Exploring Brannerite-Type Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> (<i>M</i> = Mn, Cu, Co, or Ni) Oxides: Crystal Structure and Optical Properties

Exploring Brannerite-Type Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> (<i>M</i> = Mn, Cu, Co, or Ni) Oxides: Crystal Structure and Optical Properties

Environmentally benign, highly stable oxides exhibiting desirable optical properties and high near-IR reflectance are being researched for their potential application as pigments. Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<...

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Main Authors: Hua-Chien Hsu, Narayanan Lakshminarasimhan, Jun Li, Arthur P. Ramirez, Mas A. Subramanian
Format: Article
Language:English
Published: MDPI AG 2025-01-01
Series:Crystals
Subjects:
optical properties
magnetic properties
transition metal oxides
Online Access:https://www.mdpi.com/2073-4352/15/1/86
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author Hua-Chien Hsu
Narayanan Lakshminarasimhan
Jun Li
Arthur P. Ramirez
Mas A. Subramanian
author_facet Hua-Chien Hsu
Narayanan Lakshminarasimhan
Jun Li
Arthur P. Ramirez
Mas A. Subramanian
author_sort Hua-Chien Hsu
collection DOAJ
description Environmentally benign, highly stable oxides exhibiting desirable optical properties and high near-IR reflectance are being researched for their potential application as pigments. Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> (<i>M</i> = Mn, Cu, Co, or Ni) oxides with brannerite-type structures were synthesized by the conventional solid-state reaction method to study their optical properties. These series exhibit structural transitions from brannerite (<i>C</i>2/<i>m</i>) to distorted brannerite (<i>P</i><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mover accent="true"><mrow><mn>1</mn></mrow><mo>¯</mo></mover></mrow></semantics></math></inline-formula>) and NiV<sub>2</sub>O<sub>6</sub>-type (<i>P</i><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mover accent="true"><mrow><mn>1</mn></mrow><mo>¯</mo></mover></mrow></semantics></math></inline-formula>) structures. The average color of Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> compounds varies from reddish-yellow to brown to dark brown. The <i>L</i>*<i>a</i>*<i>b</i>* color coordinates reveal that Mg<sub>1−<i>x</i></sub>Cu<i><sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> and Mg<sub>1−<i>x</i></sub>Ni<i><sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> show more red hues in color with <i>x</i> = 0.4 and <i>x</i> = 0.5, respectively. The UV–Vis diffuse reflectance spectra indicate a possible origin for these results include the ligand-to-metal charge transfer (O<sup>2−</sup> 2p-V<sup>5+</sup> 3d), metal-to-metal charge transfer (from Mn<sup>2+</sup> 3d/Cu<sup>2+</sup> 3d/Co<sup>2+</sup> 3d/Ni<sup>2+</sup> 3d to V<sup>5+</sup> 3d), band gap transitions, and d–d transitions. Magnetic property measurements revealed antiferromagnetic behavior for the compounds Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> (<i>M</i> = Mn, Cu, Co, and Ni), and an oxidation state of +2 for the <i>M</i> ions was deduced from their Curie–Weiss behavior. The system Mg<sub>1−<i>x</i></sub>Mn<i><sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> has a NIR reflectance in the range between 40% and 70%, indicating its potential to be utilized in the pigment industry.
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spelling doaj-art-d7ed1489067744779058a6a821dea0942025-01-24T13:28:15ZengMDPI AGCrystals2073-43522025-01-011518610.3390/cryst15010086Exploring Brannerite-Type Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> (<i>M</i> = Mn, Cu, Co, or Ni) Oxides: Crystal Structure and Optical PropertiesHua-Chien Hsu0Narayanan Lakshminarasimhan1Jun Li2Arthur P. Ramirez3Mas A. Subramanian4Department of Chemistry, Oregon State University, Corvallis, OR 97331, USADepartment of Chemistry, Oregon State University, Corvallis, OR 97331, USADepartment of Chemistry, Oregon State University, Corvallis, OR 97331, USADepartment of Physics, University of California Santa Cruz, Santa Cruz, CA 95064, USADepartment of Chemistry, Oregon State University, Corvallis, OR 97331, USAEnvironmentally benign, highly stable oxides exhibiting desirable optical properties and high near-IR reflectance are being researched for their potential application as pigments. Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> (<i>M</i> = Mn, Cu, Co, or Ni) oxides with brannerite-type structures were synthesized by the conventional solid-state reaction method to study their optical properties. These series exhibit structural transitions from brannerite (<i>C</i>2/<i>m</i>) to distorted brannerite (<i>P</i><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mover accent="true"><mrow><mn>1</mn></mrow><mo>¯</mo></mover></mrow></semantics></math></inline-formula>) and NiV<sub>2</sub>O<sub>6</sub>-type (<i>P</i><inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mover accent="true"><mrow><mn>1</mn></mrow><mo>¯</mo></mover></mrow></semantics></math></inline-formula>) structures. The average color of Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> compounds varies from reddish-yellow to brown to dark brown. The <i>L</i>*<i>a</i>*<i>b</i>* color coordinates reveal that Mg<sub>1−<i>x</i></sub>Cu<i><sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> and Mg<sub>1−<i>x</i></sub>Ni<i><sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> show more red hues in color with <i>x</i> = 0.4 and <i>x</i> = 0.5, respectively. The UV–Vis diffuse reflectance spectra indicate a possible origin for these results include the ligand-to-metal charge transfer (O<sup>2−</sup> 2p-V<sup>5+</sup> 3d), metal-to-metal charge transfer (from Mn<sup>2+</sup> 3d/Cu<sup>2+</sup> 3d/Co<sup>2+</sup> 3d/Ni<sup>2+</sup> 3d to V<sup>5+</sup> 3d), band gap transitions, and d–d transitions. Magnetic property measurements revealed antiferromagnetic behavior for the compounds Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> (<i>M</i> = Mn, Cu, Co, and Ni), and an oxidation state of +2 for the <i>M</i> ions was deduced from their Curie–Weiss behavior. The system Mg<sub>1−<i>x</i></sub>Mn<i><sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> has a NIR reflectance in the range between 40% and 70%, indicating its potential to be utilized in the pigment industry.https://www.mdpi.com/2073-4352/15/1/86optical propertiesmagnetic propertiestransition metal oxides
spellingShingle Hua-Chien Hsu
Narayanan Lakshminarasimhan
Jun Li
Arthur P. Ramirez
Mas A. Subramanian
Exploring Brannerite-Type Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> (<i>M</i> = Mn, Cu, Co, or Ni) Oxides: Crystal Structure and Optical Properties
Crystals
optical properties
magnetic properties
transition metal oxides
title Exploring Brannerite-Type Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> (<i>M</i> = Mn, Cu, Co, or Ni) Oxides: Crystal Structure and Optical Properties
title_full Exploring Brannerite-Type Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> (<i>M</i> = Mn, Cu, Co, or Ni) Oxides: Crystal Structure and Optical Properties
title_fullStr Exploring Brannerite-Type Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> (<i>M</i> = Mn, Cu, Co, or Ni) Oxides: Crystal Structure and Optical Properties
title_full_unstemmed Exploring Brannerite-Type Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> (<i>M</i> = Mn, Cu, Co, or Ni) Oxides: Crystal Structure and Optical Properties
title_short Exploring Brannerite-Type Mg<sub>1−<i>x</i></sub><i>M<sub>x</sub></i>V<sub>2</sub>O<sub>6</sub> (<i>M</i> = Mn, Cu, Co, or Ni) Oxides: Crystal Structure and Optical Properties
title_sort exploring brannerite type mg sub 1 i x i sub i m sub x sub i v sub 2 sub o sub 6 sub i m i mn cu co or ni oxides crystal structure and optical properties
topic optical properties
magnetic properties
transition metal oxides
url https://www.mdpi.com/2073-4352/15/1/86
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AT narayananlakshminarasimhan exploringbranneritetypemgsub1ixisubimsubxsubivsub2subosub6subimimncucoornioxidescrystalstructureandopticalproperties
AT junli exploringbranneritetypemgsub1ixisubimsubxsubivsub2subosub6subimimncucoornioxidescrystalstructureandopticalproperties
AT arthurpramirez exploringbranneritetypemgsub1ixisubimsubxsubivsub2subosub6subimimncucoornioxidescrystalstructureandopticalproperties
AT masasubramanian exploringbranneritetypemgsub1ixisubimsubxsubivsub2subosub6subimimncucoornioxidescrystalstructureandopticalproperties

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