CN115212901A - 一种原位析出Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法和应用 - Google Patents
一种原位析出Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法和应用 Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 53
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Abstract
本发明属于发光和光催化材料技术领域,特别涉及一种原位析出Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法和应用。所述的制备方法包括如下步骤:将铋源、稀土离子源和聚乙烯吡咯烷酮溶于乙二醇中,搅拌混匀后加入含有氯源的水溶液,得到混合溶液进行水热(溶剂热)反应,反应完毕,降温,离心、干燥,退火,得Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料。本发明通过表面活性剂改性,使氯氧化铋纳米片厚度变薄,尺寸变小,分散性提高;通过退火使其析出金属Bi单质;通过稀土离子掺杂,使其在提高光催化性能的同时和具有发光性能,可以广泛应用于光催化、发光材料等领域,具有很高的实用价值。
Description
技术领域
本发明属于发光和光催化材料技术领域,特别涉及一种原位析出Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法和应用。
背景技术
半导体光催化是一种清洁能源的高效利用技术,在光催化降解污染物、CO2还原、水解制氢等方面具有广阔的应用前景,被认为是解决当前能源短缺和环境污染问题的有效手段之一。BiOCl是一种由V-VI-VII元素构成的层状半导体,在光学、电学、磁学和光催化等方面具有较好的性能,从而引起了广泛的关注与研究。但由于光谱响应范围窄、光生电子-空穴对易复合,使其光催化效率受到限制。因此,开发具有高光生载流子分离效率、宽光谱响应、低成本的BiOCl基复合材料仍然是巨大的兴趣和挑战。
近年来,稀土离子掺杂已成为改善半导体材料光催化性能的有效方式之一。研究表明,掺杂稀土离子能够提供光生电子的浅势捕获陷阱,并提高电子分离及载流子转移效率,可降低电子-空穴对的复合几率。然而,光响应范围窄仍然是制约其光催化效率的关键因素之一。
将具有表面等离子体共振效应(surface plasmon resonance,SPR)效应的贵金属(例如Au、Ag和Pt等)与半导体耦合构建异质结是同时拓展光响应范围和提高电荷分离效率的一种有效手段,但其昂贵的成本极大地限制了其实际应用。最近,研究发现金属铋(Bi)也表现出类似贵金属的SPR效应,有望成为贵金属表面等离子体的替代品。到目前为止,仅有少数文献如Applied Catalysis B:Environmental 225(2018)218–227,JournalofMaterials Chemistry A,2017,5,4894-4903,Journal ofAlloys and Compounds 836(2020)155380报道了Bi金属纳米颗粒用于提高BiOCl的光催化活性,且Bi纳米颗粒的析出方式多为硼氢化钠还原,导致BiOCl光催化活性的提高有限。此外,利用Bi的SPR效应改性稀土离子发光性能的研究还未见报道。因此,发展新的方法,制备Bi等离子体修饰的稀土掺杂氯氧化铋复合材料,对于发展Bi系材料及其应用具有较好的研究意义与研究价值。
发明内容
针对现有技术的不足,本发明提供了一种原位析出Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料及其制备方法和应用。本发明通过表面活性剂改性,使氯氧化铋纳米片厚度变薄,尺寸变小,分散性提高;通过退火使其析出金属Bi单质;通过稀土离子掺杂,使其在提高光催化性能的同时和具有发光性能,可以广泛应用于光催化、发光材料等领域,具有很高的实用价值。
本发明所述的一种原位析出Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法,包括如下步骤:
将铋源、稀土离子源和聚乙烯吡咯烷酮溶于乙二醇中,搅拌混匀后加入含有氯源的水溶液,得到混合溶液进行水热(溶剂热)反应,反应完毕,降温,离心、干燥,退火,得Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料。
所述的聚乙烯吡咯烷酮的平均分子量为30000~130000;所述的聚乙烯吡咯烷酮与铋源的质量比为0.1~2:1。
所述的铋源的质量与乙二醇体积比为0.1~3g:20~50mL。
所述的铋源为五水硝酸铋或碳酸铋或磷酸铋或硫酸铋或三氧化二铋;
所述的氯源为氯化钠或氯化钾或氯化钙或氯化铵或十六烷基三甲基氯化铵;所述的含有氯源的水溶液的浓度为0.5~5M。
所述的稀土离子源选自其硝酸盐或氯化物或氧化物;所述稀土离子为Eu3+或Dy3+或Tb3+。本发明中所述稀土离子源优选以水溶液的形式加入,浓度为0.5M。
以摩尔比计,Bi离子︰稀土离子︰氯离子的摩尔比=0.994-0.996:0.004-0.006:1,优选的,Bi离子︰稀土离子︰氯离子的摩尔比=0.995:0.005:1。
所述的水热反应温度为120℃~220℃,水热反应时间为6~36h。温度过小或反应时间短会造成反应不充分,材料结晶性能不好。温度过高或反应时间过长,会造成材料的团聚,影响材料性能
所述退火温度为450℃,空气氛围退火2h。
