CN112058292B - 一种复合光催化剂的制备方法 - Google Patents
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Abstract
本发明提供一种NaYF4:Yb,Tm@MS g‑C3N4复合光催化剂的制备方法,属于纳米材料光催化技术领域。具体包括以下步骤:用热分解法合成掺杂有Yb3+、Tm3+的β‑NaYF4上转换材料;用反胶束法将CTAB修饰在上转换材料表面;并与CTAB混合,调节分散液酸碱度,并加入BTSE和TEOS进行反应,使有机硅颗粒连续生长后,进一步水热处理,再加入乙醇及浓盐酸去除CTAB后,离心取固体物质并干燥;研磨固体,煅烧;并向其中加入三聚氰胺,加水反应后,离心取固体物质,冷冻干燥;研磨固体,煅烧;加入碳酸钠刻蚀二氧化硅模板,得最终复合光催化剂。本发明催化剂提高了光谱利用范围,可加强反射光的利用。
Description
技术领域
本发明属于纳米材料光催化技术领域,尤其涉及一种NaYF4:Yb,Tm@MS g-C3N4复合光催化剂的制备方法。
背景技术
纳米非均相光催化是一种很先进的氧化技术,近年来在净化空气、水消毒和废水处理中利用很多。
然而,现有技术大多着重加强光催化剂的催化效果,但因其中大多数未将利用不同波段光的材料集成起来,所以对光谱利用范围不够宽广。
发明内容
针对现有技术存在的上述问题,本发明申请人提供了一种NaYF4:Yb,Tm@ MS g-C3N4复合光催化剂的制备方法。本发明有着广泛的光谱利用范围,且具多孔结构,可加强反射光与散射光的利用。
本发明的技术方案如下:
本发明有益的技术效果在于:
一种NaYF4:Yb,Tm@MS g-C3N4复合光催化剂的制备方法,包括以下步骤:
(1)将YCl3·6H2O、YbCl3·6H2O、TmCl3·6H2O、油酸OA及1-十八烯ODE 混合均匀,通入惰性气体,并升温至140-160℃,反应30min,结束后冷却至室温,之后加入经过超声的NaOH与NH4F的甲醇溶液,混匀并在80℃下恒温30-50 min,待甲醇完全蒸发,随后将溶液升温至290-300℃,恒温反应60-80min,反应结束固液分离取固相,将固相用环己烷/乙醇混合溶剂洗涤,最后即得上转换纳米NaYF4:Yb,Tm(UCNP-OA);
(2)将步骤(1)中所得上转换纳米NaYF4:Yb,Tm分散于环己烷中,加入浓度为1mg/mL十六烷基三甲基溴化铵CTAB溶液,在80℃条件下反应2-4h,蒸去环己烷,反应结束后水洗离心得到CTAB修饰的NaYF4:Yb,Tm,即 NaYF4:Yb,Tm-CTAB(UCNP-CTAB);
(3)将步骤(2)中所得NaYF4:Yb,Tm-CTAB分散在水中,并加入去离子水、无水乙醇与CTAB,超声混均,在35℃条件下静置1h,并加入氨水,在剧烈的磁力搅拌下,分三次滴加1,2-双(三乙氧基硅基)乙烷BTSE与正硅酸乙酯 TEOS,每次滴加结束后持续搅拌10-25h后,固液分离取固相 NaYF4:Yb,Tm@3SiO2,向固相中加入水,并置于120-130℃反应5-6h使固相分散,待冷却后离心,离心后取固体物质,并加入无水乙醇与浓HCl,置于60℃环境磁力搅拌3-4h后,固液分离取固相并干燥;
(4)将步骤(3)中所得固相研磨,600℃煅烧,冷却后并研磨得到粉末;
(5)将步骤(4)中所得粉末与三聚氰胺、水混合均匀并摇床反应8-10h,反应结束后取固体物质并放至-80℃冰箱中,预冻12-48h,取出再冷冻干燥24-48 h;
(6)将步骤(5)中所得冷冻干燥固体物质进行研磨,于550℃煅烧,冷却至室温,之后加入碳酸钠溶液,于55-65℃下反应24h,反应结束后固液分离得固相,所得固相即为NaYF4:Yb,Tm@MS g-C3N4复合光催化剂。
所述复合光催化剂为NaYF4:Yb,Tm@MS g-C3N4。
