CN109967124A - 有机硼共价修饰的多金属氧簇,制备方法及其在光催化产氢领域的应用 - Google Patents

有机硼共价修饰的多金属氧簇,制备方法及其在光催化产氢领域的应用 Download PDF

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CN109967124A
CN109967124A CN201910130393.0A CN201910130393A CN109967124A CN 109967124 A CN109967124 A CN 109967124A CN 201910130393 A CN201910130393 A CN 201910130393A CN 109967124 A CN109967124 A CN 109967124A
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metal oxygen
covalent modification
oxygen cluster
organic boron
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李书军
周艳芳
麻娜娜
陈学年
张絜
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Henan Normal University
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Abstract

本发明公开了一种有机硼共价修饰的多金属氧簇,制备方法及其在光催化产氢领域的应用,属于多金属氧簇化合物的合成及光催化领域。本发明的技术方案要点为:选用3‑吡啶硼酸为硼源,选用含过氧基团的混配型多酸K8H[P2W15(NbO2)3O59]·12H2O为前驱体,选用NaHSO3为脱过氧的还原剂,以水为溶剂、稀土盐EuCl3·6H2O为辅助试剂,用盐酸调节混合体系的pH值为1~3,采用简单的常规反应方法,反应时间为20~30min,所得的有机硼共价修饰的多金属氧簇是一个Dawson型的四聚结构,其分子式为Na2H20(C5NH6)2[(3‑HPyB)4(P2W15Nb3O62)4]·37H2O。本发明首次合成了新型有机硼共价修饰的多金属氧簇,其合成过程简单且成本低廉,制得的有机硼共价修饰的多金属氧簇在光催化领域具有较好的应用前景。

