CN115624983A - 一种二维Ti3C2-MoS2纳米异质结的制备方法 - Google Patents
一种二维Ti3C2-MoS2纳米异质结的制备方法 Download PDFInfo
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Abstract
本发明公开了一种二维Ti3C2‑MoS2纳米异质结的制备方法,包括如下步骤:通过超声剥离法制备单层或少层二维Ti3C2纳米片,然后用二甲基亚砜和聚二烯丙基二甲基氯化铵处理Ti3C2纳米片,增加其层间距并使其带正电荷;最后通过水热法在Ti3C2纳米片上原位生长MoS2纳米片,即制备得到二维Ti3C2‑MoS2纳米异质结。本发明的制备方法简单,工艺参数易控制,成本低廉,所制备的二维Ti3C2‑MoS2纳米异质结尺寸均一,水分散性良好,物理及化学稳定性良好,可在单一波长激光照射下同时具备优异的光热和光动力性能,同时其生物相容性好,化学惰性高,加之其二维的比表面积较大,可以负载多种类型的药物,实现疾病的多效协同治疗,在肿瘤治疗等生物医学及能源开发等领域具有广泛的应用前景。
Description
技术领域
本发明涉及纳米功能材料领域,具体地说,涉及一种Ti3C2-MoS2二维纳米异质结材料的制备技术。
背景技术
光热疗法(PTT)和光动力疗法(PDT)与传统化疗相比,具有低创伤、且不会产生放疗和化疗产生的毒副作用的优势,理论上能够实现对所有实体肿瘤进行治疗。
PTT是一种非侵入式的激光治疗方法,光敏剂通过靶向性识别技术选择性地富集在肿瘤区域,对肿瘤局部进行近红外光照后累积的光敏剂会把光能量转化为热。使肿瘤产生局部高温(大于42 ℃),特异性地“烧伤”肿瘤细胞,同时避免肿瘤部位周围健康组织细胞的损伤,达到治疗的目的。PDT是利用光动力效应进行治疗的一种新技术。这是一种有氧分子参与的伴随生物效应的光敏化反应。其过程是,特定波长的激光照射使组织吸收的光敏剂受到激发,激发态的光敏剂又把能量传递给周围的氧,使其生成性质活泼的活性氧,活性氧再与相邻的生物大分子发生氧化反应,从而产生细胞毒性作用,进而导致肿瘤细胞受损乃至死亡。PTT与PDT结合,通过光热协同增强光动力效果以提高肿瘤治疗效果。
MXenes是一类新型的二维纳米材料,可通过前驱体MAX相进行蚀刻处理得到,MAX相是一类三元层状化合物,其化学式可用Mn+1AnTx表示(n = 1~3),其中M代表过渡族金属,T指C或N,X指表面封端基团(如-O、-OH、-F、-Cl等),A代表III、IV主族元素。近年来,二维MXenes纳米材料因其独特的理化和生物学特性被广泛应用于生物医学等多功能纳米平台的构建。在已发现的MXenes材料中,Ti3C2因其成本低、性能好、光热和光动力性能优良而备受关注。然而,大量暴露的金属原子(如Ti原子)和较高的表面能使得Ti3C2材料在热力学上十分不稳定,易被氧化。此外,在制备Ti3C2纳米材料时,常用的水热、溶剂热或退火工艺会加剧Ti3C2的氧化。例如,在水热过程中,由于溶解氧的存在使Ti3C2容易被氧化形成TiO2纳米粒子,导致其结构和性能改变。而且在单一激发波长下,无法同时实现光热和光动力效应。为了提高Ti3C2的稳定性及光学性质,可对其进行元素掺杂或与其他材料进行复合,利用两者的协同作用来提高其稳定性,同时可提高其光催化活性。此外,Ti3C2 MXene具有金属性能,可与其他半导体形成肖特基异质结,并通过异质结界面捕获和转移光生电子,有效促进电子和空穴的分离。
近年来,MoS2作为一种紫外及可见光响应的二维金属材料,由于其较窄的禁带宽度(约1.8 eV)、比表面积大、化学稳定性好及制备方法简单等优点被广泛用于生物医学、晶体管、催化剂、润滑剂等领域的研究。同时纳米结构的MoS2因具有更大的比表面积,能进一步增强其在可见光下的催化活性。然而,由于紫外及可见光的组织穿透深度有限,光生载流子的快速复合导致其光催化活性效率低,限制了其在生物医学领域的应用和发展。
