CN109174161B - 可磁分离TNTs/g-C3N4纳米复合材料的制备方法和应用 - Google Patents
可磁分离TNTs/g-C3N4纳米复合材料的制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种可磁分离TNTs/g‑C3N4纳米复合材料的制备方法,为了利用Fe3O4的磁响应性以及石墨相氮化碳(g‑C3N4)优良的光催化活性,以g‑C3N4、P25、水溶性二价铁盐及三价铁盐为原料,在碱性水热条件下,Fe3O4纳米颗粒和TiO2纳米管(TNTs)在g‑C3N4片层上原位生长,合成TNTs/Fe3O4/g‑C3N4纳米复合材料。本发明同时公开了上述方法制得的可磁分离TNTs/g‑C3N4纳米复合材料。可磁分离Fe3O4‑TNTs/g‑C3N4纳米复合材料具有较好的磁性,饱和磁化强度为28.26emu/g,可实现复合材料的分离回收;光照60min时,Fe3O4‑TNTs/g‑C3N4纳米复合材料对亚甲基蓝的去除率为98.8%,制备的Fe3O4‑TNTs/g‑C3N4纳米复合材料具有优良的吸附性能、光催化活性和磁性,可通过外加磁场进行分离与回收。
Description
技术领域
本发明属于光催化磁性材料制备技术领域,特别涉及一种可磁分离TNTs/g-C3N4纳米复合材料的制备方法。
背景技术
半导体光催化氧化技术利用可见光或紫外光将环境中的有机物降解为水和二氧化碳,在空气净化、杀菌除臭、废水处理等方面具有广阔的应用前景。在目前的半导体光催化材料中,二氧化钛纳米管(TNTs)具有巨大的比表面积,较高的电子空穴分离效率,被认为是最有应用潜力的光催化剂之一。但TNTs在光催化处理废水的应用中存在固液分离困难,可见光催化活性低等缺点,限制了光催化技术的应用。
将光催化材料与磁性材料(Fe3O4、CoFeO4等)复合,不仅能够实现光催化剂的回收和循环利用,而且不会降低光催化剂的吸附性和光催化活性,是实现光催化剂循环利用的有效手段之一。氮化碳(g-C3N4)是近年来发现的具有半导体性质的层状纳米材料,具有良好的稳定性、吸附性,将g-C3N4与TNTs进行复合形成异质结,不仅能够提高可见光响应能力,而且延长电子和空穴的寿命,进而大幅提高其光催化活性。
发明内容
为了解决上述技术问题,本发明提供一种可磁分离TNTs/g-C3N4纳米复合材料的制备方法,包括以下步骤,称取一定量的g-C3N4分散在50ml去离子水超声处理0.8—1.2 小时得到均匀的分散液,通过搅拌将一定量的P25缓慢加入g-C3N4分散液中,持续超声 0.4-0.6h,搅拌0.4-0.6h确保完全混合,再加入一定量摩尔比为2.5-3.5:1的 FeCl3·6H2O和FeSO4·7H2O,然后再持续超声12-16分钟,搅拌15分钟确保完全混合;将0.8-1.2M的NaOH溶液逐滴加入上述混合液,使溶液的pH值等于10,然后再加入一定量的NaOH将混合物转移至水热反应釜中,然后将反应釜于100-140℃下加热24小时;冷却先用去离子水洗至中性,用0.01M的HCl溶液浸泡0.8-1.2小时;最后用去离子水洗涤数次,然后用无水乙醇洗涤数次磁性分离,在40-80℃下真空干燥,N2保护下 240-320℃煅烧40min-80min,得到Fe3O4-TNTs/g-C3N4复合材料。
优选地,所述g-C3N4的制备方法包括以下步骤:
称取15g尿素,研细后放入马弗炉中,以12℃/min-18℃/min的升温速率升温至500℃-550℃,煅烧2.5h-3.5h,随炉冷却,取出于玛瑙研钵中研磨,即得淡黄色g-C3N4。
本发明同时公开了一种上述方法制得的可磁分离TNTs/g-C3N4纳米复合材料。
可磁分离TNTs/g-C3N4纳米复合材料的在光催化领域的应用。
为了利用Fe3O4的磁响应性以及石墨相氮化碳(g-C3N4)优良的光催化活性,本发明以g-C3N4、P25、水溶性二价铁盐及三价铁盐为原料,在碱性水热条件下,Fe3O4纳米颗粒和TiO2纳米管(TNTs)在g-C3N4片层上原位生长,合成TNTs/Fe3O4/g-C3N4纳米复合材料。
