skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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. Univ. of Tokyo, Tokyo (Japan)
  2. Univ. of Utah, Salt Lake City, UT (United States)
  3. Kyoto Inst. of Technology, Kyoto (Japan); RIKEN SPring-8 Centre, Hyogo (Japan)
  4. Japan Synchrotron Radiation Research Institute (JASRI), 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:  
FG02-04ER46148; DE FG02-04ER46148
Resource Type:
Journal Article: Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 12; 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

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 States: 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 States. 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. Tue . "Bis(aminothiolato)nickel nanosheet as a redox switch for conductivity and an electrocatalyst for the hydrogen evolution reaction". United States. 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},
issn = {2041-6520},
number = 12,
volume = 8,
place = {United States},
year = {2017},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/c7sc02688a

Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science

Figures / Tables:

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

Save / Share:

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Projector augmented-wave method
journal, December 1994


Electric Field Effect in Atomically Thin Carbon Films
journal, October 2004


Electronics and optoelectronics of two-dimensional transition metal dichalcogenides
journal, November 2012

  • Wang, Qing Hua; Kalantar-Zadeh, Kourosh; Kis, Andras
  • Nature Nanotechnology, Vol. 7, Issue 11, p. 699-712
  • DOI: 10.1038/nnano.2012.193

Detection of individual gas molecules adsorbed on graphene
journal, July 2007

  • Schedin, F.; Geim, A. K.; Morozov, S. V.
  • Nature Materials, Vol. 6, Issue 9, p. 652-655
  • DOI: 10.1038/nmat1967

Prediction of a Two-Dimensional Organic Topological Insulator
journal, May 2013

  • Wang, Z. F.; Su, Ninghai; Liu, Feng
  • Nano Letters, Vol. 13, Issue 6, p. 2842-2845
  • DOI: 10.1021/nl401147u

New Porous Crystals of Extended Metal-Catecholates
journal, August 2012

  • Hmadeh, Mohamad; Lu, Zheng; Liu, Zheng
  • Chemistry of Materials, Vol. 24, Issue 18, p. 3511-3513
  • DOI: 10.1021/cm301194a

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.