CN114477108A - 一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法 - Google Patents
一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法 Download PDFInfo
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Abstract
一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,它涉及近红外光响应的纳米片制备方法。本发明要解决现有半金属纳米材料生物相容性差,光热稳定性低的问题,同时解决现有半金属纳米材料性质单一的问题。制备方法:一、采用高温有机溶液相法制备VSe2/Mn;二、在VSe2/Mn纳米片表面包覆壳聚糖。本发明用于近红外光响应的锰离子掺杂二硒化钒纳米片的制备。
Description
技术领域
本发明涉及近红外光响应的纳米片制备方法。
背景技术
在所有的癌症治疗中,非侵入性的治疗技术成为了人们关注的重点。光热疗法是一种可以精准靶向肿瘤,抑制其生长并且可以避开健康组织的治疗方式,光诱导的体温升高可以有效的减缓病原体的生长速度,相应的酶活性也会受到抑制。因此,光热疗法被认为是一种有前途的并且有效的非侵入性治疗方式。但是,用于光热治疗的外源性光热剂(PTA)由于有限的穿透深度,在肿瘤部位的过高温导致对健康细胞的损伤以及稍低温度下由癌细胞自身产生的热休克蛋白的抵制都限制了光热治疗的发展。
纳米材料的光热转化机制与其内部的电子或空穴有着极大的关系。大量电子在激光电场的驱动下集体运动引起等离子体共振效应,是纳米粒子的载流子将光能转化为热能。贵金属纳米材料(金、银、铂和钯)、碳基纳米材料由于良好的光吸收性和高光热转化效率而常被用作光热治疗剂。同时,细胞的氧化还原稳态使其维持正常的生理活动。氧化还原态的失衡会导致脂质、蛋白质和DNA的氧化损伤。癌细胞较正常细胞具有更高水平的氧化和还原物质,癌细胞内强大的细胞呼吸使活性氧的水平升高,GSH浓度增加,用来平衡这种氧化应激。这也导致了癌细胞对只针对增加活性氧治疗癌症的策略的耐受性更强。
目前绝大多数的光热剂具有生物难降解性,不稳定性以及在水中很差的分散性;还有一些光热剂虽然具有良好的光稳定性,低毒性等优势,但其光热转化效率较低,限制了他们在临床医学中的应用;因此选择载流子比金属少,但比半导体多的半金属纳米材料可能是一种比较好的解决方法,但目前有关半金属纳米材料在光热治疗上的应用依旧存在较差的光热稳定性;已制备的半金属纳米材料的功能单一,无法实现诊断与治疗相结合,导致半金属材料作为光热剂方面的报道极少,因此限制了它们在肿瘤治疗中的应用。
发明内容
本发明要解决现有半金属纳米材料生物相容性差,光热稳定性低的问题,同时解决现有半金属纳米材料性质单一的问题,而提供一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法。
一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,它是按以下步骤进行的:
一、采用高温有机溶液相法制备VSe2/Mn:
①、在磁力搅拌条件下,将十八烯和油胺混合均匀,加入四水合氯化锰,在真空状态下,加热至温度为100℃~120℃,并在温度为100℃~120℃的条件下,保温20min~30min;
②、关闭真空装置,通入氮气,在温度为100℃~120℃的条件下,注入氯化钒的十八烯溶液,并在温度为100℃~120℃的条件下,保温20min~30min;
③、将温度升温至300℃~320℃,并在温度为300℃~320℃的条件下,加入硒粉的十八烯溶液,再在温度为300℃~320℃的条件下,反应1h~1.5h,反应结束后自然冷却降至室温,离心收集并洗涤干燥,得到VSe2/Mn纳米片;