本发明采用一步法合成可磁分离TNTs/g-C3N4纳米复合材料,使Fe3O4纳米颗粒和TNTs在g-C3N4片层上同步生成,相互牵制而保持均匀分散的状态,有效地限制了纳米粒子的团聚和生长。通过TNTs/g-C3N4异质结有效提高纳米复合材料的电子和空穴分离效率,拓展可见光响应范围,进而提高可见光催化活性,同时解决光催化剂回收困难的难题,有助于二氧化钛(TiO2)光催化技术推广和应用。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的描述。
图1是g-C3N4、Fe3O4、TNTs及Fe3O4-TNTs/g-C3N4纳米复合材料采用日本理学公司 D/Max-2400型粉末衍射仪,Cu Kα射线,管电压为40kV,管电流为100mA,扫描范围为5°-80°,步速为10°/min的XRD图。
图2是g-C3N4的TEM图。
图3是Fe3O4-TNTs/g-C3N4复合材料放大不同倍数的TEM图。
图4是Fe3O4-TNTs/g-C3N4复合材料的EDX谱图。
图5是Fe3O4-TNTs/g-C3N4纳米复合材料及纯Fe3O4粒子饱和VSM测试曲线。
图6是Fe3O4-TNTs/g-C3N4纳米复合材料对亚甲基蓝的光催化降解图。
具体实施方式
实施例1
本发明公开了一种可磁分离TNTs/g-C3N4纳米复合材料的制备方法,包括以下步骤,称取一定量的g-C3N4分散在50ml去离子水超声处理1小时得到均匀的分散液,通过搅拌将一定量的P25缓慢加入g-C3N4分散液中,持续超声0.5h,搅拌0.5h确保完全混合,再加入一定量摩尔比为2:1的FeCl3·6H2O和FeSO4·7H2O,然后再持续超声15分钟,搅拌15分钟确保完全混合。将1M的NaOH溶液逐滴加入上述混合液,使溶液的pH值等于10,然后再加入一定量的NaOH将混合物转移至水热反应釜中,然后将反应釜于120℃下加热24小时。冷却先用去离子水洗至中性,用0.01M的HCl溶液浸泡1小时。最后的产品用去离子水洗涤数次,然后用无水乙醇洗涤数次磁性分离,在60℃下真空干燥,N2保护下300℃煅烧 60min,得到Fe3O4-TNTs/g-C3N4复合材料。
所述g-C3N4的制备方法包括以下步骤:
称取15g尿素,研细后放入马弗炉中,以15℃/min的升温速率升温至520℃,煅烧3h,随炉冷却,取出于玛瑙研钵中研磨,即得淡黄色g-C3N4。
本发明同时公开了一种上述方法制得的可磁分离TNTs/g-C3N4纳米复合材料。
本发明申请人试验主要原料:尿素(上海建信化工有限公司试剂厂),FeCl3·6H2O(安阳市兴亚化学试剂有限公司),FeSO4·7H2O(北京化学试剂厂),NaOH(天津市致远化学试剂有限公司),HCl(洛阳昊华化学试剂有限公司)钛酸丁酯(国药集团),无水乙醇(国药集团),亚甲基蓝(天津凯通化学试剂有限公司),药品均为分析纯,实验均使用去离子水。
本发明所用原料并不限于以上厂家。
XRD分析
图1是g-C3N4、Fe3O4、TNTs及Fe3O4-TNTs/g-C3N4纳米复合材料采用日本理学公司 D/Max-2400型粉末衍射仪,Cu Kα射线,管电压为40kV,管电流为100mA,扫描范围为 5°-80°,步速为10°/min的XRD图。图1a是g-C3N4的XRD图,谱图2θ=27.5°为g-C3N4无定型状峰。图1b是TNTs的XRD图,与锐钛矿TiO2纳米粒的衍射峰相比强度有所减弱,但在2θ为25.4°、37.9°、48.0°、55.1°和62.9°处还是出现了较强的吸收峰,是锐钛矿的101、004、 200、211和204晶面的特征衍射峰。图1c分别位于30.3°、35.6°、43.5°、54.1°、57.6°及63.2°处强衍射峰是Fe3O4的220、311、400、422、511、440晶面的特征衍射峰。