CN112892565A - 一种多酸基铜金属有机无机杂化材料及其制备方法和应用 - Google Patents
一种多酸基铜金属有机无机杂化材料及其制备方法和应用 Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 68
- 239000002184 metal Substances 0.000 title claims abstract description 68
- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000010949 copper Substances 0.000 title claims abstract description 55
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910001868 water Inorganic materials 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000013110 organic ligand Substances 0.000 claims abstract description 16
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 6
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- 239000000126 substance Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- 239000011941 photocatalyst Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
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- 125000004429 atom Chemical group 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 8
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- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
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- 229910052721 tungsten Inorganic materials 0.000 description 2
- AZVPUVHTLAXDBK-UHFFFAOYSA-N 4-(3,5-dimethyl-1h-pyrazol-4-yl)-3,5-dimethyl-1h-pyrazole Chemical compound CC1=NNC(C)=C1C1=C(C)NN=C1C AZVPUVHTLAXDBK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种多酸基铜金属有机无机杂化材料,其化学式为:Cu(HPW12O40)0.5(H2bpz)2(OH)·(H2O)6;合成方法是将磷钨酸、硝酸铜、3,3’,5,5’,‑四甲基‑4,4’‑连吡唑有机配体溶解到水中并超声混合均匀得到反应液,将反应液加入到反应釜中进行水热反应,冷却降温至室温得到蓝紫色块状晶体即为多酸基铜金属有机无机杂化材料。本发明还公开了上述多酸基铜金属有机无机杂化材料在光催化制氢中的应用。本发明合成的材料包含具有良好光敏性的磷钨酸盐,且多酸与金属有机配合物所形成的半导体结构禁带宽度较合适,具有良好的光催化分解水产氢的性能。
Description
技术领域
本发明属于一种有机无机杂化材料,具体涉及一种多酸基铜金属有机无机杂化材料及其制备方法和在光催化制氢中的应用。
背景技术
