CN110975852B - 一种二氧化钛纳米簇@碳球多级复合结构材料及其制备方法和应用 - Google Patents
一种二氧化钛纳米簇@碳球多级复合结构材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及光催化材料技术领域,尤其涉及一种二氧化钛纳米簇@碳球多级复合结构材料及其制备方法和应用。本发明的制备方法包括以下步骤:将二氯二茂钛、液态直链羧酸和液态直链烷烃混合,进行溶剂热反应,固液分离后,得到二氧化钛纳米簇@碳球多级复合结构材料。本发明采用二氯二茂钛为钛源,以液态直链羧酸为溶剂,以液态直链烷烃为混合溶剂,经一步溶剂热即可得到二氧化钛纳米簇@碳球多级复合结构材料,方法简单高效,光催化活性的二氧化钛纳米结构完全暴露于材料表面,且具有良好的有机污染物去除效果。
Description
技术领域
本发明涉及光催化材料技术领域,尤其涉及一种二氧化钛纳米簇@碳球多级复合结构材料及其制备方法和应用。
背景技术
随着全球人口数量的增加,社会经济的不断发展,人民生活水平的提高,全球工业化等带来的环境污染和能源需求问题也变得愈发严重。污水处理、空气净化、清洁能源生产等环境和能源相关问题逐渐引起了人们的广泛关注。光催化技术作为一个高级氧化过程,在环境污染和新能源发展方面具有巨大的潜在优势,已经被视为一种可替代性方法用于消除在污水、空气以及土壤中许多有毒有机化合物。在众多光催化半导体材料中,二氧化钛(TiO2)由于其良好的光催化活性、稳定的化学性、优异的量子效应、易得且价廉等优点,成为了最普遍使用的光催化材料。但是TiO2存在较大的禁带宽度和较差的电子-空穴分离能力等缺点,因而在一定程度上限制了其实际的光催化性能。碳材料具有良好的热稳定性、光电特性、机械性能、化学耐腐蚀性以及可控的孔结构和表面性能,因而被认为是TiO2的适宜载体,以提高其光催化性能。
碳材料中活性炭纤维、碳纳米管、石墨烯等常被作为复合材料载体。将TiO2与碳材料进行复合,一方面可以有效降低光催化材料中电子-空穴复合率,提高其光量子效应;另一方面可以形成光催化-吸附协同效应,并增多其表面光催化反应活性位点,从而显著提高其光催化性能。为此,二氧化钛/碳复合材料的制备及性能研究对于污水处理、空气净化、新能源生产等环境和能源具有重大意义。
但是目前TiO2的生产和应用还是聚焦单纯的纳米颗粒,而其与碳材料如活性炭纤维、碳纳米管、石墨烯的复合往往需要多步过程完成,繁琐复杂。
发明内容
本发明的目的在于提供一种二氧化钛纳米簇@碳球多级复合结构材料及其制备方法和应用,该多级复合结构材料为一步溶剂热合成,简单高效,且具有良好的有机污染物去除效果。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种二氧化钛纳米簇@碳球多级复合结构材料的制备方法,包括以下步骤:将二氯二茂钛、液态直链羧酸和液态直链烷烃混合,进行溶剂热反应,固液分离后,得到二氧化钛纳米簇@碳球多级复合结构材料。
优选的,所述液态直链羧酸包括甲酸、乙酸、正丙酸、正丁酸、正戊酸、正己酸、正庚酸和正辛酸中的一种或多种。
优选的,所述液态直链烷烃包括正戊烷、正己烷、正庚烷、正辛烷、正壬烷、正癸烷、正十一烷、正十二烷、正十三烷、正十四烷、正十五烷和正十六烷中的一种或多种。
优选的,所述二氯二茂钛、液态直链羧酸和液态直链烷烃的用量比为(0.1~1.5)g:(3~50)mL:(0.5~30)mL。
优选的,所述溶剂热反应的温度为180~300℃,时间为10~48h。
优选的,进行溶剂热反应前,还包括对混合后的体系依次进行超声和搅拌,所述超声的时间为10~60min,所述搅拌的时间为5~60min。
优选的,所述固液分离后,还包括对固液分离后的固体依次进行洗涤和干燥。