发明内容
针对上述问题,本发明提供了一种Ti3C2-MoS2二维纳米异质结的制备方法。本发明以二维MXenes材料Ti3C2纳米片为基体,在其表面原位生长MoS2形成Ti3C2-MoS2纳米异质结,该制备方法简单,参数易于控制,适合大规模生产,所制备的二维Ti3C2-MoS2纳米异质结尺寸均一、分散性良好,同时具备在单一激发波长照射下良好的光热和光动力性能,在光催化、疾病治疗、能源开发等领域具有良好的应用前景。
为了达到上述目的,本发明采用的技术方案为:
一种二维Ti3C2-MoS2纳米异质结的制备方法,包括如下步骤:通过超声剥离法制备单层或少层二维Ti3C2纳米片,然后用二甲基亚砜(DMSO)和聚二烯丙基二甲基氯化铵(PDDA)处理Ti3C2纳米片,增加其层间距并使其带正电荷;最后通过水热法在Ti3C2纳米片上原位生长MoS2纳米片,即制备得到二维Ti3C2-MoS2纳米异质结。
为了增大Ti3C2纳米片的层间隙和改变其表面电荷,使其带正电,用DMSO和PDDA对Ti3C2纳米片进行修饰。插层是改性粘土的一种重要方法,MXenes类材料从结构和性能上看属于“导电亲水粘土”,因此我们通过DMSO增加Ti3C2层间距,并利用原位生长的MoS2纳米片作为表面屏障来隔离溶解氧稳定Ti3C2材料。同时MoS2纳米片与Ti3C2纳米片可形成Ti3C2-MoS2异质结结构,实现光生载流子的快速分离,可以有效改善MoS2带隙小、光生电子与空穴易复合的问题,大大提高活性氧的产生效率。
作为优选的,在上述的Ti3C2-MoS2二维纳米异质结的制备方法中,具体包括下列步骤:
(1)Ti3C2纳米片的制备:取块状Ti3C2,加入25%四丙基氢氧化铵(TPAOH),室温下避光搅拌,置于超声清洗器中超声,产物分别用去离子水和乙醇洗涤多次除去溶剂四丙基氢氧化铵,冷冻干燥,即得Ti3C2纳米片;
(2)PDDA修饰的Ti3C2的制备:取Ti3C2纳米片加入到PDDA和DMSO的混合溶液中,搅拌,沉淀用去离子水-乙醇洗涤多次,离心收集产物,即得PDDA修饰的Ti3C2纳米片;
(3)Ti3C2-MoS2二维纳米异质结的制备:取上述制备的PDDA修饰的Ti3C2纳米片,置于去离子水中,超声分散均匀后,加入四硫钼酸铵,继续超声处理5~10 min,之后加入二甲基甲酰胺(DMF)中,将其转移至不锈钢高压反应釜中,于150~250℃的马弗炉反应8~24 h,沉淀离心,去离子水洗涤后,冷冻干燥,即得二维Ti3C2-MoS2纳米异质结。
作为优选的,在上述的Ti3C2-MoS2二维纳米异质结的制备方法中,步骤(1)中所述搅拌的时间为12~48 h,所述超声的时间为24~72 h。
作为优选的,在上述的Ti3C2-MoS2二维纳米异质结的制备方法中,步骤(2)所述DMSO 和PDDA 的混合溶液中DMSO与PDDA体积比范围为15~20:1;所述搅拌的时间为12~24h;所述洗涤的次数为3~6次,所述离心的速度为8000~13000 rpm/min,时间为10~30 min。
作为优选的,在上述的Ti3C2-MoS2二维纳米异质结的制备方法中,步骤(3)所述四硫钼酸铵与Ti3C2的质量比范围1:2~5:1;所述离心的速度为10000~13000 rpm/min,离心时间为10~30 min。
与现有技术相比,本发明具有如下有益效果:
(1)本发明用热溶剂法在Ti3C2纳米片表面原位生长MoS2纳米片,所制备的二维纳米异质结横向尺寸为50~200 nm,厚度为2~6 nm。二维Ti3C2与MoS2之间能形成较好的接触,且由于Ti3C2本身的金属特性,有利于光生电子快速向Ti3C2转移,因此有益于提高电子-空穴对的分离效率,提高载流子的转移速率,从而有利于提高其光催化性能。同时增强非辐射去激发过程,产生更多热量,提高其光热性能。
