CN110272439B - 一种无机有机杂化草酸氟化镓光致变色材料的合成和应用 - Google Patents
一种无机有机杂化草酸氟化镓光致变色材料的合成和应用 Download PDFInfo
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- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 32
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- PEKIAHWVRGDDMN-UHFFFAOYSA-N oxalic acid;hydrofluoride Chemical compound F.OC(=O)C(O)=O PEKIAHWVRGDDMN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 title claims description 6
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 30
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- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 18
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 15
- 239000013110 organic ligand Substances 0.000 claims abstract description 14
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Abstract
本发明公开了一种无机有机杂化草酸氟化镓光致变色材料的合成方法，将含镓金属源、有机配体、氢氟酸和DESs的混合物在120～160℃密封条件下反应2～8天，所述DESs为氯化胆碱和草酸，所述含镓金属源、有机配体、氢氟酸和DESs中氯化胆碱的摩尔比为：0.5～1：1～2：5～10：5～20。本发明合成的无机有机杂化草酸氟化镓光致变色材料，其光响应速度快、褪色迅速，并有较好的光热稳定性和耐疲劳性，可用于光催化性能的可控调控。
Description
技术领域
本发明涉及光致变色材料技术领域，具体涉及一种无机有机杂化氟化镓光致变色材料的合成和应用。
背景技术
光催化技术作为一种可再生能源技术已经被广泛的应用于产生氢能、降解环境污染物和催化多种重要的有机反应(如氢化、甲酰化、醇氧化、氧化偶联等)。与传统的热化学途径相比，光化学可以很容易的产生高活性的自由基，从而可在绿色温和的条件下进行一些具有挑战性的反应(如光解水制氢，Csp 3-H键活化等)。近年来，虽基于联吡啶钌、铱、钯配合物等均相催化剂来构筑C-H键活化以及C-杂原子键的策略发展迅速，但非均相光催化剂因其稳定性和易分离性引起了更广泛的关注。据统计，自1967年日本科学家藤岛昭发现TiO2作为非均相催化剂用于光解水以来，已有数万篇关于光催化的论文发表。目前，人们已将光催化技术应用于生产和生活的方方面面，如光催化分解水制氢、光催化净化空气、人工光合作用、自清洁、抗菌除臭等。2001年Asahi在Science上发表了N掺杂TiO2实现可见光光催化，自此可见光响应催化材料一直是光催化领域的研究热点。提高光催化性能的关键是增强光生电子-空穴对的分离并抑制其随后的重组，目前的流行策略是构建异质结纳米结构材料。然而，这一策略需要构建相界面，而接触界面的总面积十分有限，从而阻碍了光催化性能的进一步提高。目前，实现光催化性能的可控调控仍然是一个亟待解决的难题，需要寻找新的策略来实现这一目标。
光致变色行为是指一些材料能够在一定强度和波长的光照作用下发生颜色变化且在光照或加热条件下可实现颜色可逆恢复的现象，因其在防伪保护、光致变色装饰、有害射线检测、光学存储器、智能窗口、光学开关和非线性光学材料等领域实际或潜在的应用而备受关注。近年来，随着人们对光致变色材料研究的不断深入，光致变色材料的研究范围也不断扩大，其研究的主要目的是改进现有的光致变色材料、制备光致变色器件及探索光致变色材料的新应用。然而，在它们被市场广泛接受之前，它们的性能和成本问题仍有待解决。
