CN109233812A - 一种椅式铜碘簇及其硝基苯酚的选择性传感应用 - Google Patents
一种椅式铜碘簇及其硝基苯酚的选择性传感应用 Download PDFInfo
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- CZZBXGOYISFHRY-UHFFFAOYSA-N copper;hydroiodide Chemical compound [Cu].I CZZBXGOYISFHRY-UHFFFAOYSA-N 0.000 title description 8
- 239000010949 copper Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 19
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims abstract description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims abstract description 5
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- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims abstract description 4
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- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 150000004696 coordination complex Chemical class 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种铜碘四核分子簇Cu4I4(Etmbt)4的合成及及其硝基苯酚选择性荧光传感应用。本发明的目的在于合成一种能选择性传感识别硝基苯酚的铜碘基传感材料Cu4I4(Etmbt)4，其中Etmbt=2‑乙巯基苯并噻唑。此材料含有一个梯子形状的Cu4I4核和四个Etmbt配体，可发射出较强的黄绿色磷光。可通过碘化亚铜、2‑巯基苯并噻唑、乙醇、乙腈和氢碘酸在溶剂热条件下反应得到，可用于选择性传感识别废水中的邻硝基苯酚。
Description
技术领域
在本发明涉及一种铜碘基簇材料的酚类化合物传感应用，特别是涉及椅式铜碘四核分子簇Cu4I4(Etmbt)4的合成及其邻硝基苯酚的传感探测应用，其中Etmbt = 2-乙巯基苯并噻唑。
背景技术
酚类物质作为重要的有机化工原料，可以用作溶剂、试剂和消毒剂，在合成纤维、合成橡胶等领域均有应用，属于生产生活中常见的有毒有害物。随着国内化工工业的飞速发展，酚类物质生产行业，以及以酚类物质作为原料的下游行业，如医药生产厂、炼钢厂、合成纤维等排放的含酚废水逐年增加。因此，在满足人们日益增长的物质需求的同时，酚类物质造成的水环境问题日益凸显，对人类的健康和社会的可持续发展构成了严重威胁，该问题已被世界各国所重视，因此此类废水的检测和处理研究是目前环境科学科研人员关注的焦点。
酚类物质对周围生活的人群和动植物都有严重的危害作用，如酚类化合物可以通过生物的外表皮或呼吸系统进入到体内，使细胞组织失去活性，对神经系统破坏性尤为严重，会诱发神经系统产生病变现象；且其毒性能够阻碍到水中的微生物新陈代谢的速度，打破水体的生态系统，造成水环境的恶化；人如果长期饮用含有酚类化合物的水，极容易导致慢性中毒，出现头晕、耳鸣、头痛、肝肾损坏以及各种神经系统的疾病，严重的会导致死亡。因此为了更好的自然环境和人类健康，社会迫切需要开发有效的在废水体系中去除酚类物质的技术；目前也已有物化方法、生化方法、化学方法、电化学方法处理酚类废水研究报道。更重要地，在应用去除技术之前的酚类物质探测确认以及实施去除技术之后的残留物浓度探测方面，建立一种灵敏、快速、高效、可靠定的定量检测方法是十分重要的。
