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 PDFInfo
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 47
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000001301 oxygen Substances 0.000 title claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 238000012986 modification Methods 0.000 title claims abstract description 41
- 230000004048 modification Effects 0.000 title claims abstract description 41
- 239000001257 hydrogen Substances 0.000 title claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 20
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Inorganic materials O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- ABMYEXAYWZJVOV-UHFFFAOYSA-N pyridin-3-ylboronic acid Chemical compound OB(O)C1=CC=CN=C1 ABMYEXAYWZJVOV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910016644 EuCl3 Inorganic materials 0.000 claims abstract description 5
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims abstract description 5
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- 239000013078 crystal Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
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- 238000001914 filtration Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
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- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
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- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
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- 238000007146 photocatalysis Methods 0.000 abstract description 3
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- 150000002910 rare earth metals Chemical class 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
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- 150000003839 salts Chemical class 0.000 abstract description 2
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- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000001907 polarising light microscopy Methods 0.000 description 11
- 229920006324 polyoxymethylene Polymers 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- UMLDUMMLRZFROX-UHFFFAOYSA-N pyridin-2-ylboronic acid Chemical group OB(O)C1=CC=CC=N1 UMLDUMMLRZFROX-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
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- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- -1 organotin Chemical group 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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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
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。
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