Description

有机硼共价修饰的多金属氧簇,制备方法及其在光催化产氢 领域的应用
技术领域
本发明属于多金属氧簇化合物的合成及光催化产氢技术领域,具体涉及一种有机硼共价修饰的多金属氧簇,制备方法及其在光催化产氢领域的应用。
背景技术
在有机-无机杂化材料领域中,根据有机和无机组分之间相互作用力的不同可以将这类材料分为两类,第一类是有机和无机部分之间没有共价键,只有静电相互作用、氢键或范德华力等弱作用力;第二类是有机和无机部分通过强共价键或离子键连接。多金属氧酸盐简称多酸(POMs)是一类由前过渡金属(M=Mo、W、V、Nb和Ta)和氧组成的无机簇合物。将有机基团共价修饰接到多酸表面是调节其物理和化学性质的最有效策略之一。多酸的阴离子特性使得它们很容易与有机抗衡阳离子结合形成第一类杂化物。位于POM表面的氧原子具有亲核性,可与带有有机基团的亲电子基团形成共价键,从而形成第二类杂化物。将有机片段接到POM上需要一个链接位点,该链接密切依赖于无机实体的化学性质和电子性质。
实际上,通过形成M-O-X桥(X:p-区元素)来修饰位于POM外围的氧原子是最常规的合成路线。有机基团的主要配位模式通过p-区元素与POM通过共价键连接。到目前为止,POM可以与烷氧基、羧基、硅氧烷基、有机锡、有机氮、有机砷和有机膦酰基衍生物通过形成共价键合成具有POM的有机-无机杂化物。
位于第三主族的硼(B)是典型的亲氧元素,并且是唯一具有缺电子的非金属元素,其特殊性可能会赋予POM独特的性质。然而,有机硼共价修饰的POM尚未见报道。目前已知的含硼POM主要限于一些无机的硼钒酸盐(Angew. Chem. Int. Ed. 2014, 53, 3608)和一些硼钨酸盐(Inorg. Chem. 2007, 46, 4383;Angew. Chem. Int. Ed. 2009, 48, 4986),其中无机硼酸盐充当杂原子,例如:[BW12O40]5-和[HBW11O39]8-及其衍生物。因此探索由M-O-B桥键连接的硼酸共价修饰POM的合成、性质、结构并开发其在光催化产氢领域的应用具有重要的科学意义和实用价值。
发明内容
本发明解决的技术问题是提供了一种有机硼共价修饰的多金属氧簇及其制备方法,该方法制得的有机硼共价修饰的多金属氧簇表现出很好的光催化产氢效果,进而能够用于光催化产氢领域。
本发明为解决上述技术问题采用如下技术方案:第一例有机硼共价修饰的多金属氧簇,是第一例有机硼共价修饰的多金属氧簇,该有机硼共价修饰的多金属氧簇是一个Dawson型的四聚结构,其分子式为Na2H20(C5NH6)2[(3-HPyB)4(P2W15Nb3O62)4]·37H2O,其晶体结构单元如图1所示,该化合物由四个Dawson型{P2W15Nb3O62}片段被四个3-PyB基团通过十二个Nb-O-B桥连接组成,B-O的平均键长为1.45Å,每个B原子采用四面体sp3杂化,并与来自三个{P2W15Nb3O62}的三个O(Nb)配位,所有的B原子都是三价的,所有的O(B)都是未质子化的,四个3-PyB基团和四个{Nb3}团簇形成一个直径为3.0Å的中心对称的空洞,其中心是钠离子。
本发明所述的有机硼共价修饰的多金属氧簇的制备方法,其特征在于具体过程为:选用3-吡啶硼酸(3-PyB)为硼源,选用含过氧基团的混配型多酸K8H[P2W15(NbO2)3O59]·12H2O为前驱体,选用NaHSO3为脱过氧的还原剂,以水为溶剂、稀土盐EuCl3·6H2O为辅助试剂,用盐酸调节混合体系的pH值为1~3,采用简单的常规反应方法,反应时间为20~30min。优选的K8H[P2W15(NbO2)3O59]·12H2O、NaHSO3、3-吡啶硼酸与EuCl3·6H2O的投料质量比为0.2:0.04:0.01:0.02。
本发明所述的有机硼共价修饰的多金属氧簇在光催化产氢领域的应用,其特征在于具体过程为:将有机硼共价修饰的多金属氧簇浸泡在甲醇和盐酸的混合溶液中,在助催化剂氯铂酸存在下,用300W汞灯照射,该有机硼共价修饰的多金属氧簇表现出很好的光催化产氢效果。
本发明首次合成了新型有机硼共价修饰的多金属氧簇,其合成过程简单且成本低廉,制得的有机硼共价修饰的多金属氧簇在光催化产氢领域具有较好的应用前景。
附图说明
图1是实施例1制得的有机硼共价修饰的多金属氧簇的晶体结构图;
图2是实施例1制得的有机硼共价修饰的多金属氧簇的红外光谱图;
图3是实施例1制得的有机硼共价修饰的多金属氧簇的核磁图谱;
图4是实施例1制得的有机硼共价修饰的多金属氧簇光催化产氢中时间与释放氢气总量的关系曲线,其中反应体系的pH值为1,催化剂有机硼共价修饰的多金属氧簇的用量为0.063mmol/L。
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
将K8H[P2W15(NbO2)3O59]·12H2O(0.2g)和NaHSO3(0.04g)溶于25mL高纯水中并于75℃水浴中反应直至溶液被还原至无色,再加入3-吡啶硼酸(0.01g)和EuCl3·6H2O(0.02g),用1mol/L的盐酸调节混合体系的pH值约为1.0,反应约20min取出溶液,然后将溶液冷却至室温,过滤静置3天得到浅黄色双锥状晶体即有机硼共价修饰的多金属氧簇,产率为75%。
图1是本实施例制得的有机硼共价修饰的多金属氧簇的晶体结构图,图中深灰色四方锥代表NbO5,灰色八面体代表WO6,黑色球代表B原子,灰色球代表C原子,深色球代表N原子,浅灰色球代表Na原子。
图2是本实施例制得的有机硼共价修饰的多金属氧簇的红外光谱图,其中1620cm-1处出现的强峰可以认为是化合物的晶格水和配位水分子的振动;在1091cm-1、953cm-1、900cm-1和747cm-1出现的特征峰,可归结为Dawson型多阴离子[P2W15(NbO2)3]9-中的Vas(P-Oa)、Vas(W=Ot)、Vas(W-Ob)和Vas(W-Oc)的特征吸收峰;化合物的1547cm-1、1461cm-1、1401cm-1、1203cm-1峰可以认为是3-吡啶硼酸的特征吸收峰。
图3是本实施例制得的有机硼共价修饰的多金属氧簇的核磁31P谱,位移在-7.9ppm和-13.5ppm。
实施例2
有机硼共价修饰的多金属氧簇光催化产氢的活性测试
向石英光催化反应器中加入35mL甲醇及175mL、pH=1的盐酸溶液和0.2mL、0.046MH2PtCl6溶液,然后加入0.1g实施例1制得的有机硼共价修饰的多金属氧簇,用300W汞灯照射,通过光解水制氢装置完成,用气相色谱检测该气体为氢气,如附图4所示,每1h记录一次氢气的累积量,5h释放氢气总量达到986μmol。
以上实施例描述了本发明的基本原理、主要特征及优点,本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明原理的范围下,本发明还会有各种变化和改进,这些变化和改进均落入本发明保护的范围内。

Claims (5)