(2)本发明的制备方法简单,工艺参数易控制,成本低廉,所制备的二维Ti3C2-MoS2纳米异质结尺寸均一,水分散性良好,物理及化学稳定性良好,可在单一波长激光照射下同时具备优异的光热和光动力性能,同时其生物相容性好,化学惰性高,加之其二维的比表面积较大,可以负载多种类型的药物,实现疾病的多效协同治疗,在肿瘤治疗等生物医学及能源开发等领域具有广泛的应用前景。
附图说明
图1为实施例1的碳化钛(Ti3C2)纳米片的透射电镜图。
图2为实施例1的碳化钛-二硫化钼(Ti3C2-MoS2)纳米异质结的透射电镜图。
图3为实施例1的水、Ti3C2纳米片及Ti3C2-MoS2二维纳米异质的光热升温-时间变化图;
图4为实施例1的Ti3C2纳米片及Ti3C2-MoS2二维纳米异质的在808 nm激光照射下产生的活性氧对DPBF降解图。
具体实施方式
实施例1:二维Ti3C2-MoS2纳米异质结的制备
(1)Ti3C2纳米片的制备:首先用25%的四丙基氢氧化铵(TPAOH)溶液对块状Ti3C2粉末进行预处理。具体过程为:称50 mg块状Ti3C2,加入至10 mL的TPAOH,室温下避光搅拌24h,置于超声清洗器中超声48 h,产物分别用去离子水和乙醇洗涤3~5次除去溶剂TPAOH,冷冻干燥,即得少层的二维Ti3C2纳米片。
(2)PDDA修饰的Ti3C2的制备:为了增大Ti3C2纳米片的层间隙和改变其表面电荷,使其带正电,用DMSO和PDDA对Ti3C2纳米片进行修饰。称取Ti3C2纳米片10 mg加入到10 mL含有10% PDDA的DMSO溶液,搅拌24 h,沉淀用去离子水-乙醇洗涤3~5次,13000 rpm/min离心10 min,收集产物,即得PDDA修饰的Ti3C2纳米片。
(3)Ti3C2-MoS2二维纳米异质结的制备:称取10 mg上述制备的PDDA修饰的Ti3C2纳米片,置于10 mL去离子水中,超声5 h分散均匀后,加入10 mg四硫钼酸铵((NH4)2MoS4),继续超声处理10 min,之后加入15 mL的DMF中,将其转移至不锈钢高压反应釜中,于200℃的马弗炉反应20 h,沉淀离心,去离子水洗涤3~5次后,冷冻干燥24 h,即得Ti3C2-MoS2二维纳米异质结。
图1表明:本实施例步骤(1)得到的Ti3C2纳米片为二维平面结构,横向尺寸为100nm左右,尺寸均一,因此具有较大的比表面积。
图2表明:本实施例得到的Ti3C2-MoS2纳米异质结为二维结构,横向尺寸为120 nm左右,因此具有较大的比表面积。
图3表明:本实施例得到的Ti3C2-MoS2纳米异质结在808 nm激光照射下具有优异的光热性能,其光热性能高于单一Ti3C2的光热性能。
图4表明:本实施例得到的Ti3C2-MoS2纳米异质结在808 nm激光照射下也具有较好的光动力性能,其性能高于单一Ti3C2的光动力性能。
实施例2:二维Ti3C2-MoS2纳米异质结的制备
(1)Ti3C2纳米片的制备:称取25 mg块状Ti3C2,加入5 mL 25%的TPAOH,室温下避光搅拌24 h,置于超声清洗器中超声72 h,产物分别用去离子水和乙醇洗涤多次除去溶剂TPAOH,冷冻干燥,即得Ti3C2纳米片。
(2)PDDA修饰的Ti3C2的制备:为了增大Ti3C2纳米片的层间隙和改变其表面电荷,使其带正电,用DMSO和PDDA对Ti3C2纳米片进行修饰。称取Ti3C2纳米片5 mg加入到5 mL含有5% PDDA的DMSO溶液,搅拌12 h,沉淀用去离子水-乙醇洗涤3~5次,离心收集产物,即得PDDA修饰的Ti3C2纳米片。
