CN109400657A - 一种具有电催化活性的磺胺喹噁啉钴化合物及其制备方法和用途 - Google Patents
一种具有电催化活性的磺胺喹噁啉钴化合物及其制备方法和用途 Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 23
- 229960003097 sulfaquinoxaline Drugs 0.000 title claims abstract description 19
- -1 sulfaquinoxaline cobalt compound Chemical class 0.000 title claims abstract description 16
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- 239000000463 material Substances 0.000 claims abstract description 10
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- NHZLNPMOSADWGC-UHFFFAOYSA-N 4-amino-N-(2-quinoxalinyl)benzenesulfonamide Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=CN=C(C=CC=C2)C2=N1 NHZLNPMOSADWGC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 7
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- 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
- B01J31/1805—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 the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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Abstract
本发明公开了一种具有电催化活性的磺胺喹噁啉钴化合物及其制备方法和用途，该化合物是一种具有电催化活性的钴配位化合物，其分子式为C42H42N10O6S2Co，晶系为单斜，空间群为C2/c，晶胞参数α＝90°，β＝126.579°，γ＝90°，钴离子为六配位的八面体几何构型。该化合物是由钴盐、磺胺喹噁啉、4,4’‑二联吡啶按一定比例混合反应而制得，合成步骤简单。本该钴化合物对过氧化氢呈现出良好的电催化活性，从而作为潜在的电催化活性材料有广阔的应用前景。
Description
技术领域
本发明涉及材料化学领域，尤其涉及一种具有电催化活性的磺胺喹噁啉钴化合物及其制备方法和用途。
背景技术
电催化反应是使电极、电解质界面上的电荷转移加速的一种催化作用反应。电催化作用覆盖着电极反应和催化作用两个方面，因此电催化材料必需同时具有这两种功能：(1)能自由地传递电子；(2)能对底物进行有效的催化活化作用。电催化反应主要应用于燃料电池、有机污水的电催化处理，含铬废水的电催化降解，烟道气及原料煤的电解脱硫，电催化同时脱除NOx和SO2，二氧化碳的电解还原，甲醛、过氧化氢等的电解还原等。
传统电催化材料主要以铂族金属及其合金为主，这类材料由于存在价格昂贵或资源不足等问题限制了其应用和发展。因此，开发价格低廉的非贵族金属电催化材料成为研究的热点之一。目前，电催化剂研究较多的有硼化镍、碳化钨、钠钨青铜、尖晶石型与钨态矿型的半导体氧化物，以及过渡金属大环配合物，如铁离子的卟啉、酞菁或四偶氮轮烯等活性催化剂。半导体氧化物的稳定性比较差和催化活性比较低，尚处于研究开发阶段；酞菁、卟啉大环共轭配合物由于其本身特殊的大环共轭结构使其具有良好的电催化活性，并且可以通过改变其共轭环上的取代基及中心金属原子和分子聚集方式而具有结构可调变性，赋予了它作为电催化剂性能开发的广阔空间，是铂系催化剂有应用前景的替代品之一，但是催化剂的制备过程过于复杂，副产物较多。过渡金属离子如Cu(II)、Co(II)价电子层有空余的d轨道和未成对的d电子，过渡金属化合物作为催化剂与反应物分子接触，这些催化剂分子中的空余d轨道能够与底物分子的价轨道形成特定的过渡态型的价键，从而活化底物分子，改变反应途径，降低反应的活化能，最终达到催化反应的目的(冉繁敏等人，一种对甲醛具有电化学响应的磺胺嘧啶化合物，专利号为ZL201310349347.2；赵亚云等人，一种对过氧化氢具有电催化活性的钴配合物，专利号为ZL201310420205.0；李星等，一种对过氧化氢具有电催化活性的铜配合物ZL201310420150.3)。在过渡金属离子配位化合物中，有机功能配体的共轭基元能够与不同金属离子的d电子产生不同相互作用，进而改变金属离子能级结构，从而使配位化合物具有良好的催化活性。
发明内容
本发明所要解决的技术问题是针对现有技术，提供一种对过氧化氢具有电催化活性的钴化合物及其合成步骤简单、反应条件温和的制备方法。