图1d为 Fe3O4-TNTs/g-C3N4复合材料的XRD图,与图1a、1b和1c各纯物质的XRD的对比分析可以看出,复合材料中2θ位于27.5°处出现了g-C3N4的特征峰,图1d中方框为g-C3N4的衍射峰,在分别位于25.4°、27.5°、30.3°、35.6°、43.5°、48.0°、55.1°、57.6°和63.2°处出现了相应强衍射峰,其中37.9°、54.1°和62.9°处的衍射峰相对较弱,是被附近的强吸收所掩盖,与图1a、图1b、图1c三种纯的物质的谱图一致,表明磁性Fe3O4粒子、TNTs和g-C3N4三者成功复合。
TEM和EDX分析
图2是g-C3N4的TEM图,可以清楚的看到g-C3N4形态,其褶皱明显以单层形式存在,具有较大的比表面积。
图3(a)和图3(b)是Fe3O4-TNTs/g-C3N4复合材料放大不同倍数的TEM图,可以看出Fe3O4-TNTs/g-C3N4纳米复合材料的形态分布的特征,磁性Fe3O4粒子、TNTs清晰可见,且均匀负载在g-C3N4的单层结构上。由图3(a)和3(b)可见g-C3N4以单层形式分散在复合材料中,Fe3O4纳米粒子直径为15~20nm范围内,TNTs的管外径约为10nm左右,内径为3nm左右,长度在200nm左右。磁性Fe3O4粒子、TNTs和g-C3N4以纳米尺寸均匀分散,形成了的纳米复合结构。
图4是Fe3O4-TNTs/g-C3N4复合材料的EDX谱图。从EDX谱图可以看出复合材料中含有C、N、O、Ti和Fe五种元素,依据XRD、TEM和EDX的分析,可以确定复合材料含有g-C3N4、TNTs和Fe3O4三种物质,表明在g-C3N4片层上复合了大量的TNTs,且复合了大量的Fe3O4颗粒。从图3(a)和3(b)可以观察到Fe3O4粒子和TNTs均匀负载在 g-C3N4片层上,没有明显团聚现象,这是由于水热共沉淀法制备Fe3O4-TNTs/g-C3N4纳米复合材料的过程一步完成,磁性Fe3O4粒子和TNTs的形成同步进行,相互牵制而保持均匀分散的状态,有效地限制了纳米粒子的团聚和生长,并达到纳米尺度的均匀负载在光催化载体,是一种高效的制备Fe3O4-TNTs/g-C3N4纳米复合材料的方法。
VSM分析
图5是在Quantum Design Model 6000PPMS磁强计上进行,测量4.2~295K温度范围内的零场磁化率χAC随温度的变化,所加驱动场为1Oe,频率为300Hz,所加外场 0~10kOe的Fe3O4-TNTs/g-C3N4纳米复合材料及纯Fe3O4粒子饱和VSM测试曲线。从图 5(a)可知纯Fe3O4粒子饱和磁化强度为60.02emu/g,从图5b可以看到Fe3O4-TNTs/g-C3N4纳米复合材料的饱和磁化强度为28.26emu/g,二者相比复合材料饱和磁化强度有较大程度的减弱。饱和磁化强度值与Fe3O4粒子的百分含量有关,含量越高,饱和磁化强度越大。同时,磁性Fe3O4粒子和TNTs同时均匀分散负载在光催化剂载体g-C3N4片层上,形成了Fe3O4-TNTs/g-C3N4纳米复合材料,g-C3N4片层和TiO2纳米管对磁性粒子起到包覆作用,使饱和磁化强度减小,使磁响应性降低。纯Fe3O4粒子饱和磁化强度与 Fe3O4-TNTs/g-C3N4纳米复合材料的饱和磁化强度相比有较大幅度的下降,即便如此, Fe3O4-TNTs/g-C3N4纳米复合材料在外加磁场的作用下仍能顺利提取。图5的插图(1)是 Fe3O4-TNTs/g-C3N4纳米复合材料分散在亚甲基蓝的水溶液中,形成均匀悬浊液的数码照片,图5的插图(2)是亚甲基蓝降解后Fe3O4-TNTs/g-C3N4纳米复合材料在磁场作用下定向提取的数码照片。将0.001gFe3O4-TNTs/GN纳米复合材料分散在50mL浓度40mg/L亚甲基蓝的水溶液中,在紫外光的照射下,亚甲基蓝的悬浊液蓝色褪去,Fe3O4-TNTs/g-C3N4纳米复合材料在1.44T外加磁场作用下定向移向磁铁,经过30s,全部移向磁铁,显示出优异的磁响应性。Fe3O4-TNTs/g-C3N4纳米复合材料在磁场作用完全可分离,实现可磁分离进而反复使用的复合光催化材料。利用g-C3N4作为模板,充分发挥了TNTs的光催化性能和磁性粒子在外加磁场可提取的优势,使得复合材料的理化性能得到很好的改善。磁性Fe3O4粒子和TNTs在形成过程中均匀分散,有效地限制了纳米粒子的团聚和生长。通过水热共沉淀一步法制备出Fe3O4-TNTs/g-C3N4纳米复合材料,具有较大的比表面积,材料具有良好的光催化性能同时兼具磁性,可通过外加磁场对光催化材料进行靶向定位、分离和重复使用。
