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Two-Dimensional MoS2 Catalyzed Oxidation of Organic Thiols
Chemistry of Materials ( IF 7.2 ) Pub Date : 2018-09-19 00:00:00 , DOI: 10.1021/acs.chemmater.8b01454 Xin Chen 1 , Ciara McGlynn 1 , Aidan R. McDonald 1
Chemistry of Materials ( IF 7.2 ) Pub Date : 2018-09-19 00:00:00 , DOI: 10.1021/acs.chemmater.8b01454 Xin Chen 1 , Ciara McGlynn 1 , Aidan R. McDonald 1
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Thiol-chemistry directed techniques have been extensively employed to modify the properties of two-dimensional MoS2 nanosheets, aiming to heal or functionalize sulfur vacancies. However, the exact nature of the organic thiol/exfoliated MoS2 interaction remains under dispute. Herein, the reactions between 2H-MoS2 and organic thiols are explored in detail. We quantitatively monitor the consumption of 1-octanethiol in the presence of exfoliated 2H-MoS2 nanosheets using 1H nuclear magnetic resonance spectroscopy. The generation of dioctyl-disulfide product was detected as the only product of the 2H-MoS2/1-octanethiol reaction. Furthermore, it was found that this reaction was catalytic, and was not caused by atmospheric dioxygen. In addition, we found that the following affected the kinetics of the reaction: the thickness of the exfoliated 2H-MoS2 nanosheets, the use of deuterated substrate (kinetic isotope effect = 2), and the electron donating nature of the thiol substrate. The disulfide product was postulated to be formed via the intermolecular exchange between free thiols and either adsorbed thiolate (or thiyl radicals) or desorbed thiyl radicals. Our studies demonstrate that the “functionalization” of 2H-MoS2 nanosheets with organic thiols is likely simply 2H-MoS2 catalyzed oxidation of the thiol, with no evidence for any bond-forming (covalent or dative) interaction between the thiols and MoS2.
中文翻译：
二维MoS 2催化氧化有机硫醇
硫醇化学定向技术已被广泛用于修饰二维MoS 2纳米片的性能，旨在修复或官能化硫空位。然而，有机硫醇/剥落的MoS 2相互作用的确切性质仍存在争议。在此，详细探讨了2H-MoS 2与有机硫醇之间的反应。我们使用1 H核磁共振波谱定量监测在剥落的2H-MoS 2纳米片存在下1-辛烷硫醇的消耗量。检测到二辛基二硫化物产物的生成是2H-MoS 2的唯一产物+ 1-辛硫醇反应。此外，发现该反应是催化的，并且不是由大气中的双氧引起的。此外，我们发现以下因素会影响反应的动力学：脱落的2H-MoS 2纳米片的厚度，氘化底物的使用（动力学同位素效应= 2）以及硫醇底物的供电子性质。假定二硫化物产物是通过游离硫醇与吸附的硫醇盐（或硫醇基）或解吸的硫醇基之间的分子间交换形成的。我们的研究表明，用有机硫醇对2H-MoS 2纳米片进行“功能化”可能只是2H-MoS 2催化硫醇的氧化，没有证据表明硫醇与MoS 2之间有任何键形成（共价或确定性）相互作用。
更新日期：2018-09-19
中文翻译：
二维MoS 2催化氧化有机硫醇
硫醇化学定向技术已被广泛用于修饰二维MoS 2纳米片的性能，旨在修复或官能化硫空位。然而，有机硫醇/剥落的MoS 2相互作用的确切性质仍存在争议。在此，详细探讨了2H-MoS 2与有机硫醇之间的反应。我们使用1 H核磁共振波谱定量监测在剥落的2H-MoS 2纳米片存在下1-辛烷硫醇的消耗量。检测到二辛基二硫化物产物的生成是2H-MoS 2的唯一产物+ 1-辛硫醇反应。此外，发现该反应是催化的，并且不是由大气中的双氧引起的。此外，我们发现以下因素会影响反应的动力学：脱落的2H-MoS 2纳米片的厚度，氘化底物的使用（动力学同位素效应= 2）以及硫醇底物的供电子性质。假定二硫化物产物是通过游离硫醇与吸附的硫醇盐（或硫醇基）或解吸的硫醇基之间的分子间交换形成的。我们的研究表明，用有机硫醇对2H-MoS 2纳米片进行“功能化”可能只是2H-MoS 2催化硫醇的氧化，没有证据表明硫醇与MoS 2之间有任何键形成（共价或确定性）相互作用。
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