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Title: Bis(aminothiolato)nickel nanosheet as a redox switch for conductivity and an electrocatalyst for the hydrogen evolution reaction

Abstract

A π-conjugated coordination nanosheet comprising bis(aminothiolato)nickel (NiAT) moieties was synthesized by the reaction of Ni(acac) 2 with 1,3,5-triaminobenzene-2,4,6-trithiol at liquid–liquid and gas–liquid interfaces. The sheet thickness could be controlled down to a single layer (0.6 nm). Selected area electron diffraction and grazing incidence X-ray diffraction analyses indicated the formation of a flat crystalline sheet with a kagome lattice stacked in a staggered alignment. NiAT was reversibly interconverted to a bis(iminothiolato)nickel (NiIT) nanosheet by the chemical 2H +–2e - reaction, which was accompanied by a drastic change in electrical conductivity from 3 × 10 -6 to 1 × 10 -1 S cm -1. This change in conductivity was explained by the difference in band structures between NiAT and NiIT. NiAT acted as an efficient electrocatalyst for the hydrogen evolution reaction, showing strong acid durability and an onset overpotential of -0.15 V.

Authors:
 [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [2];  [2];  [2];  [3];  [4]; ORCiD logo [1]
  1. Department of Chemistry, School of Science, The University of Tokyo, Tokyo, Japan
  2. Department of Materials Science and Engineering, University of Utah, Salt Lake City, USA
  3. Faculty of Fibre Science and Engineering, Kyoto Institute of Technology, Kyoto, Japan, RIKEN SPring-8 Centre
  4. Japan Synchrotron Radiation Research Institute (JASRI)/SPring-8, Hyogo, Japan
Publication Date:
Research Org.:
Univ. of Utah, Salt Lake City, UT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1409483
Alternate Identifier(s):
OSTI ID: 1506236
Grant/Contract Number:  
DE FG02-04ER46148; FG02-04ER46148
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 8 Journal Issue: 12; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Sun, Xinsen, Wu, Kuo-Hui, Sakamoto, Ryota, Kusamoto, Tetsuro, Maeda, Hiroaki, Ni, Xiaojuan, Jiang, Wei, Liu, Feng, Sasaki, Sono, Masunaga, Hiroyasu, and Nishihara, Hiroshi. Bis(aminothiolato)nickel nanosheet as a redox switch for conductivity and an electrocatalyst for the hydrogen evolution reaction. United Kingdom: N. p., 2017. Web. doi:10.1039/C7SC02688A.
Sun, Xinsen, Wu, Kuo-Hui, Sakamoto, Ryota, Kusamoto, Tetsuro, Maeda, Hiroaki, Ni, Xiaojuan, Jiang, Wei, Liu, Feng, Sasaki, Sono, Masunaga, Hiroyasu, & Nishihara, Hiroshi. Bis(aminothiolato)nickel nanosheet as a redox switch for conductivity and an electrocatalyst for the hydrogen evolution reaction. United Kingdom. doi:10.1039/C7SC02688A.
Sun, Xinsen, Wu, Kuo-Hui, Sakamoto, Ryota, Kusamoto, Tetsuro, Maeda, Hiroaki, Ni, Xiaojuan, Jiang, Wei, Liu, Feng, Sasaki, Sono, Masunaga, Hiroyasu, and Nishihara, Hiroshi. Sun . "Bis(aminothiolato)nickel nanosheet as a redox switch for conductivity and an electrocatalyst for the hydrogen evolution reaction". United Kingdom. doi:10.1039/C7SC02688A.
@article{osti_1409483,
title = {Bis(aminothiolato)nickel nanosheet as a redox switch for conductivity and an electrocatalyst for the hydrogen evolution reaction},
author = {Sun, Xinsen and Wu, Kuo-Hui and Sakamoto, Ryota and Kusamoto, Tetsuro and Maeda, Hiroaki and Ni, Xiaojuan and Jiang, Wei and Liu, Feng and Sasaki, Sono and Masunaga, Hiroyasu and Nishihara, Hiroshi},
abstractNote = {A π-conjugated coordination nanosheet comprising bis(aminothiolato)nickel (NiAT) moieties was synthesized by the reaction of Ni(acac)2 with 1,3,5-triaminobenzene-2,4,6-trithiol at liquid–liquid and gas–liquid interfaces. The sheet thickness could be controlled down to a single layer (0.6 nm). Selected area electron diffraction and grazing incidence X-ray diffraction analyses indicated the formation of a flat crystalline sheet with a kagome lattice stacked in a staggered alignment. NiAT was reversibly interconverted to a bis(iminothiolato)nickel (NiIT) nanosheet by the chemical 2H+–2e- reaction, which was accompanied by a drastic change in electrical conductivity from 3 × 10-6 to 1 × 10-1 S cm-1. This change in conductivity was explained by the difference in band structures between NiAT and NiIT. NiAT acted as an efficient electrocatalyst for the hydrogen evolution reaction, showing strong acid durability and an onset overpotential of -0.15 V.},
doi = {10.1039/C7SC02688A},
journal = {Chemical Science},
number = 12,
volume = 8,
place = {United Kingdom},
year = {2017},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C7SC02688A

Citation Metrics:
Cited by: 15 works
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Figures / Tables:

Fig. 1 Fig. 1: Schematics and chemical structures of NiAT and NiIT. Grey: C; yellow: S; blue: N; purple: H; green: Ni.

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