由于离子液体具有溶解度好、反应温度范围宽、热稳定性高等独特的性能，其作为化学合成溶剂受到人们越来越多的关注。近年来，Morris等人在离子热合成无机晶体材料上的成功为合成新型多孔无机材料和金属有机骨架材料等无机有机杂化材料开辟了一条新途径。
通常光致变色材料两种状态间的相互转换常伴随着某些物理化学性质的变化，如氧化还原电位、电导率、荧光、光电流、光电压、二阶非线性性质等。相较于有机光致变色分子(如二芳基乙烯、偶氮苯和螺吡喃等)，无机有机杂化光致变色晶体材料两种状态之间的转换具有可忽略的结构差异。而基于电子转移的光生电荷分离状态能够调控其光响应性质，如光电流响应、光催化性质等。近年来，光致变色行为对于相关物理化学性质的调控，如气体吸附、电导、磁、光致发光和光电流响应等，引起了科研工作者强烈的兴趣，然而光致变色行为对光催化性能的影响却鲜有报道。
发明内容
本发明要解决的技术问题是提供一种可调控光响应性能的无机有机杂化草酸氟化镓光致变色材料的合成方法。
为解决上述技术问题，本发明采用的技术方案为：
一种无机有机杂化草酸氟化镓光致变色材料的合成，方法如下：将含镓金属源、有机配体、氢氟酸和DESs的混合物在120～160℃密封条件下反应2～8天，所述DESs为氯化胆碱和草酸，所述含镓金属源、有机配体、氢氟酸和DESs中氯化胆碱的摩尔比为：0.5～1：1～2：5～10：5～20。
进一步地，所述含镓金属源为氧化镓、羟基氧化镓、或镓盐中的一种。
进一步地，所述有机配体为4,4'-联吡啶或2,2'-联吡啶。
进一步地，所述DESs中氯化胆碱与草酸的摩尔比为1:1～3。
上述方法合成的无机有机杂化草酸氟化镓光致变色材料在光催化性能调控中的应用。
本发明合成的无机有机杂化草酸氟化镓光致变色材料，其光响应速度快、褪色迅速，并有较好的光热稳定性和耐疲劳性，可用于光催化性能的可控调控。
附图说明
图1为本发明实施例1中所得晶体的扫描电子显微镜照片。
图2为本发明实施例1中的所得晶体的模拟x射线粉末衍射图谱、晶体变色前后和热褪色后的x射线粉末衍射图谱的对照图。
图3为本发明实施例1中所得晶体的热失重分析图(空气条件下，升温速度为10℃/min)。
图4为本发明实施例1中所得晶体的紫外可见吸收光谱图。
图5为本发明实施例1中所得晶体的红外光谱图。
图6为本发明实施例1中所得晶体的PL谱图。
图7为本发明实施例1中所得晶体的ESR谱图。
图8为本发明实施例1中所得晶体经X射线单晶结构分析得到的球棍模型。
图9为本发明实施例1中所得晶体与JU98(亚磷酸锌化合物)、JU101(磷酸锌镓分子筛)两种光致变色材料在可见光条件下降解染料罗丹明B的效果对比图。
图10为本发明实施例1中所得晶体在可见光条件下循环降解染料罗丹明B的效果对比图。
图11为本发明在一定的外加电压条件下，实施例1中所得晶体的紫外光照射前后的光电流谱图。
图12为本发明实施例1中所得晶体的交流阻抗谱图。
图13为本发明实施例1中所得晶体的Mott-Schottky曲线。
图14为本发明实施例1中所得晶体经不同时间紫外光照射后，所得样品在可见光条件下降解染料罗丹明B的效果图。
图15为本发明实施例1中所得晶体经不同时间紫外光照射后，所得样品在紫外光条件下降解染料罗丹明B的效果图。
具体实施方式
本发明实施例提供一种无机有机杂化光致变色材料的合成方法，具体如下：将一定量的含镓金属源、有机配体、氢氟酸和DESs的混合物在120～160℃密封条件下反应2～8天；所述DESs为氯化胆碱和草酸。其中，所述含镓金属源为氧化镓、羟基氧化镓或镓盐中的一种；所述有机配体为4,4'-联吡啶或2,2'-联吡啶；所述含镓金属源、有机配体、氢氟酸和DESs中氯化胆碱的摩尔比为：0.5～1：1～2：5～10：5～20；所述DESs中氯化胆碱与草酸的摩尔比为1:1～3。
待反应完成后将反应釜取出放于室温下自然冷却，将产物移出后用去离子水反复超声洗涤3～7次，40～80℃温度条件下烘干，最后得到所需晶体。
上述方法合成的无机有机杂化草酸氟化镓光致变色材料可用于光催化性能调控方面。可通过改变光照时间影响其光致变色行为，进而实现其对染料光降解催化性能的可控调控。