本发明提供了上述方案所述制备方法制备得到的二氧化钛纳米簇@碳球多级复合结构材料。
优选的,包括碳球和离散分布于碳球表面的二氧化钛纳米团簇。
本发明提供了上述方案所述二氧化钛纳米簇@碳球多级复合结构材料在处理有机污水中的应用。
本发明提供了一种二氧化钛纳米簇@碳球多级复合结构材料的制备方法,包括以下步骤:将二氯二茂钛、液态直链羧酸和液态直链烷烃混合,进行溶剂热反应,固液分离后,得到二氧化钛纳米簇@碳球多级复合结构材料。本发明采用二氯二茂钛为钛源,以液态直链羧酸为溶剂,以液态直链烷烃为混合溶剂,经一步溶剂热即可得到二氧化钛纳米簇@碳球多级复合结构材料,方法简单高效。
本发明将TiO2与直链羧酸生成的碳材料进行复合,一方面可以有效降低光催化材料中电子-空穴复合率,光催化活性的二氧化钛纳米结构完全暴露于材料表面,提高其光量子效应;另一方面可以形成光催化-吸附协同效应,并增多其表面光催化反应活性位点,从而显著提高其光催化性能。并将其应用到水体中有机污染物的去除,其吸附去除率约为61.5%,光催化去除率为37.4%,总的吸附-光催化协同去除率可达98.9%,具有良好的应用前景。
本发明的二氧化钛纳米簇@碳球多级复合结构材料的制备及性能研究对于污水处理、空气净化、新能源生产等环境和能源具有重大意义。
附图说明
图1为实施例1制得材料的电镜图、XRD图和热重曲线图,
其中:(a)为样品的透射电镜(TEM)图,(b)为局部放大的TEM图,(c)为样品的扫描电镜透射模式(STEM)图,(d)为样品局部放大的STEM图,(e)为XRD图,(f)为热重(TG)图;
图2为实施例1制得材料放大的高分辨率的透射电镜(HRTEM)图片;
图3为实施例2制得材料的TEM图;
图4为实施例3制得材料的TEM图;
图5为实施例1制得材料对有机污染物的去除效果图。
具体实施方式
本发明提供了一种二氧化钛纳米簇@碳球多级复合结构材料的制备方法,包括以下步骤:将二氯二茂钛、液态直链羧酸和液态直链烷烃混合,进行溶剂热反应,固液分离后,得到二氧化钛纳米簇@碳球多级复合结构材料。
在本发明中,未经特殊说明,所用原料均为本领域熟知的市售商品。
在本发明中,所述液态直链羧酸优选包括甲酸、乙酸、正丙酸、正丁酸、正戊酸、正己酸、正庚酸和正辛酸中的一种或多种;所述液态直链烷烃优选包括正戊烷、正己烷、正庚烷、正辛烷、正壬烷、正癸烷、正十一烷、正十二烷、正十三烷、正十四烷、正十五烷和正十六烷中的一种或多种。
在本发明中,所述二氯二茂钛、液态直链羧酸和液态直链烷烃的用量比优选为(0.1~1.5)g:(3~50)mL:(0.5~30)mL,更优选为(0.1~1.0)g:(5~25)mL:(2~20)mL。
本发明对所述混合的方式没有特殊要求,采用本领域技术人员熟知的混合方式即可。混合后进行溶剂热反应前,本发明优选还包括对混合后的体系依次进行超声和搅拌,所述超声的时间优选为10~60min,所述搅拌的时间优选为5~60min。本发明对所述超声的功率和搅拌的速率没有特殊要求,不引起液体飞溅即可。
完成所述混合后,本发明对混合后的体系进行溶剂热反应。在本发明中,所述溶剂热反应的温度优选为180~300℃,更优选为200~250℃,时间优选为10~48h,更优选为10~30h。在本发明中,所述溶剂热反应优选在反应釜中进行。本发明利用二氯二茂钛分子特性,即具有氯离子和茂环两种配体(这两种配体具有显著的键强度差异,水解难度差异以及亲疏水差异),在溶剂热过程中二氯二茂钛分子水解,首先是失去配体氯离子变成氢氧根配体,而茂环配体的解离相对需要较高的能量,反应动力学较慢,其中的疏水亲油的茂环通过与溶剂分子的相互作用决定纳米颗粒的形貌和结构。直链羧酸和残留的茂环可以生成二氧化钛表面的碳层,而直链烷烃可以调控与茂环间的相互作用,调控产品的形貌和结构,进而得到了二氧化钛纳米簇@碳球多级复合结构。
