CN110669075B - Mo/W/Ta三元混配型多金属氧酸盐及其在光催化伯胺偶联反应中的应用 - Google Patents
Mo/W/Ta三元混配型多金属氧酸盐及其在光催化伯胺偶联反应中的应用 Download PDFInfo
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Abstract
本发明公开了Mo/W/Ta三元混配型多金属氧酸盐及其在光催化偶联反应中的应用，属于无机化学或光催化技术领域。本发明Mo/W/Ta三元混配型多金属氧酸盐，分子式为(NH4)41H7[K3(H2O)3(P2W15Ta3O62)6(Mo2O4CH3CO2)3(MoO3)2]·85H2O,由六个{P2W15Ta3O62}、三个{MoV 2O4Ac}和两个{MoVIO3}通过18个Mo‑O‑Ta键连接组成。该多金属氧酸盐在紫外光区和可见光区均有吸收，在模拟太阳光下对伯胺偶联反应具有高效的光催化活性，且无副产物生成，在光催化领域具有较好的应用前景。
Description
技术领域
本发明属于无机化学或光催化领域，具体涉及一种Mo/W/Ta三元混配型多金属氧酸盐及其在光催化伯胺偶联中的应用。
背景技术
多金属氧酸盐，简称多酸，是一类由过渡金属Mo,W,V,Nb,Ta和氧所组成的金属-氧簇化合物，在催化、材料科学、生物、医药等领域具有重要的研究及应用价值。构成多酸的这几种金属原子也称为配原子，由不同种类的配原子所形成的多酸会具有显著不同的性能。例如，多钨酸盐作为多齿配体与各种活性物质配位形成丰富的POM结构；多钼酸盐在还原条件下能够形成Mo2O4和(Mo)Mo5的基础构建单元，并形成巨大的球状或着笼状团簇；多钒酸盐有丰富的氧化还原性能，在无水条件下能够趋向于生成金属有机笼；多铌酸盐和多钽酸盐对碱有很强的依赖性，具有较高电荷密度和惰性的氧化还原活性。
将不同的配原子混合在一个簇中能够得到混配型多酸，改变配原子的比例和种类能够调节混配型多酸的电荷数、电化学性能、光化学和光催化性能。例如，在多钨酸盐或者多钼酸盐中加入一个或者多个钒(V)原可以极大的提高化合物的催化性能。[W6O19]2–阴离子是一种相对较弱亲核试剂，采用Nb(V)取代W(VI)所得到[NbW5O19]3–和[Nb2W4O19]4–具有很高的反应活性。使用“轨道工程”来调节Ta/W,Nb/W,V/Mo,V/W混配型多酸的电子结构，光吸收性质、光催化性能的研究也已有报道。但是目前人们已经发现和报道的混配型多酸都是二元混配型，包括V/W、V/Mo、V/Nb、Mo/W、Nb/W混配类型和Lindqvist、Keggin、Wells-Dawson结构类型，三元混配型多酸尚未见报道。
另一方面，亚胺及其衍生物是一类重要的有机中间体，广泛地用于有机合成和生物医药等领域。传统的合成亚胺及其衍生物的方法是利用伯胺和羰基化合物的缩合反应。这类方法过程麻烦操作复杂，并且很多原料都不容易制备。近年来，伯胺氧化偶联为制备亚胺的提供了一种新的策略。在光催化的条件下使用氧气和双氧水等氧化剂进行的绿色氧化过程也被广泛关注，但与有毒或贵金属的催化系统相比，使用分子氧作为氧化偶联反应唯一氧化剂的无贵金属催化系统比较少。多酸是一种无挥发性、无味、无毒，并且容易分离的环境友好型光催化剂。但是多酸光催化剂通常只具有紫外光催化活性，用于光催化亚胺生成的多酸光催化剂研究尚不充分。
因此，开发具有可见光活性的新型多酸光催化剂，并用于催化胺的偶联反应具有重要的科学意义和应用价值。
发明内容
为了克服上述缺陷，本发明提供了一种Mo/W/Ta三元混配型多金属氧酸盐1，分子式为：(NH4)41H7[K3(H2O)3(P2W15Ta3O62)6(Mo2O4CH3CO2)3(MoO3)2]·85H2O，同时也提供了其制备方法，并开发了其在光催化伯胺偶联反应中的应用。
