CN109395777B - 一种三元复合光催化剂BiOI@UIO-66(NH2)@g-C3N4的制备方法 - Google Patents
一种三元复合光催化剂BiOI@UIO-66(NH2)@g-C3N4的制备方法 Download PDFInfo
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Abstract
本发明涉及一种三元复合光催化剂BiOI@UIO‑66(NH2)@g‑C3N4的制备方法，包括三大步骤：g‑C3N4纳米片的制备、UIO‑66(NH2)@g‑C3N4纳米复合材料(UNCN)的制备和BiOI@UIO‑66(NH2)@g‑C3N4三元复合体系光催化剂(BiOI@UNCN)的制备。本发明的有益效果是：该制备方法较为简单，制备条件容易控制，所制备的BiOI@UIO‑66(NH2)@g‑C3N4复合催化剂具有无二次污染，光催化效率高等优点，具有一定的应用价值。
Description
技术领域
本发明属于纳米材料制备及应用技术领域，涉及一种三元复合光催化剂 BiOI@UIO-66(NH2)@g-C3N4的制备方法。
背景技术
BiOX(X＝Cl，Br，I)是一类光学活性优异的三元半导体材料，具有价格低廉、环境友好等特点。许多含铋的半导体如Bi2WO6，BiVO4，BiPO4，BiOX(X＝Cl， Br，I)因其优异的光学性能引起了人们的极大关注。其中，作为p型半导体的BiOI由于其各向异性的层状结构和合适的带隙而被开发成为有前景的光催化剂。由于BiOI具有较窄带隙(1.7-1.8eV)，因此它显示出强大的可见光响应能力。但是，纯BiOI的光催化活性受限于光诱导电荷载体的快速复合速率以及差的电导率。人们通常采用金属氧化物(TiO2，Bi2WO6)，碳材料(氮化碳，石墨烯)和金属有机骨架(MIL-88)构建BiOI异质结，增强BiOI光催化性能。
石墨相氮化碳(g-C3N4)作为一种具有可见光响应能力的聚合物半导体材料，禁带宽度2.7eV，与TiO2、ZnO、CdS相比具有更低的导带能级(-1.1eV vs NHE)，因此光生电子具有更强的还原能力。自2009年Wang等首次将g-C3N4用于光催化分解水产氢以来，该类材料已被广泛用于光催化有机合成、分解水产氢和降解有机污染物等领域。然而，光生电子-空穴的快速复合导致g-C3N4的光催化效率依然不高。为了克服这一缺点，研究人员尝试采用元素掺杂、担载共催化剂或构建异质结结构等策略提高g-C3N4的光催化能力。结果表明，与其他半导体材料复合构建异质结光催化剂能够促进光生电子和空穴的有效分离，从而提高光催化活性。例如，Zhu等报道的具有核壳结构的g-C3N4/BiPO4光催化剂能够高效降解亚甲基蓝。Cui等将具有高光催化活性的Ag3PO4与经过剥离的g-C3N4复合，构建了核壳结构的Ag3PO4@g-C3N4复合光催化剂，不但获得了高光催化活性，而且提高了Ag3PO4的稳定性，30min内对亚甲基蓝和双酚A的降解效率分别达到了97％和94.6％。
构建三元光催化体系被认为是增强光催化活性的有效策略，因为它具有协同效应和不同组分间接触良好的界面。具有多孔结构的金属有机骨架材料 (MOF)由金属铁/簇和有机配体的自组装形成。部分MOF具有类似于金属氧化物半导体的性质，可以作为优异的候选物或光催化剂被可见光激发产生电子- 空穴对。诸如MOF-5，UIO-66(NH2)，MIL-101(Cr)，MIL-88B(Fe)，MIL-125(Ti) 等可用于光催化产氢和污染物降解。MOF材料可以为光生电子的转移提供更多途径，有利于光生电荷的分离，提高光催化效率。因此，具有大比表面积的MOF 可以克服BiOI和g-C3N4低表面积和高电子-空穴复合率的缺点。此外，通过BiOI 与半导体的复合构建p-n型异质结，可以促进光催化活性。因此，构筑BiOI， g-C3N4和MOF的三元复合催化剂，可以扩大光催化剂的表面积，增加可见光响应，并有效分离光生电子-空穴对。文献调研发现，BiOI@UIO-66(NH2)@g-C3N4纳米复合材料的光催化活性尚未彻底研究。这里我们制备一种新型三元复合催化剂BiOI@UIO-66(NH2)@g-C3N4，以其为研究对象，结果表明，所制备的三元复合材料显示出优异的光催化降解罗丹明B(RhB)。因此，研究和开发这种新型的复合光催化剂是十分有意义的。
发明内容
本发明要解决的技术问题是：基于上述问题，本发明提供一种三元复合体系光催化剂BiOI@UIO-66(NH2)@g-C3N4的制备方法。
