CN111167480A - 一种新型析氧电催化剂及其制备方法和应用 - Google Patents
一种新型析氧电催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种新型析氧电催化剂及其制备方法和应用,(1)将P区金属元素的硝酸盐溶于溶剂,得到溶液A;将硫脲溶于溶剂,得到溶液B;将溶液B逐滴加入溶液A中,充分搅拌混合均匀,转移至反应釜中;(2)取清洁干燥的金属Ni泡沫垂直放入反应釜中,溶剂热反应后,得到异质结用去离子水和乙醇反复清洗几次,真空箱中干燥,即得到新型析氧电催化剂。本发明提供以P区元素非对称SP3杂化诱导电子效应显著提高电催化性能,采用简便温和的溶剂热法,以Ni泡沫网为基底和Ni源,P区元素Bi或Sb诱导制备柔性自组装的多肉状Bi2S3/Ni3S2/NF或Sb2S3/Ni3S2/NF异质结工作电极用于电催化析氧反应。Bi2S3或Sb2S3独特的非对称SP3杂化调制异质结电子结构,从而提升电催化性能。
Description
技术领域
本发明涉及电催化剂领域,具体涉及一种新型的、高效催化析氧电极材料的制备方法以及应用。
背景技术
能源短缺与环境污染是当今世界亟待解决的问题。电催化水裂解技术因其制备方法简单、水资源丰富、产物清洁,被认为是获取新能源的有效途径之一。然而,其阳极OER动力学过程缓慢,只有在较高的电位下才能发生水的分解反应,极大的制约了电解水制氢的大规模发展。故开发丰富、高效、环境友好的析氧催化剂是解决电解水制氢的核心步骤,对能源的储存和转化具有重要意义。
目前活性最高的OER电催化剂是贵金属基催化剂IrO2和RuO2,但由于贵金属材料资源稀缺、成本高、稳定性较差,不利于大规模生产[ACS Catal.2019,9(10)]。硫化镍(Ni3S2)因其固有的金属特性、较高的导电性和丰富的储量,在众多材料中脱颖而出,被广泛研究多种电化学领域。但是相对于贵金属催化剂,Ni3S2的电活性仍然有待提高[J.Am.Chem.Soc.2015,137(44)]。中国专利文献[201810212195.4]公开了一种3D自组装花球状钒修饰的Ni3S2的组合方法,将洁净的金属镍浸入钒源,进行微波溶剂热反应得到一种自组装花球状钒修饰的电催化剂材料;但该方法操作步骤复杂,条件要求苛刻且技术难度大。硫化铋(Bi2S3)是一种典型的层状结构半导体材料,由于其环境友好、生物相容性、电子转移快、吸收效率高、光电性能好等优点,已广泛应用于锂/钠电池、太阳能电池、光催化和电化学传感器等领域[J.Mater.Chem.A 2019,7(18);Chem.Eng.J.354 2018,354;Electrochim.Acta 2012,74]。中国专利文献[201310349113.8]公开了一种空心树状氧化铋-硫化铋复合物的制备与光催化降解污水中的污染物应用。相对于过渡金属基硫化物,硫化铋是一种污水处理的光催化剂,它对水体系绿色友好,并且Bi2S3这种P区元素硫化物在电催化领域少见报告。
常规的电极制备通常采用聚合物粘合剂将活性物质负载在平面电极上,这种方式将导致活性物质聚集,对O2吸附和解吸过程不利。相反,在3D衬底(如Ni网,Cu箔等)上原位生长催化剂不仅可以缓解上述问题,而且提供反应所需的表面积和暴露更多的活性位点。中国专利文献[201810393638.4]公开了一种析氧电催化剂及其制备方法和应用,通过水热法和化学气相沉积法,合成了包覆泡沫石墨烯的海绵镍骨架,但是该方法操作步骤复杂,且反应周期较长,技术难度大,催化剂结构易坍塌。
发明内容
本发明的目的在于:针对上述提到的问题,本发明提供以P区元素非对称SP3杂化诱导电子效应显著提高电催化性能,采用简便温和的溶剂热法,以Ni泡沫网为基底和Ni源,P区元素Bi或Sb诱导制备柔性自组装的多肉状Bi2S3/Ni3S2/NF或Sb2S3/Ni3S2/NF异质结工作电极用于电催化析氧反应。Bi2S3或Sb2S3独特的非对称SP3杂化调制异质结电子结构,从而提升电催化性能。
本发明采用的技术方案如下:
一种新型析氧电催化剂的制备方法,包括以下步骤:
(1)将P区金属元素的硝酸盐溶于溶剂,得到溶液A;将硫脲溶于溶剂,得到溶液B;将溶液B逐滴加入溶液A中,充分搅拌混合均匀,转移至反应釜中;
