CN112044423A - 石墨-二氧化钛复合光催化剂及其制备方法 - Google Patents
石墨-二氧化钛复合光催化剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及石墨‑二氧化钛复合光催化剂及其制备方法,属于光催化剂材料制备的技术领域。石墨‑二氧化钛复合光催化剂及其制备方法的制备方法,按以下步骤进行:a、将石墨粉与溶剂混匀,得石墨粉分散液;b、将二氧化钛与石墨粉分散液混匀,得石墨‑二氧化钛浆料;c、将石墨‑二氧化钛浆料水热超声分散,得到复合光催化剂前驱体;d、将复合光催化剂前驱体进行真空煅烧得到复合光催化剂煅烧料;e、将复合光催化剂煅烧料球磨8~24h,得到所述的石墨‑二氧化钛复合光催化剂。本发明工艺拓宽了光催化剂的光谱响应范围,提高了光催化活性,在污水处理领域中具有很好地应用前景。
Description
技术领域
本发明涉及石墨-二氧化钛复合光催化剂及其制备方法,属于光催化剂材料制备的技术领域。
背景技术
自1972年A.Fujishima和K.Honda在自然光照射下,发现用n型半导体二氧化钛电极上水的光电催化分解现象以来,二氧化钛以其化学稳定性高、耐酸碱、无毒等的特点而倍受关注。但是二氧化钛的禁带宽度较宽(3.2eV),对应的最低吸收边波长为387.5nm,而太阳光谱范围中低于此波长的部分仅占4%左右,从而限制了二氧化钛在自然光下的应用。同时,二氧化钛较高的电子-空穴复合率导致其较低的量子产率和可见光下无光催化活性。
因此,开发出一条能够提高二氧化钛光催化活性的方法非常有必要。
在现有技术中,制备石墨和二氧化钛的复合材料,通常都是以氧化石墨烯为原料和二氧化钛进行水热复合,再将氧化石墨烯和二氧化钛的复合材料进行还原,干燥,得到石墨烯和二氧化钛的复合材料,比如公开号为CN105561963A的专利。如果直接将石墨和二氧化钛进行水热反应,再干燥,得到的石墨和二氧化钛复合材料,不易复合,有时制备的产物可见黑白色颗粒分离。
发明内容
本发明解决的第一个技术问题是提供一种以石墨和二氧化钛为原料,制备石墨-二氧化钛复合材料的方法。本发明的制备方法制得的石墨-二氧化钛复合材料复合效果好,光催化性能优异。
石墨-二氧化钛复合光催化剂及其制备方法的制备方法,按以下步骤进行:
a、将石墨粉与溶剂混匀,得到石墨粉分散液;其中,所述溶剂为水或乙醇;
b、将二氧化钛与石墨粉分散液混匀,得到石墨-二氧化钛浆料;其中,石墨粉和二氧化钛的质量比为3~5:100;
c、将石墨-二氧化钛浆料水热超声分散,得到复合光催化剂前驱体;其中,水热超声分散的温度为45℃~85℃,时间为2~8h;
d、将复合光催化剂前驱体进行真空煅烧得到复合光催化剂煅烧料;其中,真空煅烧温度为350℃~600℃,煅烧时间2~4h;
e、将复合光催化剂煅烧料球磨8~24h,得到所述的石墨-二氧化钛复合光催化剂。
在一种实施方式中,步骤a中,石墨粉与溶剂的重量比为1:8~20;优选的,溶剂为乙醇;更优选的,所述乙醇的浓度为50%~75%。
在一种实施方式中,步骤b中,石墨粉和二氧化钛的质量比为3:100。
在一种实施方式中,步骤c中,水热超声分散的温度为55℃~75℃,时间为6~8h;优选的,水热超声分散的温度为55℃,时间为8h。
在一种实施方式中,步骤d中,真空煅烧温度为350℃~500℃;优选的,真空煅烧温度为500℃,煅烧时间4h。
在一种实施方式中,步骤e中,球磨时间为20~24h;优选的,球磨时间为24小时。
本发明还提供一种石墨-二氧化钛复合光催化剂。
石墨-二氧化钛复合光催化剂,采用所述的石墨-二氧化钛复合光催化剂的制备方法制备而成。
在一种实施方式中,光催化剂的粒度为<200nm,平均粒径>100nm。
本发明的有益效果:
1、本发明工艺简单,流程短。
2、本发明工艺可以使石墨经球磨后形成微小片层,均匀分布在二氧化钛颗粒的表面,能够有效成为电子空穴快速分离的载体,拓宽了光催化剂的光谱响应范围,提高了光催化活性,在造纸业废水、染料废水、生活污水、池塘废水的污水处理领域中具有很好地应用前景。
附图说明
图1为本发明实施例1所制备的石墨-二氧化钛复合光催化剂的XRD图;
图2为本发明实施例1所制备的石墨-二氧化钛复合光催化剂的SEM图;
图3为本发明实施例1所制备的石墨-二氧化钛复合光催化剂的TEM图;
图4为本发明实施例1所制备的石墨-二氧化钛复合光催化剂的EDS元素分布图。
具体实施方式
石墨-二氧化钛复合光催化剂及其制备方法的制备方法,按以下步骤进行:
a、将石墨粉与溶剂混匀,得到石墨粉分散液;其中,所述溶剂为水或乙醇;
b、将二氧化钛与石墨粉分散液混匀,得到石墨-二氧化钛浆料;其中,石墨粉和二氧化钛的质量比为3~5:100;
c、将石墨-二氧化钛浆料水热超声分散,得到复合光催化剂前驱体;其中,水热超声分散的温度为45℃~85℃,时间为2~8h;
d、将复合光催化剂前驱体进行真空煅烧得到复合光催化剂煅烧料;其中,真空煅烧温度为350℃~600℃,煅烧时间2~4h;
e、将复合光催化剂煅烧料球磨8~24h,得到所述的石墨-二氧化钛复合光催化剂。
其中,步骤c,采用水热超声分散,目的是使浆料中的石墨与二氧化钛能够分散均匀,便于后续球磨,让石墨与二氧化钛更好的复合包覆。
步骤d中,进行真空煅烧,其目的是利用石墨C元素的还原作用,在煅烧过程中剥夺二氧化钛中的氧,使二氧化钛失去微量的氧,成为亚氧化钛结构,亚氧化钛的禁带宽度相比于二氧化钛更小,能够拓宽光谱响应范围。
如果石墨在空气气氛下煅烧,C将与空气反应生成二氧化碳,那么石墨复合的效果会降低,复合光催化剂的光催化活性将降低。
煅烧温度控制在350-600℃,是为了不让锐钛型二氧化钛的晶型转变为金红石晶型的二氧化钛,因为金红石型二氧化钛的光催化性能差。若煅烧温度超过600℃,锐钛型二氧化钛将转变为金红石型的二氧化钛,光催化性能就会变差。
在一种实施方式中,步骤a中,石墨粉与溶剂的重量比为1:8~20;优选的,溶剂为乙醇;更优选的,所述乙醇的浓度为50%~75%。
为了提高复合光催化剂的光催化性能,在一种实施方式中,步骤b中,石墨粉和二氧化钛的质量比为3:100。
为了提高复合光催化剂的光催化性能,在一种实施方式中,步骤c中,水热超声分散的温度为55℃~75℃,时间为6~8h;优选的,水热超声分散的温度为55℃,时间为8h。
为了提高复合光催化剂的光催化性能,在一种实施方式中,步骤d中,真空煅烧温度为350℃~500℃;优选的,真空煅烧温度为500℃,煅烧时间4h。
在一种实施方式中,步骤e中,球磨时间为20~24h;优选的,球磨时间为24小时。
本发明还提供一种石墨-二氧化钛复合光催化剂。
石墨-二氧化钛复合光催化剂,采用所述的石墨-二氧化钛复合光催化剂的制备方法制备而成。
本发明的石墨-二氧化钛复合光催化剂可在造纸业废水、染料废水、生活污水、池塘废水的污水处理领域应用。
在一种实施方式中,光催化剂的粒度为<200nm,平均粒径>100nm。
下面结合实施例对本发明的具体实施方式做进一步的描述,并不因此将本发明限制在所述的实施例范围之中。
下述实施例和对比例所使用的光催化活性评价试验方法为:
在自制光催化反应器中进行光催化降解甲基橙实验。光催化反应器的容量为500ml,在上方放置300W的氙灯,用磁力搅拌器搅拌溶液。实验时,在浓度为10mg/L的200ml甲基橙溶液中加入0.02g催化剂,开启搅拌器,并在避光条件下搅拌30min,使甲基橙在样品表面的吸附与脱附达到平衡,再开启氙灯进行计时,间隔一定时间取样(5ml)并离心分离,取上层清液,用D-8型紫外可见光分光光度计于462nm处测定其吸光度来检测甲基橙浓度的变化。根据相对浓度随时间的变化评价催化剂的光催化活性,根据吸光度来计算甲基橙的光催化降解率η:
式(1)中,At:光催化降解t时刻下的溶液吸光度;A0:光催化0min时的溶液吸光度。
为进一步分析石墨/TiO2复合光催化剂催化活性,引入准一级反应(a pseudo-first-order reaction)对其动力学过程进行研究,其反应动力学方程为
式(2)中k为一阶动力学常数,指光催化反应的速率常数,C0为光催化反应开始时甲基橙溶液的浓度;Ct为光催化反应时间为t时的甲基橙溶液的浓度。根据此公式计算得到复合催化剂的降解反应速率常数,从而反映石墨-TiO2复合光催化剂催化活性。
实施例1
取3g石墨粉,30g乙醇(浓度为75%)混合搅拌,得到石墨粉分散液;将100g二氧化钛与石墨粉分散液混合,打浆,得到石墨-二氧化钛浆料;然后将石墨-二氧化钛浆料移至水热超声分散机中进行超声分散,温度55℃,超声时间8h,得到复合光催化剂前驱体;将复合光催化剂前驱体在500℃下真空煅烧4h得到复合光催化剂煅烧料;最后将复合光催化剂煅烧料球磨24h,得到石墨-二氧化钛复合光催化剂。
上述方法制备得到的石墨-二氧化钛复合光催化剂,经检测,粒度<200nm,平均粒度>100nm,禁带宽度2.68eV,光谱响应范围得到提高。
测试其光催化性能,在70min的光催化反应时间里,对甲基橙溶液的光催化反应速率常数k值为0.03663,相比工业二氧化钛(k值为0.01628),其光催化活性提高了2.25倍。
图1为本实施例所制备的石墨-二氧化钛复合光催化剂的XRD图,由图中可以看出产物为锐钛型二氧化钛相和石墨相的复合材料;图2为本实施例所制备的石墨-二氧化钛复合光催化剂的SEM图,由图中可以看出石墨-二氧化钛复合光催化剂的颗粒大小小于200nm;图3为本实施例所制备的石墨-二氧化钛复合光催化剂的TEM图;图4为本实施例所制备的石墨-二氧化钛复合光催化剂的EDS元素分布图。
实施例2
取5g石墨粉,50g乙醇(浓度为65%)混合搅拌,得到石墨粉分散液;将100g二氧化钛与石墨粉分散液混合,打浆,得到石墨-二氧化钛浆料;然后将石墨-二氧化钛浆料移至水热超声分散机中进行超声分散,温度75℃,超声时间6h,得到复合光催化剂前驱体;将复合光催化剂前驱体在500℃下真空煅烧3h得到复合光催化剂煅烧料;最后将复合光催化剂煅烧料球磨20h,得到石墨-二氧化钛复合光催化剂。
上述方法制备得到的石墨-二氧化钛复合光催化剂,粒度<200nm,禁带宽度2.48eV,光谱响应范围得到提高。在70min的光催化反应时间里,对甲基橙溶液的光催化反应速率常数k值为0.03337,相比工业二氧化钛(k值为0.01628),其光催化活性提高了2.05倍。
实施例3
取4g石墨粉,35g乙醇(浓度为50%)混合搅拌,得到石墨粉分散液;将100g二氧化钛与石墨粉分散液混合,打浆,得到石墨-二氧化钛浆料;然后将石墨-二氧化钛浆料移至水热超声分散机中进行超声分散,温度65℃,超声时间6h,得到复合光催化剂前驱体;将复合光催化剂前驱体在350℃下真空煅烧2h得到复合光催化剂煅烧料;最后将复合光催化剂煅烧料球磨8h,得到石墨-二氧化钛复合光催化剂。
上述方法制备得到的石墨-二氧化钛复合光催化剂,粒度<200nm,禁带宽度2.95eV,光谱响应范围得到提高。测试其光催化性能,在70min的光催化反应时间里,对甲基橙溶液的光催化反应速率常数k值为0.02865,相比工业二氧化钛(k值为0.01628),其光催化活性提高了1.76倍。
对比例1(对比低温煅烧(干燥),得到的催化剂效果变差)