完成溶剂热反应后,本发明对所得体系进行固液分离。本发明对所述固液分离的方式没有特殊要求,采用本领域熟知的固液分离方式即可,具体的如离心。固液分离后,本发明优选还包括对固液分离后的固体依次进行洗涤和干燥。本发明优选采用乙醇和水进行洗涤,在本发明中,所述干燥的温度优选为60℃,干燥的时间优选为24h。
本发明提供了上述方案所述制备方法制备得到的二氧化钛纳米簇@碳球多级复合结构材料。在本发明中,所述二氧化钛纳米簇@碳球多级复合结构材料包括碳球和离散分布于碳球表面的二氧化钛纳米团簇;所述二氧化钛纳米簇@碳球多级复合结构材料的粒径优选为450~550nm,更优选为500nm;所述碳球的尺寸优选为150~250nm,更优选为200nm;所述二氧化钛纳米团簇的尺寸优选为100~200nm,更优选为150nm。在本发明中,所述二氧化钛纳米簇@碳球多级复合结构材料中碳球的质量分数优选为20~30%。
本发明提供了上述方案所述二氧化钛纳米簇@碳球多级复合结构材料在处理有机污水中的应用。本发明对所述应用的方式没有特殊要求,采用本领域熟知的应用方式即可。本发明对所述有机污水中有机污染物的具体种类没有特殊要求,本领域熟知的有机污水均可。本发明将TiO2与碳材料进行复合,一方面可以有效降低光催化材料中电子-空穴复合率,光催化活性的二氧化钛纳米结构完全暴露于材料表面,提高其光量子效应;另一方面可以形成光催化-吸附协同效应,并增多其表面光催化反应活性位点,从而显著提高其光催化性能。并将其应用到处理有机污水中,对水体中有机污染物的吸附去除率约为61.5%,光催化去除率为37.4%,总的吸附-光催化协同去除率可达98.9%,具有良好的应用前景。
下面结合实施例对本发明提供的二氧化钛纳米簇@碳球多级复合结构材料及其制备方法和应用进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。
实施例1
采用0.15g二氯二茂钛为钛源,以5mL正辛酸为溶剂,以3mL正庚烷为混合溶剂,混合后超声处理10min,搅拌20min,装入反应釜中220℃溶剂热反应24h,离心分离,乙醇和水洗涤,60℃烘箱干燥24h,最终获得二氧化钛纳米簇@碳球多级复合结构材料。
对实施例1制备的材料进行电镜观察,结果如图1中的(a)~(d)所示。其中,(a)为样品的透射电镜(TEM)图,(b)为局部放大的TEM图;(c)为样品的扫描电镜透射模式(STEM)图,(d)为样品局部放大的STEM图。
由图1的(a)~(d)可以看出,该样品具有清晰可辨的多级复合结构,其总体尺寸约为500nm。(a)和图(b)中沿外层色较深的离散分布的为二氧化钛纳米团簇,颜色较浅的中间部分为碳球。(c)和(d)中,颜色亮的区域为离散分布的二氧化钛纳米团簇,颜色较暗的为碳球。二氧化钛纳米团簇的尺寸约为150nm,碳球的尺寸约为200nm。每个多级复合结构中碳球表面均匀离散分布着约10个二氧化钛纳米团簇。
图1中(e)为样品的XRD图,结果显示,材料的衍射峰很好的匹配XRD标准卡片PDF-#040477,说明样品中二氧化钛的晶型为锐钛矿型。
图1中(f)为样品的热重(TG)图,从图中可以看出从约300℃到约600℃样品的失重约为25%,说明样品中碳的质量分数约为25%。
为了更进一步说明二氧化钛纳米簇@碳球多级复合结构材料的特点,本发明在图2中给出了样品的放大的高分辨率的透射电镜(HRTEM)图片,从图中可以清晰的看到锐钛矿相二氧化钛晶格条纹((101)的晶面间距为0.35nm)和其表面存在的碳包覆层。
实施例2