步骤(1)中,所述YCl3·6H2O、YbCl3·6H2O、TmCl3·6H2O摩尔比为159: 40:1。
步骤(2)中所得上转换纳米NaYF4:Yb,Tm分散于水中浓度为5mg/mL-30 mg/mL。
步骤(2)中所述十六烷基三甲基溴化铵CTAB溶液浓度为1mg/mL。
步骤(3)中所述NaYF4:Yb,Tm-CTAB分散在水和乙醇中得到的浓度为0.35 mg/mL;所述TEOS和BTSE添加方式为以2-4滴/min速度滴加。
步骤(4)中,升温速度设为10℃/min,高温煅烧时长为120min。
步骤(5)中所述的步骤(4)中所得粉末、三聚氰胺与水的配比为20mg: 60mg:1mL。
步骤(6)中所述升温速度设为2℃/min,高温煅烧时长为180min。
在具有将近红外光转换成可见光这一光学性能的特殊材料中,稀土元素掺杂的β-NaYF4上转换材料被认为最有效,在该领域有着很高的关注度。
其中,NaYF4:Yb,Tm的FL荧光图谱见图2,从图中可知上转换的原理为: NaYF4:Yb,Tm中的Tm3+离子在980nm激光照射下,在可见光区的450nm和 475nm的两处出现了发射峰,分别来源于Tm3+离子的1D2→3F4和1G4→3H6放射性跃迁,其跃迁能量大于g-C3N4的禁带宽度,可以通过Tm3+离子的跃迁过程激发可见光催化剂g-C3N4。
本发明制备出结合稀土离子高效上转换发光特性与g-C3N4高光催化活性的复合材料,该复合光催化剂能有效利用广谱的太阳光,近红外光和可见光都可使其响应。
本发明材料具多孔结构,提供了丰富的催化活性中心,同时光在其中反射和散射可以增强光的捕获。
其他同样涉及合成NaYF4:Yb,Tm的工艺实施例单次合成量较少,效率不足,且加热蒸发甲醇一步分别加热50℃、70℃到两次,步骤冗余,本申请中,单次合成投料量按其余工艺约3倍进行解决了这个问题,使得单次产量提高了3倍,且蒸发甲醇一步本发明采用加热到80℃并小幅延长加热时间来确保甲醇的去除,一步到位简化工艺。
附图说明
图1为本发明NaYF4:Yb,Tm@MS g-C3N4复合光催化材料制备方法的工艺流程图。
图2为本发明实施例1制备得到的NaYF4:Yb,Tm-OA的FL荧光图谱。
图3为本发明实施例1中制备得到的NaYF4:Yb,Tm-OA(a)和 NaYF4:Yb,Tm-CTAB(b)的FT-IR图。
图4为本发明实施例1中制备得到的NaYF4:Yb,Tm-OA(A)和 NaYF4:Yb,Tm@3SiO2(B)的TEM图。
图5为本发明实施例1中制备得到的NaYF4:Yb,Tm-OA(a)和 NaYF4:Yb,Tm@3SiO2(b)的XRD图。
具体实施方式
下面结合附图和实施例,对本发明进行具体描述。
实施例1:
一种NaYF4:Yb,Tm@MS g-C3N4复合光催化剂的制备方法,其特征在于,包括以下步骤:
(1)分别加入0.7230g,0.2325g,0.0058g,18mL,45mL的YCl3·6H2O, YbCl3·6H2O,TmCl3·6H2O、油酸(OA)及1-十八烯(ODE)到三口烧瓶中,启动磁力搅拌,同时向其中通氮气15min后,升温至160℃,并保持30min,随后停止加热冷却至室温;加入超声过的含有0.3gNaOH和0.444g NH4F的甲醇溶液 30mL,随后,将浑浊液在80℃下保持40min,将甲醇完全蒸发。随后将溶液升温至300℃,并在N2流下及持续的磁力搅拌下,保持加热60min后停止,冷却至室温。离心分离,用环己烷/乙醇离心洗涤三次,最后分散于6mL环己烷中,使得NaYF4:Yb,Tm-OA的浓度为50mg/mL,置于4℃冰箱中保存;
(2)称取0.3g十六烷三甲基溴化铵(CTAB),加入30mL水,取上述以 OA为配体的NaYF4:Yb,Tm(NaYF4:Yb,Tm-OA)溶液6mL加入CTAB的水溶液中,放入80℃水浴锅3h,蒸去环己烷,收集得到的NaYF4:Yb,Tm-CTAB,水洗离心后,溶入10mL水中;