本发明解决其技术问题所采用的一个技术方案是：一种三元复合体系光催化剂BiOI@UIO-66(NH2)@g-C3N4的制备方法，包括以下步骤：
(1)g-C3N4纳米片的制备：将NH4Cl氯化铵和C3H6N6三聚氰胺分别分散到60mL乙醇中，然后在室温下搅拌2h。将上述悬浮液在80℃加热12h以蒸发乙醇，并将混合物在550℃下煅烧4h以获得黄色粉末。然后，将固体分散在 6M HCl(120mL)中，再转移到200mL的高压釜中，密封并保持在120℃下 8h。通过超声处理将产物分散在150mL水中2h，过滤得到产物，并用去离子水洗涤直至溶液达到中性；
(2)UIO-66(NH2)@g-C3N4纳米复合材料(UNCN)的制备：将g-C3N4，ZrCl4和2-NH2-BDC超声分散在50mL DMF中以形成均匀的悬浮液。随后，将溶液转移至100mL高压釜中密封，并在120℃下保持24h。过滤得产物，并用DMF 和甲醇洗涤数次。最后，沉淀物在80℃下干燥24h；
(3)BiOI@UNCN三元复合催化剂的制备：将UNCN超声分散在20mL乙二醇中以形成均匀悬浮液A。同时，分别将Bi(NO3)3·5H2O和KI溶解于50mL 乙二醇中。随后，在剧烈搅拌下将上述溶液加入到悬浮液A中。将所得混合物进一步搅拌2h，然后转移至150mL高压釜中密封，并保持在120℃下12h。最后，将产物过滤并用去离子水洗涤数次。所合成的BiOI@UNCN样品表示为 BiOI@UNCN-x，其中x表示UNCN与BiOI的标称重量比，采用此原位水热法合成了一系列BiOI@UNCN。
进一步地，所述的步骤(1)中过滤所得的产物必须用去离子水洗涤直至溶液达到中性；
进一步地，所述的步骤(2)中ZrCl4和2-NH2-BDC的摩尔比为1:1；
进一步地，所述的步骤(3)中BiOI:UNCN质量比分别为20wt％、40wt％、 60wt％。
进一步地，所述的步骤(3)中水热温度为120℃，反应时间为12h。
BiOI@UNCN三元体系复合催化剂的应用，用于光催化降解罗丹明B (RhB)，按照下述步骤进行：
称取20mg催化剂放入试管中，加入50mL 20mg/L RhB溶液，用带有420 nm滤光片的500W氙灯作为光源，进行光催化降解反应。暗反应时间为60min，光照后，每20min取次样，进行离心，进而测其吸光度。
本发明的有益效果是：该制备方法较为简单，制备条件容易控制，所制备的三元体系BiOI@UNCN复合光催化剂具有无污染，催化效率高等优点，具有一定的应用价值。
附图说明
下面结合附图对本发明进一步说明。
图1是本发明实施例1制备得到的(a)UIO-66(NH2),(b)BiOI,(c)UNCN和(d) BiOI@UNCN的扫描电镜图；
图2是本发明实施例1制备得到的三元体系BiOI@UNCN复合光催化剂的 X射线衍射图；
图3是本发明实施例1制备得到一系列BiOI@UNCN-x的复合光催化剂降解罗丹明B的活性图。
具体实施方式
现在结合具体实施例对本发明作进一步说明，以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1
(1)g-C3N4纳米片的制备：将NH4Cl氯化铵(0.1869mol,10g)和C3H6N6三聚氰胺(0.0396mol,5g)分别分散到60mL乙醇中，然后在室温下搅拌2h。将上述悬浮液在80℃加热12h以蒸发乙醇，并将混合物在550℃下煅烧4h以获得黄色粉末。然后，将固体分散在6M HCl(120mL)中，再转移到200mL的高压釜中，密封并保持在120℃下8h。通过超声处理将产物分散在150mL水中 2h，过滤得到产物，并用去离子水洗涤直至溶液达到中性；
(2)UIO-66(NH2)@g-C3N4纳米复合材料(UNCN)的制备：将g-C3N4 0.0777 g，ZrCl4(0.2332g，1.0mmol)和2-NH2-BDC(0.1812g，1.0mmol)超声分散在50mL DMF中以形成均匀的悬浮液。随后，将溶液转移至100mL高压釜中密封，并在120℃下保持24h。过滤得产物，并用DMF和甲醇洗涤数次。最后，沉淀物在80℃下干燥24h；