本发明中,稀土元素在材料中作为发光中心存在,不同稀土离子受激发后可发出不同的波长的光。本发明主要是利用金属Bi等离子共振效应提高材料的上转换发光和近红外光催化性能。
本发明是采用PVP,一方面是作为表面活性剂是使氯氧化铋纳米片厚度变薄,另一方面是,本发明采用方法水热反应完后不经去离子水和乙醇洗涤,离心烘干后进行退火,退火过程中残留的PVP产生CO,进而在材料表面原位还原出Bi单质。
采用本发明所述的制备方法制得的原位析出Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料可以作为光催化材料应用在降解有机染料、抗生素中,也可以作为发光材料应用于三维立体显示、RGB三基色打印、光学防伪、光学温度传感、生物成像、光动力治疗等领域。
本发明中具有以下优点:
(1)Bi离子似贵金属的SPR效应可以吸收近红外光,在BiOCl上析出后利用Bi离子SPR效应的可有效拓宽BiOCl的吸收光谱。
(2)相较于贵金属,Bi的价格相对低很多,且本发明是在BiOCl上原位析出金属Bi离子,进一步缩减了成本。
(3)Bi离子SPR效应的可有效拓宽BiOCl的吸收光谱,且金属Bi离子电阻低,可作为光生载流子分离的载体,提高其分离效率,从而提高了光催化效率。
(4)相较于采用硼氢化钠还原的方法,本发明采用退火的方式可进一步提高材料的结晶性,更有利于提高发光和催化性能。
附图说明
图1为实施例1和2制备的Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的X射线衍射图谱。
图2为实施例1和2制备的Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的紫外-可见-红外吸收光谱图。
图3为实施例1和2制备的Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料在313nm波长激光激发下的荧光发射光谱图。
图4为实施例1和2制备的Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料在近红外光照射下光降解亚甲基蓝效率图。
具体实施方式
实施例1
一种Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法,包括步骤如下:
(1)将0.5g聚乙烯吡咯烷酮(平均分子量58000),2.413g五水硝酸铋,0.05ml硝酸铕水溶液(0.5M)溶解于30mL乙二醇溶液中,搅拌至溶液透明后;然后加入5ml KCl水溶液(1M),得到的混合溶液转入带有聚四氟乙烯内衬的水热釜中,装填度为0.7,并升温至160℃,保温12小时,反应完成后自然冷却至室温。
(2)将步骤(1)中所得反应沉淀离心后,在70℃下干燥;将干燥所得样品放在马弗炉中450℃,空气氛围退火2h,即得Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料。
该材料在313nm波段紫外光照射下可以得到属于Eu3+明亮的红色发光,如图3所示,其中发射峰主要在700nm,Bi等离子体修饰后,发光增强剧烈。
实施例2
一种Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备与应用方法,包括步骤如下:
(1)将0.5g聚乙烯吡咯烷酮(平均分子量130000),1.7565g硫酸铋,0.05ml硝酸镝水溶液(0.5M)溶解于30mL乙二醇溶液中,搅拌至溶液透明后;然后加入2.5ml NaCl水溶液(2M),得到的混合溶液转入带有聚四氟乙烯内衬的水热釜中,装填度为0.7,并升温至160℃,保温12小时,反应完成后自然冷却至室温。
(2)将步骤(1)中所得反应沉淀离心后,在70℃下干燥;将干燥所得样品放在马弗炉中450℃,空气氛围退火2h,即得Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料。
该材料在365nm波段紫外光照射下可以得到明亮的属于Dy3+的蓝色和黄色发光,Bi等离子体修饰后,发光增强剧烈。
实施例3
一种Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法,包括步骤如下:
(1)将0.5g聚乙烯吡咯烷酮(平均分子量30000),2.413g五水硝酸铋,0.05ml硝酸铽水溶液(0.5M)溶解于30mL乙二醇溶液中,搅拌至溶液透明后;然后加入2.5ml十六烷基三甲基氯化铵水溶液(2M),得到的混合溶液转入带有聚四氟乙烯内衬的水热釜中,装填度为0.7,并升温至180℃,保温24小时,反应完成后自然冷却至室温。
(2)将步骤(1)中所得反应沉淀离心后,在70℃下干燥。将干燥所得样品放在马弗炉中450℃,空气氛围退火2h,即得Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料。
该材料在365nm波段紫外光照射下可以得到属于Tb3+离子的绿色发光,Bi等离子体修饰后,发光增强剧烈。
实施例4
一种Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法,包括步骤如下:
(3)将1g聚乙烯吡咯烷酮(平均分子量58000),2.413g五水硝酸铋,0.05ml硝酸铒水溶液(0.5M)溶解于35mL乙二醇溶液中,搅拌至溶液透明后;然后加入5ml KCl水溶液(1M),得到的混合溶液转入带有聚四氟乙烯内衬的水热釜中,装填度为0.8,并升温至160℃,保温12小时,反应完成后自然冷却至室温。