硝基苯酚是酚类物质的典型代表之一，由于具有良好的生化稳定性，不易被降解，被广泛应用于农药、医药、染料等行业。含硝基苯酚有机废水的大量排放，可造成严重的水体污染，并最终威胁人类健康。目前光谱学分析技术仍是硝基苯酚污染物的主要探测技术，但此类方法仍存在一些无法克服的缺点，如仪器昂贵，操作难度大且样品前处理复杂。因此，发展快速，高效和简便的硝基苯酚探测方法具有重大的实际意义。基于传感器与样品间相互作用的光学传感探测技术，因具有容易操作，高灵敏度、高选择性，短的信号响应时间等优点，与其它传感技术相比具有较大的优越性。然而，目前已有的光学传感探测技术，大多基于一些碳和贵金属基量子点，存在合成复杂，灵敏度低，较长的相应时间等缺点。因铜元素无毒无味，且在地壳中含量较丰富；铜碘簇基化合物因其优异的光致发光性能，在传感研究应用方表现出很大潜力，但至今为止仍没有铜碘基簇材料用于硝基苯酚传感的报道。
发明内容
本发明的目的在于以铜碘分子簇材料Cu4I4(Etmbt)4，其中Etmbt = 2-乙巯基苯并噻唑为传感器，提供一种邻硝基苯酚的高选择性和高灵敏度光学传感识别方法。该传感材料对硝基苯酚类污染物具有良好的选择性探测性能，能从邻、间和对硝基苯酚三个同分异构体中，高选择性地识别邻硝基苯酚，且不受其它常见有机污染物的干扰；克服了传统碳基、贵金属基量子点以及金属有机配合物传感器合成复杂，选择性不高的缺点。
本发明包括如下技术方案：
1. 一种能高效选择性传感识别邻硝基苯酚的铜碘基四核分子簇材料Cu4I4(Etmbt)4，其中Etmbt = 2-乙巯基苯并噻唑，其特征在于：该化合物为单斜晶系，结晶于空间群P21/c，单胞参数为a = 11.30(1) Å, b = 14.16(1) Å, c = 15.17(1) Å, α= 90 º, β = 107.88(1) º γ = 90(1) º, Z = 2, V = 2309(1) Å3；
2. 该铜碘基四核分子簇材料由以下方法制备而成，反应物碘化亚铜、2-巯基苯并噻唑的摩尔比例为1：1，准确称取相应质量的固体反应物，加入体积比为10:50:3的乙醇，乙腈和氢碘酸，采用溶剂热合成的方法，在120゜C下恒温48小时，然后降至室温。
3. 该铜碘基四核分子簇材料的用途，其特征在于：该化合物是一种磷光发光材料，在不同的有机物溶液中表现出不同的淬灭行为，基于此光学特性用于选择性传感识别废水中的邻硝基苯酚。
具体实施方式
我们选择了碘化亚铜、2-巯基苯并噻唑为反应原料，乙醇，乙腈和氢碘酸作为反应原料或溶剂，在溶剂热条件下得到化合物Cu4I4(Etmbt)4的单晶。有机组分Etmbt由反应原料2-巯基苯并噻唑在酸性条件下原位乙基化生成。
本发明的有益效果为所涉及的四核铜碘簇材料的合成原料无毒，易得，合成思路简单，易操作，成本低廉。该发明所涉及的四核铜碘簇材料具有优异的光致发光性能，并能在水体系中高选择性探测邻硝基苯酚，不受其同分异构体间硝基苯酚和对硝基苯酚，以及其它常见有机物的干扰，具有较高的灵敏度和稳定性，可用于探测酚类废水中的硝基苯酚，且能重复使用。
附图说明：
图1为铜碘基四核分子簇的分子结构，其中铜和碘采取了一种梯子形状的四核中心构型，2-乙巯基苯并噻唑分子通过形成铜硫共价键和铜氮共价键生成四核铜碘分子簇。
图2为实施例1的化合物的光致发光谱图。在396 nm光的照射下，金属配合物在580nm附近发出较强的黄绿色的光。将测试得到的荧光发射光谱数据利用CIE1931色坐标计算软件计算得知化合物的色坐标为（0.43，0.47）。
图3中a图为实施例1的化合物的发光强度随邻硝基苯酚浓度的变化图。从图中可以看出，邻硝基苯酚的水溶液能明显地使样品的发光发生淬灭效果，且b图显示在0.01–0.8mmol×L–1范围内具有良好的线性淬灭关系。
图4 为实施例1对硝基苯酚的选择性传感识别图。测试的酚类溶液包括邻硝基苯酚（简写为o-NP，饱和），对硝基苯酚（p-NP，1 mmol·L–1），间硝基苯酚（3-NP，1 mmol·L–1），对苯醌（BQ，1 mmol·L–1），氟他胺（Flutamide，饱和）,硝基苯（NB，饱和），苯胺（aniline，1mmol·L–1），双酚A（BP，饱和），苯酚（Phenol，1 mmol·L–1）。整个光学传感测试过程中，样品池的位置保持不动，光学测试条件保持一致。测试结果表明，样品对硝基苯酚的水溶液具有明显的选择性淬灭行为，其中邻硝基苯酚淬灭效率为61%，对硝基苯酚淬灭效率为37%，间硝基苯酚淬灭效率为15%，其余化合物溶液的淬灭效率均在15%以下。
图5 为实施例1的传感识别可循环性图，重复传感实验五次后，样品的空白发光依然保持初始的强度，加入淬灭剂后淬灭效率也基本无衰减。
