CN109400656B - 一种钴配合物催化剂及碳纳米管/钴配合物复合催化剂和应用 - Google Patents
一种钴配合物催化剂及碳纳米管/钴配合物复合催化剂和应用 Download PDFInfo
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
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- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
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Abstract
本发明公开一种钴配合物催化剂及碳纳米管/钴配合物复合催化剂和应用。采用以具有稳定结构的分子水平钴配合物Co(salophen)为催化剂,通过将催化剂与碳纳米管复合,构成碳纳米管/分子催化剂(CNTs/Co(salophen))复合催化剂,该钴配合物催化剂在强酸、碱性条件下分解成相应的水/羟基络合物和游离配体,通过nafion将CNTs/Co(salophen)复合催化剂固定在玻碳电极上,由于nafion显弱酸性,不会改变钴配合物结构,本发明设计的复合阴极不仅大大提高了催化剂的催化活性,而且实现了非均相催化剂的复合阴极在外加电压驱动下电催化还原二氧化碳。
Description
技术领域
本发明属于电催化领域,特别涉及一种钴配合物催化剂及碳纳米管/钴配合物复合催化剂
背景技术
当今,人类面临着两大难题:大气中CO2含量不断升高而导致全球温室效应;燃料资源日益匮乏。充分利用自然界富有的CO2进行转化和固定,不仅有利于消除大气温室效应,又能生成有机燃料,合成其它有机化工原料、中间体或有机化工产品,同时可以减少由其它化工原料反应而带来的环境污染问题。所以,CO2的综合利用具有化学反应绿色化、积极保护环境的重要意义。由于电催化CO2还原反应可以应用电将二氧化碳消除,而其体系简便易控,因此正成为人们研究的一个重要方向。
早期的研究,主要是以Ru,Ir等贵金属单质及相应的氧化物,配合物为分子催化剂,在均相体系中实现二氧化碳的还原。经过近十年的研究,二氧化碳还原从最初的化学催化体系逐渐发展到电催化体系和光电化学电池等多种反应体系。与传统的金属氧化物多相催化剂相比,许多分子水平的二氧化碳还原催化剂在催化活性以及结构可调性上,有明显优势。因此研究非均相催化体系的分子水平的二氧化碳还原催化剂具有实际意义。
发明内容
本发明致力于催化二氧化碳还原的研究,设计并构建了碳纳米管/钴配合物复合催化剂修饰的玻碳电极阴极,对构建新型电化学电池具有十分重要的意义。电催化结果显示,利用本发明所述负载方式,当外加偏压为-1.3V(vs RHE)时,新型复合光阴极CNTs/Co(salophen)电极的光电流为-1.2mA,约是CNTs电极的10倍,催化活性远优于碳管修饰的玻碳电极。
本发明采用的技术方案是:钴配合物催化剂,所述的钴配合物催化剂为Co(salophen),具有如(I)所示的结构式:
上述的钴配合物催化剂的制备方法,包括如下步骤:
1)salophen配体的制备:于乙醇中加入水杨醛和邻苯二胺,在70-80℃下加热回流反应6-7h,反应完全后,将溶液冷却至室温后减压蒸馏并抽滤,然后真空干燥12小时,得salophen配体;反应式如下:
2)钴配合物催化剂Co(salophen)的制备:在氮气保护下,于乙醇中加入salophen配体和Co(OAc)2·4H2O,在70-80℃下加热回流反应2-3h,反应液冷却至室温后,乙醇洗涤,抽滤,真空干燥,得钴配合物催化剂Co(salophen),反应式如下:
优选的,上述的钴配合物催化剂的制备方法,按摩尔比,邻苯二胺:水杨醛=1:2;salophen配体:Co(OAc)2·4H2O=1:1.2。
一种碳纳米管/钴配合物复合催化剂,是将上述的钴配合物催化剂Co(salophen)与碳纳米管CNTs复合,构成的碳纳米管/钴配合物复合催化剂CNTs/Co(salophen)。
上述的一种碳纳米管/钴配合物复合催化剂的制备方法,包括如下步骤:室温下,将上述的钴配合物催化剂Co(salophen)溶于去离子水中,将碳纳米管CNTs分散在乙醇中,然后将Co(salophen)的水溶液和CNTs的乙醇溶液混合,搅拌12-13小时,离心,真空干燥,得碳纳米管/钴配合物复合催化剂CNTs/Co(salophen)。
优选的,上述的一种碳纳米管/钴配合物复合催化剂的制备方法,按质量比,CNTs:Co(salophen)=(1-10):1。
上述的一种碳纳米管/钴配合物复合催化剂作为非均相催化剂在电催化还原二氧化碳的应用。方法如下:
1)CNTs/Co(salophen)修饰电极的制备:将上述的碳纳米管/钴配合物复合催化剂分散在乙醇中,然后均匀滴涂到已抛光的玻碳电极GC表面上后,将玻碳电极GC在烘箱中干燥3-4小时,得CNTs/Co(salophen)修饰电极;
2)以CNTs/Co(salophen)修饰电极为工作电极,以铂丝或铂网为对电极,以Ag/AgCl电极为参比电极,电催化二氧化碳还原。
本发明采用分子催化剂π-π非共价修饰碳纳米管的表面,以具有稳定结构的分子水平钴配合物Co(salophen)为催化剂,通过将催化剂与碳纳米管复合,构成碳纳米管/钴配合物(CNTs/Co(salophen))复合光阴极催化体系,因为维持配合物的完整性只有有限的pH范围,该钴配合物催化剂在强酸、碱性条件下分解成相应的水/羟基络合物和游离配体,通过nafion将催化剂固定在玻碳电极上,因为nafion显弱酸性,不会改变钴配合物结构。本发明的复合阴极不仅大大提高了催化剂的催化活性,而且实现了非均相催化剂的复合阴极在外加电压驱动下催化还原二氧化碳。
本发明具有如下优点:
1)本发明设计合成了钴配合物催化剂,通过将钴配合物催化剂负载到CNTs表面,制备了碳纳米管/分子催化剂复合的阴极。
2)用大量存在的非贵金属钴分子催化剂代替贵金属钌、铱等分子催化剂;用通过非π-π共价修饰碳纳米管,将钴配合物催化剂与CNTs来替代常见的酸性粘合剂nafion、PMAA等,实现催化剂结构稳定,将两者相结合,制备可以在碱性、低电位条件下高效、稳定电解还原二氧化碳的复合阴极;此种阴极未见报道。初步实现了分子催化剂的电催化的器件化,为二氧化碳还原分子催化剂的应用开辟了新的途径。
3)以Mn,Fe,Cu,Ni,Co等地球富含大量过渡金属的异构化水氧化催化剂,是直接利用太阳能分解水的可持续能源技术的理想选择。与均相催化剂相比,非均相催化剂的优点在于是容易从反应体系中分离出来,从工程角度来看,由于组装简单,所以期望固态的阴极。本发明通过将分子催化剂非π-π共价修饰碳纳米管的表面,从而改变碳纳米管的表面性质,构建新型复合阴极。为过渡金属配合物催化剂与碳纳米管复合材料的应用提供了更多的可能。
4)本发明用分子催化剂π-π非共价修饰碳纳米管的表面,以具有稳定结构的分子水平钴配合物Co(salophen)为催化剂,通过将催化剂与碳纳米管复合,构成碳纳米管/钴配合物(CNTs/Co(salophen))复合光阴极催化体系,在环境保护、开发新能源、太阳能及燃料电池等领域有着非常广阔的应用前景。
附图说明
图1为碳纳米管CNTs的扫描电子显微镜图(SEM图)。
图2为碳纳米管CNTs的投射电子显微镜图(TEM图)。
图3为实施例3CNTs、单独Co(salophen)和CNTs与Co(salophen)质量比为2:1的Co(salophen)在含有0.1M碳酸氢钠溶液中的CV。
图4为实施例3不同比例的CNTs与Co(salophen)在碳酸氢钠溶液中的CV。
图5为实施例3不同电压下碳管与Co(salophen)的碳酸氢钠溶液中的it。
具体实施方式
为了更好地理解本发明的技术方案,特以一系列的测试及对比实验作进一步详细说明。
实施例1钴配合物催化剂Co(salophen)
(一)制备方法如下:
(1)salophen配体的制备
向100ml乙醇中加入0.54g(0.005mol)的水杨醛和1.22g(0.010mol)的邻苯二胺,在75℃条件下加热回流反应6h,反应完全后,将溶液冷却至室温,减压蒸馏并抽滤,然后真空干燥12小时,得到棕色的salophen配体。
(2)钴配合物催化剂Co(salophen)的制备
在氮气保护条件下,向10ml乙醇中加入1.65g(0.01mol)的salophen配体以及2.98g(0.012mol)的Co(OAc)2·4H2O,在75℃条件下加热回流反应2h,反应结束后,待反应液冷却至室温后,抽滤(用冷乙醇洗涤滤饼至少3次),然后真空干燥24小时,得到棕色固体即为钴配合物催化剂Co(salophen)。
实施例2一种碳纳米管/钴配合物复合催化剂
(一)CNTs/Co(salophen)的制备方法如下:
室温下,将4mg实施例1制备的Co(salophen)溶于20mL的去离子水中,得Co(salophen)的水溶液。按表1取碳纳米管CNTs分散在10mL的乙醇中,得不同质量碳纳米管CNTs的乙醇溶液。将Co(salophen)的水溶液和不同质量碳纳米管CNTs的乙醇溶液混合均匀,搅拌12小时,离心,真空干燥后,分别得到不同质量比碳纳米管/钴配合物复合催化剂CNTs/Co(salophen)。
表1
碳纳米管CNTs质量 | 质量比,CNTs:Co(salophen) | 产物 |
4mg | 1:1 | CNTs/Co(salophen)-1 |
8mg | 2:1 | CNTs/Co(salophen)-2 |
20mg | 5:1 | CNTs/Co(salophen)-3 |
