CN106540752B - 一种催化降解罗丹明b的光催化剂的制备方法及其应用 - Google Patents
一种催化降解罗丹明b的光催化剂的制备方法及其应用 Download PDFInfo
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- 229940043267 rhodamine b Drugs 0.000 title claims abstract description 47
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- 238000006731 degradation reaction Methods 0.000 title claims abstract description 36
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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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Abstract
本发明公开了一种催化降解罗丹明B的光催化剂的制备方法及其应用，属于光催化领域。以NaWO4·2H2O、NiF2·4H2O、Na2SiO3·9H2O和有机配体Biim为原料，蒸馏水为溶剂，采用一步水热合成法制得催化剂。所制得的催化剂不需要复合就可以在模拟太阳光光源和紫外光源及常温条件下，对罗丹明B（RhB）溶液进行降解，30min降解率分别达80.11%和90.35%，45min降解率分别达81.89%和91.62%，在pH=3.0和模拟太阳光的照射下，降解速度更快，10min降解率就达到91.05%，40min降解率高达97.50%，并且该催化剂的稳定性好，原料相对廉价易得，制备方法简单。
Description
技术领域
本发明涉及光催化领域，具体地说是涉及一种催化降解罗丹明B的光催化剂的制备方法及其应用。
背景技术
有机染料废水中多含芳香类化合物，生物毒性大，不宜使用传统的生物降解法处理，成为工业废水处理的一大难题。罗丹明B（RhB）俗称花粉红，是一种具有鲜桃红色的人工合成的染料，氧杂蒽染料中的重要代表物，广泛存在印染废水中。
杂多酸由于特殊的氧化还原及光化学性质，对难降解的有机物具有较好的氧化分解作用，可以将有机染料等污染物深度氧化成小分子，近年来引起了广泛的关注。利用杂多酸进行光催化法降解罗丹明B具有无毒、安全、稳定性好、催化活性高、见效快、能耗低、可重复使用等优点。
现阶段发现的作为降解罗丹明B的杂多酸光催化剂通常需要进行固载化才能充分发挥其催化活性，即要将杂多酸负载到各种氧化物载体、有机载体或离子交换树脂上，形成复合光催化材料，制作复杂并且成本高，降解速度缓慢，有些还需要加热、紫外光照射等条件。
发明内容
本发明的目的在于针对现有技术不足，提供催化降解罗丹明B的光催化剂的制备方法及其应用。所制得的光催化剂在模拟太阳光光源或紫外光源及常温条件下，对罗丹明B（RhB）有很好的降解效果，降解速度快，并且催化剂的稳定性好。
为实现上述目的，本发明采用如下技术方案：
一种催化降解罗丹明B的光催化剂的制备方法，以NaWO4·2H2O、NiF2·4H2O、Na2SiO3·9H2O和有机配体Biim(联咪唑，biimidazole，缩写为Biim，分子式为C6H6N4)为原料，蒸馏水为溶剂，采用一步水热合成法制得催化剂；具体包括以下步骤：
（1）将NaWO4·2H2O、NiF2·4H2O、Na2SiO3·9H2O和有机配体Biim溶解于蒸馏水中，搅拌至完全溶解，制成混合溶液；
（2）将步骤（1）得到的混合溶液的pH调成2.5；
（3）将步骤（2）所得溶液转移到内衬聚四氟乙烯的反应釜中，在145~155℃下恒温反应48~53h，冷却至室温制得所述光催化剂（{(Ni(Biim)3}2[SiW12O40] ·4H2O）。
进一步地，各反应物的用量分别为：NaWO4·2H2O：0.1566g~0.1730g；NiF2·4H2O：0.0090g~0.0100g； Na2SiO3·9H2O：0.0675g~0.0746g；有机配体Biim：0.0318g~0.0352g。
所述光催化剂应用于催化降解有机染料罗丹明B。
本发明的有益效果在于：
发明的催化剂通过一步水热合成法即可得到，反应条件温和，且不需要复合就可以在模拟太阳光光源或紫外光源及常温条件下，对罗丹明B（RhB）溶液进行有效、快速地降解，30min降解率分别达80.11%和90.35%，45min降解率分别达81.89%和91.62%，在pH=3.0和模拟太阳光的照射下，降解速度更快，10min降解率就达到91.05%，40min降解率高达97.50%，并且该催化剂的稳定性好。此外，本发明原料相对廉价易得，制备方法简单。
附图说明
图1 化合物{(Ni(Biim)3}2[SiW12O40]·4H2O的晶体结构图；