如今,我们面临着环境和能源的双重挑战。太阳能提供最丰富,取之不尽的可再生和清洁能源,为未来的能源需求解决燃眉之急。太阳能可通过光催化制氢技术转化为储氢储能,光催化剂在转化过程中起着关键作用,而新型高效催化剂的开发也越来越受到科学家们的关注。
多金属氧酸盐(POMs)是由高氧化态过渡金属(W,Mo,V)组成的一大类金属氧簇合物。由于它们的氧化还原能力和结构变化,在催化、污染物降解、电化学、磁学、医学,光致变色和其他区域都有着重要应用。尤其是POMs对水溶液具有显著的光催化活性制氢。然而,POMs合成难度大,在水溶液和极性有机溶剂中的高溶解度导致低可用性,作为光催化剂分解水产氢催化活性差等问题制约了其应用。
发明内容
本发明的目的在于克服现有技术存在的不足,提供一种多酸基铜金属有机无机杂化材料及其制备方法和应用。
为了实现以上目的,本发明的技术方案为:
一种多酸基铜金属有机无机杂化材料,其化学式为Cu(HPW12O40)0.5(H2bpz)2(OH)·(H2O)6,其中,H2bpz为3,3’,5,5’,-四甲基-4,4’-连吡唑有机配体;晶系为单斜;空间群为P21/n;单胞参数为 α=90,β=98.711(2),γ=90,z=2。元素分析结果:C20H41.5CuP0.5W6N8O27:Calcd(%):C 11.96,H 2.08,N5.58。Found:C 11.55,H 2.40,N 5.39。
可选的,所述Cu的化合价为+2价,配位方式为6配位。
可选的,结构中的化合物最小不对称结构单元中铜离子连接四个有机配体的氮原子,一个多酸阴离子中的氧和一个水中的氧原子。
上述多酸基铜金属有机无机杂化材料的制备方法包括以下步骤:
1)将磷钨酸、硝酸铜、3,3’,5,5’,-四甲基-4,4’-连吡唑有机配体溶解到水中并超声混合均匀得到反应液,其中硝酸铜、磷钨酸和3,3’,5,5’,-四甲基-4,4’-连吡唑有机配体的摩尔比为0.1:0.2~0.24:0.1~0.15;
2)将反应液加入到反应釜中,在120℃~160℃下反应80~110小时,冷却降温至室温得到蓝紫色块状晶体即为多酸基铜金属有机无机杂化材料。
可选的,所述磷钨酸的物质的量与水的体积比为0.2~0.24mmol:5~10ml,所述水是去离子水或蒸馏水。
可选的,所述反应液的pH值为2.2~2.6。
进一步优选的,所述制备方法包括以下步骤:
1)将摩尔比为0.2~0.24:0.1:0.12的磷钨酸、硝酸铜、3,3’,5,5’,-四甲基-4,4’-连吡唑有机配体溶解到去离子水中并超声混合均匀得到pH值为2.4的反应液;
2)将反应液加入到聚四氟乙烯的反应釜中,再在140℃下反应96小时,冷却降温至室温得到蓝紫色块状晶体即为多酸基铜金属有机无机杂化材料。
上述多酸基铜金属有机无机杂化材料在光催化制氢中的应用。
可选的,所述多酸基铜金属有机无机杂化材料作为光催化剂,在以40%~60%乙醇作为牺牲剂,水做溶剂的溶液中光催化分解水产氢。
可选的,所述溶液中乙醇和水的体积比为1:0.5~2。
本发明的有益效果为:
1)采用简单的一步水热合成法,利用3,3’,5,5’,-四甲基-4,4’-连吡唑有机配体、硝酸铜和磷钨酸制备了一种多酸基铜金属有机无机杂化材料,不但具有良好光敏性的磷钨酸,而且Keggin型多酸磷钨酸与金属有机配合物形成理想的半导体结构,禁带宽度较合适,这种独特的结构使本发明的以多酸基铜金属有机无机杂化材料有着优异的光催化分解水产氢性能,并且由于活性组分多酸无机单元结构按照更稳定的键合方式和空间排列方式,使本发明的多酸基铜金属有机无机杂化材料可以具有高效稳定的催化活性;
2)本发明的金属有机物配合物具有高比表面积、高稳定性和有序孔道,以功能性POMs为模板单元,与金属有机配合物相结合,制备多酸基金属有机杂化材料。多酸基金属有机无机杂化材料结合了多金属氧酸盐和金属有机配合物的优良性能,在金属基础上的结合促进了结构的稳定性和功能的多样性,这不仅充分发挥了其优势,同时也克服了它们的缺点,实现了它们功能的结合。从性能上看,这类晶体材料不仅体现了多金属氧酸盐本身的优良性能,而且体现了金属有机配合物的优良性能,从而使多酸基金属有机杂化材料具有更好的光催化应用前景。
附图说明
