TY - JOUR

T1 - Single-Walled Carbon Nanotube Reactor for Redox Transformation of Mercury Dichloride

AU - Fedoseeva, Yuliya V.

AU - Orekhov, Andrey S.

AU - Chekhova, Galina N.

AU - Koroteev, Victor O.

AU - Kanygin, Mikhail A.

AU - Senkovskiy, Boris V.

AU - Chuvilin, Andrey

AU - Pontiroli, Daniele

AU - Riccò, Mauro

AU - Bulusheva, Lyubov G.

AU - Okotrub, Alexander V.

PY - 2017/9/26

Y1 - 2017/9/26

N2 - Single-walled carbon nanotubes (SWCNTs) possessing a confined inner space protected by chemically resistant shells are promising for delivery, storage, and desorption of various compounds, as well as carrying out specific reactions. Here, we show that SWCNTs interact with molten mercury dichloride (HgCl2) and guide its transformation into dimercury dichloride (Hg2Cl2) in the cavity. The chemical state of host SWCNTs remains almost unchanged except for a small p-doping from the guest Hg2Cl2 nanocrystals. The density functional theory calculations reveal that the encapsulated HgCl2 molecules become negatively charged and start interacting via chlorine bridges when local concentration increases. This reduces the bonding strength in HgCl2, which facilitates removal of chlorine, finally leading to formation of Hg2Cl2 species. The present work demonstrates that SWCNTs not only serve as a template for growing nanocrystals but also behave as an electron-transfer catalyst in the spatially confined redox reaction by donation of electron density for temporary use by the guests.

AB - Single-walled carbon nanotubes (SWCNTs) possessing a confined inner space protected by chemically resistant shells are promising for delivery, storage, and desorption of various compounds, as well as carrying out specific reactions. Here, we show that SWCNTs interact with molten mercury dichloride (HgCl2) and guide its transformation into dimercury dichloride (Hg2Cl2) in the cavity. The chemical state of host SWCNTs remains almost unchanged except for a small p-doping from the guest Hg2Cl2 nanocrystals. The density functional theory calculations reveal that the encapsulated HgCl2 molecules become negatively charged and start interacting via chlorine bridges when local concentration increases. This reduces the bonding strength in HgCl2, which facilitates removal of chlorine, finally leading to formation of Hg2Cl2 species. The present work demonstrates that SWCNTs not only serve as a template for growing nanocrystals but also behave as an electron-transfer catalyst in the spatially confined redox reaction by donation of electron density for temporary use by the guests.

KW - HRTEM

KW - mechanism of Hg(II) reduction

KW - mercury chlorides

KW - single-walled carbon nanotubes

UR - http://www.scopus.com/inward/record.url?scp=85029957346&partnerID=8YFLogxK

U2 - 10.1021/acsnano.7b04361

DO - 10.1021/acsnano.7b04361

M3 - Article

AN - SCOPUS:85029957346

VL - 11

SP - 8643

EP - 8649

JO - ACS Nano

JF - ACS Nano

SN - 1936-0851

IS - 9

ER -