CN116328745A - 一种亲疏水可控的硫化多孔石墨烯材料及其制备方法 - Google Patents
一种亲疏水可控的硫化多孔石墨烯材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种亲疏水可控的硫化多孔石墨烯材料及其制备方法。所述亲疏水可控的硫化多孔石墨烯材料的制备方法包括:(1)将植物油、硫磺粉和熔融石英粉体混合后进行硫化处理,得到产物A;(2)将硫化后的固体在惰性气氛中、700℃~900℃下碳化3~12小时,得到产物B;(3)将碳化后材料经过破碎和过筛,先在120~350℃的碱溶液中浸泡2~12小时,再进行清洗和干燥,得到硫化石墨烯;(4)将硫化石墨烯、氧化石墨烯和去离子水混合并进行冷冻干燥,得到亲疏水可控的硫化多孔石墨烯材料。
Description
技术领域
本发明涉及一种以植物油为主要原料碳化制备亲疏水可控的硫化多孔石墨烯材料及其制备方法,属于材料领域。
背景技术
石墨烯(Graphene)是一种以sp2杂化连接的碳原子紧密堆积成单层二维蜂窝状晶格结构的新材料。由于其特殊的结构,石墨烯具有超强的疏水性和亲油性,对烟气中的多种有害的有机物具有很好的吸附效果。
三维石墨烯通常是指具有三维结构的二维石墨烯组装体,是近年来石墨烯化学领域的新型功能性材料,在能量存储、催化、环境修复、等方面展现了独特的性能。目前三维石墨烯材料的孔通常是在几百纳米到几十微米之间。三维石墨烯材料的制备大多仍以由机械剥离法、外延生长法、化学剥离法制备所得还原rGO及其功能化衍生物为原料,三维石墨烯材料的微观孔结构大多通过二维石墨烯整合过程中随机出现或致孔产生,孔结构可控性及重复性差。因此,在宽孔径范围内实现三维石墨烯孔尺寸可控仍是难点。其次,如何有效防止石墨烯纳米片在形成三维结构过程中的重新堆积、完好保持石墨烯片层性质仍是难点。另外,三维石墨烯材料的微观结构有序控制技术仍有待于进一步提高。
发明内容
针对上述问题,本发明提供了一种亲疏水可控的硫化多孔石墨烯材料及其制备方法。
一方面,本发明提供了一种亲疏水可控的硫化多孔石墨烯材料的制备方法,包括:
(1)将植物油、硫磺粉和熔融石英粉体混合后进行硫化处理,得到产物A;
(2)将硫化后的固体在惰性气氛中、700℃~900℃下碳化3~12小时,得到产物B;
(3)将碳化后材料经过破碎和过筛,先在120~350℃的碱溶液中浸泡2~12小时,再进行清洗和干燥,得到硫化石墨烯;
(4)将硫化石墨烯、氧化石墨烯和去离子水混合并进行冷冻干燥,得到亲疏水可控的硫化多孔石墨烯材料。
本发明中,植物油由于液态流动容易致使碳的大分子团接近彼此平行,在惰性气氛中,随着热处置温度的上升,植物油在碳化过程中容易形成彼此堆积排列的微晶,很容易向石墨结构方向转变。由于植物油中有较多的C=C双键,在较高的温度下很容易硫化,通过硫化作用,高温下已经石墨化的组织结构相互联结变成具有一定力学性能的三维石墨烯材料。
其次,采用熔融石英由于其粒径控制技术较为成熟,且在热的碱溶液中易于溶解,是一种很好的制备多孔材料的模板材料。熔融石英作为成孔模板可以使材料的孔结构更为可控。
第三,氧化石墨烯(graphene oxide)是石墨烯的氧化物。因经氧化后,其上含氧官能团增多而使性质较石墨烯更加活泼,具有很强的亲水性。氧化石墨烯和石墨烯混合,对烟气中的水性、油性有害物质能做到全面的吸附,是一种很好的应用前景的烟气过滤材料。
较佳的,所述植物油选自豆油、花生油、玉米油、蓖麻油、葵花籽油、菜籽油和橄榄油中的至少一种。
较佳的,所述硫磺粉的粒径为200目~325目;所述硫磺粉的加入量为植物油质量的0.5wt%~10wt%。