(2)取清洁干燥的金属Ni泡沫(NF)垂直放入反应釜中,溶剂热反应后,得到异质结用去离子水和乙醇反复清洗几次,真空箱中干燥,即得到新型析氧电催化剂。
优选地,所述P区金属元素的硝酸盐为硝酸铋或硝酸锑。
Bi2S3或Sb2S3独特的非对称SP3杂化调制异质结电子结构,从而提升电催化性能。
优选地,所述的步骤(1)中硝酸盐与硫脲的物质的量为(0.5-2.0):(0.75-3.0)。
优选地,所述的步骤(1)中硝酸盐与溶剂的物质的量的浓度为0.0125-0.05mol/L,硫脲与溶剂的物质的量的浓度为0.0375-0.15mol/L。
优选地,所述的步骤(1)中溶剂为水、乙醇、乙二醇、N,N-二甲基甲酰胺中的一种或多种。
优选地,步骤(2)中溶剂热反应的温度为120-160℃,时间为4-16h。
优选地,步骤(2)中置于60℃真空箱中干燥12h。
一种基于权利要求1~7任一所述方法制备的新型析氧电催化剂。
基于权利要求1~7任一所述方法制备的新型析氧电催化剂在电催化水裂解中的应用。
相较于现有技术,本发明的有益效果是:
1)本发明方法制备的Bi2S3/Ni3S2/NF或Sb2S3/Ni3S2/NF能对Ni3S2产生电子诱导效应,从而有效地提高异质结的电催化析氧性能;
2)相对于过渡金属硫化物,Bi是一种P区金属元素且对水体系不构成中毒的环境友好型硫化物;Bi2S3本身电催化性能不佳,但其孤对电子的不对称SP3杂化模式对Ni3S2产生电子诱导效应,从而形成Bi2S3-Ni3S2异质结协同催化电解水裂解。该异质结催化剂的环境友好及较好的催化活性使其在电催化方面有着重要的作用。
附图说明
图1为本发明的Bi2S3/Ni3S2/NF异质结的扫描电子显微镜图;
图2本发明的Bi2S3/Ni3S2/NF异质结的XRD图;
图3为本发明的不同物质的电化学析氧极化曲线图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅用以解释本发明,并不用于限定本发明,即所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。
因此,以下对在附图中提供的本发明的实施例的详细描述并非旨在限制要求保护的本发明的范围,而是仅仅表示本发明的选定实施例。基于本发明的实施例,本领域技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
将裁剪好的金属Ni泡沫(2cm×4cm)分别用3M HCl、丙酮、水和乙醇超声清洗10min,60℃下真空干燥6h,待用。称取1.0mmoL Bi(NO3)3·5H2O溶于40mL乙二醇中,得到溶液A。将1.5mmoL硫脲溶于20mL乙二醇溶剂,得到溶液B。将溶液B逐滴加入溶液A中,充分搅拌混合均匀。再将所述混合溶液转移至高压反应釜中,同时取1片上述清洁干燥的金属Ni泡沫垂直放入密封的高温反应釜中。最后将反应釜放入烘箱中,控制反应温度为160℃,溶剂热反应16h后,取出反应釜,自然冷却。用去离子水和乙醇反复清洗产物,置于60℃真空箱中干燥12h,得到Bi2S3/Ni3S2/NF异质结。如图1所示,该异质结呈多肉状结构,其X射线衍射谱图见图2所示。将所得Bi2S3/Ni3S2/NF为工作电极,Hg/HgO和铂片分别作为参比电极和对电极,组装成电催化三电极系统,进行电催化测试。见图3所示,10mA cm-2的基准电流密度下,Bi2S3/Ni3S2/NF只需要268mV的过电位。
实施例2
实施例2与实施例1类似,实施例2中溶剂为去离子水。所得Bi2S3/Ni3S2/NF为工作电极,Hg/HgO和铂片分别作为参比电极和对电极,组装成电催化三电极系统,进行电催化测试。在去离子水中所制备的电极不符合柔性工作电极的要求。
实施例3
实施例3与实施例1类似,实施例3中溶剂为乙醇。所得Bi2S3/Ni3S2/NF为工作电极,Hg/HgO和铂片分别作为参比电极和对电极,组装成电催化三电极系统,进行电催化测试。在10mA cm-2的基准电流密度下,乙醇中制备的Bi2S3/Ni3S2/NF,只需要310mV的过电位。
实施例4
实施例4与实施例1类似,实施例4中溶剂为N,N-二甲基甲酰胺。所得Bi2S3/Ni3S2/NF为工作电极,Hg/HgO和铂片分别作为参比电极和对电极,组装成电催化三电极系统,进行电催化测试。在10mA cm-2的基准电流密度下,N,N-二甲基甲酰胺中制备的Bi2S3/Ni3S2/NF,只需要360mV的过电位。