(3)定量称取0.64g CTAB,依次加入30mL去离子水、75mL无水乙醇和 5.2mL改性后的NaYF4:Yb,Tm水溶液(约合40mg纯NaYF4:Yb,Tm),超声 15min,放入35℃水浴锅中1h后,向其中一次性加入1mL氨水,在剧烈的磁力搅拌下,以3滴/min速度滴加0.1mL 1,2-双(三乙氧基硅基)乙烷(BTSE)和0.1 mL正硅酸乙酯(TEOS),持续搅拌12h后,再次滴加BTSE与TEOS,同样等待搅拌12h后,第三次滴加BTSE与TEOS,12h后,收集得到的 NaYF4:Yb,Tm@3SiO2,水洗离心后溶于24mL水,平均分成8份,分别转移入水热釜,再在每个水热釜中加入177mL水,加热120℃、保持5h,待冷却后,离心,加入720mL无水乙醇与1.44mL浓HCl,置于60℃水浴锅中磁力搅拌3 h后,将经过离心分离后的下层固体置入60℃烘箱干燥12h;
(4)研磨所述固体,放入马弗炉,于600℃煅烧120min,升温速度设为 10℃/min;
(5)冷却后,称量60mg三聚氰胺与20mg煅烧后粉末混合,加入1mL水,置于40℃摇床中8h,离心后将下层固体放至-80℃冰箱中,预冻12h,再冷冻干燥48h;
(6)研磨所述固体,放入管式炉,于550℃煅烧180min,升温速度设为 2℃/min;
(7)加入0.3mol/L碳酸钠溶液,置于60℃水浴锅中反应24h,离心即得 NaYF4:Yb,Tm@MS g-C3N4复合光催化剂NaYF4:Yb,Tm@MS g-C3N4。
测试例1光谱分析:
将实施例1中步骤(1)制备得到的NaYF4:Yb,Tm-OA用980nm近红外激光照射,测试其荧光光谱(FL),其结果见图2,其中NaYF4:Yb,Tm在290nm、 345nm、361nm、450nm和475nm五处出现了发射峰,分别来源于激活剂 Tm3+离子的1I6→3H6、1I6→3F4、1D2→3H6、1D2→3F4和1G4→3H6放射性跃迁,其中g-C3N4能利用的可见光区两处(450nm和475nm)跃迁能量大于g-C3N4的禁带宽度,证实可以通过Tm3+离子的跃迁过程激发可见光催化剂g-C3N4。将实施例1中制备得到的NaYF4:Yb,Tm-OA和NaYF4:Yb,Tm-CTAB通过傅里叶红外光谱仪(FT-IR)进行测试,其结果如图3,图中可见,CTAB改性后的与前者谱图相比,发生了明显变化:在1378cm-1和1629cm-1处均出现了分别归属于 C-N和N-H的振动产生的峰;2854cm-1和2924cm-1处出峰的增强代表-CH2- 数量增加;由于O-H和N-H的振动结合,3000cm-1-3700cm-1处出峰亦大大增强;含N官能团的出现、-CH2-峰高的增加,无不说明NaYF4:Yb,Tm表面成功修饰上了原料中唯一有含N基团、且化学结构中每分子多达15个-CH2-基团的 CTAB。
测试例2材料表征:
将实施例1中制备得到的NaYF4:Yb,Tm-OA和NaYF4:Yb,Tm@3SiO2通过透射电子显微镜(TEM)及X射线衍射仪(XRD)分别表征形貌特征及材料的晶型,表征结果见图4、图5。从图4(A)可看出,合成的NaYF4:Yb,Tm呈六方相,形貌规则,尺寸分布均匀在40nm附近;从图4(B)可看出,NaYF4:Yb,Tm@3SiO2外围明显包被上了3层的SiO2壳层,且深颜色的内核NaYF4:Yb,Tm的尺寸在包裹SiO2壳层滴加BTSE与TEOS的剧烈反应中无明显变化,仍处于40nm附近范围。从图5(a)可看出,NaYF4:Yb,Tm衍射峰与其标准卡片(JCPDS 16-0334) 相一致,无其他杂质衍射峰,证实所制材料成功形成六方相晶型。图5(b)中显示,NaYF4:Yb,Tm@3SiO2除具β-NaYF4的衍射峰外,还在2θ为24.8°处具备宽且弱的衍射峰,这对应着SiO2标准卡(JCPDS:46-1045)中最显著的特征,这证实了120℃高温水热反应后,成功形成了SiO2壳层。且由图中NaYF4:Yb,Tm 本身的特征峰位置、强度均未发生明显变化,表明了NaYF4:Yb,Tm的晶相结构并未受到120℃的高温水热处理的影响。