较佳的,所述熔融石英的粒径范围为80nm~200000nm;所述熔融石英的加入量为植物油质量的10wt%~60wt%。
较佳的,所述硫化处理为:在120~180℃的加热搅拌器中搅拌1~3小时至膏状后停止搅拌继续加热2~6小时;所述加热搅拌器的转速为50~200转/分钟。
较佳的,所述惰性气氛为氩气或氮气。
较佳的,所述过筛为过40~100目筛。
较佳的,所述碱液为含有NaOH或/和KOH的溶液;溶质的浓度为5wt%~60wt%;
较佳的,所述氧化石墨烯的加入量为硫化石墨烯质量的0%~50wt%。
较佳的,步骤(4)中,所述冷冻干燥的温度为-5~-40℃,时间为6~24小时;优选地,在冷冻干燥之前,进行在300~2000转/min下离心处理0.5~2小时。
另一方面,本发明还提供了一种根据上述制备方法制备的亲疏水可控的硫化多孔石墨烯材料。
有益效果:
本发明公开一种以植物油为主要原料碳化制备亲疏水可控的硫化多孔石墨烯及其工艺,即将植物油、单质硫及纳米和亚微米级的熔融石英粉末混合后加热硫化,然后在高温下碳化,得到包裹有熔融石英颗粒的硫化石墨烯材料,使用热的碱溶液将材料中的熔融石英颗粒溶解,得到多孔的硫化石墨烯,将该种多孔石墨烯和氧化石墨烯混合,便制备出亲疏水可控的硫化石墨烯材料。
附图说明
图1为植物油碳化后形成的三维多孔结构,从图中可知植物油碳化后形成较多的孔隙,且碳化形成了石墨烯片层结构,可以提供大量的吸附位点;
图2为烟气吸附装置。
具体实施方式
以下通过下述实施方式进一步说明本发明,应理解,下述实施方式仅用于说明本发明,而非限制本发明。
在本发明中,以植物油为主要原料碳化制备亲疏水可控的硫化多孔石墨烯材料。
将植物油、硫磺粉和熔融石英粉体在加热搅拌器中充分混合。该步骤中所用的植物油为豆油、花生油、玉米油、蓖麻油、葵花籽油、菜籽油及橄榄油中的一种或多种。所使用的硫磺粉粒径为200目-325目。硫磺粉的质量为植物油质量的0.5wt%-10wt%。熔融石英的粒径范围为80nm-200000nm。熔融石英的质量为植物油质量的10wt%-60wt%。该步骤中使用的混合设备主要是高速分散机或双行星搅拌机,搅拌时间为1-6h。加入硫磺粉主要作为交联剂,在植物油分子链之间形成三维桥连,从而制备出三维多孔材料。
在可选的实施方式中,将加热搅拌器的温度加热到120℃-180℃,当容器中液体变为膏状后停止搅拌,在该温度下继续加热2-6h,让植物油充分硫化。
将硫化后的固体放入石墨炉中,通入惰性气体,在700℃-900℃条件下碳化3-12h。其中,惰性气体为氩气或氮气。
将碳化后材料破碎、过40-100目筛。其中,破碎的设备为颚式破碎机、锤片式破碎机或滚磨机。
将过筛后的粉体浸泡在热的碱溶液中2-12h。其中,碱液为NaOH、KOH溶液或两者的混合溶液,溶液浓度为5wt%-60wt%。碱液的温度可为120℃-350℃。碱洗后用清水洗2-5次,除去其中的熔融石英颗粒和碱金属离子。
将洗涤后的粉体在-5~-40℃下冷冻干燥10-24h,得到硫化石墨烯。
将干燥后的硫化石墨烯粉末和氧化石墨烯在去离子水中按一定比例混合,得到混合液。其中,氧化石墨烯的质量为硫化石墨烯质量的0%-50wt%,两者的混合在高速分散机、篮式球磨机或滚磨机中进行,混料时间为3-12h。
将混合液进行离心处理,滤去上层清夜。将下层混合物-5~-40℃下冷冻干燥10-20h,得到亲疏水可控的硫化多孔石墨烯材料。
在本发明中,所得亲疏水可控的硫化多孔石墨烯材料具有如下结构特征:
材料主要有两部分组成,植物油硫化、碳化后制备的三维石墨烯多孔材料以及氧化石墨烯材料。此外,碳化后制备的三维石墨烯多孔材料中孔道为氧化石墨烯提供更多的反应活性位点,协同提升吸附性能。其中,氧化石墨烯经混合后以片状插层的方式混合在三维石墨烯材料中,两种材料相互掺杂,随机分布。植物油硫化、碳化后制备的三维石墨烯多孔材料整体上为三维网状结构,结构内部有亚微米级的熔融石英除去后留下的孔洞。所得亲疏水可控的硫化多孔石墨烯材料中孔结构丰富,且不同孔径结构搭配错落有致,具有很高的比表面可达800-1500m2/g,显示出很好的吸附能力。
下面进一步例举实施例以详细说明本发明。同样应理解,以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例,即本领域技术人员可以通过本文的说明做合适的范围内选择,而并非要限定于下文示例的具体数值。
实施例1:
1)将大豆油、硫磺粉和熔融石英粉体在搅拌器中充分混合,所使用的硫磺粉粒径为325目,硫磺粉的质量为大豆油质量的0.5wt%;熔融石英为400目熔融石英粉,中位径为200nm,熔融石英的质量为植物油质量的60wt%,该步骤中使用的混合设备主要是双行星搅拌机,搅拌时间为6h;
2)加热搅拌器,将搅拌器的温度加热到150℃,当容器中液体变为膏状后停止搅拌,在该温度下继续加热6h,让植物油充分硫化;
3)将硫化后的固体放入石墨炉中,通入惰性气体,在900℃条件下碳化12h,惰性气体为氮气;
4)将碳化后材料破碎、过40目筛,破碎的设备为锤片式破碎机或滚磨机;
5)将过筛后的粉体浸泡在热的碱溶液中12h,碱液为NaOH溶液溶液浓度为30wt%,碱液的温度为250℃,碱洗后用清水洗5次,除去其中的熔融石英颗粒和碱金属离子;
6)将洗涤后的粉体冷冻干燥24h;
7)将干燥后的硫化石墨烯粉末和氧化石墨烯在去离子水中按一定比例混合,氧化石墨烯的质量为硫化石墨烯质量的50wt%,两者的混合在高速分散机中进行,混料时间为3h;
8)将步骤7)中的混合液进行离心处理,滤去上层清夜,将下层混合物冷冻干燥20h,得到亲疏水可控的硫化多孔石墨烯材料。
实施例2
1)将菜籽油、硫磺粉和熔融石英粉体在搅拌器中充分混合,所使用的硫磺粉粒径为200目,硫磺粉的质量为菜籽油质量的5wt%;熔融石英为325目熔融石英粉,中位径为40000nm,熔融石英的质量为植物油质量的60wt%,该步骤中使用的混合设备主要是双行星搅拌机,搅拌时间为6h;
2)加热搅拌器,将搅拌器的温度加热到130℃,当容器中液体变为膏状后停止搅拌,在该温度下继续加热6h,让植物油充分硫化;
3)将硫化后的固体放入石墨炉中,通入惰性气体,在900℃条件下碳化12h,惰性气体为氮气;
4)将碳化后材料破碎、过40目筛,破碎的设备为锤片式破碎机或滚磨机;
5)将过筛后的粉体浸泡在热的碱溶液中12h,碱液为KOH溶液,溶液浓度为30wt%,碱液的温度为250℃,碱洗后用清水洗5次,除去其中的熔融石英颗粒和碱金属离子;
6)将洗涤后的粉体冷冻干燥24h;
7)将干燥后的硫化石墨烯粉末和氧化石墨烯在去离子水中按一定比例混合,氧化石墨烯的质量为硫化石墨烯质量的20wt%,两者的混合在高速分散机中进行,混料时间为6h;
8)将步骤7)中的混合液进行离心处理,滤去上层清夜,将下层混合物冷冻干燥20h,得到亲疏水可控的硫化多孔石墨烯材料。
实施例3
本实施例3中亲疏水可控的硫化多孔石墨烯材料的制备过程参照实施例1,区别仅在于:氧化石墨烯的质量为硫化石墨烯质量的5wt%。
实施例4
本实施例4中亲疏水可控的硫化多孔石墨烯材料的制备过程参照实施例1,区别仅在于:氧化石墨烯的质量为硫化石墨烯质量的10wt%。
实施例5
