CN114561214A - 一种Mn掺杂的CISe@ZnSe核壳结构量子点及其制备方法和应用 - Google Patents
一种Mn掺杂的CISe@ZnSe核壳结构量子点及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种Mn掺杂的CISe@ZnSe核壳结构量子点及其制备方法和应用,该量子点包括核体和包覆在核体外的壳体,所述核体为Mn掺杂的CuInSe量子点,所述壳体为ZnSe。本发明的Mn掺杂的CISe@ZnSe核壳结构量子点自身稳定性良好,且能显著提高利用该量子点敏化的光电化学电池的光电性能,这主要归功于过渡金属Mn掺杂CISe体系后,创造了中间能级,不仅能提供额外电子注入光阳极,还能延缓电子空穴对的复合,促进电子空穴对分离,从而提高了光电化学电池的光电性能,其光阳极的饱和光电流达到2.9mA cm‑2。
Description
技术领域
本发明涉及光电化学电池技术领域,具体涉及一种Mn掺杂的CISe@ZnSe核壳结构量子点及其制备方法和应用。
背景技术
光电化学电池技术是一种直接利用光能,并将其转化为化学能的新型电池技术,通常由具备光活性的光电极、电解液以及电路组成,其结构简单,广泛应用于太阳能转化领域。光电化学电池制氢相比于先光伏发电再电解水制氢技术具备更低的器件成本,但其目前不能大规模投入实际应用,主要限制在含有Pb、Cd等重金属元素的量子点上,尽管量子点由于其具有能带结构可调、光谱宽吸收等特点,被广泛用于光电化学电池,但是大部分量子点含有铅镉等有毒金属,从绿色环保的角度上阻碍了这类技术的发展,而环境友好型的量子点材料的光电化学电池性能却普遍偏低,因此,迫切需要一种环境友好型的量子点材料以制备性能优良的光电化学电池。
发明内容
为了解决上述技术问题,本发明的目的是提供一种Mn掺杂的CISe@ZnSe核壳结构量子点及其制备方法和应用,以解决现有量子点不环保以及其制备的光电化学电池活性低的问题。
本发明解决上述技术问题的技术方案如下:提供一种Mn掺杂的CISe@ZnSe核壳结构量子点,该量子点包括核体和包覆在核体外的壳体,所述核体为Mn掺杂的CuInSe量子点,所述壳体为ZnSe。
本发明的有益效果为:本发明的Mn掺杂的CISe@ZnSe核壳结构量子点自身稳定性良好,且能显著提高利用该量子点敏化的光电化学电池的光电性能,这主要归功于过渡金属Mn掺杂CISe(CuInSe简称CISe)体系后,创造了中间能级,不仅能提供额外电子注入光阳极,还能延缓电子空穴对的复合,促进电子空穴对分离,从而提高了光电化学电池的光电性能,其光阳极的饱和光电流达到2.9mA cm-2。
发明机理:传统CISe@ZnSe能带排列结构为typeⅠ型,不利于光生电子空穴对的转移和分离,通过Mn掺杂引入中间能级,使得在核体的导带边和壳体导带边建立一个偏移,更有利于电子空穴对对的分离,减少电子空穴的复合,从而提高光电化学电池性能;此外,掺杂的Mn还能给导带提供更多电子,有利于电子注入电极。
在上述技术方案的基础上,本发明还可以做如下改进:
进一步,所述Mn掺杂的CISe@ZnSe核壳结构量子点的平均粒径为2-3nm。
进一步,所述Mn掺杂的CISe@ZnSe核壳结构量子点的平均粒径为2.3nm。
本发明还提供上述Mn掺杂的CISe@ZnSe核壳结构量子点的制备方法,包括以下步骤:
(1)将铜源、锰源、铟源、有机溶剂和有机配体混合后,于90-110℃条件下,脱气,然后滴加硒前驱溶液,再于100-180℃条件下,保温15-25min,得到核体溶液,即Mn掺杂的CuInSe量子点溶液;
