CN114106039B - 一种银纳米团簇及其制备方法 - Google Patents
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- 238000002360 preparation method Methods 0.000 title abstract description 16
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- 239000007788 liquid Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
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- 239000011241 protective layer Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
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- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 description 1
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- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
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- 150000003573 thiols Chemical class 0.000 description 1
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
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Abstract
高核银硫纳米团簇因其多样的结构、相对低廉的价格以及在催化、生物、医学、新能源等领域具有较大的潜在应用前景,目前制备方法中,硫醇配体、膦配体、炔配体或其组合是构筑高核银硫纳米团簇的重要有机配体;本发明通过[AgSFuran]n、dpppt与S(SiMe3)2,制备出典型的“核‑壳”结构[Ag194S60(SFuran)72(dpppt)8],结构稳定性好,制备方法简单、有效,无需复杂的反应条件,同时晶体产率高,具有较大的规模生产价值和应用价值。
Description
技术领域
本发明涉及纳米团簇领域,具体涉及一种银纳米团簇及其制备方法。
背景技术
金属纳米团簇可看作是在配体的保护下由数个到几百个金属原子聚集而成的超小金属纳米粒子。该超小尺寸与电子费米波长相当,在该尺寸范围内,物质经历着从微观原子、分子向宏观凝聚态的转变,因此金属纳米团簇往往呈现出许多和宏观、微观截然不同的独特性质。
高核银纳米团簇因其多样的结构、相对低廉的价格以及在催化、生物、医学、新能源等领域具有较大的潜在应用前景而受到化学家们的广泛关注。高核银纳米团簇的合成过程涉及到多组分的组装,可以合成出不同构型的纳米团簇。如[CO3@Ag20(tBuS)10(CH3CO2)8(DMF)4]、[Ag262S100(StBu)62(dppb)6]、[Ag352S128(StC5H11)96]、[Ag490S188(StC5H11)114]等不同组成的银团簇,也都取得了不同的应用效果。然而,银团簇的合成结构与诸多因素有关,不同配体、不同方法得到的团簇结构差异明显。现有技术中很多主要以硫醇配体、膦配体、炔配体或其组合为保护配体的原子精确的币金属纳米团簇的制备方法普遍过程繁琐、周期长、产率低、不适合大批量生产的问题。
