CN106391027B - 具有自组装花状微球结构的TiO2-Ni(OH)2光催化剂及其制备方法与应用 - Google Patents
具有自组装花状微球结构的TiO2-Ni(OH)2光催化剂及其制备方法与应用 Download PDFInfo
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- 229910018661 Ni(OH) Inorganic materials 0.000 title description 2
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Abstract
本发明提供了一种TiO2‑Ni(OH)2光催化剂,其制备方法为:将六水合氯化镍的水溶液、无水乙醇、尿素的水溶液混合,然后在搅拌下滴加氨水,滴完后升温至120~160℃反应11~12h,之后经后处理,得到氢氧化镍粉末;将所得氢氧化镍粉末、钛酸四丁酯、无水乙醇混合,搅拌5~15min,然后加入去离子水、氢氟酸,继续搅拌5~15min,接着升温至120~180℃反应13~14h,之后经后处理,即得目标产物;本发明催化剂可作为储能光催化材料应用于染料废水中污染物的催化降解;本发明催化剂能够储存光照氧化型能量,从而更加有效地储存和利用光能,提高催化剂的光催化效率。
Description
(一)技术领域
本发明涉及光催化剂及其制备方法与应用,具体涉及一种具有自组装花状微球结构的 TiO2-Ni(OH)2光催化剂及其制备方法与应用,本发明所述的光催化剂能够储存光照时的氧化还原能量,并在黑暗条件下释放并继续体现出催化活性。
(二)背景技术
在众多环境污染治理技术中,以半导体氧化物TiO2为催化剂的多相光催化降解污染物已成为一种热门、高效、理想的治理技术。TiO2光催化剂在紫外光照射下,价带上的电子活跃到导带,相应的在价带上产生了空穴,存在的电子和空穴分别发生氧化和还原反应。然而这些反应都局限于在光照的条件下才能发生。如果能够克服这个困难,那么TiO2光催化材料将会具有更好的实用性。因此在不断的研究过程中,我们提出了储能型光催化材料。储能型光催化材料是将储能材料与光催化剂相结合,可以在光照下产生光生电子和空穴,提高光催化降解能力;另外,其在光照时储存的氧化还原能量,可以在黑暗条件下释放并继续体现出催化活性。然而,目前所形成的能量储存型光催化材料能够将光照下产生的还原能量储存起来,但不具备储存更具催化能力的氧化能量的特性,如果氧化能量也能够被储存或者说氧化型的能量储存催化剂材料能够被制造出来,那么如果将氧化能量储存型和还原型能量储存催化剂材料合并使用,就能够更加有效地储存和利用光能。
(三)发明内容
现在我们提出关于TiO2储存氧化能量的模型:p—n结模型,p—型半导体与TiO2结合形成p—n结。通过研究发现,p—型半导体和n—型半导体在两者晶界之间可以形成p—n异质结结构,不仅可以抑制光生电子和光生空穴的复合,提高光催化能力,还可以将产生的氧化能量储存在p—型半导体中,达到在黑暗中继续发挥催化作用的效果。在研究中发现,Ni(OH)2是一种良好的p—型半导体,能有效的与n—型半导TiO2形成p—n结;此外,Ni(OH)2为一种具有相对极性的氧化还原电位作为中等电池阴极活性材料。我们利用Ni(OH)2作为一种储能材料,将其和TiO2合成复合物,从而将TiO2在光照下产生的氧化能量储存起来。
本发明的目的是解决现有能量储存型光催化材料的不足,提供一种具有自组装花状微球结构的TiO2-Ni(OH)2光催化剂及其制备方法与应用。本发明采用均匀沉淀法制备出具有花状微球结构的TiO2-Ni(OH)2光催化剂,该光催化剂能够将在光照下产生的氧化能量储存起来,并在黑暗条件下继续表现出催化活性。
本发明采用如下技术方案:
一种具有自组装花状微球结构的TiO2-Ni(OH)2光催化剂,其制备方法为:
(1)将0.1~0.4mol/L六水合氯化镍的水溶液、无水乙醇、1~4mol/L尿素的水溶液混合,然后在搅拌下滴加9wt%~26wt%氨水,滴完后升温至120~160℃反应11~12h,之后自然冷却至室温,反应混合物经离心、洗涤、干燥,得到氢氧化镍粉末;
步骤(1)中,所述六水合氯化镍的水溶液与无水乙醇、尿素的水溶液、氨水的体积比为 2~3:4~5:2~3:1,优选2.5:5:2.5:1;
