CN109422296A - 产生单线态氧的多金属氧簇光敏化剂及其制备和应用 - Google Patents
产生单线态氧的多金属氧簇光敏化剂及其制备和应用 Download PDFInfo
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- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 43
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 16
- 239000001301 oxygen Substances 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 13
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims 2
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Abstract
水溶性杂金属单原子分散waugh型杂多酸(NH4)6[CoMo9O32]的制备方法,该方法可以可控高效的合成具有CoVI作为中心杂原子,同时具有可逆氧化还原n型无机半导体特征的纳米级多金属氧簇。该合成方法是以B型Anderson[NH4]3[Co(OH)6Mo6O18]杂多酸母体为反应原料,通过调节体系中pH及加入Na2MoO4及H2O2制备。本发明涉及的合成路线,其具有高度可控,反应条件简单易行,操控简单的优点。(NH4)6[CoMo9O32]作为光敏化剂具有可以被多种不同的光源激发条件下产生单线态氧的特点,并且产生单线态氧的效率约为传统机光敏剂NMB的1.25倍。
Description
技术领域
本发明属于光电催化技术领域,特别涉及产生单线态氧的一种产生单线态氧的多金属氧簇光敏化剂及其制备和应用。
背景技术
单线态氧(1O2)作为一种性质及其活泼的活性氧物种,在化学、生命及环境科学等领域都有着非常重要的作用,如广泛应用于对肿瘤的光动力治疗分析、水净化、选择性氧化反应等。产生1O2的方法有很多,除了在正常的生物代谢过程中产生外,通常方法是光敏化法和化学反应法。光敏作用涉及到一个光激发过程,就是要求存在一种吸收光的物质,即光敏剂(sens)。处于单线基态的光敏剂(sens),吸收光子后被激发到激发单线态(1sens);随后通过系间窜跃,形成激发三线态(3sens);最后激发三线态能使三线态氧激发为单线态,光敏剂变到基态又进行循环产生1O2。以上过程能够发生的前提条件为:光敏剂的激发三线态能量高于三线态氧的活化能,即0.97eV。
近年来,由于独特的催化性能,精确原子数可控合成的多金属氧簇受到了广泛的关注。特别是杂多酸可以将过渡金属引入到多酸簇合物骨架中,达到非常便捷的达到设计与调控多酸阴离子簇合物的相关性能。杂多酸阴离子簇合物的电子能带通常非连续和量子化分布,呈现无机半导体的性质。杂多酸阴离子簇合物中心杂原子的不同,表现出相应独特的光电及氧化还原的性质。同时随着拓扑结构的不同,杂多酸阴离子簇合物HOMO-LUMO带隙略有不同。从中可以发现,HOMO-LUMO带隙能量高于0.97eV的杂多酸阴离子簇合物可以用为一种新型的光敏化剂来产生单线态氧。相对于传统的光敏化剂(玫瑰红、荧光黄、亚甲基蓝、叶绿素和血卟啉),部分杂多酸阴离子簇合物具有更高的量子产率。近期,也有科研工作者发表的,杂多酸阴离子簇合物作为光敏剂用于太阳能染料敏化电池的制备。
发明内容
本发明的目的是提供了一种新型的水溶性产生单线态氧的光敏化剂。杂金属单原子分散的多金属氧簇光敏化剂二维材料合成高度可控,量子产率高,能够广泛应用于生物体及医疗方面。
本发明目的是通过以下方式实现的:
以(NH4)6[CoMo9O32]为例,通过化学探针吸光光度法来检测单线态氧,具体包括以下实验步骤:以B型Anderson[NH4]3[Co(OH)6Mo6O18]杂多酸母体为反应原料,将其置于50ml的烧杯中,溶于一定量的水体系中,接着用1M HCl将反应溶液体系调节到pH=4.0-5.0,然后90-100℃搅拌0.5-1小时,接着加入一定比例的Na2MoO4和H2O2,将反应溶液体系调节到pH=2.0-2.5剧烈搅拌回流2-3小时。然后通过冷却至室温,Waugh型的杂多酸簇合物(NH4)6[CoMo9O32]以晶体的形式析出。通过紫外可见分光光度计(UV-vis)和水溶性1O2化学探针3,3′-二氨基联苯胺(DAB)来观察(NH4)6[CoMo9O32]产生单线态氧的能力。其激发三重态和三线态氧分子发生电子交换,高效产生单线态氧。该光敏化剂水溶性,生物相容性好,稳定性高,同时容易被人体代谢降解可广泛应用于医疗及生物体内,尤其是为肿瘤的光动力治疗分析提供了更多的选择。杂多酸簇合物作为单线态氧产生的敏化剂,能够显著提高选择性氧化反应的转化率。
1.所述新型光敏化剂,HOMO-LUMO带隙为1.67eV。
2.所述新型光敏化剂,合成控制B型Anderson[NH4]3[Co(OH)6Mo6O18]杂多酸母体与Na2MoO4的摩尔比为1:3;与H2O2的摩尔比为1:0.5。
3.所述新型光敏化剂,合成反应在90-100℃下进行;
4.所述新型光敏化剂,1O2化学探针吸光光度法检测过程中,需加入DAB,控制其与(NH4)6[CoMo9O32]浓度。
5.所述新型光敏化剂,所述光敏剂在可见光或激光的激发条件下产生单线态氧。
本发明有益效果在于:
(1)本发明所研究的水溶性新型产生单线态氧的光敏化剂合成方法高度可控,简单易行、产率高。
(2)本发明所研究的水溶性新型产生单线态氧的光敏化剂在可见光及激光照射下均能有效地产生单线态氧。
(3)本发明所研究的水溶性新型产生单线态氧的光敏化剂相比于常用的有机染料,量子产率更高。
(4)本发明所研究的水溶性新型产生单线态氧的光敏化剂,可显著提高选择性氧化反应的转化率。
(5)本发明所研究的新型产生单线态氧的光敏化剂是水溶性的,生物相容性好,稳定性高同时容易被人体代谢降解可广泛应用于医疗及生物体内。
水溶性杂金属单原子分散waugh型杂多酸(NH4)6[CoMo9O32]的制备方法可以可控高效的合成具有CoVI作为中心杂原子,同时具有可逆氧化还原n型无机半导体特征的纳米级多金属氧簇。(NH4)6[CoMo9O32]可以作为光敏剂产生单线态氧而在在化学、生命及环境科学等领域有广阔的应用前景。
该合成方法是以B型Anderson[NH4]3[Co(OH)6Mo6O18]杂多酸母体为反应原料,通过调节体系中pH及加入Na2MoO4和H2O2制备。通过紫外可见分光光度计(UV-vis)和水溶性1O2化学探针3,3′-二氨基联苯胺(DAB)来检测(NH4)6[CoMo9O32]产生单线态氧的能力。
本发明涉及的合成路线,其具有高度可控,反应条件简单易行,操控简单的优点。(NH4)6[CoMo9O32]作为光敏化剂具有可以被多种不同的光源激发条件下产生单线态氧的特点,并且产生单线态氧的效率约为传统机光敏剂NMB的1.25倍。本发明所研究的新型产生单线态氧的光敏化剂是水溶性的,生物相容性好,稳定性高同时容易被人体代谢降解可广泛应用于医疗及生物体内。
附图说明
图1为实施例1(NH4)6[CoMo9O32]的制备路线;
图2为实施例1制备(NH4)6[CoMo9O32]的单晶结构及其B型Anderson[NH4]3[Co(OH)6Mo6O18]杂多酸母体原料;
图3为实施例1制备(NH4)6[CoMo9O32]的阴离子(左)及其酸化的B型Anderson型[NH4]3[Co(OH)6Mo6O18]杂多酸中间体(右)其单晶热椭球拓扑结构;
图4为实施例1制备(NH4)6[CoMo9O32]的红外光谱(FT-IR);
图5为实施例1制备(NH4)6[CoMo9O32]的紫外-可见吸收光谱图(UV-Vis);
图6为实施例1制备(NH4)6[CoMo9O32]的X射线光电子能谱全谱(XPS);
图7为实施例1制备(NH4)6[CoMo9O32]的紫外光电子能谱及HOMO-LUMO带隙;
图8为实施例1制备(NH4)6[CoMo9O32]的电化学循环伏安曲线(左)及莫特-肖特基特征曲线(右);
