skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Intrinsic thermal expansion and tunability of thermal expansion coefficient in Ni-substituted Co 2 V 2 O 7
Abstract Framework oxide materials are well-known for exhibiting not only negative thermal expansion (NTE), but also demonstrating thermal expansion that can be controlled using composition as a tuning parameter. In this work, we study the intrinsic thermal expansion properties of Co2V2O7, which has shown bulk linear NTE, and attempt to understand how substituting Ni2+for Co2+will affect the thermal expansion. The isomorphic solid solution is synthesized through solid-state methods and characterized using x-ray diffraction (XRD), diffuse reflectance spectroscopy, and neutron diffraction. The size difference between Ni2+and Co2+as well as the polyhedral volume of each Co2+metal coordination environment in the crystal structure allows Ni2+to partially be directed toward one crystallographic site over the other. Variable temperature synchrotron XRD data are employed to understand intrinsic thermal expansion. Across the solid solution, no intrinsic NTE is observed at the microscopic level, yet a degree of tunability in the thermal expansion coefficient with Ni substitution is demonstrated. The disparities between the intrinsic and bulk thermal expansion properties suggest that a morphological mechanism may have resulted in NTE in the bulk.  more » « less
Award ID(s):
2137437
PAR ID:
10468001
Author(s) / Creator(s):
; ; ;
Publisher / Repository:
IOP Publishing
Date Published:
Journal Name:
Journal of Physics: Materials
Volume:
6
Issue:
4
ISSN:
2515-7639
Format(s):
Medium: X Size: Article No. 045011
Size(s):
Article No. 045011
Sponsoring Org:
National Science Foundation
More Like this
  1. (, Journal of the American Ceramic Society)
    Tatsuki Ohji, Ph. D. Editor (Ed.)
    ZrW2O8 (ZrO2•2WO3) and HfW2O8 (HfO2•2WO3) have been the focus of thermal expansion studies due to their isotropic negative thermal expansion (NTE) measured previously at temperatures below 775◦C. This work presents measurements of these materials at their thermodynamically stable temperature ranges of 1105 and 1257◦C for ZrW2O8 and 1105–1276◦C for HfW2O8, where they were characterized with in situ, powder X-ray diffraction. The linear coefficients of thermal expansion were measured to be −5.52 × 10−6 and −4.87 × 10−6◦C−1 for ZrW2O8 and HfW2O8, respectively. The mechanism leading to this NTE is discussed. Powder samples were synthesized by a solution-based process called the organic–inorganic steric entrapment method. In situ characterization in air was carried out at the National Synchrotron Light Source II using a hexapole lamp, optical furnace and theAdvanced Photon Source using a quadrupole lamp, optical furnace to achieve elevated temperatures. 
    more » « less
  2. ; ; (, ChemNanoMat)
    Abstract Self‐sustaining photocatalytic NO3−reduction systems could become ideal NO3−removal methods. Developing an efficient, highly active photocatalyst is the key to the photocatalytic reduction of NO3−. In this work, we present the synthesis of Ni2P‐modified Ta3N5(Ni2P/Ta3N5), TaON (Ni2P/TaON), and TiO2(Ni2P/TiO2). Starting with a 2 mM (28 g/mL NO3−−N) aqueous solution of NO3−, as made Ni2P/Ta3N5and Ni2P/TaON display as high as 79% and 61% NO3−conversion under 419 nm light within 12 h, which correspond to reaction rates per gram of 196 μmol g−1 h−1and 153 μmol g−1 h−1, respectively, and apparent quantum yields of 3–4%. Compared to 24% NO3−conversion in Ni2P/TiO2, Ni2P/Ta3N5and Ni2P/TaON exhibit higher activities due to the visible light active semiconductor (SC) substrates Ta3N5and TaON. We also discuss two possible electron migration pathways in Ni2P/semiconductor heterostructures. Our experimental results suggest one dominant electron migration pathway in these materials, namely: Photo‐generated electrons migrate from the semiconductor to co‐catalyst Ni2P, and upshift its Fermi level. The higher Fermi level provides greater driving force and allows NO3−reduction to occur on the Ni2P surface. 
    more » « less
  3. ; ; ; (, Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials)
    Characterization of the thermal expansion in the rare earth di-titanates is important for their use in high-temperature structural and dielectric applications. Powder samples of the rare earth di-titanates R 2 Ti 2 O 7 (or R 2 O 3 ·2TiO 2 ), where R = La, Pr, Nd, Sm, Gd, Dy, Er, Yb, Y, which crystallize in either the monoclinic or cubic phases, were synthesized for the first time by the solution-based steric entrapment method. The three-dimensional thermal expansions of these polycrystalline powder samples were measured by in situ synchrotron powder diffraction from 25°C to 1600°C in air, nearly 600°C higher than other in situ thermal expansion studies. The high temperatures in synchrotron experiments were achieved with a quadrupole lamp furnace. Neutron powder diffraction measured the monoclinic phases from 25°C to 1150°C. The La 2 Ti 2 O 7 member of the rare earth di-titanates undergoes a monoclinic to orthorhombic displacive transition on heating, as shown by synchrotron diffraction in air at 885°C (864°C–904°C) and neutron diffraction at 874°C (841°C–894°C). 
    more » « less
  4. ; ; ; ; ; ; ; ; ; (, Angewandte Chemie International Edition)
    Abstract Here we report a series of nitrogen‐rich conjugated macrocycles that mimic the structure and function of semiconducting 2D metal–organic and covalent organic frameworks while providing greater solution processability and surface tunability. Using a new tetraaminotriphenylene building block that is compatible with both coordination chemistry and dynamic covalent chemistry reactions, we have synthesized two distinct macrocyclic cores containing Ni−N and phenazine‐based linkages, respectively. The fully conjugated macrocycle cores support strong interlayer stacking and accessible nanochannels. For the metal–organic macrocycles, good out‐of‐plane charge transport is preserved, with pressed pellet conductivities of 10−3 S/cm for the nickel variants. Finally, using electrochemically mediated CO2capture as an example, we illustrate how colloidal phenazine‐based organic macrocycles improve electrical contact and active site electrochemical accessibility relative to bulk covalent organic framework powders. Together, these results highlight how simple macrocycles can enable new synthetic directions as well as new applications by combining the properties of crystalline porous frameworks, the processability of nanomaterials, and the precision of molecular synthesis. 
    more » « less
  5. ; ; ; ; ; ; ; (, Angewandte Chemie International Edition)
    Abstract AMXcompounds with the ZrBeSi structure tolerate a vacancy concentration of up to 50 % on theM‐site in the planarMX‐layers. Here, we investigate the impact of vacancies on the thermal and electronic properties across the full EuCu1−xZn0.5xSb solid solution. The transition from a fully‐occupied honeycomb layer (EuCuSb) to one with a quarter of the atoms missing (EuZn0.5Sb) leads to non‐linear bond expansion in the honeycomb layer, increasing atomic displacement parameters on theMand Sb‐sites, and significant lattice softening. This, combined with a rapid increase in point defect scattering, causes the lattice thermal conductivity to decrease from 3 to 0.5 W mK−1at 300 K. The effect of vacancies on the electronic properties is more nuanced; we see a small increase in effective mass, large increase in band gap, and decrease in carrier concentration. Ultimately, the maximumzTincreases from 0.09 to 0.7 as we go from EuCuSb to EuZn0.5Sb. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email