图2 化合物{(Ni(Biim)3}2[SiW12O40]·4H2O的 X-射线粉末衍射图；
图3 化合物{(Ni(Biim)3}2[SiW12O40]·4H2O的红外谱图；
图4 化合物{(Ni(Biim)3}2[SiW12O40]·4H2O的拉曼谱图；
图5 化合物{(Ni(Biim)3}2[SiW12O40]·4H2O的固体紫外可见漫反射光谱图；
图6 有机染料罗丹明B(RhB)的紫外可见吸收光谱图；
图7 模拟可见光照射无催化剂（a）、有催化剂（b）时RhB的紫外可见吸收光谱图；
图8 模拟紫外光照射无催化剂（c）、有催化剂（d）时RhB的紫外可见吸收光谱图；
图9 模拟太阳光照射无催化剂（e）、有催化剂（f）时RhB的紫外可见吸收光谱图；
图10 模拟太阳光照射pH=3.0无催化剂（g）、有催化剂（h）时RhB的紫外可见吸收光谱图；
图11 模拟不同光源照射下RhB的降解率；
图12 催化剂使用前后X-射线粉末衍射图。
具体实施方式
以下结合具体实施例对本发明做进一步说明，但本发明不仅仅限于这些实施例。
实施例1
称取NaWO4·2H2O(0.1648 g, 0.5000 mmol)，NiF2·4H2O (0.0095g, 0.0563mmol)和Na2SiO3·9H2O (0.0710 g，0.2500 mmol)以及有机配体Biim(0.0335 g, 0.2500mmol)溶解于10.0 mL的蒸馏水中，搅拌30 min后用1M HCl溶液将pH调至2.5，把溶液转移到25 mL内衬聚四氟乙烯的反应釜中，在150℃下恒温反应49 h，冷却室温后可得到暗红色块状晶体(按钨计算产率约为57%)。Anal. Calcd. (wt %)：C，11.17；H，1.14；N，8.69；Found：C，11.18；H，1.15；N, 8.68 % (wt %)。
实施例2
称取NaWO4·2H2O(0.1566 g)，NiF2·4H2O (0.0090 g)和Na2SiO3·9H2O (0.0675g)以及有机配体Biim(0.0318 g)溶解于9.5 mL的蒸馏水中，搅拌30 min后用1M HCl溶液将pH调至2.5，把溶液转移到25 mL内衬聚四氟乙烯的反应釜中，在145℃下恒温反应53 h，冷却室温后可得到暗红色块状晶体(按钨计算产率约为55%)。
实施例3
称取NaWO4·2H2O(0.1730 g)，NiF2·4H2O (0.0100 g)和Na2SiO3·9H2O (0.0746g)以及有机配体Biim(0.0352 g)溶解于10.5 mL的蒸馏水中，搅拌30 min后用1M HCl溶液将pH调至2.5，把溶液转移到25 mL内衬聚四氟乙烯的反应釜中，在155℃下恒温反应48 h，冷却室温后可得到暗红色块状晶体(按钨计算产率约为56%)。
性能测试和表征
一、催化剂结构与表征
1）催化剂的单晶衍射解析
本发明的化合物是在福州大学物理化学国家重点学科公共测试中心的RigakuSaturn 724 CCD衍射仪上，于293 K温度下，采用石墨单色化的Mo靶Kα射线(λ=0.71073 Å)，以ω-2θ扫描方式在一定的范围内收集衍射点数据，并选择I>2σ(I)的独立衍射点来进行单晶结构分析，化合物的结构如图1，晶体学数据如表1所示。
表1 化合物的晶体学数据
2）X-射线粉末衍射(XRD)
X-射线粉末衍射数据是在福州大学国家化肥催化剂工程研究中心的PANalytical X`pert Pro Panalytic衍射仪上测定所得。Cu靶Ka(λ=1.5418 Å)衍射，扫描范围2θ为5º~55º，功率40 kV×40 mA，扫描速率10 deg·min-1。根据单晶结构模拟的XRD谱图（图2下部）和化合物在室温下的XRD谱图（图2上部），除了强度上的差异，谱图中衍射线与单晶数据拟合的主要峰，位置符合很好，这表明所合成的晶体较纯，可以用于其他性质的表征。
3）红外光谱表征(FT-IR)
化合物红外光谱(FT-IR)在福州大学物理化学重点学科的Thermo ScientificNicolet iS50 FT-IR光谱仪上完成的，采用该光谱仪内置的固定中远红外衰减全反射(ATR)检测装置，以大气为背景，扫描次数16次，扫描波数范围为4000-400 cm-1。从图3可以看出，3540cm-1附近出现的宽吸收峰归属于νas (O-H) （反对称伸缩）振动吸收峰，3316cm-1附近出现的吸收峰归属于νas (N-H)振动吸收峰，Biim环的C-H伸缩振动峰位于3160 cm-1和3121 cm-1；1638 cm-1归属于δ(O-H)振动吸收峰，1611(w) cm-1,1528(s) cm-1,1432(m) cm-1归属于芳环的骨架伸缩振动峰，976 cm-1，922 cm-1归属于ν(W=Ot)反对称和对称伸缩振动吸收峰，887 cm-1、766 cm-1和802 cm-1、688 cm-1分别归属于νas (W-Oμ)反对称伸缩振动吸收峰和νs (W-Oμ)对称伸缩振动吸收峰，532 cm-1是W-O笼的骨架振动吸收峰。