40mg | 10:1 | CNTs/Co(salophen)-4 |
(二)检测
如图1所示,测试了商业CNTs的扫描电镜图。由图1中(a)可以看出,CNTs表面均是无序管状相互叠加,且具有很大的比表面积,为催化剂吸附量提供了保证。由图1中(b)可以看出,从形貌上来看,与图1中(a)对比,能够更加清楚的看到碳管的管状结构。
如图2所示,测试了商业CNTs的投射电镜图,可以清楚的看到CNTs的结构。
实施例3碳纳米管/钴配合物复合催化剂作为非均相催化剂在电催化二氧化碳还原中的应用(一)CNTs/Co(salophen)修饰电极的制备
1、玻碳电极GC预处理:用2.0μm氧化铝粉对GC(0.07cm2)电极进行抛光,然后用去离子水和丙酮进行超声波清洗,并在空气中干燥。
2、将4mg实施例2制备好的不同质量比碳纳米管/钴配合物复合催化剂CNTs/Co(salophen)分散在10mL的乙醇中,取10μL溶液滴涂到预处理后的玻碳电极GC的表面上,之后将GC在烘箱中于40℃下干燥3小时,制得不同质量比的CNTs/Co(salophen)修饰电极。
(二)光电化学性能的研究
本实验所有测试,均采用上海辰华公司的CHI660E电化学工作站,以铂丝或铂网做对电极,以Ag/AgCl电极(2.5M饱和氯化钾溶液)做参比电极。
催化剂的循环伏安(CV)测试在碳酸氢钠溶液中进行。采用三电极体系,以CNTs/Co(salophen)修饰电极为工作电极,Ag/AgCl电极作为参比电极,铂网作为对电极,以充满二氧化碳的0.1M的碳酸氢钠溶液作为电解质溶液,进行电化学测试。电化学测试结果如图3、图4和图5。
从图3可以看出,碳纳米管CNTs、钴配合物催化剂Co(salophen)在电压为-1.3VvsAg/AgCl时的电流为-0.12mA,碳管与催化剂以2:1的比例复合时得到的CNTs/Co(salophen)-2,在电压在-1.3Vvs Ag/AgCl时的电流为-1.2mA,是CNTs、单独Co(salophen)10倍的电流,所以可以得出Co(salophen)与碳管复合能够得到很好的催化活性。
从图4可以看出,CNTs和Co(salophen)质量比分别为1:1、2:1、5:1、10:1时,开始随着比例的增加电流不断增加,当质量比达到2:1后,随着比例的增加电流减小,当CNTs:Co(salophen)=2:1时,所获得的CNTs/Co(salophen)-2,在电压为-1.3Vvs Ag/AgCl时的电流为-1.2mA,是其他比例的几倍。由此可以看出,当CNTs和Co(salophen)的复合比例在2:1时,催化剂拥有最好的催化效果。
图5为在不同电压下碳管与Co(salophen)在碳酸氢钠溶液中的it,从图5中可以看出,在不同的电压下,随着时间的不断延长,催化剂的效果没有较大下降,从而可以看出本发明的CNTs/Co(salophen)复合催化剂拥有较好的稳定性,便于应用。
Claims (1)
1.一种碳纳米管/钴配合物复合催化剂作为非均相催化剂在电催化还原二氧化碳的应用,其特征在于,方法如下:
1)CNTs/ Co(salophen)修饰电极的制备:将碳纳米管/钴配合物复合催化剂分散在乙醇中,然后均匀滴涂到已抛光的玻碳电极GC表面上后,将玻碳电极GC在烘箱中干燥3-4小时,得CNTs/ Co(salophen) 修饰电极;
2)以CNTs/ Co(salophen) 修饰电极为工作电极,以铂丝或铂网为对电极,以Ag/AgCl电极为参比电极,电催化还原二氧化碳;
所述碳纳米管/钴配合物复合催化剂的制备方法,包括如下步骤:
1)salophen配体的制备:向100 ml乙醇中加入0.005 mol的水杨醛和0.010 mol的邻苯二胺,在75 ℃条件下加热回流反应6 h,反应完全后,将溶液冷却至室温,减压蒸馏并抽滤,然后真空干燥12小时,得到棕色的salophen配体
2)钴配合物催化剂Co(salophen)的制备:在氮气保护条件下,向10 ml乙醇中加入0.01mol的salophen配体以及0.012 mol的Co(OAc)2·4H2O,在75℃条件下加热回流反应2 h,反应结束后,待反应液冷却至室温后,抽滤,然后真空干燥24小时,得到棕色固体即为钴配合物催化剂Co(salophen);
3)按质量比,CNTs :Co(salophen)=2 : 1备料,室温下,将钴配合物催化剂Co(salophen)溶于去离子水中,将碳纳米管CNTs分散在乙醇中,然后将Co(salophen)的水溶液和CNTs的乙醇溶液混合,搅拌12-13小时,离心,真空干燥,得碳纳米管/钴配合物复合催化剂CNTs/ Co(salophen)。
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