CN108745381A - 以mof为基底制备硫化钴催化剂的方法 - Google Patents
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Abstract
本发明公开了以MOF为基底制备硫化钴催化剂的方法，通过调节不同煅烧时间和气氛以及原位硫化法制备的四种以MOF为前驱体的硫化钴催化剂，Co‑MOF自身含有硫和氮元素，可以不在外加硫源的条件下原位硫化，并且通过调节不同煅烧时间和气氛，利用硫在高温下升华的特点，制备出四种硫化钴，分别为CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO。其中复合相Co9S8&CoS1.097/rGO具有很好的酸性条件下电催化产氢的性质。本发明提供的制备方法安全并且简单易行，是理想的电催化产氢催化剂。
Description
技术领域
本发明涉及电解水产氢催化剂技术领域，具体涉及通过调节不同煅烧时间和气氛以及原位硫化法制备的四种以MOF为前驱体的CoxSy催化剂，分别为CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO
背景技术
金属-有机框架(Metal-Organic Framework，MOFs)，又称为多孔配位聚合物(Porous CoordinationPolymers,PCPs)，是由金属离子或金属簇与有机配体通过配位键形成的一类具有周期性网络结构的晶态多孔框架材料，因其高比表面积、多孔、结构可调等特性，在气体的吸附分离、催化、传感和质子传导等方面具有潜在的应用前景。参见：Nandasiri,M.I.；Jambovane,S.R.；McGrail,B.P.；Schaef,H.T.；Nune,S.K.Coord.Chem.Rev.2016,311,38-52；H.Furukawa,N.Ko,Y.B.Go,N.Aratani,S.B.Choi,E.Choi,A.Yazaydin，R.Q.Snurr,M.O'Keeffe,J.Kim,O.M.Yaghi,Science 2010,329,424.随着社会发展，对化石燃料的需求不断增加，随之而来的环境污染也不断加剧，如何在发展经济的同时保护自然环境成为亟待解决的问题。氢能因其环境友好性和高的能量密度成为未来有潜力替代化石能源的重要清洁能源。近年来，科研人员致力于探索将地球丰度高的过渡金属化合物发展成活性高的电催化分解水产氢催化剂以替代贵金属催化剂。金属有机框架材料(MOFs)的结构具有可调整、可修饰和易功能化等特点，使其在磁性、储存、分离、催化和识别等方面表现出广阔的应用前景。其次，以它们作为前驱体构筑碳基催化材料，在杂原子掺杂、粒子限域以及孔道设计方面具有独特的优势。参见：Yu,M.H.；Zhang,P.；Feng,R.；Yao,Z.Q.；Yu,Y.C.；Hu,T.L.；Bu,X.H.ACS Appl.Mater.Interfaces,2017,9:26177；Chang,Z.；Yang,D.H.；Xu,J；Hu,T.L.；Bu,X.H.Adv.Mater.,2015,27,5432；Zhong,M.；Yang,D.H.；Xie,C.C.；Zhang,Z.；Zhou,Z.；Bu,X.H.Small,2016,12,5564.
发明内容
本发明的目的在于探索以MOF为基底制备硫化钴催化剂的方法，同时也提供了一种通过改变煅烧时间和煅烧气氛制备不同复合物的方法。制得的四种硫化钴分别为CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO。
本发明的技术方案：
以MOF为基底制备硫化钴催化剂的方法，通过MOF原位硫化法制备硫化钴电解水产氢催化剂，通过调节不同煅烧时间和气氛以及通过MOF原位硫化法制备硫化钴催化剂。
四种CoxSy的制备方法，包括以下步骤：
Co-MOF：硫氰酸钴溶于去离子水，4,4-联吡啶溶于乙醇溶液，室温下搅拌下，将4,4-联吡啶乙醇溶液滴加到硫氰酸钴水溶液中，即可得到。
CoS1.097：Co-MOF氩气气氛下700℃煅烧一小时。
Co9S8&CoS1.097：Co-MOF氩气气氛下700℃煅烧两个小时。
Co9S8：Co-MOF氩氢混合气气氛下700℃煅烧两个小时。
Co9S8&CoS1.097/rGO：Co-MOF与氧化石墨烯结合后，氩气气氛下700℃煅烧两个小时。
有益效果:
1.本发明在MOF的选择上，选择一个自身含有S和N的Co-MOF，通过煅烧可以通过原位硫化法直接生成硫化钴，不需要外加硫源。
2.本发明可以通过调节煅烧时间和煅烧气氛，利用高温下硫的升华使得S含量不同，从而得到不同的硫化钴复合物。
3.通过加入石墨烯，提高材料导电性，防止煅烧过程中MOF的团聚从而使得电催化性能进一步提高复合相其电催化性能达到起始电位50mV，当电流密度达到10mA cm-2时过电位为188mV。
附图说明
图1为制备流程图。
图2为Co9S8&CoS1.097/rGO的扫描电镜、透射电镜、高分辨透射电镜图。
图3为Co-MOF、CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO的粉末衍射图以及Co9S8&CoS1.097/rGO的X射线光电子能谱。
图4为CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO的孔径分布图。
图5为CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO电催化性能图。
