CN113896898A - 手性镍基金属有机框架材料的制备方法及电催化应用 - Google Patents
手性镍基金属有机框架材料的制备方法及电催化应用 Download PDFInfo
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- 239000013099 nickel-based metal-organic framework Substances 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- DAXBISKSIDBYEU-UHFFFAOYSA-N tidiacic Chemical compound OC(=O)C1CSC(C(O)=O)N1 DAXBISKSIDBYEU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000013110 organic ligand Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002178 crystalline material Substances 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000012621 metal-organic framework Substances 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- -1 alkane alcohols Chemical class 0.000 claims description 2
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- 239000000126 substance Substances 0.000 claims description 2
- 238000012512 characterization method Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 21
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 abstract description 10
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- 238000005406 washing Methods 0.000 abstract description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 150000002815 nickel Chemical class 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 19
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 5
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- 239000000843 powder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 238000001142 circular dichroism spectrum Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 239000010410 layer Substances 0.000 description 1
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- RPZHFKHTXCZXQV-UHFFFAOYSA-N mercury(i) oxide Chemical compound O1[Hg][Hg]1 RPZHFKHTXCZXQV-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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Abstract
本发明提供了一种二维的手性镍基金属有机框架材料的制备方法及电催化应用,属于电催化技术领域。其主要制备步骤是:将镍盐和有机配体噻唑烷‑2,4‑二羧酸、吡啶分别溶解在去离子水中,经过超声波混合均匀后,在100~140℃温度下保温72小时;自然冷却至室温后,经洗涤、干燥后得到上述蓝色块状的手性Ni‑MOF电催化剂。本发明的方法所具有成本低廉、合成工艺简单、无需表面活性剂参与调控、反应产物产量高等优点,适用于大规模生产。所制备的手性Ni‑MOF材料作为电催化剂时,性能稳定,具有优异的电催化甲醇、乙醇、正丙醇氧化的活性,适用于电催化领域。