二、在VSe2/Mn纳米片表面包覆壳聚糖:
①、将壳聚糖与乙二胺四乙酸二钠溶解在水中,得到混合溶液;
②、将VSe2/Mn纳米片超声分散在水中,得到VSe2/Mn溶液;
③、将VSe2/Mn溶液滴入到混合溶液中,随后加入乙醇和戊二醛,室温下搅拌4h~4.5h,离心收集并洗涤干燥,得到VSe2/Mn-CS纳米片,即完成近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法。
本发明的有益效果是:
①、本发明制备了一种光热稳定性及生物相容性良好、近红外光响应的锰离子掺杂二硒化钒纳米片,具有较高的光热转换效率。
②、采用高温有机溶液相法,氯化钒作为钒源,硒粉作为硒源,氯化锰作为锰源,壳聚糖用于提高生物相容性,在高温下反应生成片状锰掺杂的硒化钒。
③、近红外光对人体组织具有较深的组织穿透深度,可达到5mm~10mm。所制得的片状锰掺杂硒化钒作为半金属性质的纳米材料,在近红外光的照射下,具有较高的光热转换效率(34.61%),由于硒化钒层间的硒-硒键具有弱的范德华力,在肿瘤微环境独特的条件下可以通过与谷胱甘肽形成Se-S键的方式来消耗谷胱甘肽,间接上调活性氧水平;在弱酸性条件下,展示出优异的过氧化物酶活性,有效的将过氧化氢转化为活性氧物质(羟基自由基)。因此,锰离子掺杂二硒化钒诊疗纳米片实现了光热和酶催化治疗结合的抗肿瘤治疗。
④、锰离子掺杂的硒化钒可作为磁共振成像造影剂、光热成像剂和光声成像对比剂用于实时监测肿瘤治疗过程。
因此,本发明的近红外光响应的锰离子掺杂二硒化钒纳米片制备方法简单、近红外光具有较深的组织穿透深度,兼具多模式成像(包括核磁共振、光声和光热成像)和治疗(光热和酶催化抗肿瘤治疗)等多功能于一体。
本发明用于一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法。
附图说明
图1为实施例一VSe2/Mn-CS纳米片合成过程示意图;
图2为实施例一步骤一制备的VSe2/Mn纳米片TEM成像图;
图3为实施例一步骤一制备的VSe2/Mn纳米片的EDS能谱图;
图4为实施例一步骤一制备的VSe2/Mn纳米片的元素映射图;
图5为X射线衍射谱图,1为实施例一制备的VSe2/Mn-CS纳米片,2为实施例一步骤一制备的VSe2/Mn纳米片,3为对比实验二制备的VSe2,4为对比实验一制备的VSe2;
图6为在90分钟内,VSe2和VSe2/Mn纳米片对谷胱甘肽降解的影响图,a为实施例一步骤一制备的VSe2/Mn纳米片,b为对比实验一制备的VSe2,1为0min,2为10min,3为20min,4为30min,5为50min,6为70min,7为90min;
图7为不同反应时间下VSe2和VSe2/Mn纳米片对亚甲基蓝降解的影响,a为实施例一步骤一制备的VSe2/Mn纳米片,b为对比实验一制备的VSe2,1为0min,2为1.5min,3为2min,4为2.5min,5为3min;
图8为实施例一步骤一制备的VSe2/Mn纳米片及实施例一制备的VSe2/Mn-CS纳米片分别溶解在不同生理介质中24小时后的图片;
图9为不同浓度的VSe2/Mn-CS纳米片溶液的紫外可见近红外吸收光谱图,1为250μg/mL,2为500μg/mL,3为1mg/mL;
图10为不同激光功率密度下,808nm激光照射不同浓度VSe2/Mn-CS纳米片溶液的不同光照时间的红外热成像照片;
图11为不同激光功率密度下,808nm激光照射500μg/mL的VSe2/Mn-CS纳米片溶液的温度变化曲线图,1为1W/cm2,2为0.8W/cm2,3为0.4W/cm2;
图12为激光功率密度为0.8W/cm2下,808nm激光照射500μg/mL的VSe2/Mn-CS纳米片溶液三次的升温降温曲线图;
图13为激光功率密度为0.8W/cm2下,808nm激光照射浓度为500μg/mL的VSe2/Mn-CS纳米片溶液的光照过程温度变化曲线和冷却过程变化曲线图,1为光照过程温度变化和冷却过程温度变化曲线,2为VSe2/Mn-CS纳米片溶液冷却时间随-ln(θ)的线性变化图。