本发明解决上述技术问题所采用的技术方案为：一种磺胺喹噁啉钴化合物，该化合物是一种对过氧化氢具有良好电催化活性的钴配位化合物，简称钴化合物，其结构简式为[Co(L)2(bpy)]·2(C2H5OH)(L＝脱去一个质子的磺胺喹噁啉，bpy＝4,4’-二联吡啶)，分子式为C42H42N10O6S2Co，晶系为单斜，空间群为C2/c，晶胞参数 α＝90°，β＝126.579°，γ＝90°，钴离子为六配位的八面体几何构型，其中两个氮配位原子来自于4,4’-二联吡啶，四个氮配位原子来自于两个磺胺喹噁啉，每个结构单元包含一个中心钴离子、两个磺胺喹噁啉、一个4,4’-二联吡啶和两个客体乙醇分子，所述钴化合物制备方法包括以下步骤：
将钴盐、磺胺喹噁啉和4,4’-二联吡啶按摩尔比1:2:1的比例混合置于有聚四氟乙烯内衬的高压反应釜中，然后添加水、乙醇和DMF体积比为4:8～10:1的混合溶剂；
将上述反应釜密封、置于鼓风恒温箱中，60～90℃加热24～72h后冷却至室温，过滤分离，得红色针状晶体；
用X射线单晶衍射仪对上述红色针状晶体进行测试分析，确认红色针状晶体即为所述的一种磺胺喹噁啉钴化合物即为所述的钴化合物。
所述参加反应的磺胺喹噁啉，简称HL，分子式为C14H12N4O2S，结构式为：
所述参加反应的钴盐为氯化钴、硝酸钴或醋酸钴中的一种或几种；
所述参加反应的物质为化学纯。
进一步的，本发明还提供了所述的磺胺喹噁啉钴化合物的用途，所述钴化合物作为电催化材料对过氧化氢具有良好的电催化活性。
与现有技术相比，本发明的优点在于：将磺胺喹噁啉和具有共轭π电子结构的4,4’-二联吡啶与具有电化学活性的钴离子配位，形成钴配位化合物，该化合物具有明确的空间结构和准确的分子式，该化合物的配位结构单元如图1所示，该结构单元通过4,4’-二联吡啶配体桥联形成一维链结构(图2)，通过氢键连接，一维链进一步拓展成三维网络结构(图3)；实验测试分析显示所制备的钴化合物对过氧化氢具有良好的电催化活性(图4)，其作为电催化活性材料具有潜在的应用前景。
附图说明
图1为本发明的钴化合物的配位结构单元图，为清晰起见，氢原子被省略；
图2为本发明的钴化合物的一维链结构，为清晰起见，客体分子和氢原子被省略；
图3为本发明的钴化合物的三维网络结构；
图4，a为裸印刷碳电极响应曲线，b为在没有添加H2O2时裸印刷碳电极+钴化合物的响应曲线，c为在添加H2O2后裸印刷碳电极+钴化合物的响应曲线。
具体实施方式
以下结合实施例对本发明作进一步详细描述。
实施例1：
称取CuCl2·2H2O(0.17g，1.0mmol)、HL(0.54g，2.0mmol)、4,4’-二联吡啶(0.16g，1.0mmol)置于有聚四氟乙烯内衬的反应釜中，加水4mL、乙醇8mL、DMF 1mL，密封反应釜，置于鼓风恒温箱中，60℃加热72h后冷却至室温，过滤分离，得红色针状晶体。
实施例2：
称取Cu(NO3)2·3H2O(0.48g，2.0mmol)、HL(1.18g，4.0mmol)、4,4’-二联吡啶(0.31g，2.0mmol)置于有聚四氟乙烯内衬的反应釜中，加水4mL、乙醇10mL、DMF 1mL，密封反应釜，置于鼓风恒温箱中，90℃加热24h后冷却至室温，过滤分离，得红色针状晶体。
实施例3：
称取Cu(OAc)2·H2O(0.40g，2.0mmol)、HL(1.18g，4.0mmol)、4,4’-二联吡啶(0.31g，2.0mmol)置于有聚四氟乙烯内衬的反应釜中，加水4mL、乙醇9mL、DMF 1mL，密封反应釜，置于鼓风恒温箱中，80℃加热48h后冷却至室温，过滤分离，得红色针状晶体。
上述实施例中制得的红色针状晶体用X射线单晶衍射仪进行测试分析，确认红色针状晶体即为所述的一种磺胺喹噁啉钴化合物，配位结构单元如图1所示，一维链结构如图2所示，三维网络结构如图3所示。
将所制得的磺胺喹噁啉钴化合物进行H2O2电催化性能测试，其电催化活性响应图如图4所示，从图4可见，该化合物对H2O2表现出良好的电催化性能。
本发明采用廉价易得的磺胺喹噁啉和4,4’-二联吡啶作为配体，钴离子为中心离子，通过自组装反应合成的钴化合物，对过氧化氢具有良好的电催化活性，该化合物作为功能材料在电催化传感检测中具有潜在的应用前景。
Claims (3)
1.一种具有电催化活性的磺胺喹噁啉钴化合物，其特征在于，该化合物分子式为C42H42N10O6S2Co，晶系单斜，空间群C2/c，晶胞参数 α＝90°，β＝126.579°，γ＝90°，钴离子为六配位的八面体几何构型，其中两个氮配位原子来自于4,4’-二联吡啶，四个氮配位原子来自于两个磺胺喹噁啉，每个结构单元包含一个中心钴离子、两个磺胺喹噁啉、一个4,4’-二联吡啶和两个客体乙醇分子。
2.根据权利要求1所述的磺胺喹噁啉钴化合物的制备方法，其特征在于，所述制备方法包括以下步骤：
1)将钴盐、磺胺喹噁啉和4,4’-二联吡啶按摩尔比1:2:1的比例混合置于有聚四氟乙烯内衬的高压反应釜中，然后添加水、乙醇和DMF体积比为4:8～10:1的混合溶剂；
2)将上述反应釜密封、置于鼓风恒温箱中，60～90℃加热24～72h后冷却至室温，过滤分离，得红色针状晶体即为所述的钴化合物。
所述参加反应的钴盐为氯化钴、硝酸钴或醋酸钴中的一种或几种；
所述参加反应的物质为化学纯。
3.根据权利要求1所述的磺胺喹噁啉钴化合物的用途，其特征在于，所述钴化合物作为电催化材料对过氧化氢具有良好的电催化活性。
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