图9为实施例2中365nm激光器(a)及太阳光作为光源(b)(NH4)6[CoMo9O32]作为光敏催化剂,DAB作为水溶性1O2化学探针,吸光光度法随时间变化紫外-可见吸收光谱;
图10为实施例2中365nm激光器作为光源,新亚甲基蓝(NMB)作为有机光敏剂,DAB作为水溶性1O2化学探针,吸光光度法随时间变化紫外-可见吸收光谱;
图11为实施例2中365nm激光器,532nm激光器,太阳光和聚焦太阳光分别作为光源,(NH4)6[CoMo9O32]和NMB作为光敏催化剂,DAB作为水溶性1O2化学探针,1O2产生速率曲线;
图12为实施例2中365nm激光器,532nm激光器,太阳光和聚焦太阳光分别作为光源,(NH4)6[CoMo9O32]和NMB作为光敏催化剂,DAB作为水溶性1O2化学探针,1O2产生速率线性拟合方程。
具体实施方式
下面结合附图及具体实施案例来对本发明作进一步的详细说明。
实施例1:(NH4)6[CoMo9O32]的合成
称量1.097g的B型Anderson[NH4]3[Co(OH)6Mo6O18]杂多酸母体加入到50mL三口瓶中,加入10mL H2O,溶液为绿色。接着用1M HCl将反应溶液体系调节到pH=4.0-5.0(在此为4.5),然后回流搅拌0.5-1(在此为0.5)小时,溶液仍为绿色。此时加入0.615g Na2MoO4及1mlH2O2,将反应溶液体系调节到pH=2.0-3.0(在此为2.5)剧烈搅拌100℃回流2小时,溶液变成墨绿色。然后通过冷却至室温,Waugh型的杂多酸簇合物(NH4)6[CoMo9O32]以墨绿色晶体的形式析出。如果停止在回流搅拌0.5小时溶液仍为绿色的状态,不加入额外的Mo源及H2O2,则形成酸化的B型Anderson型[NH4]3[Co(OH)6Mo6O18]杂多酸中间体;
如图1为实施例1制备(NH4)6[CoMo9O32]的具体制备路线。
如图2为实施例1制备(NH4)6[CoMo9O32]的墨绿色单晶结构及其B型Anderson[NH4]3[Co(OH)6Mo6O18]杂多酸母体原料
如图3为实施例1制备(NH4)6[CoMo9O32]的阴离子(左)及其酸化的B型Anderson型[NH4]3[Co(OH)6Mo6O18]杂多酸中间体(右)其单晶热椭球拓扑结构
相关晶体数据
CCDC-1550103and 1550104包含相关晶体学数据,这些数据可以从剑桥晶体数据中心通过https://www.ccdc.cam.ac.uk/structures/免费获取
如图4为实施例1制备(NH4)6[CoMo9O32]的红外光谱图(FT-IR),(NH4)6[CoMo9O32]在952,3741,3502,3186,2544,2360,2136,2024,1609,1404,886,and 725波数有明显的特征吸收峰
如图5为实施例1制备(NH4)6[CoMo9O32]的紫外-可见吸收光谱图(UV-Vis),(NH4)6[CoMo9O32]在248,604nm处有明显的特征吸收峰。光学带隙为1.67eV
如图6实施例1制备(NH4)6[CoMo9O32]的X射线光电子能谱全谱(XPS),可以很明显看到(NH4)6[CoMo9O32]各个元素分别对应的X射线光电子能谱
如图7为实施例1制备(NH4)6[CoMo9O32]的紫外光电子能谱及HOMO-LUMO带隙,从价带区域的尖峰可以很明显看出Co4+3d5的电子价态,和1.67eV HOMO-LUMO带隙与观测到光学带隙一致。
如图8实施例1制备(NH4)6[CoMo9O32]的电化学循环伏安曲线(左)及莫特-肖特基特征曲线(右),(NH4)6[CoMo9O32]具有两个氧化还原过程,第一个过程是CoVI/CoIII氧化还原对,还原电势Epc(-154mV)和氧化电势Epa(29.4mV)具有一个电子电荷转移的过程。第二个过程是MoVI/MoV氧化还原对,还原电势Epc(-312mV)和氧化电势Epa(-227mV)具有一个电子电荷转移的过程。莫特-肖特基特征曲线曲线斜率为正,表明(NH4)6[CoMo9O32]具有n型半导体的性质。
实施例2:用吸光光度法来检测光源照射下的(NH4)6[CoMo9O32]作为光敏剂产生单线态氧
