Interfacial transmetallation synthesis of a platinadithiolene nanosheet as a potential 2D topological insulator
Abstract
The construction of two-dimensional metal complex materials is fascinating because of the structural and functional diversity of these materials. Previously, we have reported the synthesis of electroconductive nickelladithiolene (NiDT) and palladadithiolene (PdDT) nanosheets using benzenehexathiol (BHT). Down the group from Ni, Pd to Pt, there is a distinct positive shift in the reduction potential; as a result, it becomes synthetically more challenging to stabilize Pt2+ than to form metallic Pt(0) in the presence of BHT as a reducing agent. Herein, a novel synthetic strategy for the preparation of platinadithiolene nanosheet (PtDT) using a dibutyltin-protected BHT ligand is reported, leading to transmetallation in the presence of dioxygen. Both free-standing stacked sheets and atomic layer sheets were obtained and characterized by microscopic techniques such as AFM, SEM, and TEM. To study the morphology of the sheets and determine their charge neutrality, X-ray photoelectron (XP) and infrared (IR) spectroscopic techniques were used. Powder X-ray diffraction analysis of the multilayer PtDT indicates a half-way slipped hexagonal configuration in the P3¯1m space group. The band structure of this PtDT exhibits a band gap at the Fermi level, which is different from that of NiDT in the staggered configuration, and a Dirac gap, indicating the possibilitymore »
- Authors:
-
[1];
[1];
[1];
[1]
- The Univ. of Tokyo, Tokyo (Japan)
- Kyoto Institute of Technology, Kyoto (Japan); RIKEN SPring-8 Centre, Sayo-gun (Japan)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1527024
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 20; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Pal, Tigmansu, Doi, Shotaro, Maeda, Hiroaki, Wada, Keisuke, Tan, Choon Meng, Fukui, Naoya, Sakamoto, Ryota, Tsuneyuki, Shinji, Sasaki, Sono, and Nishihara, Hiroshi. Interfacial transmetallation synthesis of a platinadithiolene nanosheet as a potential 2D topological insulator. United States: N. p., 2019.
Web. doi:10.1039/c9sc01144g.
Pal, Tigmansu, Doi, Shotaro, Maeda, Hiroaki, Wada, Keisuke, Tan, Choon Meng, Fukui, Naoya, Sakamoto, Ryota, Tsuneyuki, Shinji, Sasaki, Sono, & Nishihara, Hiroshi. Interfacial transmetallation synthesis of a platinadithiolene nanosheet as a potential 2D topological insulator. United States. https://doi.org/10.1039/c9sc01144g
Pal, Tigmansu, Doi, Shotaro, Maeda, Hiroaki, Wada, Keisuke, Tan, Choon Meng, Fukui, Naoya, Sakamoto, Ryota, Tsuneyuki, Shinji, Sasaki, Sono, and Nishihara, Hiroshi. Wed .
"Interfacial transmetallation synthesis of a platinadithiolene nanosheet as a potential 2D topological insulator". United States. https://doi.org/10.1039/c9sc01144g. https://www.osti.gov/servlets/purl/1527024.
@article{osti_1527024,
title = {Interfacial transmetallation synthesis of a platinadithiolene nanosheet as a potential 2D topological insulator},
author = {Pal, Tigmansu and Doi, Shotaro and Maeda, Hiroaki and Wada, Keisuke and Tan, Choon Meng and Fukui, Naoya and Sakamoto, Ryota and Tsuneyuki, Shinji and Sasaki, Sono and Nishihara, Hiroshi},
abstractNote = {The construction of two-dimensional metal complex materials is fascinating because of the structural and functional diversity of these materials. Previously, we have reported the synthesis of electroconductive nickelladithiolene (NiDT) and palladadithiolene (PdDT) nanosheets using benzenehexathiol (BHT). Down the group from Ni, Pd to Pt, there is a distinct positive shift in the reduction potential; as a result, it becomes synthetically more challenging to stabilize Pt2+ than to form metallic Pt(0) in the presence of BHT as a reducing agent. Herein, a novel synthetic strategy for the preparation of platinadithiolene nanosheet (PtDT) using a dibutyltin-protected BHT ligand is reported, leading to transmetallation in the presence of dioxygen. Both free-standing stacked sheets and atomic layer sheets were obtained and characterized by microscopic techniques such as AFM, SEM, and TEM. To study the morphology of the sheets and determine their charge neutrality, X-ray photoelectron (XP) and infrared (IR) spectroscopic techniques were used. Powder X-ray diffraction analysis of the multilayer PtDT indicates a half-way slipped hexagonal configuration in the P3¯1m space group. The band structure of this PtDT exhibits a band gap at the Fermi level, which is different from that of NiDT in the staggered configuration, and a Dirac gap, indicating the possibility of 2D topological insulation at room temperature. PtDT is insulating but chemically activated by oxidation with I2 to increase the conductivity by more than 106 folds up to 0.39 S cm–1. The MDT sheets exhibit electrocatalytic activity for the hydrogen evolution reaction, and the activity order is NiDT < PdDT < PtDT.},
doi = {10.1039/c9sc01144g},
journal = {Chemical Science},
number = 20,
volume = 10,
place = {United States},
year = {Wed Apr 17 00:00:00 EDT 2019},
month = {Wed Apr 17 00:00:00 EDT 2019}
}
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Cited by: 31 works
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Figures / Tables:
Scheme 1: Synthesis of SnBHT and SnPtDT. (A) Schematic of the synthesis of the protected BHT. (B) Schematic of the synthesis of PtDT containing Bu2SnO (SnPtDT). (C) An optical image of the experimental setup. (D) Mechanism of air oxidation in the dithiolene platinum complex reaction for nanosheet formation.
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