CN109534386B - 一种书页状形貌锌铝类水滑石及其制备方法和应用 - Google Patents
一种书页状形貌锌铝类水滑石及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种书页状形貌锌铝类水滑石及其制备方法和应用，属于功能材料技术领域，针对目前的锌铝水滑石制备方法制备出的水滑石均为不规则片状或六边形片状微晶粉末，无法得到特殊形貌，其次形貌也不能做到可控合成，为了解决该问题，本发明提出了一种水热合成的方法，通过调控反应时间、反应温度和反应物的浓度即可控制材料的生长尺寸和层间距，做到可控制备。该方法所制备的书页状锌铝水滑石具有层状结构，结晶度高，催化效率高，可应用于对孔雀石绿的催化反应中，20分钟染料孔雀石绿的降解率达到91％。
Description
技术领域
本发明属于功能材料技术领域，具体涉及一种具有书页状微观结构的层状双金属氢氧化物及其制备方法，以其作为高效催化剂催化降解染料的应用。
背景技术
层状双金属氢氧化物(Layered Double Hydroxides，LDHs)是由带正电荷的金属离子层板和带负电荷的层间阴离子通过非共价键的相互作用组装而成的化合物，又称类水滑石。其化学通式为[M2+ 1-xM3+ x(OH)2][An-]x/n·zH2O，其中M2+和M3+是主体层板八面体配位的二价和三价金属离子(M2+可以是Mg2+、Zn2+、Ni2+等，M3+可以是Fe3+、Mn3+、Co3+、Al3+等)，An-是层间客体水合阴离子，X代表层板中三价金属离子所占的摩尔比，一般为0.2～0.4，通常简写为M2+M3+-A-LDHs。LDHs的主体层板金属组成、主体层板电荷密度及其分布、层间客体种类及数量、层内空间尺寸、主客体相互作用等均具有可调变性。这些结构特点使其在诸多领域展示了广阔的应用前景，例如催化材料、吸附材料、光电转换材料、生物/医药材料、电子信息材料及环境友好功能助剂材料等。
自上个世纪90年代以来，LDHs的制备方法得到了迅速发展。共沉淀法是最常用的LDHs制备技术，该方法是将构成LDHs层板的二价、三价金属离子和层间阴离子在过饱和条件下共同沉淀析出LDHs。共沉淀法制备的材料颗粒尺寸不均匀，易形成不规则的石头状结构，比表面积小，理化性能差。溶胶凝胶法是以易于水解的金属有机配合物或金属烷氧基化合物为前驱体，经水解、缩聚逐渐凝胶化，再经干燥、焙烧制备LDHs的方法。采用溶胶凝胶法制备水滑石原料价格昂贵且水解较难控制。焙烧重构法是利用LDHs的结构“记忆效应”，将前驱体LDHs在一定温度下焙烧去除层间阴离子，再于低温下将焙烧产物加入到含待插层客体阴离子的溶液中，使之自动重建LDHs的结构，同时引入待插层阴离子，从而获得目标LDHs的方法。此方法需要制备前驱体，不能避免副产物的生成和洗涤过程。离子交换法是利用LDHs层间阴离子的可交换性，将前驱体LDHs置于含有待引入客体阴离子的溶液中，使待引入客体阴离子与前驱体LDHs层间的阴离子在一定条件下交换，获得目标LDHs。离子交换法工艺复杂，耗时长。我们采用的水热法具有工艺操作简单，制备时间短，能源消耗少，产物尺寸易于控制等优点，是目前合成普通锌铝水滑石的主要方法之一。
目前，从大量文献报道来看，绝大多数LDHs合成产物为不规则片状或六边形片状微晶粉末，有关LDHs控制特殊形貌制备方面的文献也很少，而具有书页形貌的锌铝水滑石的制备尚未见报道。
发明内容
本发明目的在于提供一种书页状形貌的锌铝双金属氢氧化物及其制备方法，本发明所采用的方法操作简单，反应条件温和，耗时短，制备的锌铝水滑石产物结晶度高，形貌和尺寸均一，且催化性能优异。
本发明所制备的具有书页状锌铝水滑石具有书页状的微观形貌，其化学通式如下所示：
[Zn1-xAlx(OH)2][NO3 -]x·zH2O
通式中，x为层板金属离子中三价铝离子所占的摩尔比，其取值范围为0.2～0.4；z为结晶水的数量，其取值范围为0～2。
