CN110871101B - 一种介孔碳-钛酸铋复合光催化材料的制备及应用 - Google Patents
一种介孔碳-钛酸铋复合光催化材料的制备及应用 Download PDFInfo
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Abstract
本发明提供一种介孔碳‑钛酸铋复合光催化材料及其制备方法和应用,所述介孔碳‑钛酸铋复合光催化材料为掺杂有碳系材料g‑C3N4的Bi12TiO20,掺杂量不高于10%,可由水热反应法制备得到。本发明所述介孔碳‑钛酸铋复合光催化材料的催化性能较未复合的钛酸铋材料好,对四环素具有良好的光催化降解作用。
Description
技术领域
本发明涉及复合光催化材料技术领域,具体涉及一种介孔碳-钛酸铋复合光催化材料及其制备方法和应用。
背景技术
环境污染和能源短缺已成为当今全球面临的最紧迫问题。自从Fujishima和Honda报道TiO2电极光催化分解水的研究以来,半导体光催化剂在太阳能转化和光催化降解污染物的应用受到了广大研究者极大的关注。40多年来的研究证明,光催化技术是解决能源和环境问题的一种极具前景的新思路和新方法。在众多的光催化剂中,TiO2因其本身无毒性,高光催化活性及化学稳定性,研究最为广泛和深入。然而TiO2的带隙为3.2eV,它只吸收紫外线(<400nm),而紫外线只占太阳光大约4%。为了提升太阳光的利用效率,开发可见光驱动稳定的氧化物光催化剂成为光催化研究领域的热点。铋因其理想的价带而成为候选者。
三元氧化铋半导体,如Bi2WO6、BiVO4、NaBiO3和Bi12TiO20,作为一类具有可见光催化活性的光催化剂而被广泛研究,其中Bi12TiO20作为光催化材料尤其受到人们的关注,Bi12TiO20晶体属于硅线石类矿物,用通式Bi12MO20表示,其中M表示四价离子或离子组合。Bi12TiO20的框架是由Bi-O多面体构成的,其中Bi离子与五个O离子配位,与立体化学活性Bi3 +的6s2孤电子对形成八面体排列,Bi12TiO20的独特结构有利于其在光催化领域的应用,但纯Bi12TiO20光催化的效率较低,因此,具有可控微结构和提高光催化效率的光响应Bi12TiO20光催化剂的合成是一个研究的热点。
发明内容
针对上述问题,本发明的目的在于提供一种高量子效率的铋酸盐复合结构光催化材料,利用太阳光,将光能转变为化学能,以期实现温和条件下的高效、低成本光催化降解,以解决日益严重的环境污染与能源短缺问题。
本发明的目的采用以下技术方案来实现:
一种介孔碳-钛酸铋复合光催化材料,所述介孔碳-钛酸铋复合光催化材料为掺杂有碳系材料g-C3N4的Bi12TiO20,掺杂量不高于10%,由水热法制备;
优选的,所述碳系材料g-C3N4的制备方法为:将盛放有三聚氰胺的坩埚在80℃的烘箱中干燥24h,再入马弗炉以1℃/min的升温速率上升到550℃并保持3h,冷却后得到淡黄色的g-C3N4。
本发明还提供一种前述介孔碳-钛酸铋复合光催化材料的制备方法,制备步骤如下:
称取7.1411g Bi(NO3)3·5H2O与0.2944g Ti(SO4)2,溶于10ml 20%HNO3,剧烈搅拌1h得到溶液A;称取1.8g PEG溶于10ml去离子水,逐滴加入到溶液A中,用浓NaOH调节pH=12,溶液由透明溶液变为白色悬浮液,继续搅拌30min,加入掺杂量不高于10%的g-C3N4,超声混合后,转入100ml反应釜,160℃水热反应24h,反应结束后,关闭烘箱并让反应釜随烘箱自然冷却至室温,产物用去离子水洗涤2次,再用无水乙醇洗涤3次,80℃干燥,制得所述光催化材料。
本发明的有益效果为:
(1)本发明所述制备方法,操作简便、安全、环保,制备过程中不产生明显毒性的废弃物,制备原料经济易得,所述制备方法制得的复合光催化剂具有介孔碳结构。
(2)本发明所述介孔碳-钛酸铋复合光催化材料的催化性能较未复合的钛酸铋材料好,具有更宽的响应波长范围,对四环素有良好的光催化降解作用。
附图说明
利用附图对本发明作进一步说明,但附图中的实施例不构成对本发明的任何限制,对于本领域的普通技术人员,在不付出创造性劳动的前提下,还可以根据以下附图获得其它的附图。
图1是X射线衍射光谱图;
图2是紫外-可见吸收光谱图;
图3是四环素标准曲线;
图4是光催化降解四环素趋势图。
具体实施方式
结合以下实施例对本发明作进一步描述。
实施例1