Claims (8)
1.一种复合光催化剂的制备方法,其特征在于,包括以下步骤:
(1)将YCl3·6H2O、YbCl3·6H2O、TmCl3·6H2O、油酸OA及1-十八烯ODE混合均匀,通入惰性气体,并升温至140-160℃,反应30min,结束后冷却至室温,之后加入经过超声的NaOH与NH4F的甲醇溶液,混匀并在80℃下恒温30-50min,待甲醇完全蒸发,随后将溶液升温至290-300℃,恒温反应60-80min,反应结束固液分离取固相,将固相用环己烷/乙醇混合溶剂洗涤,最后即得上转换纳米NaYF4:Yb,Tm-OA;
(2)将步骤(1)中所得上转换纳米NaYF4:Yb,Tm-OA分散于环己烷中,加入浓度为1mg/mL十六烷基三甲基溴化铵CTAB溶液,在80℃条件下反应2-4h,蒸去环己烷,反应结束后水洗离心得到CTAB修饰的NaYF4:Yb,Tm,即NaYF4:Yb,Tm-CTAB;
(3)将步骤(2)中所得NaYF4:Yb,Tm-CTAB分散在水中,并加入去离子水、无水乙醇与CTAB,超声混均,在35℃条件下静置1h,并加入氨水,在剧烈的磁力搅拌下,分三次滴加1,2-双(三乙氧基硅基)乙烷BTSE与正硅酸乙酯TEOS,每次滴加结束后持续搅拌10-25h后,固液分离取固相NaYF4:Yb,Tm@3SiO2,向固相中加入水,并置于120-130℃反应5-6h使固相分散,待冷却后离心,离心后取固体物质,并加入无水乙醇与浓HCl,置于60℃环境磁力搅拌3-4h后,固液分离取固相并干燥;
(4)将步骤(3)中所得固相研磨,600℃煅烧,冷却后并研磨得到粉末;
(5)将步骤(4)中所得粉末与三聚氰胺、水混合均匀并摇床反应8-10h,反应结束后取固体物质并放至-80℃冰箱中,预冻12-48h,取出再冷冻干燥24-48h;
(6)将步骤(5)中所得冷冻干燥固体物质进行研磨,于550℃煅烧,冷却至室温,之后加入碳酸钠溶液,于55-65℃下反应24h,反应结束后固液分离得固相,所得固相即为复合光催化剂。
2.根据权利要求1所述的复合光催化剂的制备方法,其特征在于,所述复合光催化剂为NaYF4:Yb,Tm@MSg-C3N4。
3.根据权利要求1所述的复合光催化剂的制备方法,其特征在于,步骤(1)中,所述YCl3·6H2O、YbCl3·6H2O、TmCl3·6H2O摩尔比为159:40:1。
4.根据权利要求1所述的复合光催化剂的制备方法,其特征在于,步骤(2)中所得上转换纳米NaYF4:Yb,Tm-CTAB分散于水中浓度为5mg/mL-30mg/mL。
5.根据权利要求1所述的复合光催化剂的制备方法,其特征在于,步骤(3)中所述NaYF4:Yb,Tm-CTAB分散在水和乙醇中得到的浓度为0.35mg/mL;所述TEOS和BTSE添加方式为以2-4滴/min速度滴加。
6.根据权利要求1所述的复合光催化剂的制备方法,其特征在于:步骤(4)中,升温速度设为10℃/min,高温煅烧时长为120min。
7.根据权利要求1所述的复合光催化剂的制备方法,其特征在于,步骤(5)中所述的步骤(4)中所得粉末、三聚氰胺与水的配比为20mg:60mg:1mL。
8.根据权利要求1所述的复合光催化剂的制备方法,其特征在于,步骤(6)中所述升温速度设为2℃/min,高温煅烧时长为180min。
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