4）拉曼光谱表征(Raman)
化合物的拉曼光谱是在福州大学国家化肥催化剂工程研究中心的Renishawn公司的inVia Reflex 型的显微共聚焦拉曼光谱仪测定的。采用的是632 nm波长激光光源及独立优化的分立光路，用50倍物镜，1秒曝光时间，10%激光功率取谱，扫描的拉曼位移范围为1842~100 cm-1，扫描次数为10次。从图4中可以看到，化合物在217 cm-1出现了红外光谱观察不到的Ni-N拉曼位移峰；而其它的峰在红外光谱中均已表述。
5）固体紫外可见漫反射光谱表征（UV-Vis-DRS）
UV-Vis-DRS是在福州大学国家化肥催化剂研究工程中心的Perkin-Elmer Lambda950型紫外-可见近红外光谱仪上测试的，扫描范围为200-800 nm。从图5中可以看出，252nm处出现的跃迁峰归属于Oμ→W之间的荷移跃迁(LMCT)，304 nm和318 nm对应于Biim的π→π*跃迁，434 nm对应于金属Ni的d-d跃迁。
二、催化剂对有机染料罗丹明B（RhB）光降解的测试与分析
（1）有机染料罗丹明B（RhB）溶液吸收曲线测定
配制10 mg·L-1 (约0.02 mmol·L-1)的RhB溶液，在常温下，用紫外-可见分光光度计扫描RhB溶液的紫外可见吸收光谱，如图6所示，其最大吸收波长为556 nm。
（2）催化剂对有机染料罗丹明B（RhB）光催化降解的测试
在常温下，取浓度为10 ppm的RhB溶液30.0 mL于50.0 mL的无色透明烧杯中。每组实验均量取30.0 mL且分别加入相应用量的催化剂粉末，选用北京畅拓公司的PLS-SXE300UV高压氙灯作为降解光源，分别模拟可见光、太阳光和紫外光，测试样品均在距离氙灯约12 cm处进行光照，放在磁力搅拌器上以850 r/min的速度搅拌，之后每间隔5 min取上层清液3.0 mL进行测试。实验列于表2。
表2 光催化降解RhB实验
从图7（b）和表3可以看出，加入催化剂的10 ppm RhB溶液在氙灯模拟可见光作为光源的条件下，45min时降解率高达77.41%，而未加催化剂的RhB溶液降解率为2.07%（图7（a），表3）。在紫外光下，催化降解RhB溶液的能力比在模拟太阳光的照射下更强，45min时降解率分别达91.62%（图8（d），表3）和81.89%（图9（f），表3），但由于生活中处理有机染料使用紫外光不太现实，故我们在模拟太阳光下，用1M HCl调节溶液pH值，发现在pH=3.0和模拟太阳光的照射下，40min时RhB降解率高达97.50%（图10（h），表3），这说明酸性条件下，加快了RhB溶液的降解（在图7~10中，随着时间的增长，吸收峰的峰值下降）。此外，为了证明该催化剂的稳定性，把化合物光催化降解RhB后的粉末和原来的粉末进行对比，如图12，催化剂在催化前后其XRD曲线吻合好，这意味着该化合物作为催化剂的稳定性好。
表3 在不同模拟光源下催化剂降解RhB溶液的能力(45min)
降解率的计算公式：(A0-A)/A0×100%
A0——RhB未光照未加催化剂时的吸光度
A——RhB不同测试条件下的吸光度
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (4)
1.一种催化降解罗丹明B的光催化剂的制备方法，其特征在于：以NaWO4·2H2O、NiF2·4H2O、Na2SiO3·9H2O和有机配体Biim为原料，蒸馏水为溶剂，采用一步水热合成法制得催化剂。
2.根据权利要求1所述的催化降解罗丹明B的光催化剂的制备方法，其特征在于：具体包括以下步骤：
（1）将NaWO4·2H2O、NiF2·4H2O、Na2SiO3·9H2O和有机配体Biim溶解于蒸馏水中，搅拌至完全溶解，制成混合溶液；
（2）将步骤（1）得到的混合溶液的pH调成2.5；
（3）将步骤（2）所得溶液转移到内衬聚四氟乙烯的反应釜中，在145~155℃下恒温反应48~53h，冷却至室温制得所述光催化剂。
3.根据权利要求2所述的催化降解罗丹明B的光催化剂的制备方法，其特征在于：各反应物的用量分别为：NaWO4·2H2O：0.1566g~0.1730g；NiF2·4H2O：0.0090g~0.0100g；Na2SiO3·9H2O：0.0675g~0.0746g；有机配体Biim：0.0318g~0.0352g。
4.一种如权利要求1所述的制备方法制得的光催化剂的应用，其特征在于：所述光催化剂应用于催化降解有机染料罗丹明B。
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| "一种具有綈铭氧簇夹心铜氧簇化合物的合成与性质研究";李奕等;《光谱学与光谱分析》;20141031;第34卷(第10期);第59-60页 |
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