低共熔溶剂(DESs)作为一种离子液体，由离子盐和分子化合物两种有机固体组成，具有传统离子液体的许多特点。兼具离子液体和分子溶剂两种特性的DESs能够单独或与其他组分结合参与自组装过程，从而有可能创造出单独在离子液体或分子溶剂中无法获得的新型化学环境。此外，DESs如氯化胆碱/草酸(或尿素及其衍生物)廉价易得且环境友好。本发明选用廉价易得的金属源和非光致变色有机配体，在组成多样且廉价易得的DESs体系中，采用离子热合成法，通过调控有机配体、体系酸度、DESs组成和用量、反应温度和时间来调控晶体的生长条件，合成了一种新型无机有机杂化草酸氟化镓光致变色晶体材料。其光响应速度快、褪色迅速，并有较好的光热稳定性和耐疲劳性。其中，加入的氢氟酸作为促进晶体晶化的矿化剂促进了晶体的合成。通过大量工艺参数的调整实验，最终确定反应温度应控制在120～160℃，反应时间为2～8天，金属源、有机配体、酸和DESs中氯化胆碱的摩尔比范围为：0.5～1：1～2：5～10：5～20。另外，我们系统的研究了该无机有机杂化草酸氟化镓光致变色材料在紫外线照射下的光致变色行为，光致变色前后材料的稳定性以及光致变色的机理。该材料展现出有趣的光致变色行为，具有从紫外到可见光的光响应范围和超长寿命的电荷分离状态，此外它还展现出可调控的光响应性质，可通过改变光照时间影响其光致变色行为进而实现其对染料光降解催化性能的可控调控。
实施例1一种无机有机杂化氟化镓光致变色材料的合成方法和应用
以氧化镓、4,4’-联吡啶、氢氟酸、氯化胆碱和草酸作为离子溶剂，在140℃、3天条件下反应合成晶体材料。
将氧化镓0.5mmol、4,4’-联吡啶1mmol、氢氟酸5mmol、氯化胆碱5mmol、草酸10mmol，加入到25mL聚四氟乙烯为衬里的不锈钢釜中，最后将反应釜密封后放入140℃的烘箱内加热3天。待反应完成后将反应釜取出放于室温下自然冷却；将产物移出，用去离子水反复超声洗涤3次，70℃温度条件下烘干。
制备的晶体表征结果如下：
如图1所示，所得晶体为长条形，粒径约为30×5μm。
如图2所示，所得晶体的模拟x射线粉末衍射图谱与变色前后和热褪色后的x射线粉末衍射图谱一致，说明晶体结构没有发生改变。
如图3所示，所得晶体能稳定到400℃，400℃之前脱出的是物理吸附的水。
如图4所示，所得晶体的紫外可见吸收光谱图表明该化合物在385nm，554nm和620nm处有吸收峰，这些吸收峰是质子化联吡啶自由基的典型吸收峰。
如图5所示，所得晶体变色前后与加热褪色后的样品各组峰对应的很好，说明样品结构没有发生变化。
如图6所示，随着光照时间的不断增加，所得晶体在紫外光激发下，其荧光响应信号也逐渐减弱，180分钟后的荧光强度变为起初的五分之三，这进一步验证了在光致变色发生过程中伴随着光诱导电子转移的过程。
如图7所示，所得晶体的ESR波谱可进一步确定质子化联吡啶的产生。在光照前没有发生ESR信号，而光照颜色发生变化后，在g＝2.0028处有强的响应信号，这个信号对应着质子化联吡啶自由基的信号。同时可以发现在加热颜色褪去后，ESR信号也对应消失。这表明在照射后H2bpy2+被还原为H2bpy+自由基，并且在空气中加热时H2bpy+自由基恢复为H2bpy2 +。
如图8所示，由晶体结构可知，所得晶体的分子式为C14H10N2O8FGa。各元素的质量分数分别为：H：2.38％，C：39.76％，N：6.62％，O：30.26％，F：4.49％，Ga：16.48％。
如图9所示，在相同情况下使用所得晶体、JU98(亚磷酸锌光致变色化合物)和JU101(磷酸锌镓光致变色分子筛)作为光催化剂，以染料罗丹明B作为光催化降解对象，先在黑暗条件下搅拌30min以达到吸附平衡，后在可见光条件下进行光催化，结果显示样品的光催化性能优于JU98、JU101。
如图10所示，所得晶体作为光催化剂，以染料罗丹明B作为光催化降解对象，先在黑暗条件下搅拌30min以达到吸附平衡，后在可见光条件下进行光催化，结果显示催化循环效果良好。
如图11所示，在一定的外加电压下，所得晶体的光照-黑暗电流密度曲线变化十分明显。在黑暗条件下，其暗电流很小可以忽略不计，当打开光源进行光照的时候，立刻产生较强的光电流。从图可知，紫外光照射前的晶体的光电流明显强于紫外光照射后的晶体，且紫外光照射时间越长，光电流越低。这与理论上紫外光照射后的样品光生电子减少相符合。即可通过改变光照时间影响其光致变色行为进而实现对光电流性能的可控调控。
如图12所示，所得晶体变色后样品的交流阻抗圆弧半径明显大于变色前样品的圆弧半径。在相同频率下，阻抗环半径大则表示电极的电容常数小，法拉第电流阻抗值大，该电极反应需要较大的能垒，电极反应较难发生或反应速率较慢。意味着电极表面氧化还原反应的速度减慢。故表明晶体变色后电极表面氧化还原反应的速度减慢，光催化反应难以进行。