采用0.35g二氯二茂钛为钛源,以25mL正己酸为溶剂,以12mL正癸烷为混合溶剂,混合后超声处理20min,搅拌50min,装入反应釜中250℃溶剂热反应12h,离心分离,乙醇和水洗涤,60℃烘箱干燥24h,最终获得二氧化钛纳米簇@碳球多级复合结构材料。
对实施例2制得的材料进行透射电镜观察,结果如图3所示。图3显示,该样品具有清晰可辨的多级复合结构,其总体尺寸约为500nm。图中沿外层色较深的离散分布的为二氧化钛纳米团簇,颜色较浅的中间部分为碳球。
实施例3
采用0.2g二氯二茂钛为钛源,以10mL正戊酸为溶剂,以7mL正辛烷为混合溶剂,混合后超声处理40min,搅拌60min,装入反应釜中300℃溶剂热反应10h,离心分离,乙醇和水洗涤,60℃烘箱干燥24h,最终获得二氧化钛纳米簇@碳球多级复合结构材料。
对实施例3制得的材料进行透射电镜观察,结果如图4所示。图4显示,该样品具有清晰可辨的多级复合结构,其总体尺寸约为500nm。图中沿外层色较深的离散分布的为二氧化钛纳米团簇,颜色较浅的中间部分为碳球。
应用例1
将实施例1制得的二氧化钛纳米簇@碳球多级复合结构材料用于处理亚甲基蓝废水。应用的条件为:100mL亚甲基蓝溶液,浓度为15mg/L,多级复合结构材料用量为25mg,每间隔约30min取样2mL,离心分离出多级复合结构材料后,在664nm检测波长分析亚甲基蓝浓度,绘制亚甲基蓝降解曲线(Co为初始浓度,C为降解后浓度)。吸附性能(Dark)是在不开紫外灯情况下,暗箱测试的,光催化和吸附协同性能是在紫外光照情况下测试的(Light),测试条件为100W氙灯,加装AM1.5滤光片模拟太阳光。测试结果如图5所示。由图5可知,6h后,二氧化钛纳米簇@碳球多级复合结构材料的吸附去除率约为61.5%,光催化去除率为37.4%,总的吸附-光催化协同去除率可达98.9%,具有良好的有机污染物去除效果。
由以上实施例可知,本发明提供了一种二氧化钛纳米簇@碳球多级复合结构材料及其制备方法和应用,该多级复合结构材料为一步溶剂热合成,简单高效,且具有良好的有机污染物去除效果。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (7)
1.一种二氧化钛纳米簇@碳球多级复合结构材料的制备方法,其特征在于,包括以下步骤:将二氯二茂钛、液态直链羧酸和液态直链烷烃混合,进行溶剂热反应,固液分离后,得到二氧化钛纳米簇@碳球多级复合结构材料;所述二氯二茂钛、液态直链羧酸和液态直链烷烃的用量比为(0.1~1.5)g:(3~50)mL:(0.5~30)mL;所述溶剂热反应的温度为180~300℃,时间为10~48h;所述二氧化钛纳米簇@碳球多级复合结构材料包括碳球和离散分布于碳球表面的二氧化钛纳米团簇。
2.根据权利要求1所述的制备方法,其特征在于,所述液态直链羧酸包括甲酸、乙酸、正丙酸、正丁酸、正戊酸、正己酸、正庚酸和正辛酸中的一种或多种。
3.根据权利要求1所述的制备方法,其特征在于,所述液态直链烷烃包括正戊烷、正己烷、正庚烷、正辛烷、正壬烷、正癸烷、正十一烷、正十二烷、正十三烷、正十四烷、正十五烷和正十六烷中的一种或多种。
4.根据权利要求1所述的制备方法,其特征在于,进行溶剂热反应前,还包括对混合后的体系依次进行超声和搅拌,所述超声的时间为10~60 min,所述搅拌的时间为5~60 min。
5.根据权利要求1所述的制备方法,其特征在于,所述固液分离后,还包括对固液分离后的固体依次进行洗涤和干燥。
6.权利要求1~5任一项所述制备方法制备得到的二氧化钛纳米簇@碳球多级复合结构材料。
7.权利要求6所述二氧化钛纳米簇@碳球多级复合结构材料在处理有机污水中的应用。
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