称取7.1411g Bi(NO3)3·5H2O与0.2944g Ti(SO4)2,溶于10ml 20%HNO3,剧烈搅拌1h得到溶液A;称取1.8g PEG溶于10ml去离子水,逐滴加入到溶液A中,用浓NaOH调节pH=12,溶液由透明溶液变为白色悬浮液,继续搅拌30min;加入1%的g-C3N4,超声混合后,转入100ml反应釜,160℃水热反应24h,反应结束后,关闭烘箱并让反应釜随烘箱自然冷却至室温,产物用去离子水洗涤2次,再用无水乙醇洗涤3次,80℃干燥,制得所述光催化材料。
实施例2
称取7.1411g Bi(NO3)3·5H2O与0.2944g Ti(SO4)2,溶于10ml 20%HNO3,剧烈搅拌1h得到溶液A;称取1.8g PEG溶于10ml去离子水,逐滴加入到溶液A中,用浓NaOH调节pH=12,溶液由透明溶液变为白色悬浮液,继续搅拌30min,加入5%的g-C3N4,超声混合后,转入100ml反应釜,160℃水热反应24h,反应结束后,关闭烘箱并让反应釜随烘箱自然冷却至室温,产物用去离子水洗涤2次,再用无水乙醇洗涤3次,80℃干燥,制得所述光催化材料。
实施例3
称取7.1411g Bi(NO3)3·5H2O与0.2944g Ti(SO4)2,溶于10ml 20%HNO3,剧烈搅拌1h得到溶液A;称取1.8g PEG溶于10ml去离子水,逐滴加入到溶液A中,用浓NaOH调节pH=12,溶液由透明溶液变为白色悬浮液,继续搅拌30min,加入10%的g-C3N4,超声混合后,转入100ml反应釜,160℃水热反应24h,反应结束后,关闭烘箱并让反应釜随烘箱自然冷却至室温,产物用去离子水洗涤2次,再用无水乙醇洗涤3次,80℃干燥,制得所述光催化材料。
实验例1
以纯Bi12TiO20为对照,X射线衍射(XRD)、紫外-可见吸收光谱(DRS)表征实施例1-3制备的不同g-C3N4掺量的光催化材料。
X射线衍射表征结果见图1,紫外-可见吸收光谱(DRS)表征结果见图2。
在160℃时制备的钛酸铋复合光催化材料的XRD谱图有明显的衍射峰,且峰位相互对应。样品结构单一,为四方晶系,没有出现其他杂质衍射峰。
实验例2
抗生素(antibiotics)是生物在生长过程中所产生的,具有生物活性的一类代谢产物,能干扰或抑制其他活细胞的生长发育,对细菌、霉菌等致病微生物有良好的抑制和杀灭作用。抗生素结构复杂、生物降解困难且水溶性较好,很容易在环境中存储和积累。这些抗生素进入环境中会对微生物及植物种群产生严重影响,进而对人类的健康、生存造成危害,因此被视为重要的污染物。
以实施例1-3制备的光催化材料用于降解四环素,测定不同处理时间的降解浓度。
四环素标准曲线见图3,不同处理时间的降解浓度见图4。
本申请所述介孔碳-钛酸铋复合光催化材料对四环素具有良好的光催化降解效果,且其催化性能较未复合的钛酸铋材料好,而复合了1%-10%的钛酸铋材料中,Bi12TiO20/10%g-C3N4的光催化性能最好。
最后应当说明的是,以上实施例仅用以说明本发明的技术方案,而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细地说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (3)
1.一种介孔碳-钛酸铋复合光催化材料,其特征在于,所述介孔碳-钛酸铋复合光催化材料为掺杂有碳系材料g-C3N4的Bi12TiO20,掺杂量不高于10%,由水热法制备,制备步骤如下:
称取7.1411g Bi(NO3)3·5H2O与0.2944g Ti(SO4)2,溶于10ml 20%HNO3,剧烈搅拌1h,得到溶液A;称取1.8g PEG溶于10ml去离子水,逐滴加入到溶液A中,用浓NaOH调节pH=12,溶液由透明溶液变为白色悬浮液,继续搅拌30min,加入掺杂量不高于10%的g-C3N4,超声混合后,转入100ml反应釜,160℃水热反应24h,反应结束后,关闭烘箱并让反应釜随烘箱自然冷却至室温,产物用去离子水洗涤2次,再用无水乙醇洗涤3次,80℃干燥,制得所述复合光催化材料。
2.根据权利要求1所述的一种介孔碳-钛酸铋复合光催化材料,其特征在于,所述碳系材料g-C3N4的制备方法为:将盛放有三聚氰胺的坩埚在80℃的烘箱中干燥24h,再入马弗炉以1℃/min的升温速率上升到550℃并保持3h,冷却后得到淡黄色的g-C3N4。
3.权利要求1-2任一所述的一种介孔碳-钛酸铋复合光催化材料在光催化降解有机污染物中的应用。
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