具体实施方式
具体实施方式一:本实施方式一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,它是按以下步骤进行的:
一、采用高温有机溶液相法制备VSe2/Mn:
①、在磁力搅拌条件下,将十八烯和油胺混合均匀,加入四水合氯化锰,在真空状态下,加热至温度为100℃~120℃,并在温度为100℃~120℃的条件下,保温20min~30min;
②、关闭真空装置,通入氮气,在温度为100℃~120℃的条件下,注入氯化钒的十八烯溶液,并在温度为100℃~120℃的条件下,保温20min~30min;
③、将温度升温至300℃~320℃,并在温度为300℃~320℃的条件下,加入硒粉的十八烯溶液,再在温度为300℃~320℃的条件下,反应1h~1.5h,反应结束后自然冷却降至室温,离心收集并洗涤干燥,得到VSe2/Mn纳米片;
二、在VSe2/Mn纳米片表面包覆壳聚糖:
①、将壳聚糖与乙二胺四乙酸二钠溶解在水中,得到混合溶液;
②、将VSe2/Mn纳米片超声分散在水中,得到VSe2/Mn溶液;
③、将VSe2/Mn溶液滴入到混合溶液中,随后加入乙醇和戊二醛,室温下搅拌4h~4.5h,离心收集并洗涤干燥,得到VSe2/Mn-CS纳米片,即完成近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法。
本实施方式步骤一①中在真空状态下,保温至不再有气泡产生;步骤一②中通入氮气待稳定后升温;
本实施方式以氯化钒作为钒源,硒粉作为硒源,氯化锰作为锰源,壳聚糖用于提高生物相容性,通过高温液相法制备一种用于成像制导抗肿瘤治疗的近红外光响应的锰离子掺杂二硒化钒纳米片,其化学表达式为:VSe2/Mn-CS。
本实施方式的有益效果是:
①、本实施方式制备了一种光热稳定性及生物相容性良好、近红外光响应的锰离子掺杂二硒化钒纳米片,具有较高的光热转换效率。
②、采用高温有机溶液相法,氯化钒作为钒源,硒粉作为硒源,氯化锰作为锰源,壳聚糖用于提高生物相容性,在高温下反应生成片状锰掺杂的硒化钒。
③、近红外光对人体组织具有较深的组织穿透深度,可达到5mm~10mm。所制得的片状锰掺杂硒化钒作为半金属性质的纳米材料,在近红外光的照射下,具有较高的光热转换效率(34.61%),由于硒化钒层间的硒-硒键具有弱的范德华力,在肿瘤微环境独特的条件下可以通过与谷胱甘肽形成Se-S键的方式来消耗谷胱甘肽,间接上调活性氧水平;在弱酸性条件下,展示出优异的过氧化物酶活性,有效的将过氧化氢转化为活性氧物质(羟基自由基)。因此,锰离子掺杂二硒化钒诊疗纳米片实现了光热和酶催化治疗结合的抗肿瘤治疗。
④、锰离子掺杂的硒化钒可作为磁共振成像造影剂、光热成像剂和光声成像对比剂用于实时监测肿瘤治疗过程。
因此,本实施方式的近红外光响应的锰离子掺杂二硒化钒纳米片制备方法简单、近红外光具有较深的组织穿透深度,兼具多模式成像(包括核磁共振、光声和光热成像)和治疗(光热和酶催化抗肿瘤治疗)等多功能于一体。
具体实施方式二:本实施方式与具体实施方式一不同的是:步骤一③中所述的洗涤为用乙醇和环己烷的混合溶液进行洗涤,所述的乙醇与环己烷的体积比为(2.3~2.5):1;步骤二③中所述的洗涤为依次用水和乙醇洗涤,并重复洗涤三次。其它与具体实施方式一相同。
具体实施方式三:本实施方式与具体实施方式一或二之一不同的是:步骤一③与步骤二③中所述的离心具体为在转速为4000rpm~6000rpm的条件下,离心5min~10min。其它与具体实施方式一或二相同。
具体实施方式四:本实施方式与具体实施方式一至三之一不同的是:步骤一③与步骤二③中所述的干燥具体为在温度为60℃~65℃的条件下真空干燥过夜。其它与具体实施方式一至三相同。