如图13所示，Mott-Schottky曲线切线斜率大于0，说明所得晶体紫外光照射前后均属n型半导体。计算得到晶体材料的导电电位为-1.25eV，结合由UV-vis漫反射吸收光谱得到的禁带值，根据公式EVB＝EVB+ECB，计算得出晶体的价带点位为2.31eV。
如图14所示，将所得晶体分别光照0min、10min、20min、30min、60min后得到的样品作为光催化剂，以染料罗丹明B作为光催化降解对象，先在黑暗条件下搅拌30min以达到吸附平衡，后在可见光条件下进行光催化，70min后，染料罗丹明B被降解完全。由图可知受光照时间短的材料光催化效果更好，即可通过改变光照时间影响其光致变色行为进而实现对光催化性能的可控调控。
如图15所示，将所得晶体分别光照0min、10min、20min、30min、60min后得到的样品作为光催化剂，以染料罗丹明B作为光催化降解对象，先在黑暗条件下搅拌30min以达到吸附平衡，后在紫外光条件下进行光催化，35min后，染料罗丹明B被降解完全。由图可知受光照时间短的材料光催化效果更好，即可通过改变光照时间影响其光致变色行为进而实现对光电流性能的可控调控。
所得晶体具有良好的光致变色特性，在30W的紫外光照射下可快速变色，140℃加热20分钟又可实现褪色。是一种新型晶态无机有机杂化光致变色材料。
实施例2一种无机有机杂化氟化镓光致变色材料的合成方法和应用
以硝酸镓、4,4’-联吡啶、氢氟酸、氯化胆碱和草酸作为离子溶剂，在135℃、5天条件下反应合成晶体材料。
将硝酸镓0.5mmol、4,4’-联吡啶2mmol、氢氟酸10mmol、氯化胆碱10mmol、草酸30mmol，加入到25mL聚四氟乙烯为衬里的不锈钢釜中，最后将反应釜密封后放入135℃的烘箱内加热5天；待反应完成后将反应釜取出放于室温下自然冷却；将产物移出，用去离子水反复超声洗涤3次，70℃温度条件下烘干。
制备的晶体表征结果如下：
所得晶体具有良好的光致变色特性，在30W的紫外光照射下可快速变色，140℃加热20分钟又可实现褪色，是一种新型晶态无机有机杂化光致变色材料。将所得晶体作为光催化剂，以染料罗丹明B作为光催化降解对象，先在黑暗条件下搅拌30min以达到吸附平衡，后在紫外光条件下进行光催化，35min后染料罗丹明B被降解完全。
实施例3一种无机有机杂化氟化镓光致变色材料的合成方法和应用
以羟基氧化镓、2,2’-联吡啶、氢氟酸、氯化胆碱和草酸作为离子溶剂，在150℃、6天条件下反应合成晶体材料。
将羟基氧化镓1mmol、2,2’-联吡啶1mmol、氢氟酸8mmol、氯化胆碱20mmol、草酸20mmol，加入到25mL聚四氟乙烯为衬里的不锈钢釜中，最后将反应釜密封后放入150℃的烘箱内加热6天。待反应完成后将反应釜取出放于室温下自然冷却；将产物移出，用去离子水反复超声洗涤3次，70℃温度条件下烘干。
制备的晶体表征结果如下：
所得晶体具有良好的光致变色特性，在30W的紫外光照射下可快速变色，140℃加热20分钟又可实现褪色，是一种新型晶态无机有机杂化光致变色材料。将所得晶体作为光催化剂，以染料罗丹明B作为光催化降解对象，先在黑暗条件下搅拌30min以达到吸附平衡，后在紫外光条件下进行光催化，35min后染料罗丹明B被降解完全。
最后所应说明的是，以上具体实施方式仅用以说明本发明的技术方案而非限制，尽管参照实例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，其均应涵盖在本发明的权利要求范围当中。
Claims (4)
1.一种无机有机杂化草酸氟化镓光致变色材料的合成，其特征在于：方法如下：将含镓金属源、有机配体、氢氟酸和DESs的混合物在120～160℃密封条件下反应2～8天，所述DESs为氯化胆碱和草酸，所述含镓金属源、有机配体、氢氟酸和DESs中氯化胆碱的摩尔比为：0.5～1：1～2：5～10：5～20；所述有机配体为4,4'-联吡啶或2,2'-联吡啶
2.如权利要求1所述的方法，其特征在于：所述含镓金属源为氧化镓、羟基氧化镓、或镓盐中的一种。
3.如权利要求1所述的方法，其特征在于：所述DESs中氯化胆碱与草酸的摩尔比为1:1～3。
4.权利要求1-3任一合成的无机有机杂化草酸氟化镓光致变色材料在光催化性能调控中的应用。
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