具体实施方式
本发明具体涉及通过调节不同煅烧时间和气氛以及原位硫化法制备的四种以MOF为前驱体的硫化钴催化剂，分别为CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO，制备流程参见附图1。下面结合附图与实施例对本发明做进一步说明。
1.0.326g Co(SCN)2溶于20mL去离子水,0.63g 4’4-联吡啶溶于30mL乙醇溶液室温下边搅拌边将4’4-联吡啶乙醇溶液逐滴加入到Co(SCN)2水溶液中，离心得到粉晶Co-MOF，所得Co-MOF的粉末衍射图见附图3(a)。
2.0.2g Co-MOF放入管式炉中氩气气氛下700℃煅烧一小时得到CoS1.097；氩气气氛下700℃煅烧两个小时，得到Co9S8&CoS1.097；氩氢混合气气氛下700℃煅烧2h得到Co9S8
3.20mL去离子水中加入100mg氧化石墨烯超声30min，搅拌30min至均匀分散，边搅拌边滴加Co(SCN)2水溶液(0.326g，2mL)。搅拌1h后，边搅拌边滴加4’4-联吡啶乙醇溶液(0.63g，30mL)。搅拌10min，得到Co-MOF/GO，其粉末衍射图见附图3(a)。取0.2g放入管式炉中，氩气气氛下700℃煅烧2h得到Co9S8&CoS1.097/rGO。
参见附图2，a为扫描电镜图，b为a的区域放大扫描电镜图，从扫描电镜图中可以看出Co-MOF生成的复合相Co9S8&CoS1.097均匀的附着在石墨烯表面。c、d为透射电镜图。从透射电镜图中可以观察到许多小于10nm纳米颗粒附着在石墨烯上。e为块状Co9S8&CoS1.097高分辨透射电镜图，从晶格条纹可以进一步证明块状为复合相Co9S8&CoS1.097，f为纳米颗粒高分辨电镜图，从晶格条纹可以证明，该纳米颗粒为Co9S8。
参见图3，Co-MOF以及所得四种催化剂CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO的粉末衍射图见附图3(a)(b)与标准卡片都可以很好的对应上；证明合成的相纯度高。Co9S8&CoS1.097/rGO的X射线光电子能谱参见,(c)-(f)。从图中可以看出，该材料的碳层有许多S、N杂原子掺杂，并且N元素主要以石墨N和吡啶N的形式存在，进一步提高了其电催化性能。S元素xps图中有两组S元素的P峰，进一步证明其由两相组成。
参见附图4，从孔径分布图中可以看出，石墨烯的加入防止了Co-MOF在煅烧过程中的团聚，从而增大了比表面积和孔径。
参见附图5，a为在0.5MH2SO4水溶液中以5mV s-1扫速得到的产氢极化曲线，从图中可以看出与石墨烯的复合相Co9S8&CoS1.097/rGO性能最好，当电流达到10mA cm-2时，电位仅为381mV。b图为tafel曲线图，从图中可以看出复合相Co9S8&CoS1.097/rGO的tafel斜率虽然比CoS1.097大，但是和其他相相比较小，说明其电催化产氢反应动力学较快。c图为循环1000全之后极化曲线，可以看出该材料稳定性很好，极化曲线偏移很小。d图为电流密度差-扫速曲线，从中可以看出复合相的双电层电容最大，证明其电化学活性面积最大。综合以上测试可以证明与石墨烯复合相Co9S8&CoS1.097/rGO的电催化产氢性能最好。
Claims (9)
1.以MOF为基底制备硫化钴催化剂的方法，其特征在于：通过MOF原位硫化法制备硫化钴电解水产氢催化剂，通过调节不同煅烧时间和气氛以及通过MOF原位硫化法制备硫化钴催化剂。
2.根据权利要求1所述的以MOF为基底制备硫化钴催化剂的方法，其特征在于：所述的硫化钴催化剂为四种以MOF为前驱体的硫化钴催化剂，分别为CoS1.097,Co9S8,Co9S8&CoS1.097和Co9S8&CoS1.097/rGO。
3.根据权利要求2所述的以MOF为基底制备硫化钴催化剂的方法，其特征在于：CoS1.097是由Co-MOF氩气气氛下700℃煅烧一小时得到。
4.根据权利要求2所述的以MOF为基底制备硫化钴催化剂的方法，其特征在于：Co9S8&CoS1.097是由Co-MOF氩气气氛下700℃煅烧两个小时得到。
5.根据权利要求2所述的以MOF为基底制备硫化钴催化剂的方法，其特征在于：Co9S8是由Co-MOF氩氢混合气气氛下700℃煅烧两个小时得到。
6.根据权利要求2所述的以MOF为基底制备硫化钴催化剂的方法，其特征在于：Co9S8&CoS1.097/rGO是由Co-MOF与氧化石墨烯结合后得到Co-MOF/GO，氩气气氛下700℃煅烧两个小时得到。
7.根据权利要求3-6任一项所述的以MOF为基底制备硫化钴催化剂的方法，其特征在于：Co-MOF制备步骤是：硫氰酸钴溶于去离子水，4,4-联吡啶溶于乙醇溶液，室温下搅拌下，将4,4-联吡啶乙醇溶液滴加到硫氰酸钴水溶液中，即可得到。
8.根据权利要求2-6任一项所述的以MOF为基底制备硫化钴催化剂的方法，其特征在于：所得产品起始电位50mV，当电流密度达到10mA cm-2时过电位为188mV，并且具有很好的稳定性。
9.根据权利要求6所述的以MOF为基底制备硫化钴催化剂的方法，其特征在于：Co-MOF/GO是在去离子水中加入氧化石墨烯超声30min，搅拌30min至均匀分散，边搅拌边滴加Co(SCN)2水溶液，搅拌1h后，边搅拌边滴加4’4-联吡啶乙醇溶液，搅拌10min得到Co-MOF/GO。
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