(2)将核体溶液冷却至90-110℃时,滴加硬脂酸锌溶液,然后加热至180-220℃,并保温25-35min,冷却后,制得Mn掺杂的CISe@ZnSe核壳结构量子点。
进一步,步骤(1)中铜源、锰源、铟源的摩尔比为0.4-0.6:0.4-0.6:1,有机溶剂和有机配体的体积比为9-12:1,铜源和有机溶剂的摩尔体积比为(0.04-0.06)mmol:(4-6)mL,硒前驱溶液中硒和铜源的摩尔比为3-5:1。
进一步,步骤(1)中铜源、锰源、铟源的摩尔比为0.5:0.5:1,有机溶剂和有机配体的体积比为10:1,铜源和有机溶剂的摩尔体积比为0.05mmol:5mL,硒前驱溶液中硒和铜源的摩尔比为4:1。
进一步,步骤(1)中铜源为碘化亚铜、碘化铜或醋酸铜,锰源为醋酸锰或氯化锰,铟源为乙酸铟或硬脂酸铟。
进一步,步骤(1)中有机溶剂为十二硫醇,有机配体为油酸。
采用上述进一步技术方案的有益效果为:以正十二硫醇作为溶剂是为了降低Cu离子的活性,避免Cu离子在体系中生成大量的硒化铜,造成分相。
进一步,脱气是在真空状态下脱气20-40min完成脱气过程。
进一步,步骤(1)中硒前驱溶液通过将硒粉溶解于十八烯溶液中制得;其中,硒粉和十八烯溶液的摩尔体积比为(0.1-0.3)mmol:1mL。
进一步,硒粉和十八烯溶液的摩尔体积比为0.2mmol:1mL。
采用上述进一步技术方案的有益效果为:利用十八烯溶解的硒粉作为硒前驱溶液,能够成功地制作高质量核/壳纳米晶体中生长的硒前体,取代了昂贵、高毒性的硒磷化氢、双三甲基硅酰硒等硒前体,此外,采用的十八烯溶解的硒粉作为硒前驱溶液,还能降低CISe的成核温度,使其仅仅在100-180℃就能成核。
进一步,步骤(2)中硬脂酸锌溶液中硬脂酸锌和铜源的摩尔比为1-3:1。
进一步,硬脂酸锌溶液中硬脂酸锌和铜源的摩尔比为2:1。
进一步,步骤(2)中,硬脂酸锌溶液通过以下方法制得:将硬脂酸锌溶解于油胺和十八烯的混合溶液中,然后超声,制得;其中,混合溶液中硬脂酸锌的浓度为90-110mmol/L,油胺和十八烯的体积比为0.8-1.2:1。
进一步,硬脂酸锌溶液通过以下方法制得:将硬脂酸锌溶解于油胺和十八烯的混合溶液中,然后超声,制得;其中,混合溶液中硬脂酸锌的浓度为100mmol/L,油胺和十八烯的体积比为1:1。
进一步,步骤(2)中,冷却后的反应液经过纯化制得Mn掺杂的CISe@ZnSe核壳结构量子点,纯化的具体过程为:向冷却后的反应液中加入甲苯,离心,收集上清液,然后加入乙醇,离心,收集沉淀,再加入甲苯,制得。
本发明还提供上述Mn掺杂的CISe@ZnSe核壳结构量子点在制备光电化学电池方面的应用。
本发明具有以下有益效果:本发明的Mn掺杂的CISe@ZnSe核壳量子点显著提高了利用该量子点敏化的光电化学电池的光电性能,其光阳极的饱和光电流达到2.9mA cm-2,同时,具有优秀的光电流稳定性;而未掺杂Mn的量子点敏化的光阳极的饱和光电流仅为1.1mAcm-2。
附图说明
图1为实施例1制得的Mn掺杂的CISe@ZnSe核壳结构量子点的电镜照片;
图2为实施例1制得的量子点构建的光电化学电池的光电流测试图;
图3为对比例1制得的量子点构建的光电化学电池的光电流测试图;
图4为实施例制得的量子点构建光电化学电池的光电流稳定性测试图;
图5为实施例1和对比例1制得的量子点的能带排列示意图。
具体实施方式