Description
技术领域
本发明书属于电催化技术领域,涉及镍基手性金属有机框架材料的制备以及电催化应用。
技术背景
自从进入21世纪,人类社会飞速发展,但伴随着经济发展的背后是以消耗有限的化石能源以及牺牲自然环境为代价的,受制于环境压力,人们对于新型、清洁、可持续的能源体系需求越来越迫切,直接醇类燃料电池(DAFCs)具有低温快速启动、燃料洁净环保以及电池结构简单等优点受到广泛的研究。并且部分直接醇类燃料电池,例如直接甲醇燃料电池已投入试验应用。但目前所使用的直接醇类燃料电池催化剂电极材料存在易中毒,低活性等缺点,且多为Pd,Pt等贵金属材料,造价高昂,存量稀少。因此探寻一种高效、廉价和非贵金属直接醇类燃料电池电极材料来取代贵金属材料具有重要意义。
金属-有机金属框架材料(MOFs),是一种以金属离子或金属簇为节点,有机配体为桥连单元的高度结晶的多孔材料。目前,MOFs在诸多方面有深入的研究及应用,例如气体吸附与分离、生物传感、药物控释、光/电催化等,尤其是电催化方面,由于MOFs所具有的丰富的孔隙结构和大量暴露的活性位点,使得MOFs成为未来在电催化析氧反应、析氢反应、氧还原反应、二氧化碳还原反应,燃料电池等的潜在电催化剂。然而,目前鲜有报道利用手性金属有机框架材料用做电催化材料的文献,并不清楚手性金属有机框架材料在电催化领域的应用优势。因此,直接醇类燃料电池可利用非贵、过渡金属镍、钴作为电极材料,并利用MOFs材料的优势,构筑新型MOFs材料并探索其在直接醇类燃料电池中的应用。在本发明中,通过合成手性镍基金属有机框架材料,针对不同醇类,均具有较高的电催化醇类氧化性能。
发明内容
本发明提供了一种以噻唑烷-2,4-二羧酸(H2TDA),吡啶(PY)为有机配体,过渡金属镍为金属中心,经过简单的水热法一步反应,形成的纯度高、产量高的二维手性镍基金属有机框架材料(简称Ni-MOF)的合成方法。利用该手性镍基金属有机框架材料的做为电催化剂,具有优异的电催化醇类氧化活性,并且具有广阔的应用前景。
为实现上述发明目的,本发明采取以下技术方案:
手性镍基金属有机框架的制备及电催化应用,化学式为: [Ni2(H2TDA)2(PY)2]n(简称Ni-MOF),该晶态材料结晶于单斜晶系,属于P21手性空间群,晶胞参数为:a=10.53690(10)Å,b=9.62020(10)Å,c= 11.92750(10)Å,α=90˚,β= 92.5600(10)˚,γ=90˚。
本发明的目的是通过以下技术方案实现的,本发明的所述手性镍基金属有机框架材料是通过一步水热法制备,具体包括以下步骤:
(1)取有机配体H2TDA与PY溶于去离子水,经超声后得到均相溶液,再将硝酸镍加入上述溶液之中;
(2)将装有混合溶液的玻璃小瓶置于恒温烘箱中恒温反应,然后自然冷却至室温,可分别得到蓝色块状晶体(Ni-MOF);
(3)将所得晶体用去离子水洗涤,并在室温下自然干燥,得到纯净的晶态材料。
步骤(1)所述的噻唑烷-2,4-二羧酸与硝酸镍的摩尔比为1: 1~2。
步骤(2)所述的反应温度为100~140℃,反应时间为70-72h。
本发明的另一种技术方案是将上述所得的手性镍基金属有机框架材料作为电催化剂,用作分别针对不同醇类氧化的电催化剂。所述的醇类包括C1-C3的低级链烷烃醇。
作为电催化醇类氧化的技术方案,其步骤是分别称量经玛瑙研埚研磨均匀的本发明所制备的Ni-MOF材料,加入去离子水,无水乙醇,Nafion溶液,超声使其分散均匀得到悬浮液,将悬浮液滴加至打磨干净的玻碳电极表面,在室温下自然干燥,得到手性镍基金属有机框架材料修饰的工作电极,随后将之用于电催化醇类氧化性能测试。
所述的手性镍基金属有机框架材料首先在KOH溶液中活化,在KOH与MeOH(或EtOH,n-PrOH)的混合溶液中测试其电催化醇类氧化性能。
本发明所涉及的室温均指常压下的环境温度即可。
本发明由于采取以上技术方案,具有以下优点:
(1)合成方法简便,重现性好,产率及产物纯度高,容易分离及洗涤干净。
(2)本发明所用原料相对廉价易得,可以有效降低催化剂成本,有利于大规模化生产。
(3)所得手性晶态材料分别针对不同低级醇均有较高的催化活性。
附图说明
图1为实施例2所合成Ni-MOF的配位环境图(a),三维堆积图(b)。
图2为实施例2所合成Ni-MOF的扫描电子显微镜图像。
图3为实施例2所合成Ni-MOF的粉末衍射图谱。
图4为实施例2所合成Ni-MOF的固态圆二色图谱。
图5为实施例2所合成Ni-MOF的电催化甲醇氧化性能图。
图6为实施例2所合成Ni-MOF的电催化乙醇氧化性能图。
图7为实施例2所合成Ni-MOF的电催化正丙醇氧化性能图。
具体实施方式
实施例1
取噻唑烷-2,4-二羧酸8.9mg于10mL玻璃小瓶中,加入去离子水4mL,将混合液超声分散均匀得到澄清溶液,准确移取吡啶(100μL)混合均匀,再加入六水合硝酸镍29.1mg,经超声得到均匀的澄清溶液。将密闭的玻璃小瓶置于140℃的烘箱恒温72小时,随后自然冷却至室温,产物为黑色沉淀,没有晶态材料生成,无法进行XRD的检测。