图6 为实施例1在各种条件下的粉末衍射花样，从图看出传感测试后样品的衍射花样与单晶结构模拟和新鲜制备的Cu4I4(Etmbt)4衍射花样吻合良好，说明样品具有良好的稳定性。
图7 为实施例1在混合溶液中对邻硝基苯酚的选择性传感识别图。测试的酚类溶液包括苯酚（Phenol，0.5 mmol·L–1）,双酚A（BP，0.5 mmol·L–1），苯胺（aniline，0.5mmol·L–1），硝基苯（NB，0.5 mmol·L–1），苯酚、双酚A、苯胺、硝基苯混合（简写为mixed，均0.5 mmol·L–1等体积混合），邻硝基苯酚与苯酚混合（简写为Phenol+o-NP，0.5mmol·L–1），邻硝基苯酚与双酚A混合（简写为BP+o-NP，0.5 mmol·L–1），邻硝基苯酚与苯胺混合（简写为aniline+o-NP，0.5 mmol·L–1），邻硝基苯酚与硝基苯混合（简写为NB+o-NP，0.5 mmol×L–1），邻硝基苯酚与苯酚、双酚A、苯胺、硝基苯混合（简写为mixed+o-NP，均0.5 mmol·L–1等体积混合）。整个光学传感测试过程中，样品池的位置保持不动，光学测试条件保持一致。测试结果表明，样品对混合溶液中邻硝基苯酚的水溶液具有明显的选择性淬灭行为。
实施例1：
化合物的制备
称取CuI (0.25 mmol), 2-巯基苯并噻唑(0.25 mmol), 氢碘酸 (0.3 mL)，再加入1.0mL乙醇和5.0 mL乙腈，装入密闭的25 mL的反应釜中，采用溶剂热合成方法，在120 °C 恒温48小时，随后取出自然降至室温，手工提纯便可得到无色透明片状晶体。经X射线单晶结构测定，该晶体为Cu4I4(Etmbt)4，其中Etmbt = 2-乙巯基苯并噻唑。
化合物性能测试
1、光致发光性能测试
将制备的Cu4I4(Etmbt)4晶体研磨得到固体粉末，在Edinburgh EI920光谱仪上进行光致发光性能测试。光学寿命测试表明580 nm位置发射的寿命在微秒级，说明其为磷光发射。
2、对酚类溶液的传感识别
把Cu4I4(Etmbt)5研成粉末，并用模具压成直径为5 mm的圆形片，并小心粘在石英片上，把此石英片放入石英比色皿中，得到一个自制的光学传感测试池。把不同浓度的酚类及其其它常见的有机污染物水溶液分批注入到上述石英测试池中，用Edinburgh EI920光谱仪表征样品Cu4I4(Etmbt)4磷光发光强度的变化。整个光学传感测试过程中，样品池的位置保持不动，光谱测试条件保持一致；测试灵敏度为2.30 mmol·L–1。
3、对硝基苯酚的选择性识别
把Cu4I4(Etmbt)4研成粉末，压成直径为 5 mm的片，并小心粘在石英片上，并把此石英片放入石英比色皿中。把不同酚类的1.0 mmol·L–1或者饱和溶液注入到石英测试池中，表征样品Cu4I4(Etmbt)4磷光发光强度的变化。
4、可重复性表征
我们以蒸馏水为空白，在上述自制石英测试池中测试样品Cu4I4(Etmbt)4的发光强度；用带有长针头的注射器抽出蒸馏水后，注入1 mmol·L–1的邻硝基苯酚溶液，待其与样品充分相互作用后，用Edinburgh EI920光谱仪记录其发光强度。用蒸馏水清洗样品四次，再次测试空白发光强度。
Claims (1)
1.一种椅式铜碘四核分子簇材料Cu4I4(Etmbt)4的用途，其中Etmbt = 2-乙巯基苯并噻唑，该材料用于高选择性光学传感识别水体系中的邻硝基苯酚；该分子簇材料的特征在于：结晶于空间群P21/c，单胞参数为a = 11.30(1) Å, b = 14.16(1) Å, c = 15.17(1) Å, α = 90 º, β = 107.88(1) º γ = 90(1) º, Z = 2, V = 2309.4(1) Å3；
它由以下方法制备而成，称取摩尔比例为1：1的碘化亚铜和2-巯基苯并噻唑，然后加入体积比为10:50:3的乙醇，乙腈和氢碘酸，采用溶剂热合成的方法，在120℃下反应48小时后冷却至室温。
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| CN110590816A (zh) * | 2019-10-10 | 2019-12-20 | 济南大学 | 一种一维铜碘基杂化半导体材料及其光电应用 |
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