(4)将步骤(1)中所得反应沉淀离心后,在70℃下干燥;将干燥所得样品放在马弗炉中450℃,空气氛围退火2h,即得Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料。该材料在313nm波段紫外光照射下可以得到属于Eu3+明亮的红色发光。
对比例1
一种Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备与应用方法,包括步骤如下:
(1)将2.413g五水硝酸铋,0.05ml硝酸铕水溶液(0.5M)溶解于30mL乙二醇溶液中,搅拌至溶液透明后;然后加入含有5ml KCl的水溶液(1M),得到的混合溶液转入带有聚四氟乙烯内衬的水热釜中,装填度为0.7,并升温至160℃,保温12小时,反应完成后自然冷却至室温。
(2)将步骤(1)中所得反应沉淀离心后,在70℃下干燥。将所得样品放在马弗炉中450℃,空气氛围退火2h,即得Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料。与实施例1相比本对比例中因为缺少PVP作为修饰物,得到的氯氧铋分散性降低,同时导致材料表面并未析出等离子Bi金属,使得到的氯氧铋材料光催化和发光性能均降低。
对比例2
一种Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备与应用方法,包括步骤如下:
(1)将0.5g聚乙烯吡咯烷酮(平均分子量58000),2.413g五水硝酸铋,0.05ml硝酸铕水溶液(0.5M)溶解于30mL乙二醇溶液中,搅拌至溶液透明后;然后加入含有5ml KCl的水溶液(1M),得到的混合溶液转入带有聚四氟乙烯内衬的水热釜中,装填度为0.7,并升温至160℃,保温12小时,反应完成后自然冷却至室温。
(2)将步骤(1)中所得反应沉淀离心后,在70℃下干燥。将所得样品放在马弗炉中450℃,空气氛围退火1h,即得Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料。与实施例1相比本对比例中退火时间缩短,等离子Bi和的含量降低,催化和发光性能均降低。
由对比例1可知,在制备Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料过程中,PVP不仅能够抑制氯氧化铋纳米片的生长,同时其本身具有空间排斥作用,可以显著提高纳米片的分散性,利于具体应用。同时,在退火过程中PVP在高温下产生CO,促进等离子Bi的形成。由对比例2可知。退火时间缩短导致材料表面残留的PVP在高温下产生的CO与材料反映不充分,减少了材料表面等离子Bi金属的析出,降低了其光催化和发光性能。如附图3和图4所示,材料表面析出的等离子Bi金属显著增强了BiOCl:Eu的下转换发光和近红外光催化效率。
Claims (10)
1.一种原位析出Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法,其特征在于:包括如下步骤:
将铋源、稀土离子源和聚乙烯吡咯烷酮溶于乙二醇中,搅拌混匀后加入含有氯源的水溶液,得到混合溶液进行水热(溶剂热)反应,反应完毕,降温,离心、干燥,退火,得Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料。
2.根据权利要求1所述的原位析出Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法,其特征在于,所述的聚乙烯吡咯烷酮的平均分子量为30000~130000;所述的聚乙烯吡咯烷酮与铋源的质量比为0.1~2:1。
3.根据权利要求1所述的原位析出Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法,其特征在于,所述的铋源的质量与乙二醇体积比为0.1~3g:20~50mL。
4.根据权利要求1所述的Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法,其特征在于,所述的铋源为五水硝酸铋或碳酸铋或磷酸铋或硫酸铋或三氧化二铋;所述的稀土离子源选自其硝酸盐或氯化物或氧化物;所述稀土离子为Eu3+或Dy3+或Tb3+。
5.根据权利要求1所述的Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法,其特征在于,所述的氯源为氯化钠或氯化钾或氯化钙或氯化铵或十六烷基三甲基氯化铵;所述的含有氯源的水溶液的浓度为0.5~5M。
6.根据权利要求1所述的Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法,其特征在于,以摩尔比计,Bi离子︰稀土离子︰氯离子的摩尔比=0.994-0.996:0.004-0.006:1。
7.根据权利要求1所述的Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法,其特征在于,所述的水热反应温度为120℃~220℃,水热反应时间为6~36h。
8.根据权利要求1所述的Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料的制备方法,其特征在于,所述退火温度为450℃,空气氛围退火2h。
9.一种如权利要求1至8任一项所述的制备方法制得的原位析出Bi等离子体修饰的稀土掺杂氯氧化铋多功能复合材料。
10.如权利要求1至8任一项所述的制备方法所制得的多功能复合材料或权利要求9所述的多功能复合材料在光催化材料和/或发光材料中的应用。
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