以下结合附图对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
实施例1:
一种Mn掺杂的CISe@ZnSe核壳结构量子点,其制备方法包括以下步骤:
(1)合成Mn掺杂的CuInSe量子点溶液
将0.05mmol碘化亚铜、0.05mmol醋酸锰、0.1mmol乙酸铟、5mL十二硫醇和0.5mL油酸加入50mL的三颈烧瓶中,混合后,于真空和100℃条件下,脱气30min,然后滴加1mL硒前驱溶液,再于150℃条件下,保温20min,使量子点成核,得到核体溶液,即Mn掺杂的CuInSe量子点溶液;其中,硒前驱溶液通过将0.2mmol硒粉溶解于1mL十八烯溶液中制得;
(2)合成Mn掺杂的CISe@ZnSe核壳结构量子点
将核体溶液冷却至100℃时,滴加1mL硬脂酸锌溶液,然后加热至200℃,并保温30min,冷却后,将2mL反应液转移至离心管中,加入3mL甲苯,3000rpm离心3min,收集上清液,再加入6mL乙醇,12000rpm离心3min,收集沉淀,最后加入8mL甲苯,制得Mn掺杂的CISe@ZnSe核壳结构量子点;其中,硬脂酸锌溶液通过以下方法制得:将0.1mmol硬脂酸锌溶解于0.5mL油胺和0.5mL十八烯的混合溶液中,然后超声,制得。
实施例2:
一种Mn掺杂的CISe@ZnSe核壳结构量子点,其制备方法包括以下步骤:
(1)合成Mn掺杂的CuInSe量子点溶液
将0.05mmol碘化亚铜、0.06mmol醋酸锰、0.1mmol乙酸铟、4.5mL十二硫醇和0.5mL油酸加入50mL的三颈烧瓶中,混合后,于真空和90℃条件下,脱气40min,然后滴加1mL硒前驱溶液,再于100℃条件下,保温25min,使量子点成核,得到核体溶液,即Mn掺杂的CuInSe量子点溶液;其中,硒前驱溶液通过将0.3mmol硒粉溶解于1mL十八烯溶液中制得;
(2)合成Mn掺杂的CISe@ZnSe核壳结构量子点
将核体溶液冷却至90℃时,滴加1mL硬脂酸锌溶液,然后加热至180℃,并保温35min,冷却后,将2mL反应液转移至离心管中,加入3mL甲苯,3000rpm离心3min,收集上清液,再加入6mL乙醇,12000rpm离心3min,收集沉淀,最后加入8mL甲苯,制得Mn掺杂的CISe@ZnSe核壳结构量子点;其中,硬脂酸锌溶液通过以下方法制得:将0.11mmol硬脂酸锌溶解于0.5mL油胺和0.5mL十八烯的混合溶液中,然后超声,制得。
实施例3:
一种Mn掺杂的CISe@ZnSe核壳结构量子点,其制备方法包括以下步骤:
(1)合成Mn掺杂的CuInSe量子点溶液
将0.05mmol碘化亚铜、0.04mmol醋酸锰、0.1mmol乙酸铟、6mL十二硫醇和0.5mL油酸加入50mL的三颈烧瓶中,混合后,于真空和110℃条件下,脱气20min,然后滴加1mL硒前驱溶液,再于180℃条件下,保温15min,使量子点成核,得到核体溶液,即Mn掺杂的CuInSe量子点溶液;其中,硒前驱溶液通过将0.1mmol硒粉溶解于1mL十八烯溶液中制得;
(2)合成Mn掺杂的CISe@ZnSe核壳结构量子点
将核体溶液冷却至110℃时,滴加1mL硬脂酸锌溶液,然后加热至220℃,并保温25min,冷却后,将2mL反应液转移至离心管中,加入3mL甲苯,3000rpm离心3min,收集上清液,再加入6mL乙醇,12000rpm离心3min,收集沉淀,最后加入8mL甲苯,制得Mn掺杂的CISe@ZnSe核壳结构量子点;其中,硬脂酸锌溶液通过以下方法制得:将0.09mmol硬脂酸锌溶解于0.5mL油胺和0.5mL十八烯的混合溶液中,然后超声,制得。