本发明采用如下技术方案，Mo/W/Ta三元混配型多金属氧酸盐1为六聚体，棕红色棒状晶体，具有近似D3h对称结构，由六个{P2W15Ta3O62}、三个{Mo2Ac}、两个{MoVIO3}，通过18个Mo-O-Ta键链接组成。其结构及分子式通过单晶-X射线衍射、粉末XRD、红外光谱、元素分析、热重分析等表征手段确定。
本发明所述Mo/W/Ta三元混配型多金属氧酸盐1的制备方法，包括如下步骤：
将K8H[P2W15(TaO2)3O59]·12H2O、钼源和还原剂溶于去离子水中，然后加入CH3COOH和CH3COONH4，升温搅拌反应，冷却后过滤得到三元混配型多金属氧酸盐。
进一步优化，所述Mo/W/Ta三元混配型多金属氧酸盐的制备方法，使用CH3COOH和CH3COONH4调节pH值至3.0-4.0。升温搅拌反应在80℃下搅拌不低于20分钟，得到澄清反应液。
进一步优化，所述Mo/W/Ta三元混配型多金属氧酸盐的制备方法，使用的钼源选自钼酸钠或者钼酸铵。
进一步优化，所述Mo/W/Ta三元混配型多金属氧酸盐的制备方法，使用的还原剂优选肼类还原剂，例如硫酸肼、水合肼或盐酸肼等。
本发明所述的Mo/W/Ta三元混配型多金属氧酸盐，能有效吸收可见光，在紫外光或/和可见光照射下，在氧化剂存在下，对胺自身偶联反应表现出高效的光催化活性。
进一步优化，紫外或/和可见光选自模拟太阳光照射，氧化剂选自以空气中或氧气，胺类主要对伯胺进行了研究。采用反应方程式表示为：
附图说明
图1是本发明实施例1合成的多金属氧酸盐化合物的晶体结构图。
图2是本发明实施例1合成的多金属氧酸盐化合物的红外吸收光谱。
图3是本发明实施例1合成的多金属氧酸盐化合物的热重曲线。
图4是本发明实施例1合成的多金属氧酸盐化合物的粉末XRD图谱。
图5是本发明实施例合成的多金属氧酸盐化合物的漫反射图谱。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
以钼酸铵为前驱体，制备Mo/W/Ta三元混配型多酸1
前驱体K8H[P2W15(TaO2)3O59]·12H2O按照文献(J.Am.Chem.Soc.,2012,19716-19721)报道的方法制备。在100mL烧杯中加入20mL去离子水，接着再加入0.5g K8H[P2W15(TaO2)3O59]·12H2O、0.17g(NH4)6Mo7O24·4H2O、0.06gN2H4·H2SO4，搅拌均匀至溶液澄清，之后依次再向溶液中加入2.5mL CH3COOH和0.5g CH3COONH4，在水浴搅拌器中80℃条件下搅拌大约30分钟左右得到棕色悬浊液，冷却到室温后过滤得到澄清液，静置一周左右得到目标产物的棕红色棒状晶体，过滤收集得到Mo/W/Ta三元混配型多酸1，产率为40％。
对得到的Mo/W/Ta三元混配型多酸1分别进行了单晶-X射线衍射、粉末XRD、红外光谱、漫反射、热重等手段进行了表征和分析。
图1中：棍状图代表六个{P2W15Ta3O62}建筑块，多面体代表三个{Mo2Ac}和两个{MoVIO3}建筑块。
图2中：952,917,763,563,521,466cm-1处为M-O-M(M＝W,Ta or Mo)振动峰,1089cm-1为P-O键振动峰，3158和1403cm-1为[NH4]+基团振动峰，1539和2819cm-1为甲基基团振动峰。3436和1616cm-1为水振动峰。
图3中：热重曲线分别在30-220℃、220-290℃和290-550℃显示了连续地三步失重过程。第一步和第二步失重8.31％(计算值为8.38％)，相当于损失了88个水分子，41个铵根离子和3个乙酸配体。第三步失重4.50％对应着多酸骨架的坍塌，质子的脱水和P2O5的升华。