实施例2
取噻唑烷-2,4-二羧酸8.9mg于10mL玻璃小瓶中,加入去离子水4mL,将混合液超声分散均匀得到澄清溶液,准确移取吡啶(100μL)混合均匀,再加入六水合硝酸镍29.1mg,经超声得到均匀的澄清溶液。将密闭的玻璃小瓶置于120℃的烘箱恒温72小时,随后自然冷却至室温,得到蓝色透明块状晶态材料(Ni-MOF),产物产率为65%(基于原料噻唑烷-2,4-二羧酸所使用质量计算)。
图1展示了所得Ni-MOF的配位环境图(a)与三维堆积图(b)。如配位环境图(图1(a))所示,每个Ni-MOF的最小不对称单元包括两个Ni2+,两个TDA,以及两个PY。其中,每个Ni2+分别与来自两个TDA配体的四个O,一个来自TDA配体的一个N,一个来自PY的N配位,构成六配位模式。又如三维堆积图(图1(b))所示,Ni-MOF是沿a轴方向的二维单层结构,层间距为4.0Å。
图2展示了所得Ni-MOF的低倍扫描电子显微镜图像,如图所示,通过此比例和条件制得的Ni-MOF样品形状、大小均一。
由图3粉末衍射图谱可知,制得的Ni-MOF样品的粉末衍射图谱与通过单晶衍射数据解析模拟的衍射图谱的衍射峰相吻合,所得的样品为纯度较高的Ni-MOF材料。
由图4固态圆二色图谱可知,其负的科顿效应表明制得的Ni-MOF样品具有单一左旋手性,与由单晶解析到的P21手性空间群相对应。
实施例3
取噻唑烷-2,4-二羧酸8.9mg于10mL玻璃小瓶中,加入去离子水4mL,将混合液超声分散均匀得到澄清溶液,准确移取吡啶(100μL)混合均匀,再加入六水合硝酸镍29.1mg,经超声得到均匀的澄清溶液。将密闭的玻璃小瓶置于100℃的烘箱恒温72小时,随后自然冷却至室温,得到蓝色透明块状晶态材料,产物产率为41%(基于原料噻唑烷-2,4-二羧酸所使用质量计算)。
通过此比例和条件制得的Ni-MOF样品形状、大小均一,但所得晶态材料产率低于实施例2。经检测所述Ni-MOF的结构与实施例2的结构相同。
实施例4
取噻唑烷-2,4-二羧酸17.6mg于10mL玻璃小瓶中,加入去离子水4mL,将混合液超声分散均匀得到澄清溶液,再使用移液枪准确移取吡啶(200μL)混合均匀,再加入六水合硝酸镍29.1mg,经超声得到均匀的澄清溶液。将密闭的玻璃小瓶分别置于120℃的烘箱恒温72小时,随后自然冷却至室温,产物有蓝色块状晶体,但伴随着体积分数一半以上的黑色沉淀。
实施例5
取噻唑烷-2,4-二羧酸17.6mg于10mL玻璃小瓶中,加入去离子水4mL,将混合液超声分散均匀得到澄清溶液,再使用移液枪准确移取吡啶(200μL)混合均匀,再加入六水合硝酸镍29.1mg,经超声得到均匀的澄清溶液。将密闭的玻璃小瓶分别置于100℃的烘箱恒温72小时,随后自然冷却至室温,产物有蓝色块状晶体,但伴随着体积分数一半以下的黑色沉淀。
实施例6
取优选条件实施例2制得的Ni-MOF材料4mg,经玛瑙研埚研磨均匀,加入1.3mL去离子水、0.5mL无水乙醇、0.2mL Nafion溶液,超声30min,使之分散均匀的到悬浮液,然后取上述悬浮液5μL,滴加至打磨干净的玻璃碳电极表面(直径:3mm),室温下自然干燥,得到由手性镍基金属有机框架材料修饰的工作电极。
电催化醇类氧化测试是在辰华CHI660e电化学工作站上进行,采用三电极体系,分别使用汞-氧化汞电极为参比电极,铂柱为对电极,以及所制备的由手性Ni-MOF修饰的工作电极。以下所有测试所用工作电极均已在0.1M KOH溶液中通过循环伏安扫描活化至稳定。如图5所示,在电催化甲醇氧化测试中,在0.1M+1.0M MeOH溶液中测得Ni-MOF材料的最高甲醇氧化峰达到25.67mA cm-2。如图6所示,在电催化乙醇氧化测试中,在0.1M +1.0M EtOH溶液中测得Ni-MOF材料的最高乙醇氧化峰达到29.66mA cm-2。如图7所示,在电催化正丙醇氧化测试中,在0.1M +1.0M n-PrOH溶液中测得Ni-MOF材料的最高正丙醇氧化峰达到21.50mAcm-2。
上述的实施例仅为本发明的优选技术方案,而不应视为本发明的限制,本申请中的实施例及实施例中的特征在不冲突的情况下,可以互相任意组合,任何熟悉本技术领域的技术人员在本发明的思想和原则之内可轻易想到的变化、替换和改进都应涵盖在本发明的保护范围内。
Claims (8)
1.手性镍基金属有机框架材料,其特征在于,手性镍基金属有机框架材料是以噻唑烷-2,4-二羧酸为配体构筑的金属有机框架晶态材料,化学式为 [Ni2(H2TDA)2(PY)2]n,其中,H2TDA表示噻唑烷-2,4-二羧酸,PY表示吡啶。
2.根据权利要求1所述的手性镍基金属有机框架材料,其特征在于, Ni-MOF晶态材料结晶于单斜晶系,属于P21手性空间群,晶胞参数为:a=10.53690(10)Å,b= 9.62020(10)Å,c= 11.92750(10)Å,α=90˚,β= 92.5600(10)˚,γ=90˚。
