CN114377705B - 一种基于粉煤灰的磷掺杂碳点光催化材料及其制备方法和应用 - Google Patents
一种基于粉煤灰的磷掺杂碳点光催化材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种基于粉煤灰的磷掺杂碳点光催化材料及其制备方法和应用,属于光催化材料技术领域,本发明将蔗糖、磷酸和粉煤灰加入水中超声搅拌混合后得到的混合液微波作用后,蔗糖和磷酸成块状类石墨态炭纳米材料附着在粉煤灰球形表面,形成了碳层负载的粉煤灰负载磷化碳点的多层次结构,碳化材料本身对污染物的吸附能力强,加入磷酸使得纳米级的碳能够附着在基底材料上,粉煤灰上的金属离子能够起到助催化作用,形成类半导体材料,实现粉煤灰的光催化降解效果。
Description
技术领域
本发明涉及光催化材料技术领域,具体涉及到一种基于粉煤灰的磷掺杂碳点光催化材料及其制备方法和应用。
背景技术
粉煤灰是煤炭能源生产燃烧过程产生的粉状固体废物,俗称飞灰(FA),粉煤灰产量巨大,全球每年排放的粉煤灰约为5亿吨,而我国每年粉煤灰的排放量就占世界的30%。因此,粉煤灰的综合利用引起各国极大的关注。目前,粉煤灰在我国主要用于建筑制砖、水泥原料、路基材料、土壤改良剂和橡胶填料等,但其较高的综合利用率只能达到70%,平均综合利用率只有30%,远低于发达国家水平。因此,开发粉煤灰的其它应用途径,提升粉煤灰资源的经济价值和综合利用率,减少其对环境的危害,已成为当务之急。
国内外文献已报道了诸多粉煤灰的应用途径,而做的得较多的包括作为水处理吸附材料,制备沸石、分子筛、陶瓷、玻璃和白炭黑等功能材料,制备氢氧化铝和氧化铝等化工产品。近年来,虽然粉煤灰利用率逐渐升高,但对于粉煤灰还含有许多有用的金属元素并没有高效的利用起来,同时存在制备方法复杂且成本高的问题。
发明内容
针对上述的不足,本发明的目的是提供一种基于粉煤灰的磷掺杂碳点光催化材料及其制备方法和应用,本发明采用负载碳点的方法将粉煤灰制成一种光催化材料,将粉煤灰的金属离子作为自身的助催化剂,极大提高了粉煤灰的利用率,且光催化效果显著;该光催化材料本身强韧度较高,又以碳点负载,吸附效果也十分显著,使得废弃的粉煤灰的利用率可达85%以上,经测试,回收后反复利用吸附降解效果仍然很高,性质稳定,无毒无害,制备方法简单且成本低,应用领域广。
为达上述目的,本发明采取如下的技术方案:
本发明提供一种基于粉煤灰的磷掺杂碳点光催化材料的制备方法,包括以下步骤:将蔗糖和磷酸依次加入水中溶解均匀后再加入粉煤灰超声搅拌,然后微波处理后冷却至室温,研磨,洗涤,离心,干燥,制得光催化材料。
本发明中磷掺杂碳点光催化材料的制备原理为:将蔗糖、磷酸和粉煤灰加入水中超声搅拌混合后得到的混合液微波作用后,蔗糖和磷酸成块状类石墨态炭纳米材料附着在粉煤灰球形表面,形成了碳层负载的粉煤灰负载磷化碳点的多层次结构,碳化材料本身对污染物的吸附能力强,加入磷酸使得纳米级的碳能够附着在基底材料上,粉煤灰上的金属离子能够起到助催化作用,形成类半导体材料,实现粉煤灰的光催化降解效果;通过控制磷酸的加入量可以有效控制材料的能级,同时磷酸可以与粉煤灰的上的金属元素反应,使其加入形成的碳点结构中,有利于光催化反应的进行。
进一步地,蔗糖、磷酸和粉煤灰的质量比为3~8:2.5~7:1~3,优选为5:3.5~6.5:2,最优选为5:3.75:2。
进一步地,微波处理的工作参数为:微波功率为550~900W,优选为700W;微波处理时长为2~8分钟,优选为4分钟。
进一步地,蔗糖加入水中后采用超声溶解5~15分钟,优选为10分钟。
进一步地,干燥的工作参数为:干燥温度为50~70℃,优选为60℃;干燥时长为8~12小时,优选为9小时。
进一步地,水为超纯水。
