直接甲醇燃料电池(DMFCs)作为一种环境友好、高效的新能源,对解决世界目前面临的"能源危机"与"环境危机"这两大问题有着至关重要的意义,具有较广阔的应用前景.目前,甲醇氧化催化剂仍然以Pt基为主,但是Pt价格昂贵,且容易受甲醇氧化中间产物的毒化,从而影响了DMFCs的商业化进程.碳化钨(WC)作为非贵金属催化剂,在催化方面具有类铂的性能.在WC上负载适量的Pt,可以通过两者的协同效应加强催化剂的抗CO中毒能力.但是,由于WC的导电性能不佳,比表面积较小,因此寻找合适的载体显得尤为必要.在碳载体中,石墨烯(RGO)具有优良的导电性以及独特的片层结构,是电催化剂的理想载体.以RGO为载体,WC为插层物质制备的WC-RGO插层复合物具有化学稳定性好、电导率高且电化学活性面积大等优势.但是,由于石墨烯表面光滑且呈惰性,同时使用传统的碳化方法制备的碳化钨颗粒较大,因此,制备较小颗粒且分散均匀的WC-RGO插层复合物具有较大难度.一般以偏钨酸铵和氧化石墨烯(GO)为前驱体制备WC-RGO插层复合物,但是由于偏钨酸根和GO都带负电,因此不能成功地将偏钨酸根引入到石墨烯的片层结构中,造成WC-RGO插层复合物组装上的困难.本文采用硫脲成功地合成了具有高分散性WC纳米颗粒插层在少层RGO里的WC-RGO插层复合物.硫脲((NH2)2CS)作为阴离子接受器,具有较强的结合阴离子形成稳定复合物的能力,同时它也是合成具有片层结构的过渡金属硫化物的原料之一.因此在WC-RGO插层复合物组装过程中,硫脲既作为锚定及诱导剂,又是制备片层二硫化钨(WS2)的硫源.材料具体制备方法如下:首先利用浸渍法,将偏钨酸根阴离子([H2W(12)O(40)]-(6-))牵引到(NH2)2CS改性过的GO上形成[H2W(12)O(40)]-(6-)-(NH2)2CS-GO前驱体;然后将前驱体放入管式炉中还原?
Highly dispersed tungsten carbide(WC) nanoparticles(NPs) sandwiched between few-layer reduced graphene oxide(RGO) have been successfully synthesized by using thiourea as an anchoring and inducing reagent.The metatungstate ion,[H2W(12)O(40)]^6-,is assembled on thiourea-modified graphene oxide(GO) by an impregnation method.The WC NPs,with a mean diameter of 1.5 nm,are obtained through a process whereby ammonium metatungstate first turns to WS2,which then forms an intercalation compound with RGO before growing,in situ,to WC NPs.The Pt/WC-RGO electrocatalysts are fabricated by a microwave-assisted method.The intimate contacts between Pt,WC,and RGO are confirmed by X-ray diffraction,scanning electron microscope,transmission electron microscope,and Raman spectroscopy.For methanol oxidation,the Pt/WC-RGO electrocatalyst exhibited an electrochemical surface area value of 246.1 m^2/g Pt and a peak current density of1364.7 mA/mg Pt,which are,respectively,3.66 and 4.77 times greater than those of commercial Pt/C electrocatalyst(67.2 m^2/g Pt,286.0 mA/mg Pt).The excellent CO-poisoning resistance and long-term stability of the electrocatalyst are also evidenced by CO stripping,chronoamperometry,and accelerated durability testing.Because Pt/WC-RGO has higher catalytic activity compared with that of commercial Pt/C,as a result of its intercalated structure and synergistic effect,less Pt will be required for the same performance,which in turn will reduce the cost of the fuel cell.The present method is facile,efficient,and scalable for mass production of the nanomaterials.