实施例5
实施例5与实施例1类似,实施例5中基底为清洁干燥的碳布(CC),所得Bi2S3/CC为工作电极,Hg/HgO和铂片分别作为参比电极和对电极,组装成电催化三电极系统,进行电催化测试。在10mA cm-2的基准电流密度下,Bi2S3/CC几乎无电流响应。
实施例6
实施例6与实施例1相似,实施例6中未放入任何基底,所得Bi2S3粉末涂覆在金属Ni泡沫上,得到的Bi2S3/NF作为工作电极,Hg/HgO和铂片分别作为参比电极和对电极,组装成电催化三电极系统,进行电催化测试。见图3所示,10mA cm-2的基准电流密度下,Bi2S3/NF需要520mV的过电位。
实施例7
实施例7与实施例1相似,实施例7中反应温度为140℃,所得Bi2S3/Ni3S2/NF作为工作电极,Hg/HgO和铂片分别作为参比电极和对电极,组装成电催化三电极系统,进行电催化测试。在10mA cm-2的基准电流密度下,Bi2S3/Ni3S2/NF只需要293mV的过电位。
实施例8
实施8与实施例1相似,实施例8中反应时间为8h,所得Bi2S3/Ni3S2/NF作为工作电极,Hg/HgO和铂片分别作为参比电极和对电极,组装成电催化三电极系统,进行电催化测试。在10mA cm-2的基准电流密度下,Bi2S3/Ni3S2/NF只需要277mV的过电位。
实施例9
实施9与实施例1相似,实施例9中Bi(NO3)3·5H2O为0.5mmoL,硫脲为0.75mmoL。所得Bi2S3/Ni3S2/NF作为工作电极,Hg/HgO和铂片分别作为参比电极和对电极,组装成电催化三电极系统,进行电催化测试。见图3所示,在10mA cm-2的基准电流密度下,Bi2S3/Ni3S2/NF只需要353mV的过电位。
实施例10
实施10与实施例1相似,实施例10中Bi(NO3)3·5H2O为1.5mmoL,硫脲为3.0mmoL。所得Bi2S3/Ni3S2/NF作为工作电极,Hg/HgO和铂片分别作为参比电极和对电极,组装成电催化三电极系统,进行电催化测试。见图3所示,在10mA cm-2的基准电流密度下,Bi2S3/Ni3S2/NF只需要340mV的过电位。
以上所述实施例仅表达了本申请的具体实施方式,其描述较为具体和详细,但并不能因此而理解为对本申请保护范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本申请技术方案构思的前提下,还可以做出若干变形和改进,这些都属于本申请的保护范围。
Claims (9)
1.一种新型析氧电催化剂的制备方法,其特征在于,包括以下步骤:
(1)将P区金属元素的硝酸盐溶于溶剂,得到溶液A;将硫脲溶于溶剂,得到溶液B;将溶液B逐滴加入溶液A中,充分搅拌混合均匀,转移至反应釜中;
(2)取清洁干燥的金属Ni泡沫垂直放入反应釜中,溶剂热反应后,得到异质结用去离子水和乙醇反复清洗几次,真空箱中干燥,即得到新型析氧电催化剂。
2.根据权利要求1所述的一种新型析氧电催化剂的制备方法,其特征在于,所述P区金属元素的硝酸盐为硝酸铋或硝酸锑。
3.根据权利要求1所述的一种新型析氧电催化剂的制备方法,其特征在于,所述的步骤(1)中硝酸盐与硫脲的物质的量为(0.5-2.0):(0.75-3.0)。
4.根据权利要求1所述的一种新型析氧电催化剂的制备方法,其特征在于,所述的步骤(1)中硝酸盐与溶剂的物质的量的浓度为0.0125-0.05mol/L,硫脲与溶剂的物质的量的浓度为0.0375-0.15mol/L。
5.根据权利要求1所述的一种新型析氧电催化剂的制备方法,其特征在于,所述的步骤(1)中溶剂为水、乙醇、乙二醇、N,N-二甲基甲酰胺中的一种或多种。
6.根据权利要求1所述的一种新型析氧电催化剂的制备方法,其特征在于,步骤(2)中溶剂热反应的温度为120-160℃,时间为4-16h。
7.根据权利要求1所述的一种新型析氧电催化剂的制备方法,其特征在于,步骤(2)中置于60℃真空箱中干燥12h。
8.一种基于权利要求1~7任一所述方法制备的新型析氧电催化剂。
9.基于权利要求1~7任一所述方法制备的新型析氧电催化剂在电催化水裂解中的应用。
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