对比例1
一种CISe@ZnSe核壳结构量子点,其制备方法包括以下步骤:
(1)合成CuInSe量子点溶液
将0.1mmol碘化亚铜、0.1mmol乙酸铟、5mL十二硫醇和0.5mL油酸加入50mL的三颈烧瓶中,混合后,于真空和100℃条件下,脱气30min,然后滴加1mL硒前驱溶液,再于150℃条件下,保温20min,使量子点成核,得到核体溶液,即CuInSe量子点溶液;其中,硒前驱溶液通过将0.2mmol硒粉溶解于1mL十八烯溶液中制得;
(2)合成CISe@ZnSe核壳结构量子点
将核体溶液冷却至100℃时,滴加1mL硬脂酸锌溶液,然后加热至200℃,并保温30min,冷却后,将2mL反应液转移至离心管中,加入3mL甲苯,3000rpm离心3min,收集上清液,再加入6mL乙醇,12000rpm离心3min,收集沉淀,最后加入8mL甲苯,制得CISe@ZnSe核壳结构量子点;其中,硬脂酸锌溶液通过以下方法制得:将0.1mmol硬脂酸锌溶解于0.5mL油胺和0.5mL十八烯的混合溶液中,然后超声,制得。
试验例
实施例1-3制得的Mn掺杂的CISe@ZnSe核壳结构量子点的表征以及性能基本相同,因此,取实施例1制得的Mn掺杂的CISe@ZnSe核壳结构量子点进行如下检测:
一、形貌特征
将实施例1制得的Mn掺杂的CISe@ZnSe核壳结构量子点利用扫描电子显微镜进行电镜扫描,结果见图1,由图1可知,本发明制得的Mn掺杂的CISe@ZnSe核壳结构量子点分布均匀,大小一致,平均粒径为2.3nm。
二、性能测试
将实施例1和对比例1制得的量子点,分别采用电泳沉积技术沉积到介孔膜二氧化钛光阳极上,以铂为对电极,以含3mol/mL氯化钾的Ag/AgCl电极为参比电极,以硫化钠/亚硫酸钠(pH=12.5)为电解液,构建光电化学电池。
1、使用标准的AM1.5G的太阳光模拟器作为光源,采用电化学工作站测量不同光照条件下光电化学电池的饱和光电流。结果见图2-3,由图2可知,本发明制得的量子点的光活性明显提升,其构建的光电化学电池的饱和光电流呈上升趋势,达到2.9mA cm-2;而由图3可知,对比例1制得的量子点,其量子点的光活性低,并且连续光照下,其构建的光电化学电池的光电流呈衰减趋势,饱和光电流仅为1.1mA cm-2。
2、使用标准的AM1.5G的太阳光模拟器作为光源,采用电化学工作站测量实施例1制得的量子点构建的光电化学电池在0.6V(vs.可逆氢电极RHE)恒定电压下的光电流稳定性。结果见图4,由图4可知,本发明制得Mn掺杂的CISe@ZnSe核壳结构量子点衰减幅度较小,其构建的光电化学电池在2h结束时还能保持原始光电流密度的50%以上,显示出较好的稳定性。
3、将实施例1和对比例1制得的量子点的能带排列利用光学表征数据模拟,结果见图5(左侧为对比例1,右侧为实施例1),由图5可知,在Mn掺杂CISe体系中,引入的中间能级不仅能提供额外电子注入电极,还能延缓电子空穴对的复合,促进电子空穴对分离。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,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 (10)
1.一种Mn掺杂的CISe@ZnSe核壳结构量子点,其特征在于,该量子点包括核体和包覆在核体外的壳体,所述核体为Mn掺杂的CuInSe量子点,所述壳体为ZnSe。
