CN108440576B - 一种杂化铜碘簇及其光催化降解染料的应用 - Google Patents
一种杂化铜碘簇及其光催化降解染料的应用 Download PDFInfo
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 12
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Abstract
一种杂化铜碘簇的合成及其光催化降解染料的应用。本发明的目的在于合成一种能有效可见光催化降解罗丹明B染料的杂化铜碘簇基光催化剂Cu4I4(C9H9NS2)5，其中C9H9NS2=3‑乙基‑1,3‑苯并噻唑‑2‑硫酮。该材料中无机部分为Cu4I4四核，且铜元素与有机分子C9H9NS2的摩尔比为4:5。有机分子C9H9NS2的引入既降低了铜元素的含量，又降低了材料的带隙值，增加了材料对可见光的吸收，进而增强其可见光催化性能。该化合物是一种有效的半导体可见光催化剂，可利用其特性用于可见光催化降解废水中的罗丹明B染料。
Description
技术领域
本发明涉及一种杂化铜碘簇基可见光催化剂，特别是涉及四核杂化铜碘簇Cu4I4(C9H9NS2)5的光催化降解有机染料的应用，其中C9H9NS2 = 3-乙基-1,3-苯并噻唑-2-硫酮。
背景技术
环境污染与能源短缺两大问题已经成为当今世界面临的主要难题。有机合成类染料结构稳定，不容易被生物降解，是水体污染较难处理的环境污染物之一。因此，我们在节约用水的同时，研究生活和工业污水中有机染料的降解处理技术，使污水变废为宝，净化为无毒无害甚至可以重新使用的生活用水是非常具有现实意义的，也是一项长期的艰巨任务。另一方面，化石能源短缺问题日益突出，人类必须开发新型绿色清洁能源，作为化石能源的替代品。太阳能是取之不尽、用之不竭的绿色能源，其中可见光占43%；因此积极开发利用太阳能，特别是利用可见光处理有机染料污染物具有重大的实际意义，也已经成为当前环境领域的重要研究课题。罗丹明B（Rhodamine B）又称玫瑰红B，是一种具有鲜桃红色的人工合成染料，被广泛用于造纸工业染蜡光纸、打字纸，也可用于腈纶、麻、蚕丝等织物以及麦秆、皮革、羽毛制品的染色。
罗丹明B易溶于水，可导致人体皮下组织生肉瘤，具有致癌和致突变性。含有该染料的废水色度高，有机污染物浓度大，可生化性差，难以采用传统的物化或生化法处理，对环境的危害极大，因此必须寻找一种有效的处理技术。基于半导体催化剂的光催化降解技术是20世纪70年代发展起来的一门新兴环保技术，它可以利用太阳能在室温下将废水中的有机染料氧化成水、二氧化碳或无机离子等，无二次污染，具有传统的高温、常规催化技术以及吸附技术无法比拟的优势，符合当今社会环境污染和能源短缺的实际情况，成为环境技术领域重点研发的技术之一。但传统的无机半导体催化剂存在对可见光吸收能力较弱，催化效率不高，光稳定性较差等缺点，因此当今社会亟需新型、有效的可见光催化剂。
无机碘化亚铜是一种用途非常广泛的半导体材料，可以作为催化剂用于催化溴代芳烃、溴代杂环化合物等反应。但因其带隙值较大（约3.1 eV），对可见光吸收较弱，很少作为可见光催化剂用于光催化降解有机染料的研究。如果在分子尺度上，把一些有机小分子引入到无机碘化亚铜半导体中制备杂化半导体材料，不仅可以增强碘化亚铜在可见光区的吸收，而且可以降低铜元素的相对含量，实现增强碘化亚铜的可见光催化性能的同时，降低材料制备成本。按此思路制备的铜碘基杂化材料具备高效可见光催化降解低浓度有机染料的能力，使其有可能作为新一代半导体光催化剂。
发明内容
本发明的目的在于合成一种能有效可见光催化降解罗丹明B的四核铜碘簇光催化剂Cu4I4(C9H9NS2)5，其中C9H9NS2 = 3-乙基-1,3-苯并噻唑-2-硫酮。该材料中无机部分为Cu4I4四核，且铜元素与有机分子C9H9NS2的摩尔比为4:5。有机分子C9H9NS2的引入降低了材料的带隙值，增加了铜碘材料对可见光的吸收，增强其可见光催化性能。
本发明包括如下技术方案：
1. 一种能有效可见光催化降解罗丹明B染料的杂化铜碘四核簇Cu4I4(C9H9NS2)5，其中C9H9NS2 = 3-乙基-1,3-苯并噻唑-2-硫酮，其特征在于：该化合物为单斜晶系，晶胞参数为a = 9.2(1) Å, b = 15.0(1) Å, c = 20.3(1) Å,α= 90 º,β = 93.0(1) º,γ = 90º。
2. 一种项1的杂化铜碘四核簇的用途，其特征在于：该化合物是一种有效的半导体可见光催化剂，可利用其特性用于可见光催化降解废水中的罗丹明B染料。
具体实施方式
