Fe/Co and Ni/Co-pentlandite type electrocatalysts for the hydrogen evolution reaction  

Fe/Co和Ni/Co镍黄铁矿型析氢反应电催化剂

作　　者：Mathias Smialkowski David Tetzlaff Lars Hensgen Daniel Siegmund Ulf-Peter Apfel Mathias Smialkowski;David Tetzlaff;Lars Hensgen;Daniel Siegmund;Ulf-Peter Apfel(波鸿鲁尔大学,德国波鸿;弗劳恩霍夫环境,安全与能源技术研究所,德国奥伯豪森;特博科公司,奥地利维也纳)

机构地区：[1]Inorganic Chemistry I-Ruhr University Bochum,Universitätsstrasse 150,44801 Bochum,Germany [2]Fraunhofer UMSICHT,Osterfelder Strasse 3,46047 Oberhausen,Germany [3]Tribotecc GmbH,Fleischmarkt 3-5,1010 Vienna,Austria

出　　处：《Chinese Journal of Catalysis》2021年第8期1360-1369,共10页催化学报（英文）

摘　　要：Metal-rich transition metal sulfides recently gained increasing attention as electrocatalysts for the hydrogen evolution reaction(HER),as they are capable to overcome major challenges faced by sulfide-rich metal catalysts such as limited conductivity and the necessity of nanostructuring.Herein,we present the synthesis,characterization and electrocatalytic investigation of ternary metal-rich sulfide composites FexCo9-xS8 as well as Ni_(y)Co_(9-y)S_(8)(x=y=0-4.5),which possess pentlandite-type structures.In this study,we show a stepwise alteration of the binary cobalt pentlandite Co9S8 and report on the replacement of cobalt with up to 4.5 equivalents of either iron or nickel.These altered pentlandite composites facilitate the proton reduction in acidic media at different temperatures.We furthermore show that the stoichiometric variation has a decisive influence on the electrochemical activation/deactivation behavior of the catalysts under reductive electrocatalytic conditions.Here,Co-deficient composites display an improved HER performance in contrast to Co_(9)S_(8).Notably,Ni/Co compounds generally tend to show higher catalytic activities towards HER than their respective Fe/Co compounds.作为析氢反应的电催化剂,富金属的过渡金属硫化物因能克服富硫金属催化剂所存在的如导电性有限和缺乏必要的纳米结构等不足,近年来受到越来越多的关注.本文介绍了具有镍黄铁矿型结构的三元富金属硫化物复合材料FexCo9-xS8和Ni_(y)Co_(9-y)S_(8)(x=y=0-4.5)的合成、表征及其电催化研究.首先,研究了二元钴化合物Co_(9)S_(8)中Co逐步被Fe或Ni取代直至4.5当量的变化过程.硫镍铁矿复合物中组分的变化有助于不同温度下酸性介质中的质子还原.其次,在还原电催化条件下,复合物中元素化学计量变化对其电化学活化/失活行为有决定性的影响.与Co_(9)S_(8)相比,Co缺陷复合材料表现出了更高的HER性能.Ni/Co化合物通常表现出比类似结构Fe/Co化合物更高的电催化析氢活性.

关 键 词：Hydrogen PENTLANDITE Metal sulfides Transition metals ELECTROCATALYSIS 

分 类 号：TQ116.2[化学工程—无机化工] TQ426