(2)将步骤(1)所得氢氧化镍粉末、钛酸四丁酯、无水乙醇混合,搅拌5~15min,然后加入去离子水、氢氟酸(市售,为40wt%HF的水溶液),继续搅拌5~15min,接着升温至120~180℃反应13~14h,之后自然冷却至室温,反应混合物经离心、洗涤、干燥,即得所述TiO2-Ni(OH)2光催化剂;
步骤(2)中,所述钛酸四丁酯的体积用量以氢氧化镍粉末的质量计为12~13mL/g,优选 13mL/g;
所述钛酸四丁酯与无水乙醇、去离子水、氢氟酸的体积比为1.5~2:6.5~7.5:1:0.2~0.25,优选1.95:6.5:1:0.25。
本发明中所述的室温为20~30℃。
本发明制得的TiO2-Ni(OH)2光催化剂具有自组装花状微球结构,花球外覆有片状二氧化钛。
本发明制得的TiO2-Ni(OH)2光催化剂可作为储能光催化材料应用于染料废水中污染物的催化降解。本发明制得的TiO2-Ni(OH)2光催化剂接受紫外光照射时,可将产生的氧化能量储存到Ni(OH)2层中,颜色由无色变为棕色,储存起来的能量能够通过化学和电化学的方法释放出来,并可以通过暗反应降解刚果红来评价。
本发明采用SEM扫描电镜扫描制得的TiO2-Ni(OH)2光催化剂的形貌、组成等。所述光催化剂的性能由形貌结构、尺寸大小、粒径分布、晶相结构、表面特性决定。
本发明的有益效果主要体现在:本发明提供了一种具有自组装花状微球结构的TiO2-Ni(OH)2光催化剂,既能作为一种良好的吸附材料与催化材料,同时能够储存光照氧化型能量,从而更加有效地储存和利用光能,提高催化剂的光催化效率,且催化剂结构不发生变化,具有很好的能源战略价值和巨大的实际意义。
(四)附图说明
图1:实施例1制备的Ni(OH)2花状微球的SEM图;
图2:实施例1制备的TiO2-Ni(OH)2光催化剂的SEM图;
图3:实施例1制备的TiO2-Ni(OH)2光催化剂的XRD图;
图4:实施例2中TiO2-Ni(OH)2光催化剂对刚果红溶液的BET吸附;
图5:实施例3中TiO2-Ni(OH)2光催化剂对刚果红溶液的光催化降解;
图6:实施例4中TiO2-Ni(OH)2光催化剂对刚果红溶液的储能光催化降解。
(五)具体实施方式
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此。
实施例1制备TiO2-Ni(OH)2光催化剂
①(1)首先取烧杯,向烧杯中分别加入5ml 0.2mol/L六水合氯化镍的水溶液、10ml无水乙醇、5ml 2mol/L尿素的水溶液,混合形成淡绿色透明溶液。在搅拌下将2ml 26%氨水逐滴滴入烧杯中,形成蓝色溶液。将形成的溶液转移至50ml高压反应釜的聚四氟乙烯内衬中,高压反应釜密封后放置在恒温箱中,在120℃下反应12h。待水热反应结束后,自然冷却到室温。将所得的淡绿色浆液移入50mL离心管中,离心并用去离子水和无水乙醇各自重复清洗3次,最后在60℃烘箱中干燥6h,得到氢氧化镍粉末0.8g。
(2)称取上述制备的氢氧化镍粉末0.3g于烧杯中,加入3.9mL钛酸四丁酯、13mL无水乙醇,轻轻搅拌10min。然后在搅拌条件下加入2ml去离子水,并逐滴加入0.5mL氢氟酸。继续搅拌10min后,将混合液移入50mL高压反应釜的聚四氟乙烯内衬中,密封,在120℃恒温箱中反应14h。待水热反应结束后,自然冷却到室温。将所得的淡绿色浆液移入50mL离心管中,离心并用去离子水和无水乙醇各自重复清洗3次,最后在60℃烘箱中干燥6h,得到所述的TiO2-Ni(OH)2光催化剂0.25g。
②(1)首先取烧杯,向烧杯中分别加入5ml 0.4mol/L六水合氯化镍的水溶液、10ml无水乙醇、5ml 3mol/L尿素的水溶液,混合形成淡绿色透明溶液。在搅拌下将2ml 13%氨水逐滴滴入烧杯中,形成蓝色溶液。将形成的溶液转移至50ml高压反应釜的聚四氟乙烯内衬中,高压反应釜密封后放置在恒温箱中,在120℃下反应12h。待水热反应结束后,自然冷却到室温。将所得的淡绿色浆液移入50mL离心管中,离心并用去离子水和无水乙醇各自重复清洗3次,最后在60℃烘箱中干燥6h,得到氢氧化镍粉末0.8g。
(2)称取上述制备的氢氧化镍粉末0.3g于烧杯中,加入3.9mL钛酸四丁酯、13mL无水乙醇,轻轻搅拌10min。然后在搅拌条件下加入2ml去离子水,并逐滴加入0.5mL氢氟酸。继续搅拌10min后,将混合液移入50mL高压反应釜的聚四氟乙烯内衬中,密封,在120℃恒温箱中反应14h。待水热反应结束后,自然冷却到室温。将所得的淡绿色浆液移入50mL离心管中,离心并用去离子水和无水乙醇各自重复清洗3次,最后在60℃烘箱中干燥6h,得到所述的TiO2-Ni(OH)2光催化剂0.25g。