1mL水溶剂中分别加入10mg DAB作为水溶性1O2化学探针和2mg(NH4)6[CoMo9O32]作为光敏剂混合溶液。然后采用365nm的激光照射及太阳光作为光源,用紫外可见分光光度计检测DAB随照射时间长短特征吸收峰的变化。
如图9,DAB在单线态氧作用下发生选择性氧化生成3,3',4,4'-四硝基-1,1'-联苯,DAB在212nm有明显的紫外吸收特征峰,而3,3',4,4'-四硝基-1,1'-联苯没有特征吸收峰。基于此,DAB可以用来检测单线态氧的产生。在365nm激光照射DAB和(NH4)6[CoMo9O32]混合溶液后的紫外-可见吸收光谱图(UV-Vis)。从图中可以看出,随着照射时间的加长,212nm的特征峰逐渐减弱,15min后完全消失。说明,在365nm激光照射下,(NH4)6[CoMo9O32]的确作为光敏化剂产生单线态氧。同样的过程,使用太阳光作为光源,(NH4)6[CoMo9O32]的确作为光敏化剂也能产生单线态氧
如图10为实施例2中365nm激光器作为光源,新亚甲基蓝(NMB)作为有机光敏剂,DAB作为水溶性1O2化学探针,吸光光度法随时间变化紫外-可见吸收光谱,为了比较(NH4)6[CoMo9O32]作为光敏化剂产生单线态氧的效率,常规新亚甲基蓝(NMB)作为有机光敏剂与其作对比。在365nm激光照射DAB和NMB混合溶液后的紫外-可见吸收光谱图(UV-Vis)。从图中可以看出,随着照射时间的加长,212nm的特征峰逐渐减弱,15min后完全消失。
如图11为实施例2中365nm激光器,532nm激光器,太阳光和聚焦太阳光分别作为光源,(NH4)6[CoMo9O32]和NMB作为光敏催化剂,DAB作为水溶性1O2化学探针,1O2产生速率曲线,从图中可以看出,(NH4)6[CoMo9O32]作为光敏化剂产生单线态氧的效率高于传统机光敏剂NMB。产生单线态氧光源的效率从高到低分别是365nm激光器>532nm激光器>聚焦太阳光>太阳光。
如图12为实施例2中365nm激光器,532nm激光器,太阳光和聚焦太阳光分别作为光源,(NH4)6[CoMo9O32]和NMB作为光敏催化剂,DAB作为水溶性1O2化学探针,1O2产生速率线性拟合方程。对其不同产生单线态氧的效率进行了线性拟合,得到其准确1O2产生速率,并进行了量化比较。(NH4)6[CoMo9O32]作为光敏化剂产生单线态氧的效率约为传统机光敏剂NMB的1.25倍。
Claims (5)
1.产生单线态氧的多金属氧簇光敏化剂,其为Waugh型的杂多酸簇合物(NH4)6[XMo9O32],X为过渡金属元素包括Mn,Co等中的一种或二种。
2.一种权利要求1所述多金属氧簇光敏化剂的制备方法,具体过程如下:
以B型Anderson[NH4]3[X(OH)6Mo6O18]杂多酸母体为反应原料,X为过渡金属元素包括Mn,Co等中的一种或二种,将其置于容器中,溶于中水溶液体系中,用1M HCl将反应溶液体系调节到pH=4.0-5.0,然后90-100℃搅拌回流0.5-1小时,接着加入Na2MoO4和H2O2,将反应溶液体系调节到pH=2.0-2.5剧烈搅拌回流2-3小时;然后通过冷却至室温,Waugh型的杂多酸簇合物(NH4)6[CoMo9O32]以晶体的形式析出。
3.根据权利要求2所述的制备方法,其特征在于:合成控制B型Anderson[NH4]3[Co(OH)6Mo6O18]杂多酸母体与Na2MoO4的摩尔比为1:3;与H2O2的摩尔比为1:0.5。
4.一种权利要求1所述多金属氧簇光敏化剂在光源下产生单线态氧过程中的应用。
5.根据权利要求4所述应用,所述光源包括365nm激光器,532nm激光器,太阳光和聚焦太阳光中的一种或二种以上作为光源。
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CN110745781A (zh) * | 2019-10-30 | 2020-02-04 | 汕头大学 | 一种新型蓝光或近红外光激发小分子蒽醌电荷转移态产生单线态氧的方法 |
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