1.有机硼共价修饰的多金属氧簇,其特征在于:所述有机硼共价修饰的多金属氧簇是一个Dawson型的四聚结构,其分子式为Na2H20(C5NH6)2[(3-HPyB)4(P2W15Nb3O62)4]·37H2O,其晶体结构单元如图1所示,该有机硼共价修饰的多金属氧簇由四个Dawson型{P2W15Nb3O62}片段被四个3-PyB基团通过十二个Nb-O-B桥连接组成,B-O的平均键长为1.45Å,每个B原子采用四面体sp3杂化,并与来自三个{P2W15Nb3O62}的三个O(Nb)配位,所有的B原子都是三价的,所有的O(B)都是未质子化的,四个3-PyB基团和四个{Nb3}团簇形成一个直径为3.0Å的中心对称的空洞,其中心是钠离子。
2.一种权利要求1所述的有机硼共价修饰的多金属氧簇的制备方法,其特征在于具体过程为:将K8H[P2W15(NbO2)3O59]·12H2O和NaHSO3溶于高纯水中并于75℃水浴中反应直至溶液被还原至无色,再加入3-吡啶硼酸和EuCl3·6H2O,用盐酸调节混合体系的pH值为1~3,反应20~30min取出溶液,将溶液冷却至室温,过滤静置得到浅黄色双锥状晶体即有机硼共价修饰的多金属氧簇。
3.根据权利要求2所述的有机硼共价修饰的多金属氧簇的制备方法,其特征在于:所述K8H[P2W15(NbO2)3O59]·12H2O、NaHSO3、3-吡啶硼酸与EuCl3·6H2O的投料质量比为0.2:0.04:0.01:0.02。
4.根据权利要求2所述的有机硼共价修饰的多金属氧簇的制备方法,其特征在于具体步骤为:将K8H[P2W15(NbO2)3O59]·12H2O 0.2g和NaHSO3 0.04g溶于25mL高纯水中并于75℃水浴中反应直至溶液被还原至无色,再加入3-吡啶硼酸0.01g和EuCl3·6H2O 0.02g,用1mol/L的盐酸调节混合体系的pH值为1.0,反应20min取出溶液,然后将溶液冷却至室温,过滤静置3天得到浅黄色双锥状晶体即有机硼共价修饰的多金属氧簇,产率为75%。
5.权利要求1所述的有机硼共价修饰的多金属氧簇在光催化产氢领域的应用。
CN201910130393.0A 2019-02-21 2019-02-21 有机硼共价修饰的多金属氧簇,制备方法及其在光催化产氢领域的应用 Pending CN109967124A (zh)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110756224A (zh) * 2019-11-05 2020-02-07 江苏师范大学 一种Nb/W混配型多金属氧酸盐及其制备方法和应用
CN112094185A (zh) * 2020-08-26 2020-12-18 河南师范大学 一类结构新颖的过渡金属-多酸衍生物及其制备方法
CN115805088A (zh) * 2022-08-15 2023-03-17 河南师范大学 一种基于银簇和Nb/W混金属多酸光催化剂及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988006489A1 (en) * 1987-02-27 1988-09-07 University Of Oregon Organic solvent soluble oxide supported hydrogenation catalyst precursors
CN104649325A (zh) * 2015-01-06 2015-05-27 河南大学 一种Wells-Dawson型铌钨混配多酸稀土衍生物、其制备方法以及应用
CN104984766A (zh) * 2015-07-29 2015-10-21 河南师范大学 一类B/POMs/TiO2三元复合光催化材料及其制备方法
CN105642351A (zh) * 2014-12-02 2016-06-08 中国石油化工股份有限公司 杂多酸铵盐催化剂及其制备方法
CN108722491A (zh) * 2018-06-20 2018-11-02 河南师范大学 一种具有可见光催化活性的Ta/W混配型多酸有机-无机杂化物及其制备方法
CN109021001A (zh) * 2018-08-27 2018-12-18 河南师范大学 一种有机硼酸修饰的多金属氧酸盐的稀土衍生物及其制备方法
CN109180711A (zh) * 2018-08-27 2019-01-11 河南师范大学 一类有机硼酸-稀土-多酸配合物及其制备方法和在光致发光器件中的应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988006489A1 (en) * 1987-02-27 1988-09-07 University Of Oregon Organic solvent soluble oxide supported hydrogenation catalyst precursors
CN105642351A (zh) * 2014-12-02 2016-06-08 中国石油化工股份有限公司 杂多酸铵盐催化剂及其制备方法
CN104649325A (zh) * 2015-01-06 2015-05-27 河南大学 一种Wells-Dawson型铌钨混配多酸稀土衍生物、其制备方法以及应用
CN104984766A (zh) * 2015-07-29 2015-10-21 河南师范大学 一类B/POMs/TiO2三元复合光催化材料及其制备方法
CN108722491A (zh) * 2018-06-20 2018-11-02 河南师范大学 一种具有可见光催化活性的Ta/W混配型多酸有机-无机杂化物及其制备方法
CN109021001A (zh) * 2018-08-27 2018-12-18 河南师范大学 一种有机硼酸修饰的多金属氧酸盐的稀土衍生物及其制备方法
CN109180711A (zh) * 2018-08-27 2019-01-11 河南师范大学 一类有机硼酸-稀土-多酸配合物及其制备方法和在光致发光器件中的应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CONG-CONG LI ET AL.: "Assembly of Saturated Nb/W Mixed-Addendum Polyoxometalate [P2W15Nb3O62]9- and Lanthanide Ions (Ln: Eu,Ce)", 《CHEMINFORM ABSTRACT》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110756224A (zh) * 2019-11-05 2020-02-07 江苏师范大学 一种Nb/W混配型多金属氧酸盐及其制备方法和应用
CN112094185A (zh) * 2020-08-26 2020-12-18 河南师范大学 一类结构新颖的过渡金属-多酸衍生物及其制备方法
CN115805088A (zh) * 2022-08-15 2023-03-17 河南师范大学 一种基于银簇和Nb/W混金属多酸光催化剂及其制备方法和应用

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