其形貌为书页状，由多层锌铝水滑石罗列形成，书页叠加舒展宽度20nm～400nm，锌铝水滑石的厚度10～300nm，层间距为
本发明还提供了一种书页状类水滑石的制备方法，将锌溶液和铝溶液均匀混合在碱性环境和加热条件下反应得到书页状类水滑石，该方法具体操作步骤如下：
A：将8.999～13.5mmol六水合硝酸锌和3～4.5mmol九水合硝酸铝同时加入到含有30mL去离子水的烧杯中，在室温下搅拌溶解得到澄清溶液。
B：持续搅拌下，将1M的氢氧化钠溶液缓慢滴入上述步骤A制得的澄清溶液中，得到悬浊液，并使其pH保持在6～7。
C：将步骤B制得的悬浊液倒入带有聚四氟乙烯内衬的反应釜中后密封，反应釜内衬中填充比为30％～85％，继而将反应釜转移至100℃下反应3～24小时。
D：反应结束后，将反应釜自然冷却至室温，将反应后的产物经过去离子水和乙醇交替清洗后收集产物并干燥得到书页状锌铝水滑石。
所述步骤D的干燥温度为25～60℃，干燥时间为10～14小时。
将上述制备的书页状锌铝类水滑石应用于对孔雀石绿的催化反应中。
本发明的有益效果：
(1)本发明采用水热法一步合成目标产物，合成工艺简单，反应温和，原料廉价易得，成本低，产量高，耗时短，对环境友好，适合大规模生产。
(2)可以通过调节反应时间、反应温度和反应物的浓度等条件控制材料层间距，水滑石的厚度和书页叠加舒展宽度，实现对LDHs材料的可控制备。
(3)该方法制备的锌铝类水滑石具有层状结构，结晶度高，催化效率高等优点。
附图说明
图1是本发明实施例5的XRD图。
图2是本发明实施例5的扫描电镜图。
图3是本发明实施例5的FTIR图。
图4是本发明实施例5的催化降解曲线。
具体实施方式
下面以实施例的方式对本发明技术方案做进一步解释和说明。
实施例1
分别称取4.0161g Zn(NO3)2·6H2O和1.6883g Al(NO3)3·9H2O加入到含有30mL去离子水的烧杯中，室温下搅拌均匀配置成溶液A；配置浓度为1mol/L的氢氧化钠溶液，记为溶液B；向溶液A中缓慢滴入溶液B并持续搅拌，pH在6～7，得到悬浊液C；将悬浊液C倒入反应釜中再放入100℃烘箱，反应时间为3小时，产物用去离子水和乙醇交替洗涤常温干燥得到产物Zn-Al LDHs，记为3-Zn-Al LDHs。
实施例2
分别称取4.0161g Zn(NO3)2·6H2O和1.6883g Al(NO3)3·9H2O加入到含有30mL去离子水的烧杯中，室温下搅拌均匀配置成溶液A；配置浓度为1mol/L的氢氧化钠溶液，记为溶液B；向溶液A中缓慢滴入溶液B并持续搅拌，pH在6～7，得到悬浊液C；将悬浊液C倒入反应釜中再放入100℃烘箱，反应时间为6小时，产物用去离子水和乙醇交替洗涤常温干燥得到产物Zn-Al LDHs，记为6-Zn-Al LDHs。
实施例3
分别称取4.0161g Zn(NO3)2·6H2O和1.6883g Al(NO3)3·9H2O加入到含有30mL去离子水的烧杯中，室温下搅拌均匀配置成溶液A；配置浓度为1mol/L的氢氧化钠溶液，记为溶液B；向溶液A中缓慢滴入溶液B并持续搅拌，pH在6～7，得到悬浊液C；将悬浊液C倒入反应釜中再放入100℃烘箱，反应时间为9小时，产物用去离子水和乙醇交替洗涤常温干燥得到产物Zn-Al LDHs，记为9-Zn-Al LDHs。
实施例4
分别称取4.0161g Zn(NO3)2·6H2O和1.6883g Al(NO3)3·9H2O加入到含有30mL去离子水的烧杯中，室温下搅拌均匀配置成溶液A；配置浓度为1mol/L的氢氧化钠溶液，记为溶液B；向溶液A中缓慢滴入溶液B并持续搅拌，pH在6～7，得到悬浊液C；将悬浊液C倒入反应釜中再放入100℃烘箱，反应时间为12小时，产物用去离子水和乙醇交替洗涤常温干燥得到产物Zn-Al LDHs，记为12-Zn-Al LDHs。