本发明还提供上述制备方法制得的磷掺杂碳点光催化材料。
进一步地,上述基于粉煤灰的磷掺杂碳点光催化材料为蘑菇云装发泡材料,其材料比表面积极大(3200~3625m2/g)。
本发明还提供上述磷掺杂碳点光催化材料在光催化降解有机污染物中的应用。
综上所述,本发明具有以下优点:
1、本发明提供了一种基于粉煤灰的磷掺杂碳点光催化材料,其制备原理为:蔗糖溶液在微波作用下,首先在粉煤灰的表面上形成粒径在nm级的碳点,磷酸中磷元素富电子,这部分电子可以参与载流子的形成,同时也改变了碳点的能级结构,通过调控磷酸的量,可以有效控制磷化碳量子的能带结构,使得形成的磷化量子点材料具有更好的光催化活性。随着微波反应时间的增加碳点进一步聚集,碳化形成片层的类石墨结构将原本的负载磷化碳点的粉煤灰固定,形成较稳定的催化剂结构。本发明将粉煤灰的金属离子作为自身的助催化剂,极大提高了粉煤灰的利用率(85%以上),且光催化效果显著(如罗丹明B和甲基蓝降解率均高达99%);同时,该磷掺杂碳点光催化材料性质稳定,无毒无害,重复利用率高。
2、本发明中磷掺杂碳点光催化材料的制备方法简单,原料廉价易得,成本低,具有广泛的实际应用价值。
附图说明
图1-2为本发明磷掺杂碳点光催化材料制备过程中多孔性蘑菇云状图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明,即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。
因此,以下对提供的本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围,而是仅仅表示本发明的选定实施例。基于本发明的实施例,本领域技术人员在没有做出创造性劳动的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。
实施例1
本例提供一种基于粉煤灰的磷掺杂碳点光催化材料的制备方法,具体步骤如下:5.0g蔗糖均加入10ml超纯水超声溶解10min,加入2ml磷酸(密度为1.874g/mL)混匀后再加入2g粉煤灰充分搅拌,再次超声10min,微波(微波功率700W)处理4min(微波过程中,1.5min左右,反应液被烧干,材料开始膨胀,内部产生氢气,形成微爆,火花四溅,产生大量气孔,逐层往上生长,形成多孔性蘑菇云状材料,如图1和图2所示),冷却至室温后,捣碎研磨,洗涤,离心,在60℃下干燥9小时,得到最终磷掺杂碳点光催化材料,其比表面积极大(3625m2/g)。
实施例2
本例提供一种基于粉煤灰的磷掺杂碳点光催化材料的制备方法,与实施例1区别仅在于:蔗糖、磷酸和粉煤灰的质量分别为7g、5g和2g,其余步骤及参数均相同。
对比例1
本例提供一种基于粉煤灰的碳点光催化材料的制备方法,与实施例1区别仅在于:将蔗糖替换为麦芽糖,其余步骤及参数均相同。
对比例2
本例提供一种基于粉煤灰的碳点光催化材料的制备方法,与实施例1区别仅在于:将磷酸替换为质量分数为30%的稀硫酸,其余步骤及参数均相同。
实验例1
本例称取50mg罗丹明B加入50ml超纯水超声溶解10min,溶解后,溶液稀释20倍,分别称取25mg实施例1~2和对比例1~2所制得的碳点光催化材料加入至25mL稀释后的罗丹明B溶液中进行暗反应和光反应各2小时;测量吸光度,计算出罗丹明B降解率,结果如表1所示。
表1
编号 | 降解率(%) |
实施例1 | 99% |
实施例2 | 98.5% |
对比例1 | 75% |
对比例2 | 35% |
在上述实验步骤的基础上,将罗丹明B调整为甲基蓝进行实验,最终测得甲基蓝降解率如表2所示。
表2
编号 | 降解率(%) |
实施例1 | 99% |