具体实施方式五:本实施方式与具体实施方式一至四之一不同的是:步骤一①中所述的油胺与十八烯的体积比为(1~1.2):1;步骤一①中所述的四水合氯化锰的质量与十八烯的体积比为(10~12)mg:1mL;步骤一②中所述的氯化钒的十八烯溶液的浓度为1.9mmol/L~2mmol/L;步骤一②中所述的氯化钒的十八烯溶液与步骤一①中所述的十八烯的体积比为(0.2~0.3):1;步骤一③中所述的硒粉的十八烯溶液浓度为0.15g/mL~0.2g/mL;步骤一③中所述的硒粉的十八烯溶液与步骤一①中所述的十八烯的体积比为(0.2~0.3):1。其它与具体实施方式一至四相同。
具体实施方式六:本实施方式与具体实施方式一至五之一不同的是:步骤一②中通入氮气0.5h~1h。其它与具体实施方式一至五相同。
具体实施方式七:本实施方式与具体实施方式一至六之一不同的是:步骤一①中以升温速度为5℃/min~8℃/min,加热至温度为100℃~120℃。其它与具体实施方式一至六相同。
具体实施方式八:本实施方式与具体实施方式一至七之一不同的是:步骤二①中所述的壳聚糖的质量与水的体积比为(0.1~0.15)mg:1mL;步骤二①中所述的乙二胺四乙酸二钠与壳聚糖的质量比为(3~3.5):1。其它与具体实施方式一至七相同。
具体实施方式九:本实施方式与具体实施方式一至八之一不同的是:步骤二②中所述的VSe2/Mn溶液的浓度为0.1mg/mL~0.2mg/mL;步骤二③中所述的VSe2/Mn溶液与混合溶液的体积比为(0.05~0.1):1。其它与具体实施方式一至八相同。
具体实施方式十:本实施方式与具体实施方式一至九之一不同的是:步骤二③中所述的乙醇与VSe2/Mn溶液的体积比为(8~10):1;步骤二③中所述的戊二醛与VSe2/Mn溶液的体积比为(0.2~0.3):1。其它与具体实施方式一至九相同。
采用以下实施例验证本发明的有益效果:
实施例一,结合图1具体说明:
一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,它是按以下步骤进行的:
一、采用高温有机溶液相法制备VSe2/Mn:
①、在磁力搅拌条件下,将十八烯和油胺混合均匀,加入四水合氯化锰,在真空状态下,以升温速度为5℃/min~8℃/min,加热至温度为120℃,并在温度为120℃的条件下,保温20min;
②、关闭真空装置,通入氮气30min,在温度为120℃的条件下,注入氯化钒的十八烯溶液,并在温度为120℃的条件下,保温20min;
③、将温度升温至300℃,并在温度为300℃的条件下,加入硒粉的十八烯溶液,再在温度为300℃的条件下,反应1h,反应结束后自然冷却降至室温,离心收集并洗涤干燥,得到VSe2/Mn纳米片;
步骤一①中所述的油胺与十八烯的体积比为1:1;步骤一①中所述的四水合氯化锰的质量与十八烯的体积比为10mg:1mL;步骤一②中所述的氯化钒的十八烯溶液的浓度为2mmol/L;步骤一②中所述的氯化钒的十八烯溶液与步骤一①中所述的十八烯的体积比为0.2:1;步骤一③中所述的硒粉的十八烯溶液浓度为0.18g/mL;步骤一③中所述的硒粉的十八烯溶液与步骤一①中所述的十八烯的体积比为0.2:1;
二、在VSe2/Mn纳米片表面包覆壳聚糖:
①、将壳聚糖与乙二胺四乙酸二钠溶解在水中,得到混合溶液;
②、将VSe2/Mn纳米片超声分散在水中,得到VSe2/Mn溶液;
③、将VSe2/Mn溶液滴入到混合溶液中,随后加入乙醇和戊二醛,在转速为200r/min及室温的条件下,搅拌4h,离心收集并洗涤干燥,得到VSe2/Mn-CS纳米片,即完成近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法;
步骤二①中所述的壳聚糖的质量与水的体积比为0.14mg:1mL;步骤二①中所述的乙二胺四乙酸二钠与壳聚糖的质量比3.3:1;步骤二②中所述的VSe2/Mn溶液的浓度为0.1mg/mL;步骤二③中所述的VSe2/Mn溶液与混合溶液的体积比为0.07:1;步骤二③中所述的乙醇与VSe2/Mn溶液的体积比为9.4:1;步骤二③中所述的戊二醛与VSe2/Mn溶液的体积比为0.27:1;
