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解决“钼硫纳米管”的合成谜题并阐明其无催化剂且可扩展生产的途径。

Solving the "MoS Nanotubes" Synthetic Enigma and Elucidating the Route for Their Catalyst-Free and Scalable Production.

作者信息

Chithaiah Pallellappa, Ghosh Saptarshi, Idelevich Alexander, Rovinsky Lev, Livneh Tsachi, Zak Alla

机构信息

Faculty of Sciences, Holon Institute of Technology, Holon, 5810201, Israel.

Department of Chemistry, Centre for Nano and Soft Matter Sciences, Bengaluru, 560013, India.

出版信息

ACS Nano. 2020 Mar 24;14(3):3004-3016. doi: 10.1021/acsnano.9b07866. Epub 2020 Feb 24.

DOI:10.1021/acsnano.9b07866
PMID:32053342
Abstract

This study solves a more than two-decades-long "MoS Nanotubes" synthetic enigma: the futile attempts to synthesize inorganic nanotubes (INTs) of MoS vapor-gas-solid (VGS) reaction. Among them was replication of the recently reported pure-phase synthesis of the analogous INT-WS. During these years, successful syntheses of spherical nanoparticles of WS and MoS were demonstrated as well. All these nanostructures were obtained by VGS reaction of corresponding oxides with H/HS gases, at elevated temperatures (>800 °C), in a fluidized bed reactor (FBR) and a one-pot process. This success and apparent similarity between the two compounds "hid" from us the option of looking for the INT-MoS reaction parameters in entirely different regimes. The main challenge in the synthesis of INT-MoS VGS was the instability of the prepared suboxide nanowhiskers against over-reduction and recrystallization at high temperatures. The elucidated growth mechanism dictates separation of the reaction into five steps, as properties of the intermediate products are not consistent with a single process and require individual conditions for each step. A horizontal reactor with a porous-quartz reaction cell, which creates proper quasi-static (contrary to the FBR) conditions for the reaction involving sublimation, was imperative for the effective nanofabrication of INT-MoS. These findings render a reproducible synthetic route for the production of highly crystalline pure-phase MoS nanotubes a multistep VGS process, without the assistance of a catalyst and in a scalable fashion. Being a semiconductor, flexible, and strong, INT-MoS offers a platform for much research and numerous potential applications, particularly in the field of optoelectronics and reinforcement of polymer composites.

摘要

本研究解决了长达二十多年的“MoS纳米管”合成谜团:通过气-固-固(VGS)反应合成二硫化钼无机纳米管(INTs)的徒劳尝试。其中包括重复最近报道的类似INT-WS的纯相合成。这些年来,也证明了成功合成了WS和MoS的球形纳米颗粒。所有这些纳米结构都是通过相应氧化物与H/HS气体在高温(>800°C)下于流化床反应器(FBR)中通过一锅法进行VGS反应获得的。这两种化合物之间的这一成功及明显相似性使我们“忽略”了在完全不同的条件下寻找INT-MoS反应参数的可能性。合成INT-MoS VGS的主要挑战在于所制备的低价氧化物纳米晶须在高温下抗过度还原和再结晶的不稳定性。所阐明的生长机制要求将反应分为五个步骤,因为中间产物的性质与单一过程不一致,每个步骤需要单独的条件。对于INT-MoS的有效纳米制造而言,带有多孔石英反应池的卧式反应器至关重要,该反应池为涉及升华的反应创造了适当的准静态(与FBR相反)条件。这些发现为生产高度结晶的纯相MoS纳米管提供了一种可重复的合成路线——一种多步VGS过程,无需催化剂辅助且具有可扩展性。作为一种半导体,INT-MoS具有柔韧性且强度高,为众多研究和潜在应用提供了一个平台,特别是在光电子学和聚合物复合材料增强领域。

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