(3)Ti3C2-MoS2二维纳米异质结的制备:称取10 mg上述制备的PDDA修饰的Ti3C2纳米片,置于10 mL去离子水中,超声5 h后分散均匀后,加入15 mg四硫钼酸铵((NH4)2MoS4),继续超声处理10 min,之后加入15 mL的DMF中,将其转移至不锈钢高压反应釜中,于200℃的马弗炉反应15 h,沉淀离心,去离子水洗涤后,冷冻干燥24 h,即得Ti3C2-MoS2二维纳米异质结。本实施例制备得到的Ti3C2-MoS2二维纳米异质结为深褐色粉末,在近红外激光照射下具有较好的光热和光动力性能。
实施例3:二维Ti3C2-MoS2纳米异质结的制备
(1)Ti3C2纳米片的制备:称取40 mg块状Ti3C2,加入8 mL 25%的TPAOH,室温下避光搅拌48 h,置于超声清洗器中超声72 h,产物分别用去离子水和乙醇洗涤多次除去溶剂TPAOH,冷冻干燥,即得Ti3C2纳米片。
(2)PDDA修饰的Ti3C2的制备:为了增大Ti3C2纳米片的层间隙和改变其表面电荷,使其带正电,用DMSO和PDDA对Ti3C2纳米片进行修饰。称取Ti3C2纳米片10 mg加入到10 mL含有5% PDDA的DMSO溶液,搅拌24 h,沉淀用去离子水-乙醇洗涤3~5次,离心收集产物,即得PDDA修饰的Ti3C2纳米片。
(3)Ti3C2-MoS2二维纳米异质结的制备:称取10 mg上述制备的PDDA修饰的Ti3C2纳米片,置于10 mL去离子水中,超声分散均匀后,加入20 mg四硫钼酸铵((NH4)2MoS4),继续超声处理10 min,之后加入20 mL的DMF中,将其转移至不锈钢高压反应釜中,于200℃的马弗炉反应24 h,沉淀离心,去离子水洗涤后,冷冻干燥24 h,即得Ti3C2-MoS2二维纳米异质结。本实施例制备得到的Ti3C2-MoS2二维纳米异质结为深褐色粉末,在近红外激光照射下具有较好的光热和光动力性能。
Claims (5)
1.一种二维Ti3C2-MoS2纳米异质结的制备方法,其特征在于包括如下步骤:通过超声剥离法制备单层或少层二维Ti3C2纳米片,然后用二甲基亚砜和聚二烯丙基二甲基氯化铵处理Ti3C2纳米片,增加其层间距并使其带正电荷;最后通过水热法在Ti3C2纳米片上原位生长MoS2纳米片,即制备得到二维Ti3C2-MoS2纳米异质结。
2.根据权利要求1所述的Ti3C2-MoS2二维纳米异质结的制备方法,其特征在于包括下列步骤:
(1)Ti3C2纳米片的制备:取块状Ti3C2,加入25%四丙基氢氧化铵,室温下避光搅拌,置于超声清洗器中超声,产物分别用去离子水和乙醇洗涤多次除去溶剂四丙基氢氧化铵,冷冻干燥,即得Ti3C2纳米片;
(2)PDDA修饰的Ti3C2的制备:取Ti3C2纳米片加入到PDDA和DMSO的混合溶液中,搅拌,沉淀用去离子水-乙醇洗涤多次,离心收集产物,即得PDDA修饰的Ti3C2纳米片;
(3)Ti3C2-MoS2二维纳米异质结的制备:取上述制备的PDDA修饰的Ti3C2纳米片,置于去离子水中,超声分散均匀后,加入四硫钼酸铵,继续超声处理5~10 min,之后加入二甲基甲酰胺(DMF)中,将其转移至不锈钢高压反应釜中,于150~250℃的马弗炉反应8~24 h,沉淀离心,去离子水洗涤后,冷冻干燥,即得二维Ti3C2-MoS2纳米异质结。
3.根据权利要求2所述的制备方法,其特征在于,步骤(1)中所述搅拌的时间为12~48h,所述超声的时间为24~72 h。
4.根据权利要求2所述的制备方法,其特征在于步骤(2)中,所述DMSO 和PDDA 的混合溶液中DMSO与PDDA体积比范围为15~20:1;所述搅拌的时间为12~24 h;所述洗涤的次数为3~6次,所述离心的速度为8000~13000 rpm/min,时间为10~30 min。
5.根据权利要求2所述的制备方法,其特征在于步骤(3)中,
所述四硫钼酸铵与Ti3C2的质量比范围1:2~5:1;所述离心的速度为10000~13000 rpm/min,离心时间为10~30 min。
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