Fenske在合成[Ag344S124(StBu)96]时,(Fenske D , Anson C E , A Eichhöfer,et al. Syntheses and Crystal Structures of [Ag123S35(StBu)50] and [Ag344S124(StBu)96],Angewandte Chemie, 2010, 44(33):5242-5246)通过[AgStBu]n + dppxy+ S(SiMe3)2合成银硫簇,但其合成时间长,产率低;Anson (Anson C , Eichhfer A , Issac I, et al. Synthesis and Crystal Structures of the Ligand‐Stabilized SilverChalcogenide Clusters [Ag154Se77(dppxy)18], [Ag320(StBu)60S130(dppp)12], [Ag352S128(StC5H11)96], and [Ag490S188(StC5H11)114][J]. Angewandte Chemie InternationalEdition, 2008, 47(7))[Ag352S128(StC5H11)96] 由 [AgStC5H11]n + dppbp+ S(SiMe3)2 在四氢呋喃中合成, 3-4周之后得到晶态目标产物,晶态产物的低产率限制了其大规模应用。
因此,针对上述问题,本发明的一种银纳米团簇,其制备方法简单、高效,收率高,具有较好的推广应用价值。
发明内容
本发明的银纳米团簇是一种高核银纳米团簇,其具体的技术方案为:一种银纳米团簇及其制备方法,所述的银纳米团簇为簇合物 Ag194,所述簇合物Ag194的结构式为[Ag194S60(SFuran)72(dpppt)8],所述簇合物 Ag194属于三斜晶系,P1 ̅空间群;所述簇合物Ag194分为两个不对称结构单元,所述不对称结构单元的分子式为[Ag97S30(SFuran)36(dpppt)4];晶格参数为α=76.710(1) °,β=62.250(1)°,γ=62.530(1)°。
具体地,在所述簇合物Ag194中,[Ag194S60(SFuran)72] 核单元的直径约为 2.4 nm,即S15 至 S15ˊ的距离;
在所述不对称结构单元[Ag97S30(SFuran)36(dpppt)4]中,97个Ag原子存在线型配位、平面三角形配位、畸变四面体配位三种配位模式;所述线型配位Ag原子为29个,所成键角介于 158.3o – 176.1o 之间;所述平面三角形配位Ag原子为54 个,每个所述平面三角形配位Ag原子与对应的配位原子构成各个所述 Ag原子为中心的三角,所述三角之和均在360o 左右;所述畸变四面体配位原子为14个;
在所述不对称结构单元[Ag97S30(SFuran)36(dpppt)4]中,S包括无机硫 S2ˉ和有机硫– SFuran两种存在形式,所述不对称结构单元中S的桥联模式有七种,七种桥联模式具体为:七种桥联模式具体为:μ2:6 个 S、μ3:30 个 S、μ4:3 个 S 、μ5:18 个 S、μ6:6 个 S、μ7 :2 个 S 和 μ8:1 个 S ;
所述的七种桥联模式中,μ2-S-Ag 的平均键长为 2.548 Å;μ3-S-Ag 的平均键长为2.540 Å;μ4-S-Ag 的平均键长为 2.480 Å;μ5-S-Ag 的平均键长为 2.554 Å;μ6-S-Ag 的平均键长为 2.592 Å;μ7-S-Ag 的平均键长为 2.633 Å;μ8-S-Ag 的平均键长为 2.667 Å;
所述簇合物Ag194包括外壳保护层和内核两部分,所述外壳保护层由硫醇和双膦配体构成,所述外壳保护层围绕在簇合物Ag194核四周;所述簇合物Ag194的 Ag-S 键长介于2.338 Å-2.830 Å 之间;Ag-P 键长介于 2.383 Å-2.438 Å 之间;
所述簇合物Ag194的制备所使用的配体为[AgSFuran]n与dpppt;
所述簇合物Ag194的制备方法为:
将[AgSFuran]n与dpppt在甲苯中常温下进行混合反应,得到浅黄色澄清液;
加入双(三甲基硫化硅) S(SiMe3)2,反应2-5h后,室温下静置3天后得到黑色针状晶体。
所述[AgSFuran]n与dpppt的摩尔比为1.2-2.5:1;
所述S(SiMe3)2与dpppt的摩尔比为0.4-0.9:1;
dpppt
[AgSFuran]n
技术原理:
[AgSFuran]n一般以聚合态的形式存在,溶解性普遍较差,[AgSFuran]n与双膦配体dpppt反应,是通过dpppt占据Ag的部分配位点,生成中间态产物,以防 Ag-S聚合,进而破坏[AgSFuran]n的聚合态,增强其溶解性,从而使后续反应能在均一的液态环境下进行,同时本步反应基本决定了最终团簇的大小和形状。该类团簇都具有典型的“核-壳”结构,上述过程实现了“壳”的组装,接下来通过加入重要的硫试剂S(SiMe3)2,通过SiMe3-SFuran基团的形成和离去,释放出硫源,推动硫与银的配位作用,从而完成内核的填充;如果没有合适的配体对团簇内核进行有效保护,同样的反应最终会导致热力学更加稳定的Ag2S 粉末的形成。