图1为实施例1制备的一种多酸基铜金属有机无机杂化材料的最小不对称结构单元示意图,图1中1为磷,2为钨,3为磷钨酸的氧,4为铜,5为配位水的氧,6为氮,7为碳;
图2为实施例1制备的一种多酸基铜金属有机无机杂化材料结构三维立体示意图;
图3为实施例1制备的一种多酸基铜金属有机无机杂化材料的红外光谱图;
图4为实施例1制备的一种多酸基铜金属有机无机杂化材料PXRD图;
图5为实施例1制备的一种多酸基铜金属有机无机杂化材料的莫特肖特基电化学性能测试;
图6为实施例2的多酸基铜金属有机无机杂化材料在50%乙醇为牺牲试剂下9小时产氢速率图。
具体实施方式
以下结合附图和具体实施例对本发明做进一步解释。
实施例1
采用一步水热合成法,将摩尔比为0.1:0.24:0.12的硝酸铜、磷钨酸、3,3’,5,5’,-四甲基-4,4’-连吡唑有机配体溶解到去离子水中并超声混合均匀,磷钨酸的物质的量与去离子水的体积比为:0.24mmol:(7ml),得到pH值为2.4的反应液;将pH值为2.4的反应液加入到聚四氟乙烯的反应釜中,再在140℃下反应4天,冷却降温至室温得到蓝紫色块状晶体(化合物1)即为多酸基铜金属有机无机杂化材料。
晶体结构测定:
在室温下,通过显微镜观察实施例1制备的化合物1选取目标化合物晶体,在200(K)下进行X-射线单晶衍射实验。晶体的X-射线衍射数据在Xcalibur Eos Gemini衍射仪上收集,根据洛伦兹和偏振因子以及多重扫描的吸收对强度进行了校正,用SHELX-97直接法求解结构,用全矩阵最小二乘法拟合F2,用各向异性热参数对所有非氢原子进行细化。具体晶体学数据和结构参数如下表所示:
表1化合物1的晶体学数据和结构参数
表2化合物1主要的键长
通过表1可知,实施例1得到的多酸基铜金属有机无机杂化材料的化学式为Cu(HPW12O40)0.5(H2bpz)2(OH)·(H2O)6,分子式为C20H41.5CuP0.5W6N8O27,是具有金属有机纳米超分子结构特征的空间多酸基铜金属有机无机杂化材料结构,参考图1,结构中的化合物最小不对称结构单元中铜离子以六配位的形式存在,连接四个有机配体的氮原子,一个多酸阴离子中的氧和一个水中的氧原子;多酸簇PW12O40与金属有机配合物中的铜离子进行配位,每四个有机配体分别以氮原子和金属铜配位,形成了一种金属有机配合物网络层状结构,且多酸簇与金属铜离子进行配位形成三维结构,从而形成的空间结构有利于多酸到金属有机配合物之间的快速电子转移。
参考图2的三维结构示意图,其中多酸为经典Keggin型多酸PW12O40,金属有机配合物为金属铜通过配位键与四个有机配体进行配位,由此形成了一种多酸基铜金属有机杂化材料的平面网状结构,再由多酸负离子[PW12O40]2-与铜离子配位,连接上下两层多酸基铜金属有机杂化材料的平面网状结构,形成三维立体结构。
参考图3的红外光谱图,从图可知,在704-1100cm-1归属于多酸簇PW12O40的伸缩振动;振动峰在1496cm-1的范围,归属于有机配体H2bpz的伸缩振动峰。此外,振动峰在3009cm-1归属于化合物中水分子的振动伸缩峰。
参考图4的PXRD图;如图所示,通过X-射线单晶衍射解析其结构,从而模拟出一种多酸基铜金属有机杂化材料的模拟粉末X-射线衍射图谱。通过X-射线粉末衍射实验得出水热反应实验得出产物的X-射线衍射图谱。通过对比从实验谱图与模拟谱图比较来看,X-射线衍射图谱中主要峰位和模拟峰位基本相一致,表明该材料的纯度是比较好的。单晶X射线衍射结果表明,本发明制备的一种多酸基铜金属有机无机杂化材料包含具有良好光敏性的磷钨酸盐,在本发明的杂化材料中多酸与金属有机配合物所形成的半导体结构禁带宽度较窄且导带小于零,具有良好的光催化分解水产氢的效果,而且本发明中形成的超分子结构,多酸与金属有机配合物的空间结构有利于多酸与金属有机配合物的电子传导,从而提高了本发明中的多酸基铜金属有机无机杂化材料的催化性能,最终多酸分子与金属-有机配合物协同作用,产生优异的光催化分解水产氢性能。
