Heterovalent double-site substitution to induce the metal-to-metal charge transfer for yellow ZrSiO4: Bi3+/V5+ pigments

IF 4.5 2区工程技术 Q2 ENGINEERING, CHEMICAL

Powder Technology Pub Date : 2025-02-07 DOI:10.1016/j.powtec.2025.120746

Yuting Gong, Yanru Zhao, Junfu Liu, Chengming Qiu, Yun Gao, Xiaohong Xia, Kevin P. Homewood, Binglong Lei

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引用次数: 0

Abstract

Light extinction from charge transfer transitions can create extremely strong visible-light absorption to produce brilliant inorganic pigments. In this work, a heterovalent pair of Bi³⁺ and V⁵⁺ is incorporated into ZrSiO₄ to replace both the Zr⁴⁺ and Si⁴⁺ sites to obtain new yellow pigments of ZrSiO₄: Bi³⁺/V⁵⁺ (referred to as ZS: BiV). By comparison with the conventional yellow BiVO₄ and blue ZrSiO₄:V⁴⁺ pigments and several ZrSiO₄: M³⁺/V⁵⁺ (M = Sc, Al, B and Y) powders, it is confirmed that the coloration of the ZS: BiV pigments originates primarily from the metal-to-metal charge transfer (MMCT) from Bi-6 s to V-3d and not from the ligand-to-metal charge transfer (LMCT) from O-2p to V-3d. Calculation of the MMCT energies vindicates a lower energy requirement in ZS: BiV than that in BiVO₄. The DFT calculation and comparison with some analogous compounds further exclude any coloration contribution from the LMCT transition. Furthermore, the ZS: BiV pigments are confirmed to be thermally and chemically stable in ceramic glazes, enabling the application for ceramic decoration at temperatures over 1100 K. The strategy of heterovalent double-site substitution to construct a strong MMCT transition provides a powerful route to create many attractive coloring systems for future applications.

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来源期刊

Powder Technology 工程技术-工程：化工

CiteScore

9.90

自引率

15.40%

发文量

1047

审稿时长

46 days

期刊介绍： Powder Technology is an International Journal on the Science and Technology of Wet and Dry Particulate Systems. Powder Technology publishes papers on all aspects of the formation of particles and their characterisation and on the study of systems containing particulate solids. No limitation is imposed on the size of the particles, which may range from nanometre scale, as in pigments or aerosols, to that of mined or quarried materials. The following list of topics is not intended to be comprehensive, but rather to indicate typical subjects which fall within the scope of the journal's interests: Formation and synthesis of particles by precipitation and other methods. Modification of particles by agglomeration, coating, comminution and attrition. Characterisation of the size, shape, surface area, pore structure and strength of particles and agglomerates (including the origins and effects of inter particle forces). Packing, failure, flow and permeability of assemblies of particles. Particle-particle interactions and suspension rheology. Handling and processing operations such as slurry flow, fluidization, pneumatic conveying. Interactions between particles and their environment, including delivery of particulate products to the body. Applications of particle technology in production of pharmaceuticals, chemicals, foods, pigments, structural, and functional materials and in environmental and energy related matters. For materials-oriented contributions we are looking for articles revealing the effect of particle/powder characteristics (size, morphology and composition, in that order) on material performance or functionality and, ideally, comparison to any industrial standard.