步骤一③中所述的洗涤为用乙醇和环己烷的混合溶液进行洗涤,所述的乙醇与环己烷的体积比为7:3;步骤二③中所述的洗涤为依次用水和乙醇洗涤,并重复洗涤三次;
步骤一③与步骤二③中所述的离心具体为在转速为6000rpm的条件下,离心5min。
步骤一③与步骤二③中所述的干燥具体为在温度为60℃的条件下真空干燥过夜;
对比实验一:本对比实验与实施例一不同的是:步骤一①中不加入四水合氯化锰;步骤一③中将温度升温至300℃,并在温度为300℃的条件下,加入硒粉,再在温度为300℃的条件下,反应1h;省略步骤二,得到VSe2。其它与实施例一相同。
对比实验二:本对比实验与实施例一不同的是:步骤一①中不加入四水合氯化锰;步骤一③中将温度升温至320℃,并在温度为320℃的条件下,加入硒粉,再在温度为320℃的条件下,反应1h;省略步骤二,得到VSe2。其它与实施例一相同。
图2为实施例一步骤一制备的VSe2/Mn纳米片TEM成像图;由图可知,VSe2/Mn为片状结构,尺寸为220nm。
图3为实施例一步骤一制备的VSe2/Mn纳米片的EDS能谱图;由图可知,所制备的VSe2/Mn纳米片中含有V、Se和Mn等元素。
图4为实施例一步骤一制备的VSe2/Mn纳米片的元素映射图;由图可知,制备的VSe2/Mn为片状结构,结合图2结果表明成功的制备了VSe2/Mn纳米片。
图5为X射线衍射谱图,1为实施例一制备的VSe2/Mn-CS纳米片,2为实施例一步骤一制备的VSe2/Mn纳米片,3为对比实验二制备的VSe2,4为对比实验一制备的VSe2。由图可知,VSe2和VSe2/Mn的峰分别位于34.1°、29.2°、42.9°和14.5°,分别对应于VSe2标准卡片JCPDS,No.89-1641的(011)、(002)、(102)和(001)晶面。这一结果证实了在VSe2中掺杂Mn后,VSe2/Mn的晶型没有发生变化。VSe2/Mn-CS的宽峰位于23°,与壳聚糖的存在有关。且在不同的反应温度下制备VSe2,材料结构不会随温度的升高而改变,十八烯的沸点为314℃,为实验安全起见,后续试验选择反应温度为300℃。
通过检测谷胱甘肽酰化DTNB的吸光度降低来估计谷胱甘肽消耗。首先,将15mg实施例一步骤一制备的VSe2/Mn纳米片或对比实验一制备的VSe2与0.092g谷胱甘肽加入到30mL PBS缓冲溶液中,超声分散均匀后,室温下搅拌。在不同时间收集3mL上清液并加入DTNB(100μL,6mM),然后离心用于紫外吸收曲线测试,进而评估一段时间内VSe2和VSe2/Mn纳米片对谷胱甘肽的降解。
图6为在90分钟内,VSe2和VSe2/Mn纳米片对谷胱甘肽降解的影响图,a为实施例一步骤一制备的VSe2/Mn纳米片,b为对比实验一制备的VSe2,1为0min,2为10min,3为20min,4为30min,5为50min,6为70min,7为90min;由图a可知,随着反应时间的延长,DTNB在412nm处吸收峰强度下降,说明VSe2/Mn纳米片可以有效消耗谷胱甘肽。由图b可知,VSe2也可以消耗谷胱甘肽。对比图a和图b可知,VSe2/Mn增强了对谷胱甘肽的消耗。
检测VSe2和VSe2/Mn对亚甲基蓝降解的影响。首先,将1mg实施例一步骤一制备的VSe2/Mn纳米片或对比实验一制备的VSe2分散于6mL pH为6的含有过氧化氢的亚甲基蓝水溶液中(含有过氧化氢的亚甲基蓝水溶液中过氧化氢的浓度为50mM,亚甲基蓝的浓度为10μg/mL),超声分散均匀后,在室温下搅拌。为了避免光降解的影响,整个实验过程在避光条件下进行。在不同时间收集1mL溶液,通过离心收集上清液用于紫外吸收曲线测试,进而评估在反应不同时间VSe2/Mn和VSe2对亚甲基蓝降解的影响。
