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Title: Computational Dissection of Two-Dimensional Rectangular Titanium Mononitride TiN: Auxetics and Promises for Photocatalysis

Abstract

Recently, two-dimensional (2D) transition-metal nitrides have triggered an enormous interest for their tunable mechanical, optoelectronic, and magnetic properties, significantly enriching the family of 2D materials. Here, by using a broad range of first-principles calculations, we report a systematic study of 2D rectangular materials of titanium mononitride (TiN), exhibiting high energetic and thermal stability due to in-plane d–p orbital hybridization and synergetic out-of-plane electronic delocalization. The rectangular TiN monolayer also possesses enhanced auxeticity and ferroelasticity with an alternating order of Possion’s Ratios, stemming from the competitive interactions of intra- and inter- Ti—N chains. Such TiN nanosystem is a n-type metallic conductor with specific tunable pseudogaps. Halogenation of TiN monolayer downshifts the Fermi level, achieving the optical energy gap up to 1.85 eV for TiNCl(Br) sheet. Overall, observed electronic features suggest that the two materials are potential photocatalysts for water splitting application. Furthermore, these results extend emerging phenomena in a rich family 2D transition-metal-based materials and hint for a new platform for the next-generation functional nanomaterials.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Univ. of Science and Technology of China, Anhui (China)
  3. Queensland Univ. of Technology, Brisbane (Australia)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1374357
Report Number(s):
LA-UR-17-23312
Journal ID: ISSN 1530-6984
Grant/Contract Number:
AC52-06NA25396
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 17; Journal Issue: 7; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Two-dimensional crystals, Titanium nitride, Negative Possion’s Ratios, ferroelasticity, Pho- tocatalysis, First-principles calculations

Citation Formats

Zhou, Liujiang, Zhuo, Zhiwen, Kou, Liangzhi, Du, Aijun, and Tretiak, Sergei. Computational Dissection of Two-Dimensional Rectangular Titanium Mononitride TiN: Auxetics and Promises for Photocatalysis. United States: N. p., 2017. Web. doi:10.1021/acs.nanolett.7b01704.
Zhou, Liujiang, Zhuo, Zhiwen, Kou, Liangzhi, Du, Aijun, & Tretiak, Sergei. Computational Dissection of Two-Dimensional Rectangular Titanium Mononitride TiN: Auxetics and Promises for Photocatalysis. United States. doi:10.1021/acs.nanolett.7b01704.
Zhou, Liujiang, Zhuo, Zhiwen, Kou, Liangzhi, Du, Aijun, and Tretiak, Sergei. 2017. "Computational Dissection of Two-Dimensional Rectangular Titanium Mononitride TiN: Auxetics and Promises for Photocatalysis". United States. doi:10.1021/acs.nanolett.7b01704.
@article{osti_1374357,
title = {Computational Dissection of Two-Dimensional Rectangular Titanium Mononitride TiN: Auxetics and Promises for Photocatalysis},
author = {Zhou, Liujiang and Zhuo, Zhiwen and Kou, Liangzhi and Du, Aijun and Tretiak, Sergei},
abstractNote = {Recently, two-dimensional (2D) transition-metal nitrides have triggered an enormous interest for their tunable mechanical, optoelectronic, and magnetic properties, significantly enriching the family of 2D materials. Here, by using a broad range of first-principles calculations, we report a systematic study of 2D rectangular materials of titanium mononitride (TiN), exhibiting high energetic and thermal stability due to in-plane d–p orbital hybridization and synergetic out-of-plane electronic delocalization. The rectangular TiN monolayer also possesses enhanced auxeticity and ferroelasticity with an alternating order of Possion’s Ratios, stemming from the competitive interactions of intra- and inter- Ti—N chains. Such TiN nanosystem is a n-type metallic conductor with specific tunable pseudogaps. Halogenation of TiN monolayer downshifts the Fermi level, achieving the optical energy gap up to 1.85 eV for TiNCl(Br) sheet. Overall, observed electronic features suggest that the two materials are potential photocatalysts for water splitting application. Furthermore, these results extend emerging phenomena in a rich family 2D transition-metal-based materials and hint for a new platform for the next-generation functional nanomaterials.},
doi = {10.1021/acs.nanolett.7b01704},
journal = {Nano Letters},
number = 7,
volume = 17,
place = {United States},
year = 2017,
month = 6
}

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  • A comparative study of the hyperfine interactions in the [ital X] [sup 2][Sigma][sup +] state of TiN and the [ital X] [sup 3][Delta] state of TiO has been performed. The [sup 48]Ti[sup 14]N([ital I]=1) hyperfine structure was determined from the analysis of 19 components of the [ital N]=1--0 and [ital N]=2--1 pure rotational transitions recorded using the pump/probe microwave-optical double resonance technique. The [sup 47]Ti([ital I]=5/2) hyperfine structure of [ital X] [sup 2][Sigma][sup +] TiN was determined from an analysis of the high resolution optical spectrum of the (0,0) [ital A] [sup 2][Pi][sub 3/2]--[ital X] [sup 2][Sigma][sup +] band system.more » The resulting parameters are (in MHz) [ital B]([sup 48]Ti[sup 14]N)=18 589.3513(13), [ital D]([sup 48]Ti[sup 14]N)=0.026 31(18), [gamma]([sup 48]Ti[sup 14]N)=[minus]52.2070(13), [ital b][sub [ital F]](N)=18.480(3), [ital c](N)=0.166(7), [ital eQq][sub 0](N)=[minus]1.514(8), [ital C][sub [ital I]](N)=0.0137(12), [ital b][sub [ital F]]([sup 47]Ti) =[minus]558.8(11), [ital c]([sup 47]Ti)=[minus]15(5), and [ital eQq][sub 0]([sup 47]Ti)=62(16). An analysis of the (0,0) band of the [ital B] [sup 3][Pi]--[ital X] [sup 3][Delta] system of [sup 47]Ti[sup 16]O produced the [ital X] [sup 3][Delta] hyperfine parameters (in MHz): [ital a]([sup 47]Ti) =[minus]54.7(21), ([ital b][sub [ital F]]+2[ital c]/3)([sup 47]Ti)=[minus]231.6(60), and [ital eQq][sub 0]([sup 47]Ti)=[minus]49(31). An interpretation based upon the predicted nature of the bonding in TiO and TiN is given.« less
  • PurposeWe aimed to assess the potential of computational fluid dynamics simulation (CFD) in detecting changes in pressure and flow velocity in response to morphological changes in type B aortic dissection.Materials and MethodsPressure and velocity in four morphological models of type B aortic dissection before and after closure of the entry tear were calculated with CFD and analyzed for changes among the different scenarios. The control model (Model 1) was patient specific and built from the DICOM data of CTA, which bore one entry tear and three re-entry tears. Models 2–4 were modifications of Model 1, with two re-entry tears lessmore » in Model 2, one re-entry tear more in Model 3, and a larger entry tear in Model 4.ResultsThe pressure and velocity pertaining to each of the morphological models were unique. Changes in pressure and velocity findings were accountable by the changes in morphological features of the different models. There was no blood flow in the false lumen across the entry tear after its closure, the blood flow direction across the re-entry tears was reversed after closure of the entry tear.ConclusionCFD simulation is probably useful to detect hemodynamic changes in the true and false lumens of type B aortic dissection in response to morphological changes, it may potentially be developed into a non-invasive and patient-specific tool for serial monitoring of hemodynamic changes of type B aortic dissection before and after treatment.« less