TNTs/Fe3O4/g-C3N4纳米复合材料光催化分析
图6是TNTs/Fe3O4/g-C3N4纳米复合材料对亚甲基蓝的光催化降解性能。在光催化性能测试的实验中,以亚甲基蓝作为目标污染物,将0.05g的TNTs/Fe3O4/g-C3N4纳米复合材料、TNTs和g-C3N4分别加入50ml初始浓度为40mg/L的亚甲基蓝中进行吸附和光催化性能测试实验。在避光条件下,搅拌达到复合材料和亚甲基蓝的混合均匀,吸附30 分钟取样5mL,之后开启光源(100W汞灯),每隔30min取样5mL,离心分离,取清液,在波长664nm下测定亚甲基蓝的吸光度,根据标准曲线计算相应的浓度。在吸附 30min时,g-C3N4能够吸附13.3%的亚甲基蓝,而TNTs对亚甲基蓝具有良好的吸附性能, TNTs能够吸附81.45%的亚甲基蓝,而TNTs/Fe3O4/g-C3N4纳米复合材料吸附了73.95%的亚甲基蓝,吸附性能略低于TNTs,但是仍显示出良好的吸附性能,该复合材料良好的吸附性能归因于TNTs的大比表面积。
在光照60min时,没有加催化剂的亚甲基蓝自身光解仅为3.9%,g-C3N4、TNTs、TNTs/Fe3O4/g-C3N4纳米复合材料对亚甲基蓝的去除率分别为22.74%,91.28%, 99.79%,TNTs/Fe3O4/g-C3N4纳米复合材料对亚甲基蓝的去除率明显高于纯TNTs和 g-C3N4,显示出良好的光催化性能。这是因为在TNTs/Fe3O4/g-C3N4纳米复合材料中, g-C3N4和TNTs具有一定的协同作用,g-C3N4作为载体提高TNTs的分散性能,同时产生更多的电子和空穴。TNTs不仅具有良好的吸附性能,而且所具有的管状结构能够更好的促进电子和空穴的分离。
以上利用透射电子显微镜(TEM)、X射线衍射仪(XRD)、振动样品磁强计(VSM)等多种测试手段对复合材料进行表征,分析了该复合材料的形貌、晶型结构、饱和磁化强度等。通过模拟太阳光下Fe3O4-TNTs/g-C3N4纳米光催化吸附降解亚甲基蓝(MB)的实验,评价了Fe3O4-TNTs/g-C3N4纳米的吸附性能以及光催化性能。结果表明,可磁分离 Fe3O4-TNTs/g-C3N4纳米复合材料具有较好的磁性,饱和磁化强度为28.26emu/g,可实现复合材料的分离回收;光照60min时,Fe3O4-TNTs/g-C3N4纳米复合材料对亚甲基蓝的去除率为98.8%,制备的Fe3O4-TNTs/g-C3N4纳米复合材料具有优良的吸附性能、光催化活性和磁性,可通过外加磁场进行分离与回收。
本发明以g-C3N4、P25、水溶性二价铁盐及三价铁盐为原料,在碱性水热条件下,Fe3O4纳米颗粒和TiO2纳米管在g-C3N4片层上原位生长,磁性Fe3O4粒子和TiO2纳米管同时负载分散在g-C3N4片层上,形成TNTs/Fe3O4/g-C3N4纳米复合材料。磁性Fe3O4粒子和TiO2纳米管相互牵制而保持均匀分散的状态,有效地限制了纳米粒子的团聚和生长,实现在石墨烯载体上的均匀负载。TNTs/Fe3O4/g-C3N4纳米复合材料在紫外光照60min 时,对浓度为40mg/L的亚甲基蓝水溶液的去除率为99.8%,在外加磁场的作用下,经过 30s分钟即实现固液分离。可见,TNTs/Fe3O4/g-C3N4纳米复合材料对亚甲基蓝具有良好的光催化性能,且可通过外加磁场进行靶向定位或磁分离后反复使用,在光催化领域具有十分广阔的应用前景。