在同系列反应体系中,即有RSSiMe3或者S(SiMe3)2参与的反应体系中,普遍选用的前躯体为简单的无机银盐(如卤化银、乙酸银等)、不同官能团的苯基硫醇或硫醇银盐(如[AgSPh]n)和烷基硫醇银盐(如[AgStBu]n、[AgStC5H11]n等),在膦配体的辅助作用下构筑银硫纳米团簇。由于烷基硫醇比苯基硫醇有更强的给电子效应,配位模式更加灵活多样,由烷基硫醇构筑的银硫纳米团簇金属核覆盖范围较广,但该系列产物不可控,反应环境的微小改变,如反应配比、反应溶剂,
会导致不同结构的产物生成。与烷基硫醇相比,因苯环给电子能力变弱,导致其与银离子的配位能力弱化,因此,由苯基硫醇构筑的银硫纳米团簇的金属核普遍集中在100以下,如[Ag14S(PhS)12(PPh3)8]、[Ag70S20(PhS)28(dppm)10](CF3CO2)2,很难实现高核银硫簇的构筑。
技术效果:本方法选取呋喃基硫醇银盐[AgSFuran]n为前躯体制备银硫纳米团簇,呋喃属于五中心六电子即体系,其给电子能力介于烷基硫醇和苯基硫醇之间,所以其与银的配位能力一方面比苯基硫醇强,另一方面又不像烷基硫醇那么灵活,理论上比较适合用来制备簇核较为集中的高核银硫纳米团簇,使反应的可控性变强;配体制备形成的“核-壳”结构,可以有效保证内核Ag的配位稳定性,不会生成Ag2S,制备的纳米团簇稳定性较好;同时,本申请的方法制备简单,反应控制阶段通过[AgSFuran]n与双膦配体dpppt快速反应,使得制备过程简单易控,时间短,不需要加热或者低温复杂操作,反应快速高效;反应完成后仅需要三天静置,要远远少于其他配体方法合成的Ag纳米团簇的反应周期;另外,本申请的制备方法的反应产率高,最高产率可达70%,远高于其他方法30%-50%的产率,具有较好的规模化生产应用价值。
附图说明
图1是[Ag194S60(SFuran)72(dpppt)8] 结构示意图。
图2为[Ag194S60(SFuran)72] 骨架结构示意图(省略配体)。
图3是[Ag194S60(SFuran)72(dpppt)8]的红外光谱图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将对本发明的技术方案进行详细的描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所得到的所有其它实施方式,都属于本发明所保护的范围。
实施例1
将 144 mg ( 0.65 mmol) [AgSFuran]n 和 145 mg ( 0.33 mmol ) dpppt 在20 mL 的甲苯中常温反应得到浅黄色澄清液。然后加入 0.04 mL ( 0.19 mmol ) 的 S(SiMe3)2,溶液颜色很快完成黄色―橘红―红色的转变,继续反应三个小时后得到黑色溶液,然后室温静置。三天后即可得到黑色针状晶体。产率:70%。元素分析 (C592H600O72P16S133Ag194 ) 计算值:C 20.58; H 1.75; S 12.34%,实验值:C 20.92; H 1.73;S 12.63%。
并对所得到的晶体进行红外光谱进行表征,表征结果如图3所示。
元素分析 ( C592H600O72P16S133Ag194 ) 计算值:C 20.58%; H 1.75%; S 12.34%,实验值:C 20.92%; H 1.73%; S 12.63%。
实施例2
将 77.5 mg ( 0.35 mmol) [AgSFuran]n 和 145 mg ( 0.33 mmol ) dpppt 在20 mL 的甲苯中常温反应得到浅黄色澄清液。然后加入 0.04 mL ( 0.19 mmol ) 的 S(SiMe3)2,溶液颜色很快完成黄色―橘红―红色的转变,继续反应三个小时后得到黑色溶液,然后室温静置。三天后即可得到黑色针状晶体。但得到晶态产物较少,晶态产物产率:35%。
实施例3
将 144 mg ( 0.35 mmol) [AgSFuran]n 和 145 mg ( 0.33 mmol ) dpppt 在20 mL 的甲苯中常温反应得到浅黄色澄清液。然后加入 0.08 mL ( 0.38 mmol ) 的 S(SiMe3)2,溶液颜色很快完成黄色―橘红―红色的转变,继续反应三个小时后得到黑色溶液,然后室温静置。三天后即可得到黑色针状晶体,但得到晶态产物较少,产率:40%。