(3)BiOI@UNCN三元复合催化剂的制备：将0.1408g UNCN超声分散在 20mL乙二醇中以形成均匀悬浮液A。同时，分别将Bi(NO3)3·5H2O(0.9702g， 2.0mmol)和KI(0.4155g，2.5mmol)溶解于50mL乙二醇中。随后，在剧烈搅拌下将上述溶液加入到悬浮液A中。将所得混合物进一步搅拌2h，然后转移至150mL高压釜中密封，并保持在120℃下12h。最后，将产物过滤并用去离子水洗涤数次。所合成的BiOI@UNCN样品表示为BiOI@UNCN-x，其中x表示UNCN与BiOI的标称重量比，采用此原位水热法合成了一系列BiOI@UNCN。
扫描电镜图如图1所示，从图可以看出，本实施方式制备的(a)UIO-66(NH2) 为片层状，(b)BiOI为花球状，(c)UNCN的扫描电镜图显示UIO-66(NH2)和 g-C3N4彼此紧密接触表明UIO-66(NH2)和g-C3N4之间存在相互作用，(d) BiOI@UNCN复合光催化剂的形貌如图所示，表明BiOI很好地分散在UNCN载体表面，且分布较为均匀。
X射线衍射图谱如图2所示，由图可知，UIO-66(NH2)在7.3o，8.3o和25.6o 处显示主衍射峰；BiOI在29.3o，31.7o，45.6o和55.1o上呈现特征衍射峰，这可归因于(102)，(110)，(200)和(212)衍射平面；从UNCN的XRD得到，当引入g-C3N4纳米片后，可以观察到在27.6o的衍射峰归属于(002)衍射平面，表明通过溶剂热法成功地将UIO-66(NH2)负载在g-C3N4纳米片上；在UNCN的低质量负载下， BiOI@UNCN-20复合材料的XRD图谱没有显示UNCN的衍射峰，但是随着负载量增加BiOI@UNCN-40/60在7.3o和8.3o处显示衍射峰，说明成功制备三元体复合催化剂BiOI@UNCN。
(4)光催化降解罗丹明B(RhB)
分别称取20mg不同负载比例催化剂放入试管中，加入50mL 20mg/L RhB 溶液，用带有420nm滤光片的500W氙灯作为光源，进行光催化降解反应。暗反应时间为60min，光照以后，每隔20min取次样，并在5000rpm条件下高速离心，取上层清液用紫外可见分光光度计测其浓度变化。由图3可见，在80 分钟内罗丹明B降解率以达到94.8％，可见所制备的BiOI@UNCN复合光催化剂具有较高的光催化活性。
Claims (3)
1.一种三元复合光催化剂BiOI@UIO-66-NH2@g-C3N4的制备方法，其特征在于，包括以下步骤：
(1)g-C3N4纳米片的制备：将NH4Cl氯化铵和C3H6N6三聚氰胺分别分散到60mL乙醇中，然后在室温下搅拌2h，将得到的悬浮液在80℃加热12h以蒸发乙醇，并将混合物在550℃下煅烧4h以获得黄色粉末，然后，将固体分散在120mL的6M HCl中，再转移到200mL的高压釜中，密封并保持在120℃下8h，通过超声处理将产物分散在150mL水中2h，过滤得到产物，并用去离子水洗涤直至溶液达到中性；
(2)UIO-66-NH2@g-C3N4纳米复合材料UNCN的制备：将步骤(1)制备的g-C3N4，ZrCl4和2-NH2-BDC超声分散在50mL DMF中以形成均匀的悬浮液，随后，将溶液转移至100mL高压釜中密封，并在120℃下保持24h，冷却后，将悬浮液超声分散在20mL乙二醇中，并用DMF和甲醇洗涤数次，最后，沉淀物在80℃下干燥24h；
(3)BiOI@UNCN三元复合材料的制备：将步骤(2)制备的UNCN超声分散在20mL乙二醇中以形成均匀悬浮液A，将Bi(NO3)3·5H2O和KI溶解于50mL乙二醇中，随后，在剧烈搅拌下将上述溶液加入到上述悬浮液A中，将所得混合物进一步搅拌2h，然后转移至150mL高压釜中密封，并保持在120℃下12h，最后，将产物过滤并用去离子水洗涤数次，所合成的BiOI@UNCN样品表示为BiOI@UNCN-x，其中x表示UNCN与BiOI的标称重量比，采用此原位水热法合成了一系列BiOI@UNCN，所述的步骤(3)中UNCN的质量为0～5g，且BiOI:UNCN质量比分别为20wt％、40wt％、60wt％。
2.根据权利要求1所述的一种三元复合光催化剂BiOI@UIO-66-NH2@g-C3N4的制备方法，其特征是：所述的步骤(1)中过滤所得的产物必须用去离子水洗涤直至溶液达到中性。
3.根据权利要求1所述的一种三元复合光催化剂BiOI@UIO-66-NH2@g-C3N4的制备方法，其特征是：所述的步骤(2)中ZrCl4和2-NH2-BDC的摩尔比为1:1。
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