取3g石墨粉,30g乙醇(浓度为75%)混合搅拌,得到石墨粉分散液;将100g二氧化钛与石墨粉分散液混合,打浆,得到石墨-二氧化钛浆料;然后将石墨-二氧化钛浆料移至水热超声分散机中进行超声分散,温度55℃,超声时间8h,得到复合光催化剂前驱体;将复合光催化剂前驱体在100℃下真空干燥4h得到复合光催化剂煅烧料;最后将复合光催化剂煅烧料球磨24h,得到石墨-二氧化钛复合光催化剂。
上述方法制备得到的石墨-二氧化钛复合光催化剂,粒度<200nm,禁带宽度3.05eV,光谱响应范围有提高。测试其光催化性能,在70min的光催化反应时间里,对甲基橙溶液的光催化反应速率常数k值为0.01547,相比工业二氧化钛(k值为0.01628),其光催化活性是工业二氧化钛的0.95倍,光催化活性变差。
对比例2(对比煅烧温度相同,若后期不球磨,使颗粒变小,催化性能也差)
取3g石墨粉,30g乙醇(浓度为75%)混合搅拌,得到石墨粉分散液;将100g二氧化钛与石墨分散液混合,打浆,得到石墨-二氧化钛浆料;然后将石墨-二氧化钛浆料移至水热超声分散机中进行超声分散,温度55℃,超声时间8h,得到复合光催化剂前驱体;将复合光催化剂前驱体在500℃下真空煅烧4h得到复合光催化剂。
上述方法制备得到的石墨-二氧化钛复合光催化剂,粒度>500nm,禁带宽度2.67eV,光谱响应范围得到提高。
测试其光催化性能,在70min的光催化反应时间里,对甲基橙溶液的光催化反应速率常数k值为0.01029,相比工业二氧化钛(k值为0.01628),其光催化活性只有工业二氧化钛的0.63倍,煅烧后团聚,颗粒粒度变大,光催化活性变差。
Claims (10)
1.石墨-二氧化钛复合光催化剂的制备方法,其特征在于,按以下步骤进行:
a、将石墨粉与溶剂混匀,得到石墨粉分散液;其中,所述溶剂为水或乙醇;
b、将二氧化钛与石墨粉分散液混匀,得到石墨-二氧化钛浆料;其中,石墨粉和二氧化钛的质量比为3~5:100;
c、将石墨-二氧化钛浆料水热超声分散,得到复合光催化剂前驱体;其中,水热超声分散的温度为45℃~85℃,时间为2~8h;
d、将复合光催化剂前驱体进行真空煅烧得到复合光催化剂煅烧料;其中,真空煅烧温度为350℃~600℃,煅烧时间2~4h;
e、将复合光催化剂煅烧料球磨8~24h,得到所述的石墨-二氧化钛复合光催化剂。
2.根据权利要求1所述的石墨-二氧化钛复合光催化剂的制备方法,其特征在于,步骤a中,石墨粉与溶剂的重量比为1:8~20;优选的,溶剂为乙醇;更优选的,所述乙醇的浓度为50%~75%。
3.根据权利要求1所述的石墨-二氧化钛复合光催化剂的制备方法,其特征在于,步骤b中,石墨粉和二氧化钛的质量比为3:100。
4.根据权利要求1所述的石墨-二氧化钛复合光催化剂的制备方法,其特征在于,步骤c中,水热超声分散的温度为55℃~75℃,时间为6~8h;优选的,水热超声分散的温度为55℃,时间为8h。
5.根据权利要求1所述的石墨-二氧化钛复合光催化剂的制备方法,其特征在于,步骤d中,真空煅烧温度为350℃~500℃。
6.根据权利要求1所述的石墨-二氧化钛复合光催化剂的制备方法,其特征在于,步骤d中,真空煅烧温度为500℃,煅烧时间4h。
7.根据权利要求1所述的石墨-二氧化钛复合光催化剂的制备方法,其特征在于,步骤e中,球磨时间为20~24h。
8.根据权利要求1所述的石墨-二氧化钛复合光催化剂的制备方法,其特征在于,步骤e中,球磨时间为24小时。
9.石墨-二氧化钛复合光催化剂,其特征在于,采用权利要求1~8任一项所述的石墨-二氧化钛复合光催化剂的制备方法制备而成。
10.根据权利要求9所述的石墨-二氧化钛复合光催化剂,其特征在于,光催化剂的粒度为<200nm,平均粒径>100nm。
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