如下步骤:
(1)将二氧化锰粒子分散于水中并剧烈搅拌。
(2)保持搅拌,煮沸步骤(1)中所得分散液,停止加热并加入双氧水。
(3)立即向步骤(2)所得反应液中加入中性氧化石墨烯溶液并继续搅拌。适当补加双氧水。
(4)继续搅拌,加入盐酸和双氧水使二氧化锰全部转化为锰(II)离子。
(5)过滤步骤(4)所得反应液,透析所得液体获得石墨烯量子点。
优选的,步骤(1)中二氧化锰粒子d50 = 50 nm。
优选的,步骤(3)中加入氧化石墨烯的质量为步骤(1)中加入二氧化锰的5倍。
本发明的优点:
(1)反应无需紫外光照射,装置简单。
(2)产物易于处理,不会引入新的杂质。
本发明利用了反应生成的石墨烯量子点控制反应进程,在反应初始阶段,生成的石墨烯量子点与二氧化锰粒子复合可加速反应,当生成的石墨烯量子点进一步增多时,其覆盖二氧化锰粒子表面的活性位点,又使反应减速并最终停止。在产物处理中,加入盐酸酸化使二氧化锰氧化性增强并顺利还原为二价锰离子,此时双氧水作为还原剂转化为氧气。由于以改进的Hummers方法制备氧化石墨烯,在制备过程中不可避免地会引入锰(II)离子,所以本方法的另一个优点就是不会引入新的杂质离子。
具体实施方式
下面结合具体实施例,进一步阐述本发明。下述实施例中所使用的实验方法如无特殊说明,均为常规方法。下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。
实施例1.
.一种以非均相催化剂制备石墨烯量子点,按如下步骤制备:
(1)将1 mg二氧化锰催化剂(d50 = 50 nm)分散于50 mL中并剧烈搅拌;
(2)剧烈搅拌下加热至步骤(1)中所得分散液沸腾,停止加热,以塑料滴管向溶液内部加入0.2 mL市售双氧水(30 %),煮沸,停止加热并加入双氧水;
(3)将5 mg氧化石墨烯分散于10 mL水中,加入氢氧化钠溶液将其中和至中性;立即将所得中性氧化石墨烯分散液加入近沸的步骤(2)所得二氧化锰分散液中,保持搅拌并加热使溶液保持微沸,每间隔10 min以滴管向溶液中心补加0.2 mL市售浓度30 %双氧水,共加入1.0 mL双阳水;后停止加热;
(4)停止加热,继续搅拌使反应回到室温,加入1 mL市售浓度36 %的浓盐酸和继续搅拌并补加0.1 mL浓度30 %双氧水,使二氧化锰全部转化为锰(II)离子;
(5)过滤除去未反应的固体,将溶液透析至中性即得石墨烯量子点溶液。
上述实施例仅仅是为清楚地说明本发明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明的保护范围之中。
Claims (4)
1.一种以非均相催化剂制备石墨烯量子点的方法,其特征在于,包括如下步骤:
(1)将二氧化锰粒子分散于水中并剧烈搅拌;
(2)保持搅拌,煮沸步骤(1)中所得分散液,停止加热并加入双氧水;
(3)立即向步骤(2)所得反应液中加入中性氧化石墨烯溶液并继续搅拌,保持微沸,适当补加双氧水;
(4)停止加热,继续搅拌,加入盐酸和双氧水使二氧化锰全部转化为锰(II)离子;
(5)过滤步骤(4)所得反应液,透析所得液体获得石墨烯量子点。
2.根据权利要求1所述的一种以非均相催化剂制备石墨烯量子点的方法,其特征在于,步骤(2)所述二氧化锰粒子d50 = 50 nm。
3.根据权利要求1所述的一种以非均相催化剂制备石墨烯量子点的方法,其特征在于,步骤(3)中加入氧化石墨烯的质量是步骤(1)中加入二氧化锰质量的5倍。
4.根据权利要求1至3任一项所述的一种以非均相催化剂制备石墨烯量子点的方法,其特征在于,按如下步骤制备:
(1)将1 mg二氧化锰催化剂(d50 = 50 nm)分散于50 mL中并剧烈搅拌;
(2)剧烈搅拌下加热至步骤(1)中所得分散液沸腾,停止加热,以塑料滴管向溶液内部加入0.2 mL市售双氧水(30 %),煮沸,停止加热并加入双氧水;
(3)将5 mg氧化石墨烯分散于10 mL水中,加入氢氧化钠溶液将其中和至中性;立即将所得中性氧化石墨烯分散液加入近沸的步骤(2)所得二氧化锰分散液中,保持搅拌并加热使溶液保持微沸,每间隔10 min以滴管向溶液中心补加0.2 mL市售浓度30 %双氧水,共加入1.0 mL双阳水;后停止加热;
(4)停止加热,继续搅拌使反应回到室温,加入1 mL市售浓度36 %的浓盐酸和继续搅拌并补加0.1 mL浓度30 %双氧水,使二氧化锰全部转化为锰(II)离子;
(5)过滤除去未反应的固体,将溶液透析至中性即得石墨烯量子点溶液。
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