本实施例5中亲疏水可控的硫化多孔石墨烯材料的制备过程参照实施例1,区别仅在于:氧化石墨烯的质量为硫化石墨烯质量的30wt%。
实施例6
本实施例6中亲疏水可控的硫化多孔石墨烯材料的制备过程参照实施例1,区别仅在于:氧化石墨烯的质量为硫化石墨烯质量的40wt%。
对比例1
本对比例1中亲疏水可控的硫化多孔石墨烯材料的制备过程参照实施例1,区别仅在于:不加入氧化石墨烯。
对比例2
本对比例2中亲疏水可控的硫化多孔石墨烯材料的制备过程参照实施例1,区别仅在于:氧化石墨烯的质量为硫化石墨烯质量的60wt%。
对比例3
本对比例3中亲疏水可控的硫化多孔石墨烯材料的制备过程参照实施例5,区别在于:不加入硫磺粉。
参照图2,对烟气进行过滤试验:
1、称取一定质量的材料(50g)放入两端开孔的玻璃瓶中,制作吸附容器,玻璃瓶上下用软木塞封住,用橡胶管和外界联通;
2、将多根香烟(20根/品牌黄鹤楼)固定在吸烟机的吸嘴上,用橡胶管将吸烟机的出烟口和吸附容器进口连接,同时用橡胶管将吸附容器的出口和烟气收集处理装置相连;
3、启动抽烟机,点燃香烟,对烟气进行吸附、收集;
4、试验结束后,取出吸附容器中的材料,使用称重、红外以及GC-MS等手段对材料吸附的量和物质成分进行分析。其中亲油性物质包括亲油性物质有苯、苯乙烯、异戊二烯及其他多环芳烃类化合物。亲水性物质包括丙烯腈、尼古丁、CO等物质。
表1为本发明制备的亲疏水可控的硫化多孔石墨烯材料的性能:
Claims (10)
1.一种亲疏水可控的硫化多孔石墨烯材料的制备方法,其特征在于,包括:
(1)将植物油、硫磺粉和熔融石英粉体混合后进行硫化处理,得到产物A;
(2)将硫化后的固体在惰性气氛中、700℃~900℃下碳化3~12小时,得到产物B;
(3)将碳化后材料经过破碎和过筛,先在120~350℃的碱溶液中浸泡2~12小时,再进行清洗和干燥,得到硫化石墨烯;
(4)将硫化石墨烯、氧化石墨烯和去离子水混合并进行冷冻干燥,得到亲疏水可控的硫化多孔石墨烯材料。
2.根据权利要求1所述的制备方法,其特征在于,所述植物油选自豆油、花生油、玉米油、蓖麻油、葵花籽油、菜籽油和橄榄油中的至少一种。
3.根据权利要求1所述的制备方法,其特征在于,所述硫磺粉的粒径为200目~325目;所述硫磺粉的加入量为植物油质量的0.5wt%~10wt%。
4.根据权利要求1所述的制备方法,其特征在于,所述熔融石英的粒径范围为80nm~200000nm;所述熔融石英的加入量为植物油质量的10wt%~60wt%。
5.根据权利要求1所述的制备方法,其特征在于,所述硫化处理为:在120~180℃的加热搅拌器中搅拌1~3小时至膏状后停止搅拌继续加热2~6小时;所述加热搅拌器的转速为50~200转/分钟。
6.根据权利要求1所述的制备方法,其特征在于,所述惰性气氛为氩气或氮气。
7.根据权利要求1所述的制备方法,其特征在于,所述过筛为过40~100目筛;
所述碱液为含有NaOH或/和KOH的溶液;溶质的浓度为5wt%~60wt%。
8.根据权利要求1-7中任一项所述的制备方法,其特征在于,所述氧化石墨烯的加入量为硫化石墨烯质量的0%~50wt%。
9.根据权利要求1-8中任一项所述的制备方法,其特征在于,步骤(4)中,所述冷冻干燥的温度为-5~-40℃,时间为6~24小时;优选地,在冷冻干燥之前,进行在300~2000转/min下离心处理0.5~2小时。
10.一种根据权利要求1-9中任一项所述的制备方法制备的亲疏水可控的硫化多孔石墨烯材料。
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