实施例2 | 98.8% |
对比例1 | 68% |
对比例2 | 41% |
实验例2
本例在实施例1和实验例1的基础上,考察磷酸浓度对所制得的磷掺杂碳点光催化材料的性能的影响,结果如表1所示。具体过程如下:
(1)5.0g蔗糖均加入10ml超纯水超声溶解10min,加入X ml磷酸(密度为1.874g/mL)混匀后再加入2g粉煤灰充分搅拌,再次超声10min,微波(微波功率700W)处理4min,冷却至室温后,捣碎研磨,洗涤,离心,在60℃下干燥9小时,得到最终磷掺杂碳点光催化材料。
(2)取25mg(1)中所得的磷掺杂碳点光催化材料加入浓度为10mg/L的罗丹明B溶液20mL,光反应15分钟,暗反应15分钟;测量吸光度,计算出罗丹明B降解率。
表1
X mL磷酸 | 罗丹明B降解率 |
0.05(质量分数:0.5%) | 12% |
0.1(质量分数:1%) | 10% |
0.5(质量分数:5%) | 30% |
1(质量分数:10%) | 63% |
1.5(质量分数:14%) | 95% |
2(质量分数:18%) | 99% |
4(质量分数:35%) | 99% |
基于粉煤灰中金属离子的氧化能力,使材料禁带宽度减小,周围的电子跃迁所需要的能量降低,有利于载流子的形成,增加了光催化反应的活性,氧化能力显著增强,而若材料禁带宽度过小,载流子复合速度快,光催化活性降低,经研究发现复合材料磷酸质量分数在18%时,带宽在较为合适位置,这时候材料的降解能力佳。
掩蔽实验:空穴在光催化降解染料中起至关重要的作用,以草酸氨掩蔽空穴,罗丹明B的去除率大幅降低,用对苯醌和异丙醇分别掩蔽超氧自由基和自由基,罗丹明B的降解率几乎不变,研究表明空穴对光降解罗丹明B的影响最大,自由基与超氧自由基对此光降解过程几乎没有影响。
实验例3
本例将实验例1中降解罗丹明B后磷掺杂碳点光催化材料取出,用蒸馏水洗涤,烘干,放于马弗炉中,400℃煅烧2小时,得到再生磷掺杂碳点光催化材料,用于再次降解罗丹明B(操作过程与实验例1相同),经50次反复利用后,罗丹明B降解率仍高达95%。
以上内容仅仅是对本发明结构所作的举例和说明,所属本领域的技术人员不经创造性劳动即对所描述的具体实施例做的修改或补充或采用类似的方式替代仍属本专利的保护范围。
Claims (7)
1.一种基于粉煤灰的磷掺杂碳点光催化材料的制备方法,其特征在于,包括以下步骤:将蔗糖和磷酸依次加入水中溶解均匀后再加入粉煤灰超声搅拌,然后微波处理后冷却至室温,研磨,洗涤,离心,干燥,制得光催化材料;
所述蔗糖、磷酸和粉煤灰的质量比为3~8:2.5~7:1~3;
所述微波处理的工作参数为:微波功率为550~900 W,微波处理时长为2~8分钟。
2.如权利要求1所述的基于粉煤灰的磷掺杂碳点光催化材料的制备方法,其特征在于,所述蔗糖、磷酸和粉煤灰的质量比为5:3.5~6.5:2。
3.如权利要求1所述的基于粉煤灰的磷掺杂碳点光催化材料的制备方法,其特征在于,蔗糖加入水中后采用超声溶解5~15分钟。
4.如权利要求1所述的基于粉煤灰的磷掺杂碳点光催化材料的制备方法,其特征在于,所述干燥的工作参数为:干燥温度为50~70℃,干燥时长为8~12小时。
5.权利要求1~4任一项所述的基于粉煤灰的磷掺杂碳点光催化材料的制备方法制得的磷掺杂碳点光催化材料。
6. 如权利要求5所述的基于粉煤灰的磷掺杂碳点光催化材料,其特征在于,所述基于粉煤灰的磷掺杂碳点光催化材料为蘑菇云装发泡材料,其材料比表面积为3200~3625 m2/g。
7.权利要求5或6所述的磷掺杂碳点光催化材料在光催化降解有机污染物中的应用。
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