实施例2TiO2-Ni(OH)2对刚果红溶液的BET吸附测试
吸附实验具体步骤如下:
在250mL烧杯中加入200mL 100μg/L的染料刚果红溶液和0.05g实施例1制备的TiO2-Ni(OH)2样品粉末。将烧杯放置在暗室中的磁力搅拌器上,在搅拌条件下进行暗吸附反应。每隔10min取少量混合液于离心管中,进行离心分离,获得上层清液。用分光光度计在最大吸收波长(刚果红为498nm)处测量上层清液的吸光度值。
由图3可知,TiO2-Ni(OH)2对刚果红溶液具有很好吸附效果。表明TiO2-Ni(OH)2具有较大的比表面积,从而提高了吸附效果。
实施例3TiO2-Ni(OH)2对刚果红溶液的光催化降解
光催化降解具体步骤如下:
在250mL烧杯中加入200mL 100μg/L的染料刚果红溶液和0.05g实施例1制备的TiO2-Ni(OH)2样品粉末。将烧杯放置在暗室中的磁力搅拌器上,在搅拌条件下进行暗吸附反应。待反应达到吸附—平衡后取出少量混合液,并打开高压汞灯进行光催化反应。每隔10min取少量混合液于离心管中,与吸附—平衡后取得的少量混一起进行离心分离,获得上层清液。用分光光度计在最大吸收波长(刚果红为498nm)处测量上层清液的吸光度值。
由图4可知,TiO2-Ni(OH)2对刚果红溶液具有较好的光催化降解效果。
实施例4TiO2-Ni(OH)2对刚果红溶液的储能光催化
储能光催化实验具体步骤如下:
在250mL烧杯中加入200mL 100μg/L的染料刚果红溶液和0.05g实施例1制备的TiO2-Ni(OH)2样品粉末。将烧杯放置在暗室中的磁力搅拌器上,在搅拌条件下进行暗吸附反应。待反应达到吸附—平衡后取出少量混合液,并打开高压汞灯进行光催化反应。30min后关闭高压汞灯,并取出少量混合液,让反应继续在黑暗中进行。每隔10min取少量的混合液于离心管中,将取得的所有少量混合液均进行离心分离,获得上层清液。用分光光度计在最大吸收波长(刚果红为498nm)处测量上层清液的吸光度值。
由图5可知,TiO2-Ni(OH)2对刚果红有较好的储能光催化降解效果。表明TiO2在光照条件下产生的能量被较好的储存起来,并在黑暗条件下将能量释放出来,从而表现出良好的催化活性,即具有良好的储能效果。
本说明书实施例所述的内容仅仅是对发明构思的实现形式的列举,本发明的保护范围的不应当被视为仅限于实施例所陈述的具体形式,本发明的保护范围也及于本领域技术人员根据本发明构思所能够想到的等同技术手段。
Claims (5)
1.一种具有自组装花状微球结构的TiO2-Ni(OH)2光催化剂,其特征在于,所述TiO2-Ni(OH)2光催化剂按如下方法制备得到:
(1)将0.1~0.4mol/L六水合氯化镍的水溶液、无水乙醇、1~4mol/L尿素的水溶液混合,然后在搅拌下滴加9wt%~26wt%氨水,滴完后升温至120~160℃反应11~12h,之后自然冷却至室温,反应混合物经离心、洗涤、干燥,得到氢氧化镍粉末;
步骤(1)中,所述六水合氯化镍的水溶液与无水乙醇、尿素的水溶液、氨水的体积比为2~3:4~5:2~3:1;
(2)将步骤(1)所得氢氧化镍粉末、钛酸四丁酯、无水乙醇混合,搅拌5~15min,然后加入去离子水、氢氟酸,继续搅拌5~15min,接着升温至120~180℃反应13~14h,之后自然冷却至室温,反应混合物经离心、洗涤、干燥,即得所述TiO2-Ni(OH)2光催化剂;
步骤(2)中,所述钛酸四丁酯的体积用量以氢氧化镍粉末的质量计为12~13mL/g;
所述钛酸四丁酯与无水乙醇、去离子水、氢氟酸的体积比为1.5~2:6.5~7.5:1:0.2~0.25。
2.如权利要求1所述的TiO2-Ni(OH)2光催化剂,其特征在于,步骤(1)中,所述六水合氯化镍的水溶液与无水乙醇、尿素的水溶液、氨水的体积比为2.5:5:2.5:1。
3.如权利要求1所述的TiO2-Ni(OH)2光催化剂,其特征在于,步骤(2)中,所述钛酸四丁酯的体积用量以氢氧化镍粉末的质量计为13mL/g。
4.如权利要求1所述的TiO2-Ni(OH)2光催化剂,其特征在于,步骤(2)中,所述钛酸四丁酯与无水乙醇、去离子水、氢氟酸的体积比为1.95:6.5:1:0.25。
5.如权利要求1所述的TiO2-Ni(OH)2光催化剂作为储能光催化材料在染料废水中污染物的催化降解中的应用。
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