实施例5
分别称取4.0161g Zn(NO3)2·6H2O和1.6883g Al(NO3)3·9H2O加入到含有30mL去离子水的烧杯中，室温下搅拌均匀配置成溶液A；配置浓度为1mol/L的氢氧化钠溶液，记为溶液B；向溶液A中缓慢滴入溶液B并持续搅拌，pH在6～7，得到悬浊液C；将悬浊液C倒入反应釜中再放入100℃烘箱，反应时间为24小时，产物用去离子水和乙醇交替洗涤常温干燥得到产物Zn-Al LDHs，记为24-Zn-Al LDHs。
实施应用例
将Zn-Al LDH分散于5mg/L的孔雀石绿溶液中，使其浓度为0.5g/L，保留实验在黑暗中自然吸附直至达到吸附平衡。主波长为365nm的250W高压汞灯用作紫外光源。按一定时间间隔取约2mL的悬浮液，经离心过滤处理，在紫外分光光度计下测定孔雀石绿的浓度，计算降解率。
测试与表征
本发明中分别利用XRD(Rigaku-D/max-2500,Japan),FESEM(JSM-7800F,Japan)，FTIR(American PE company)，UV-vis DRS(Japanese Shimadzu UV-3600)对样品的结构、形貌和性能进行表征分析。
如图1所示，本发明中所制备的书页状锌铝类水滑石XRD谱图中未发现杂峰，由此可证明所生成的锌铝类水滑石为纯相。
如图2所示，本发明中所制备的书页状锌铝类水滑石的形貌为书页状，由多层锌铝水滑石罗列形成，通过调节实验条件可对下面生长参数进行调节：书页叠加舒展宽度20nm～400nm，锌铝水滑石的厚度10nm～300nm，层间距为
如图3所示，可以观察到3450cm-1附近的宽而强的吸收峰，这归因于中间层或相邻层中水分子的O-H伸缩振动。出现在1634cm-1处的特征峰归因于层间水分子中氢键键合的OH基团的变形振动，1385cm-1处的急剧吸附峰主要归因于NO3 -的N-O伸缩振动。此外，出现在800cm-1以下的两个峰通常是由于金属-氧的晶格振动，如M-O，M-O-M和O-M-O基团和M-OH基团(M＝Zn，Al)。
如图4所示，20分钟染料孔雀石绿的降解率达到91％，表明所制备的书页状Zn-AlLDH有极好的催化降解效果。
Claims (5)
1.一种书页状形貌锌铝类水滑石，其特征在于，其化学通式如下所示：
[Zn1-xAlx(OH)2][NO3 -]x·zH2O
通式中，x为层板金属离子中三价铝离子所占的摩尔比，其取值范围为0.2～0.4；z为结晶水的数量，其取值范围为0～2；
其形貌为书页状，由多层锌铝水滑石罗列形成，书页叠加舒展宽度20nm～400nm，锌铝水滑石的厚度10～300nm，层间距为
2.如权利要求1所述的书页状形貌锌铝类水滑石的制备方法，具体步骤如下：
A：将8.999～13.5mmol六水合硝酸锌和3～4.5mmol九水合硝酸铝同时加入到含有30mL去离子水的烧杯中，在室温下搅拌溶解得到澄清溶液；
B：持续搅拌下，将1M的氢氧化钠溶液缓慢滴入上述步骤A制得的澄清溶液中，得到悬浊液，并使其pH保持在6～7；
C：将步骤B制得的悬浊液倒入带有聚四氟乙烯内衬的反应釜中后密封，反应釜内衬中填充比为30％～85％，继而将反应釜转移至100℃下反应3～24小时；
D：反应结束后，将反应釜自然冷却至室温，将反应后的产物经过去离子水和乙醇交替清洗后收集产物并干燥得到书页状锌铝水滑石。
3.根据权利要求2所述的书页状形貌锌铝类水滑石的制备方法，其特征在于，步骤A中六水合硝酸锌为13.5mmol，九水合硝酸铝为4.5mmol。
4.根据权利要求2所述的书页状形貌锌铝类水滑石的制备方法，其特征在于，步骤D中的干燥温度为25～60℃，干燥时间为10～14小时。
5.一种如权利要求1所述的书页状形貌锌铝类水滑石用于对孔雀石绿的催化反应的用途。
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