我们选择碘化亚铜、2-巯基苯并噻唑为反应原料，乙醇、乙腈和氢碘酸的混合液作为反应原料和溶剂，在溶剂热条件下得到化合物Cu4I4(C9H9NS2)5的单晶。有机组分C9H9NS2由反应原料2-巯基苯并噻唑和乙醇在原位条件下烷基化生成。化合物的单晶结构测试表明结构中无机组分为四核铜碘簇Cu4I4，有机组分C9H9NS2作为配体通过生成铜-硫键形成分子基杂化四核铜碘簇Cu4I4(C9H9NS2)5。有机组分的引入既降低了铜元素在材料中的比例，又使杂化物的带隙值降低到2.5 eV，可以吸收更多的可见光用于有机染料的光催化降解。
本发明所提供的合成策略：引入有机组分3-乙基-1,3-苯并噻唑-2-硫酮降低碘化亚铜材料中铜元素的含量，并调节无机碘化亚铜带隙值的思路简单，易操作；制备的材料结构新颖，原料来源充足，合成成本低廉。
该发明所制备的铜碘基光催化剂，带隙值为2.5 eV，比无机碘化亚铜的带隙值3.1eV低，较好地增加了材料对可见光的吸收能力，具有良好的可见光催化降解罗丹明B染料的能力；为首例能用于光催化降解有机染料的四核铜碘簇材料；可利用其优良的可见光吸收和光催化性能用于污水中罗丹明B染料的可见光催化降解。
附图说明：
图1为实施例1的化合物的紫外漫反射图，从图中可以得出化合物Cu4I4(C9H9NS2)5的光学带隙值为2.5 eV；
图2为实施例1的化合物、空白和氮掺杂TiO2的光催化降解罗丹明B染料溶液浓度随时间的变化图。从图中看出，当无任何催化剂参与时，即使在可见光的照射下，罗丹明B的浓度也几乎没有任何的变化。施加可见光照，以Cu4I4(C9H9NS2)5为催化剂时，在总辐射时间为100分钟时，罗丹明B溶液降解率约为86%，远高于氮掺杂TiO2为催化剂时的降解率48%，说明Cu4I4(C9H9NS2)5具有良好的可见光催化降解罗丹明B染料的性能，可用于染料废液中罗丹明B染料的去除；
图3为实施例1的化合物作为可见光催化剂降解罗丹明B染料溶液的循环使用效果图。结果表明可见光催化剂Cu4I4(C9H9NS2)5可以至少连续使用四个循环而其催化降解效率没有明显衰减；
图4为实施例1的化合物催化降解罗丹明B后的粉末衍射花样与单晶模拟值的比较图，结果显示衍射花样与单晶模拟值吻合良好，说明催化剂具有良好的稳定性。
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),加入0.3 mL氢碘酸，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140 ℃ 恒温3天，随后取出自然降至室温，可得到黄绿色的块状晶体。经X射线单晶结构测定，该晶体为Cu4I4(C9H9NS2)5，其中C9H9NS2 = 3-乙基-1,3-苯并噻唑-2-硫酮。
化合物性能测试
1、半导体带隙值测定
室温下在Shimadzu UV-3101 PC UV-vis光谱仪上进行，以BaSO4覆盖薄玻璃片为载体，Kubelka-Munk函数α/S = (1-R)2/2R, α为吸收系数，S为散射系数，R为发射系数，结果显示Cu4I4(C9H9NS2)5的能带宽度为2.5 eV，比无机CuI的带隙值3.1 eV明显减小，表明杂化铜碘簇Cu4I4(C9H9NS2)5对可见光有更好的吸收。
2、可见光催化降解罗丹明B染料
可见光驱动的光催化降解罗丹明B溶液的反应在80 mL的烧杯中进行，上方以300W Xe灯作为辐射源，通过添加400 nm的紫外截止滤光片使得只有大于400 nm的可见光发射出来。取20.0 mg粉末多晶样品Cu4I4(C9H9NS2)5置于40 mL浓度为5.2 mg/L的罗丹明B溶液中，在暗处搅拌60 min以达到吸附/脱附平衡。然后吸取4 mL悬浮液为完成第一次取样，并立即开启光源照射悬浮液。在辐射过程中，每隔一定时间取样一次。总辐射时间为100 min，完成最后一次取样后关闭光源。每次取样后对所取样品进行离心处理。对所获得的澄清溶液进行紫外-可见吸收光谱的测量，通过对比各溶液在554 nm位置的吸收峰高度，得出不同时间段染料降解的比率，记作C/C0，其中，C代表每次取样溶液中罗丹明B的浓度，C0代表吸附/脱附达到平衡时的浓度。
3、催化剂的循环使用实验
循环实验中，每次循环后，经过离心分离催化剂都被收集起来，用蒸馏水充分洗涤并彻底干燥。收集起来的催化剂，在相同的实验条件下，被用于新一轮光催化降解罗丹明B的实验中。对完成最后一轮光催化实验的催化剂收集，并进行粉末衍射表征。
Claims (2)
1.一种能有效可见光催化降解罗丹明B染料的杂化铜碘四核簇Cu4I4(C9H9NS2)5，其中C9H9NS2 = 3-乙基-1,3-苯并噻唑-2-硫酮，其特征在于：该化合物为单斜晶系，晶胞参数为a = 9.2(1) Å, b = 15.0(1) Å, c = 20.3(1) Å,α= 90 º,β = 93.0(1) º,γ = 90 º。
2.一种权利要求1所述的杂化铜碘四核簇的用途，其特征在于：该化合物是一种有效的半导体可见光催化剂，可利用其特性用于可见光催化降解废水中的罗丹明B染料。
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