图4中：实验XRD数据与模拟数据基本一致，表明制备的样品具有较高纯度。催化前后与烘干样品的数据也基本一致，表明光催化反应前后的化合物保持不变。
图5中：从漫反射图谱上，看出该化合物在紫外光区和可见光区均有吸收。
实施例2
以钼酸钠为前驱体，制备Mo/W/Ta三元混配型多酸1
在100mL烧杯中加入20mL去离子水，接着再加入0.5g K8H[P2W15(TaO2)3O59]·12H2O、0.24g Na2MoO4·2H2O、0.06g N2H4·H2SO4，搅拌均匀至溶液澄清，之后依次再向溶液中加入2.5mL CH3COOH和0.5g CH3COONH4，检测pH＝3-4，接着在水浴搅拌器中80℃条件下搅拌大约30分钟左右得到棕色悬浊液，冷却到室温后过滤得到澄清液，静置一周左右得到目标产物的棕红色棒状晶体，过滤收集得到Mo/W/Ta三元混配型多酸1，产率为42％。
在实施例1和实施例2中，用等摩尔量水合肼或盐酸肼代替硫酸肼都可得到等量的产物1。
实施例3
光催化性能测试
实验条件为：0.2mmol苄胺或其衍生物溶于2mL溶剂中，加入催化量Mo/W/Ta三元混配型多酸1，在氙灯光源下搅拌。用GC-MS检测反应产物及产率。经过条件优选，最终我们得到最优的实验条件为：以空气中氧气为氧化剂，以乙腈为溶剂，反应温度为25℃，反应时间为24小时，催化剂的用量为1mol％，采用300W氙灯作为光源照，并配合AM-1.5G模拟太阳光滤光片，对不同的伯胺进行自身脱氨偶联，结果见表1。
表1.化合物1催化下的各种伯胺的偶联
表1中，代表性产物核磁数据：以苄胺为例，得到偶联产物，HNMR(400MHz,CDCl3):8.46(s,1H),7.75-7.77(m,2H),7.39-7.42(m,3H),7.33-7.35(m,4H),7.24-7.26(m,1H),4.77(s,2H).与标准核磁谱图数据一致。
通过表1中多个伯胺底物催化反应结果可以看出，在上述反应条件下，Mo/W/Ta三元混配型多酸1在光催化伯胺偶联反应中具有选择性高、无副产物，转化率高等特点。
Claims (6)
1.一种Mo/W/Ta三元混配型多金属氧酸盐，其特征在于：该多金属氧酸盐分子式为(NH4)41H7[K3(H2O)3(P2W15Ta3O62)6(Mo2O4CH3CO2)3(MoO3)2]·85H2O，棕红色棒状晶体，为Mo/W/Ta三种配原子组成的多金属氧簇，分子中六个P2W15Ta3O62、三个MoV 2O4Ac和两个MoVIO3通过18个Mo-O-Ta键链接而成。
2.权利要求1所述三元混配型多金属氧酸盐的制备方法，其特征在于，包括以下步骤：将K8H[P2W15(TaO2)3O59]·12H2O、钼源和还原剂溶于去离子水中，然后加入CH3COOH和CH3COONH4，升温搅拌反应，冷却后过滤得到三元混配型多金属氧酸盐；钼源选自钼酸铵或钼酸钠，还原剂选自硫酸肼、水合肼或盐酸肼。
3.根据权利要求2所述三元混配型多金属氧酸盐的制备方法，其特征在于：加入CH3COOH和CH3COONH4调节pH值至3.0-4.0；升温搅拌反应在80℃下搅拌不低于20分钟，得到澄清反应液。
4.权利要求1所述三元混配型多金属氧酸盐在光催化有机胺偶联领域中的应用，其特征在于：所述有机胺选自苄胺、4-甲基苄胺、4-甲氧基苄胺、4-三氟甲基苄胺、4-氯苄胺、噻吩-2-甲胺或呋喃-2-甲胺。
5.根据权利要求4所述三元混配型多金属氧酸盐在光催化有机胺偶联领域中的应用，其特征在于：在紫外光或/和可见光，以及氧化剂存在下，促进有机胺自身偶联反应。
6.根据权利要求5所述三元混配型多金属氧酸盐在光催化有机胺偶联领域中的应用，其特征在于：紫外光或/和可见光选自模拟太阳光，氧化剂选自空气中的氧气。
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