2.根据权利要求1所述的Mn掺杂的CISe@ZnSe核壳结构量子点,其特征在于,所述Mn掺杂的CISe@ZnSe核壳结构量子点的平均粒径为2-3nm。
3.根据权利要求1或2所述的Mn掺杂的CISe@ZnSe核壳结构量子点的制备方法,其特征在于,包括以下步骤:
(1)将铜源、锰源、铟源、有机溶剂和有机配体混合后,于90-110℃条件下,脱气,然后滴加硒前驱溶液,再于100-180℃条件下,保温15-25min,得到核体溶液,即Mn掺杂的CuInSe量子点溶液;
(2)将核体溶液冷却至90-110℃时,滴加硬脂酸锌溶液,然后加热至180-220℃,并保温25-35min,冷却后,制得Mn掺杂的CISe@ZnSe核壳结构量子点。
4.根据权利要求3所述的Mn掺杂的CISe@ZnSe核壳结构量子点的制备方法,其特征在于,步骤(1)中铜源、锰源、铟源的摩尔比为0.4-0.6:0.4-0.6:1,有机溶剂和有机配体的体积比为9-12:1,铜源和有机溶剂的摩尔体积比为(0.04-0.06)mmol:(4-6)mL,硒前驱溶液中硒和铜源的摩尔比为3-5:1。
5.根据权利要求3或4所述的Mn掺杂的CISe@ZnSe核壳结构量子点的制备方法,其特征在于,步骤(1)中铜源为碘化亚铜、碘化铜或醋酸铜,锰源为醋酸锰或氯化锰,铟源为乙酸铟或硬脂酸铟。
6.根据权利要求3或4所述的Mn掺杂的CISe@ZnSe核壳结构量子点的制备方法,其特征在于,步骤(1)中有机溶剂为十二硫醇,有机配体为油酸。
7.根据权利要求3或4所述的Mn掺杂的CISe@ZnSe核壳结构量子点的制备方法,其特征在于,步骤(1)中硒前驱溶液通过将硒粉溶解于十八烯溶液中制得;其中,硒粉和十八烯溶液的摩尔体积比为(0.1-0.3)mmol:1mL。
8.根据权利要求3所述的Mn掺杂的CISe@ZnSe核壳结构量子点的制备方法,其特征在于,步骤(2)中,硬脂酸锌溶液通过以下方法制得:将硬脂酸锌溶解于油胺和十八烯的混合溶液中,然后超声,制得;其中,混合溶液中硬脂酸锌的浓度为90-110mmol/L,油胺和十八烯的体积比为0.8-1.2:1。
9.根据权利要求3所述的Mn掺杂的CISe@ZnSe核壳结构量子点的制备方法,其特征在于,步骤(2)中,冷却后的反应液经过纯化制得Mn掺杂的CISe@ZnSe核壳结构量子点,纯化的具体过程为:向冷却后的反应液中加入甲苯,离心,收集上清液,然后加入乙醇,离心,收集沉淀,再加入甲苯,制得。
10.权利要求1或2所述的Mn掺杂的CISe@ZnSe核壳结构量子点在制备光电化学电池方面的应用。
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Title |
---|
RUI WANG ET AL: "Rational design of eco-friendly Mn-doped nonstoichiometric CuInSe/ZnSe core/shell quantum dots for boosted photoelectrochemical efficiency", NANO RES., vol. 15, no. 8, pages 7614 - 7621, XP037908553, DOI: 10.1007/s12274-022-4334-2 * |
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