‡Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technicka 5, 166 28, Prague 6, Czech Republic.
ACS Nano. 2015 May 26;9(5):5164-79. doi: 10.1021/acsnano.5b00501. Epub 2015 Apr 20.
Layered transition metal dichalcogenides (TMDs) have been the center of attention in the scientific community due to their properties that can be tapped on for applications in electrochemistry and hydrogen evolution reaction (HER) catalysis. We report on the effect of electrochemical treatment of exfoliated MoS2, WS2, MoSe2 and WSe2 nanosheets toward the goal of activating the electrochemical and HER catalytic properties of the TMDs. In particular, electrochemical activation of the heterogeneous electron transfer (HET) abilities of MoS2, MoSe2 and WSe2 is achieved via reductive treatments at identified reductive potentials based on their respective inherent electrochemistry. Comparing all TMDs, the charge transfer activation is most accentuated in MoSe2 and can be concluded that Mo metal and Se chalcogen type are more susceptible to electrochemical activation than W metal and S chalcogen type. With regards to the HER, we show that while MoS2 displayed enhanced performance when subjected to electrochemical reduction, WS2 fared worse upon oxidation. On the other hand, the HER performance of MoSe2 and WSe2 is independent of electrochemical redox treatment. We can conclude therefore that for the HER, S-containing TMDs are more responsive to redox treatment than compounds with the Se chalcogen. Our findings are beneficial toward understanding the electrochemistry of TMDs and the extent to which activation by electrochemical means is effective. In turn, when such knowledge is administered aptly, it will be promising for electrochemical uses.
分层过渡金属二硫属化物 (TMDs) 因其在电化学和析氢反应 (HER) 催化应用中可利用的特性而成为科学界关注的焦点。我们报告了剥离的 MoS2、WS2、MoSe2 和 WSe2 纳米片的电化学处理对 TMDs 的电化学和 HER 催化性能的影响。特别是,通过基于各自固有电化学的确定还原电位下的还原处理,实现了 MoS2、MoSe2 和 WSe2 的非均相电子转移 (HET) 能力的电化学激活。比较所有 TMDs,MoSe2 中电荷转移激活最为明显,可以得出结论,Mo 金属和 Se 类硫比 W 金属和 S 类硫更易受电化学激活。关于 HER,我们表明,虽然 MoS2 在经受电化学还原时表现出增强的性能,但 WS2 在氧化时表现更差。另一方面,MoSe2 和 WSe2 的 HER 性能与电化学氧化还原处理无关。因此,我们可以得出结论,对于 HER,含 S 的 TMDs 比含 Se 类硫的化合物对氧化还原处理更敏感。我们的发现有助于理解 TMDs 的电化学以及电化学手段的有效性的程度。反过来,当适当地管理这种知识时,它将有望用于电化学应用。