图7为不同反应时间下VSe2和VSe2/Mn纳米片对亚甲基蓝降解的影响,a为实施例一步骤一制备的VSe2/Mn纳米片,b为对比实验一制备的VSe2,1为0min,2为1.5min,3为2min,4为2.5min,5为3min;由图可知,随着反应时间的延长,亚甲基蓝水溶液在664nm处吸收峰强度下降,由图b可知,VSe2也可以降解亚甲基蓝。对比图a和图b可知,VSe2/Mn增强了对亚甲基蓝的消耗。说明VSe2/Mn纳米片在弱酸性条件下,有效的将过氧化氢转化为羟基自由基,展示出它的过氧化物酶活性。
对实施例一步骤一制备的VSe2/Mn纳米片及实施例一制备的VSe2/Mn-CS纳米片进行生物相容性测试,将1mg实施例一步骤一制备的VSe2/Mn纳米片或实施例一制备的VSe2/Mn-CS纳米片分别溶解在3mL四种不同生理介质(水、生理盐水、PBS缓冲溶液及DMEM培养基)中,结果如下:
图8为实施例一步骤一制备的VSe2/Mn纳米片及实施例一制备的VSe2/Mn-CS纳米片分别溶解在不同生理介质中24小时后的图片;由图可知,单独VSe2/Mn有明显的聚沉,而VSe2/Mn-CS在各种生理介质中较稳定,未出现明显的沉淀。表明VSe2/Mn-CS纳米片在生理环境中具有良好的稳定性,因此具有生物医学应用的潜力。
将实施例一制备的VSe2/Mn-CS纳米片溶解在水中,分别得到浓度为250μg/mL、500μg/mL及1mg/mL的VSe2/Mn-CS纳米片溶液,并进行如下测试:
图9为不同浓度的VSe2/Mn-CS纳米片溶液的紫外可见近红外吸收光谱图,1为250μg/mL,2为500μg/mL,3为1mg/mL;由图可知,VSe2/Mn-CS纳米片在600~900nm处有较宽且较强的近红外吸收。由此推测VSe2/Mn-CS纳米片是一种很有前途的近红外光响应的光热剂。
图10为不同激光功率密度下,808nm激光照射不同浓度VSe2/Mn-CS纳米片溶液的不同光照时间的红外热成像照片;图中十字标记处为溶液温度最高处;由图可知,在808nm激光照射下,溶液温度随激光功率密度和溶液浓度的增加而升高。证实VSe2/Mn-CS纳米片可以作为近红外光响应的光热剂。
图11为不同激光功率密度下,808nm激光照射500μg/mL的VSe2/Mn-CS纳米片溶液的温度变化曲线图,1为1W/cm2,2为0.8W/cm2,3为0.4W/cm2;由图可知,在808nm激光照射下,溶液温度随激光功率密度的增加而升高。
图12为激光功率密度为0.8W/cm2下,808nm激光照射500μg/mL的VSe2/Mn-CS纳米片溶液三次的升温降温曲线图。由图可知,激光照射VSe2/Mn-CS纳米片溶液三次后,最高温度无明显变化,证明VSe2/Mn-CS纳米片溶液具有良好的光热稳定性。
图13为激光功率密度为0.8W/cm2下,808nm激光照射浓度为500μg/mL的VSe2/Mn-CS纳米片溶液的光照过程温度变化曲线和冷却过程变化曲线图,1为光照过程温度变化和冷却过程温度变化曲线,2为VSe2/Mn-CS纳米片溶液冷却时间随-ln(θ)的线性变化图;由图可知,VSe2/Mn-CS纳米片冷却过程温度变化拟合曲线公式为:t=447.74ln(θ)+0.88(R2=0.996)。通过冷却过程温度变化曲线计算可知VSe2/Mn-CS纳米片的光热转换效率为34.61%。
Claims (10)
1.一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,其特征在于它是按以下步骤进行的:
一、采用高温有机溶液相法制备VSe2/Mn:
①、在磁力搅拌条件下,将十八烯和油胺混合均匀,加入四水合氯化锰,在真空状态下,加热至温度为100℃~120℃,并在温度为100℃~120℃的条件下,保温20min~30min;
②、关闭真空装置,通入氮气,在温度为100℃~120℃的条件下,注入氯化钒的十八烯溶液,并在温度为100℃~120℃的条件下,保温20min~30min;