实施例2
一种可磁分离TNTs/g-C3N4纳米复合材料的制备方法,包括以下步骤,称取一定量的g-C3N4分散在50ml去离子水超声处理0.8小时得到均匀的分散液,通过搅拌将一定量的P25缓慢加入g-C3N4分散液中,持续超声0.4h,搅拌0.4h确保完全混合,再加入一定量摩尔比为2.5:1的FeCl3·6H2O和FeSO4·7H2O,然后再持续超声12分钟,搅拌15 分钟确保完全混合;将0.8M的NaOH溶液逐滴加入上述混合液,使溶液的pH值等于10,然后再加入一定量的NaOH将混合物转移至水热反应釜中,然后将反应釜于100℃下加热24小时;冷却先用去离子水洗至中性,用0.01M的HCl溶液浸泡0.8小时;最后用去离子水洗涤数次,然后用无水乙醇洗涤数次磁性分离,在40℃下真空干燥,N2保护下 240℃煅烧40min,得到Fe3O4-TNTs/g-C3N4复合材料。
所述g-C3N4的制备方法包括以下步骤:
称取15g尿素,研细后放入马弗炉中,以12℃/min的升温速率升温至500℃,煅烧2.5h,随炉冷却,取出于玛瑙研钵中研磨,即得淡黄色g-C3N4。
实施例3
一种可磁分离TNTs/g-C3N4纳米复合材料的制备方法,包括以下步骤,称取一定量的g-C3N4分散在50ml去离子水超声处理1.2小时得到均匀的分散液,通过搅拌将一定量的P25缓慢加入g-C3N4分散液中,持续超声0.6h,搅拌0.6h确保完全混合,再加入一定量摩尔比为3.5:1的FeCl3·6H2O和FeSO4·7H2O,然后再持续超声16分钟,搅拌15 分钟确保完全混合;将1.2M的NaOH溶液逐滴加入上述混合液,使溶液的pH值等于 10,然后再加入一定量的NaOH将混合物转移至水热反应釜中,然后将反应釜于140℃下加热24小时;冷却先用去离子水洗至中性,用0.01M的HCl溶液浸泡1.2小时;最后用去离子水洗涤数次,然后用无水乙醇洗涤数次磁性分离,在80℃下真空干燥,N2保护下320℃煅烧80min,得到Fe3O4-TNTs/g-C3N4复合材料。
所述g-C3N4的制备方法包括以下步骤:
称取15g尿素,研细后放入马弗炉中,以18℃/min的升温速率升温至550℃,煅烧3.5h,随炉冷却,取出于玛瑙研钵中研磨,即得淡黄色g-C3N4。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (3)
1.一种可磁分离TNTs/g-C3N4纳米复合材料的制备方法,其特征在于:包括以下步骤,称取一定量的g-C3N4分散在50ml去离子水超声处理0.8—1.2小时得到均匀的分散液,通过搅拌将一定量的P25缓慢加入g-C3N4分散液中,持续超声0.4-0.6h,搅拌0.4-0.6h确保完全混合,再加入一定量摩尔比为2.5-3.5:1的FeCl3·6H2O和FeSO4·7H2O,然后再持续超声12-16分钟,搅拌15分钟确保完全混合;将0.8-1.2M的NaOH溶液逐滴加入上述混合液,使溶液的pH值等于10,然后再加入一定量的NaOH将混合物转移至水热反应釜中,然后将反应釜于100-140℃下加热24小时;冷却先用去离子水洗至中性,用0.01M的HCl溶液浸泡0.8-1.2小时;最后用去离子水洗涤数次,然后用无水乙醇洗涤数次磁性分离,在40-80℃下真空干燥,N2保护下240-320℃煅烧40min-80min,得到Fe3O4-TNTs/g-C3N4复合材料;
所述g-C3N4的制备方法包括以下步骤:
称取15g尿素,研细后放入马弗炉中,以12℃/min-18℃/min的升温速率升温至500℃-550℃,煅烧2.5h-3.5h,随炉冷却,取出于玛瑙研钵中研磨,即得淡黄色g-C3N4。
2.一种权利要求1所述方法制得的可磁分离TNTs/g-C3N4纳米复合材料。
3.一种权利要求2所述的可磁分离TNTs/g-C3N4纳米复合材料在光催化领域的应用。
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