对比例1
所有反应过程都在隔绝水和氧的纯氮气环境下进行:
AgStBu(0.1 g, 0.5 mmol)和dppxy (0.06 g, 0.125 mmol)在25 ml的甲苯中混合,室温下加入 S(SiMe)(0.04 mL,0.25 mmol),混合物变成橘红色,饼含有残留的起始物质,搅拌5min后,加入S(SiMe3)2 (0.08 mL, 0.5 mmol),继续加热30min,同时回流混合物,溶液变成深红色。溶液冷却至室温,形成红色晶体,3-5周后形成黑色晶体Ag344S124(StBu)96,产率为30%-50%。
对比例2
AgStC5H11 (0.105 g, 0.5 mmol) 和dppbp (0.1 g, 0.25 mmol)加入20 ml 四氢呋喃中,同时加入S(SiMe3)2 (0.04 mL,0.25 mmol),在-25℃下搅拌,可以加热到室温。静置3-4周后,可以得到黑色针状晶体[Ag352S128(StC5H11)96],产率为10%-20%。
根据上述实施例和对比例可知,对比例采取了不同的配位物质,需要一定的温度条件或者反应气氛条件,同时反应后需要较长时间才能得到晶体;本发明的方法合理的配比能够取得良好的效果,制备方法反应条件简单易,不需要额外的气氛控制或者温度控制,反应活性和选择性较好,结晶度高,产率高达70%,在本申请反应物摩尔配比范围之外的其他配比,其虽然也能得到少量[Ag194S60(SFuran)72(dpppt)8],但其晶体产率较低,不具有较大的应用价值。Ag194的晶体参数总结在表1中。Ag194的键长和键角列在表2中。
表1 Ag194的晶体学参数表
表2 Ag194的选择性键长键角表
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应以所述权利要求的保护范围为准。
Claims (9)
2.如权利要求1所述的一种银纳米团簇,在所述簇合物Ag194中,[Ag194S60(SFuran)72]核单元的直径为2.4nm;所述簇合物Ag194分为两个不对称结构单元,所述不对称结构单元的分子式为[Ag97S30(SFuran)36(dpppt)4]。
3.如权利要求2所述的一种银纳米团簇,在所述不对称结构单元[Ag97S30(SFuran)36(dpppt)4]中,97个Ag原子存在线型配位、平面三角形配位、畸变四面体配位三种配位模式。
4.如权利要求2所述的一种银纳米团簇,在所述不对称结构单元[Ag97S30(SFuran)36(dpppt)4]中,所述S包括无机硫S2ˉ和有机硫–SFuran两种存在形式,所述不对称结构单元中S的桥联模式有七种,七种桥联模式具体为:μ2:6个S、μ3:30个S、μ4:3个S、μ5:18个S、μ6:6个S、μ7:2个S和μ8:1个S。
5.如权利要求1所述的一种银纳米团簇,所述簇合物Ag194包括外壳保护层和内核两部分,所述外壳保护层由硫醇和双膦配体构成,所述外壳保护层围绕在簇合物Ag194核四周。
6.如权利要求3所述的一种银纳米团簇,所述线型配位Ag原子为29个,所成键角为158.3o–176.1o;所述平面三角形配位Ag原子为54个,每个所述平面三角形配位Ag原子与对应的配位原子构成各个所述Ag原子为中心的三角,所述三角之和均在360o;所述畸变四面体配位原子为14个。
8.一种如权利要求1-7中任意一项所述银纳米团簇的制备方法,其特征在于,
(1)将[AgSFuran]n与dpppt在甲苯中常温下进行混合反应,得到浅黄色澄清液;
(2)加入S(SiMe3)2,反应2-5h后,室温下静置3天后得到黑色针状晶体。
9.如权利要求8所述的一种银纳米团簇的制备方法,所述[AgSFuran]n与dpppt的摩尔比为1.2-2.5:1;所述S(SiMe3)2与dpppt的摩尔比为0.4-0.9:1。
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CN111748340A (zh) * | 2020-06-29 | 2020-10-09 | 浙江师范大学 | 一种新型荧光银纳米团簇及其合成方法与应用 |
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