3.根据权利要求1所述的手性镍基金属有机框架材料的制备方法,其特征在于,通过固态圆二色谱表征证实了所得晶态材料具有单一左旋手性。
4.根据权利要求1所述的手性镍基金属有机框架材料的制备方法,其特征在于,包括以下步骤:在密闭条件下,有机配体噻唑烷-2,4-二羧酸,吡啶与硝酸镍溶解在去离子水中,经水热反应,自然冷却到室温后得到手性金属有机框架材料[Ni2(H2TDA)2(PY)2]n。
5.根据权利要求4所述的手性镍基金属有机框架材料的制备方法,其特征在于,噻唑烷-2,4-二羧酸与硝酸镍的摩尔比为1 : 1~2。
6.根据权利要求4所述的手性镍基金属有机框架材料的制备方法,其特征在于,反应温度为100~140℃,反应时间为70-72小时。
7.根据权利要求1所述的手性镍基金属有机框架材料在电催化醇类氧化上的应用。
8.根据权利要求7所述得到应用,其特征在于,所述的醇类包括C1-C3的低级链烷烃醇。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114230807A (zh) * | 2022-01-12 | 2022-03-25 | 三峡大学 | 手性镍基配合物的制备方法及其电化学检测葡萄糖的应用 |
CN114685809A (zh) * | 2022-04-25 | 2022-07-01 | 黄金 | 一种镍基金属配合物、电催化剂及镍基金属配合物的制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102241705A (zh) * | 2011-05-13 | 2011-11-16 | 南开大学 | 一种以聚乙烯吡咯烷酮辅助合成配位聚合物的方法 |
CN105148997A (zh) * | 2015-07-12 | 2015-12-16 | 大连理工大学 | 一种手性POMOFs的制备方法 |
US20170173572A1 (en) * | 2014-03-28 | 2017-06-22 | The University Of Chicago | Chiral ligand-based metal-organic frameworks for broad-scope asymmetric catalysis |
CN111398379A (zh) * | 2020-03-12 | 2020-07-10 | 济南大学 | 一种电化学手性传感检测酪氨酸对映体的方法 |
-
2021
- 2021-10-11 CN CN202111183017.1A patent/CN113896898B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102241705A (zh) * | 2011-05-13 | 2011-11-16 | 南开大学 | 一种以聚乙烯吡咯烷酮辅助合成配位聚合物的方法 |
US20170173572A1 (en) * | 2014-03-28 | 2017-06-22 | The University Of Chicago | Chiral ligand-based metal-organic frameworks for broad-scope asymmetric catalysis |
CN105148997A (zh) * | 2015-07-12 | 2015-12-16 | 大连理工大学 | 一种手性POMOFs的制备方法 |
CN111398379A (zh) * | 2020-03-12 | 2020-07-10 | 济南大学 | 一种电化学手性传感检测酪氨酸对映体的方法 |
Non-Patent Citations (2)
Title |
---|
PRIOR, T. J.等: ""Chiral Direction and Interconnection of Helical Three-Connected Networks in Metal-Organic Frameworks"", 《INORGANIC CHEMISTRY》 * |
吴栋: ""基于多齿刚性配体的配位聚合物的合成与应用"", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114230807A (zh) * | 2022-01-12 | 2022-03-25 | 三峡大学 | 手性镍基配合物的制备方法及其电化学检测葡萄糖的应用 |
CN114230807B (zh) * | 2022-01-12 | 2022-12-20 | 三峡大学 | 手性镍基配合物的制备方法及其电化学检测葡萄糖的应用 |
CN114685809A (zh) * | 2022-04-25 | 2022-07-01 | 黄金 | 一种镍基金属配合物、电催化剂及镍基金属配合物的制备方法 |
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