参考图5的莫特肖特基电化学性能测试;如图所示在频率为500-2500Hz条件下测定的一种多酸基铜金属有机无机杂化材料的莫特肖特基曲线,从图中可以看出,所有曲线的直线部分的斜率都为正,这表明一种多酸基铜金属有机无机杂化材料属于n型半导体,在光照条件下受激发后产生的光生电子的浓度大于光生空穴的浓度,若把这种半导体作为光催化剂将具有非常良好的光催化还原活性。所得一种多酸基铜金属有机无机杂化材料平带电位约为-0.395V vs.Ag/AgCl(即-0.395V vs.NHE),通常认为n型半导体的导带底比平带电位更负0.1V,所以导带电位约为-0.295V vs.NHE。
在0.1mol/L Na2SO4溶液中,使用电化学工作站对其进行光电化学测试。表明本发明的以多酸基铜金属有机无机杂化材料的光电极在AM 1.5光照下在整个电位窗口表现出很好的光电流密度,表明电荷分离效率很高。在1.153V vs.RHE下,化合物1的光电流密度达到0.74A cm-2,结果表明有机金属框架中加入了磷钼酸增强了电子-空穴对的光生和分离,从而产生更高的光电流响应。其催化性能主要得益于其特殊的半导体结构,区别于以往多数此类多酸基金属有机框架晶体材料,本发明所制备的一种多酸基铜金属有机无机杂化材料,包含具有良好光敏性的磷钨酸盐,且多酸与金属有机配合物所形成的半导体结构禁带宽度较合适,具有良好的光催化分解水产氢的性能。
实施例2
以实施例1制得的多酸基铜金属有机无机杂化材料作为光催化剂,以50%(体积比)乙醇为牺牲剂,水做溶剂,乙醇与水1:1(体积比)的比例的溶液为光催化分解水产氢的体系,进行光催化分解水产氢测试。图6为9小时产氢速率图。20mg实施例1得到的多酸基铜金属有机无机杂化材料作为光催化剂9小时的总产氢量为400μL·g-1,平均产氢效率为44.4μL·g-1·h-1,可见本发明的多酸基铜金属有机无机杂化材料是一种高效的光催化分解水的光催化剂。
上述实施例仅用来进一步说明本发明的一种多酸基铜金属有机无机杂化材料及其制备方法和应用,但本发明并不局限于实施例,凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均落入本发明技术方案的保护范围内。
Claims (10)
2.根据权利要求1所述的多酸基铜金属有机无机杂化材料,其特征在于:所述Cu的化合价为+2价,配位方式为6配位。
3.根据权利要求2所述的多酸基铜金属有机无机杂化材料,其特征在于:结构中的化合物最小不对称结构单元中铜离子连接四个有机配体的氮原子,一个多酸阴离子中的氧和一个水中的氧原子。
4.一种权利要求1~3任一项所述的多酸基铜金属有机无机杂化材料的制备方法,其特征在于包括以下步骤:
1)将磷钨酸、硝酸铜、3,3’,5,5’,-四甲基-4,4’-连吡唑有机配体溶解到水中并超声混合均匀得到反应液,其中硝酸铜、磷钨酸和3,3’,5,5’,-四甲基-4,4’-连吡唑有机配体的摩尔比为0.1:0.2~0.24:0.1~0.15;
2)将反应液加入到反应釜中,在120℃~160℃下反应80~110小时,冷却降温至室温得到蓝紫色块状晶体即为多酸基铜金属有机无机杂化材料。
5.根据权利要求4所述的制备方法,其特征在于:所述磷钨酸的物质的量与水的体积比为0.2~0.24mmol:5~10ml。
6.根据权利要求4所述的制备方法,其特征在于:所述反应液的pH值为2.2~2.6。
7.根据权利要求4所述的制备方法,其特征在于:所述制备方法包括以下步骤:
1)将摩尔比为0.2~0.24:0.1:0.12的磷钨酸、硝酸铜、3,3’,5,5’,-四甲基-4,4’-连吡唑有机配体溶解到去离子水中并超声混合均匀得到pH值为2.4的反应液;
2)将反应液加入到聚四氟乙烯的反应釜中,再在140℃下反应96小时,冷却降温至室温得到蓝紫色块状晶体即为多酸基铜金属有机无机杂化材料。
8.权利要求1~3任一项所述的多酸基铜金属有机无机杂化材料在光催化制氢中的应用。
9.根据权利要求8所述的应用,其特征在于:所述多酸基铜金属有机无机杂化材料作为光催化剂,在以40%~60%乙醇作为牺牲剂,水做溶剂的溶液中光催化分解水产氢。
10.根据权利要求9所述的应用,其特征在于:所述溶液中乙醇和水的体积比为1:0.5~2。
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