CRANN/AMBER Nanoscience Institute, Trinity College Dublin, The University of Dublin, College Green, Dublin, 2, Ireland.
School of Chemistry, Trinity College Dublin.
Angew Chem Int Ed Engl. 2016 May 4;55(19):5803-8. doi: 10.1002/anie.201510219. Epub 2016 Apr 1.
Two-dimensional layered transition metal dichalcogenides (TMDs) have attracted great interest owing to their unique properties and a wide array of potential applications. However, due to their inert nature, pristine TMDs are very challenging to functionalize. We demonstrate a general route to functionalize exfoliated 2H-MoS2 with cysteine. Critically, MoS2 was found to be facilitating the oxidation of the thiol cysteine to the disulfide cystine during functionalization. The resulting cystine was physisorbed on MoS2 rather than coordinated as a thiol (cysteine) filling S-vacancies in the 2H-MoS2 surface, as originally conceived. These observations were found to be true for other organic thiols and indeed other TMDs. Our findings suggest that functionalization of two-dimensional MoS2 using organic thiols may not yield covalently or datively tethered functionalities, rather, in this instance, they yield physisorbed disulfides that are easily removed.
二维层状过渡金属二硫属化物(TMDs)因其独特的性质和广泛的潜在应用而引起了极大的兴趣。然而,由于其惰性,原始的 TMDs 很难进行功能化。我们展示了一种用半胱氨酸功能化剥离的 2H-MoS2 的通用方法。关键的是,在功能化过程中,发现 MoS2 促进了巯基半胱氨酸氧化为二硫键半胱氨酸。所得的胱氨酸物理吸附在 MoS2 上,而不是像最初设想的那样作为硫醇(半胱氨酸)配位填充 2H-MoS2 表面的 S 空位。这些观察结果对于其他有机硫醇和其他 TMDs 也是如此。我们的发现表明,使用有机硫醇对二维 MoS2 进行功能化可能不会产生共价或配位键合的官能团,而是在这种情况下,它们产生物理吸附的二硫键,很容易去除。
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