③、将温度升温至300℃~320℃,并在温度为300℃~320℃的条件下,加入硒粉的十八烯溶液,再在温度为300℃~320℃的条件下,反应1h~1.5h,反应结束后自然冷却降至室温,离心收集并洗涤干燥,得到VSe2/Mn纳米片;
二、在VSe2/Mn纳米片表面包覆壳聚糖:
①、将壳聚糖与乙二胺四乙酸二钠溶解在水中,得到混合溶液;
②、将VSe2/Mn纳米片超声分散在水中,得到VSe2/Mn溶液;
③、将VSe2/Mn溶液滴入到混合溶液中,随后加入乙醇和戊二醛,室温下搅拌4h~4.5h,离心收集并洗涤干燥,得到VSe2/Mn-CS纳米片,即完成近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法。
2.根据权利要求1所述的一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,其特征在于步骤一③中所述的洗涤为用乙醇和环己烷的混合溶液进行洗涤,所述的乙醇与环己烷的体积比为(2.3~2.5):1;步骤二③中所述的洗涤为依次用水和乙醇洗涤,并重复洗涤三次。
3.根据权利要求1所述的一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,其特征在于步骤一③与步骤二③中所述的离心具体为在转速为4000rpm~6000rpm的条件下,离心5min~10min。
4.根据权利要求1所述的一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,其特征在于步骤一③与步骤二③中所述的干燥具体为在温度为60℃~65℃的条件下真空干燥过夜。
5.根据权利要求1所述的一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,其特征在于步骤一①中所述的油胺与十八烯的体积比为(1~1.2):1;步骤一①中所述的四水合氯化锰的质量与十八烯的体积比为(10~12)mg:1mL;步骤一②中所述的氯化钒的十八烯溶液的浓度为1.9mmol/L~2mmol/L;步骤一②中所述的氯化钒的十八烯溶液与步骤一①中所述的十八烯的体积比为(0.2~0.3):1;步骤一③中所述的硒粉的十八烯溶液浓度为0.15g/mL~0.2g/mL;步骤一③中所述的硒粉的十八烯溶液与步骤一①中所述的十八烯的体积比为(0.2~0.3):1。
6.根据权利要求1所述的一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,其特征在于步骤一②中通入氮气0.5h~1h。
7.根据权利要求1所述的一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,其特征在于步骤一①中以升温速度为5℃/min~8℃/min,加热至温度为100℃~120℃。
8.根据权利要求1所述的一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,其特征在于步骤二①中所述的壳聚糖的质量与水的体积比为(0.1~0.15)mg:1mL;步骤二①中所述的乙二胺四乙酸二钠与壳聚糖的质量比为(3~3.5):1。
9.根据权利要求1所述的一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,其特征在于步骤二②中所述的VSe2/Mn溶液的浓度为0.1mg/mL~0.2mg/mL;步骤二③中所述的VSe2/Mn溶液与混合溶液的体积比为(0.05~0.1):1。
10.根据权利要求1所述的一种近红外光响应的锰离子掺杂二硒化钒纳米片的制备方法,其特征在于步骤二③中所述的乙醇与VSe2/Mn溶液的体积比为(8~10):1;步骤二③中所述的戊二醛与VSe2/Mn溶液的体积比为(0.2~0.3):1。
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