Bu Fanxing, Chen Wenshu, Gu Jiajun, Agboola Phillips O, Al-Khalli Najeeb Fuad, Shakir Imran, Xu Yuxi
State Key Laboratory of Molecular Engineering of Polymers , Department of Macromolecular Science , Fudan University , Shanghai 200433 , China . Email:
State Key Laboratory of Metal Matrix Composites , Shanghai Jiao Tong University , Shanghai , 200240 , China.
Chem Sci. 2018 Jul 20;9(34):7009-7016. doi: 10.1039/c8sc02444h. eCollection 2018 Sep 14.
Herein a novel and general microwave-assisted chemical vapor deposition (CVD)-like synthetic strategy was developed to realize the ultrafast synthesis of a series of well-dispersed monolayer/few-layer N-doped graphene shell encapsulated metal nanocrystals (M@NC) by using a metal-organic framework (MOF) on graphene as precursors for the first time. Unlike traditional programmed heat treatment, this microwave-assisted method decomposed the MOF into separated metal and carbon- and nitrogen-containing gases rather than aggregated metal and carbon composites during the initial thermal transformation stages. This change ensured the effective control of the subsequent formation process of carbon on the surface of metal and led to the formation of well-dispersed M@NC with monolayer/few-layer NC. Moreover, the graphene substrate promoted the full exposure of all active monolayer/few-layer NC, and thus the obtained FeNi@NC/graphene displays the best electrocatalytic properties for the oxygen evolution reaction of all of the previously reported M@NC based catalysts, including the lowest overpotential (261 mV) at 10 mA cm in alkaline electrolyte (1 M KOH), the smallest Tafel slope (40 mV dec) and excellent durability for at least 120 h.
在此,首次开发了一种新颖且通用的类似微波辅助化学气相沉积(CVD)的合成策略,以石墨烯上的金属有机框架(MOF)为前驱体,实现了一系列分散良好的单层/少层氮掺杂石墨烯壳包覆金属纳米晶体(M@NC)的超快合成。与传统的程序热处理不同,这种微波辅助方法在初始热转化阶段将MOF分解为分离的金属以及含碳和氮的气体,而不是聚集的金属和碳复合材料。这种变化确保了对随后金属表面碳形成过程的有效控制,并导致形成具有单层/少层NC的分散良好的M@NC。此外,石墨烯基底促进了所有活性单层/少层NC的充分暴露,因此所获得的FeNi@NC/石墨烯在所有先前报道的基于M@NC的催化剂中,对析氧反应表现出最佳的电催化性能,包括在碱性电解质(1 M KOH)中10 mA cm下最低的过电位(261 mV)、最小的塔菲尔斜率(40 mV dec)以及至少120小时的优异耐久性。