Compounds having a structure related to sotoveitite, and methods for producing and using the same

Abstract

Novel compounds having a sortovite-related structure are disclosed. The compounds may be colored and are useful as pigments. The compounds are durable in terms of acid stability tests, which show that the pigments do not substantially discolor when exposed to weak acids such as rain. The compounds disclosed herein are typically inexpensive to synthesize from earth-abundant, environmentally friendly elements or minerals, and therefore offer advantages over existing pigments in the art.

Description

[Technical field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims the benefit of the earlier filing date of U.S. Provisional Patent Application No. 63 / 336,913, filed April 29, 2022, which is incorporated by reference in its entirety.

[0002] The present invention relates to compounds, particularly coloured compounds, having a sortoveitite structure, compositions containing same, and methods for making and using the compounds and compositions.

[0003] [Acknowledgements for government support] This invention was made with Government support under Contract No. DMR-2025615 from the Directorate for Mathematical & Physical Sciences awarded by the National Science Foundation. DMR-2025615 was awarded by the National Science Foundation. The Government has certain rights in this invention. [Background technology]

[0004] Many of the orange / red inorganic pigments currently in use contain heavy metals such as cadmium, lead, and mercury, and as a result suffer from environmental problems. There is a need for inorganic pigments, especially intense orange / red inorganic pigments, that are environmentally friendly, earth abundant, and durable. Summary of the Invention [Means for solving the problem]

[0005] Disclosed herein are embodiments of compounds that are useful as color pigments, but that are free of toxic and / or environmentally problematic heavy metals. In some embodiments, the compounds have the formula I: Zn 2-x Ni xV2O7, where x is 0.2-0.8, or x is 1.2-1.8. In some embodiments, x is less than 0.2-0.5. The compound can have L*a*b values ​​of 34-60, a* of 10-27, and b* of 19-60. In some embodiments, x is greater than 0.2-0.8, and the compound has L*a*b values ​​of 34-51, a* of 17-27, and b* of 19-49. In other embodiments, x is 1.2-1.8, and the compound has L*a*b values ​​of 51-60, a* of 10-14, and b* of 48-60. And / or the compound is Zn 1.77 Ni 0.23 V2O7, Zn 1.76 Ni 0.24 V2O7, Zn 1.75 Ni 0.25 V2O7, Zn 1.7 Ni 0.3 V2O7, Zn 1.4 Ni 0.6 V2O7, Zn 1.2 Ni 0.8 V2O7, Zn 0.8 Ni 1.2 V2O7, Zn 0.6 Ni 1.4 V2O7, Zn 0.4 Ni 1.6 V2O7, or Zn 0.2 Ni 1.8 V2O7 can be selected.

[0006] Also, in this specification, the compound represented by formula II: Zn 2-2x Mn x M x Also disclosed are embodiments of compounds having a structure according to V2O7, where x is 0-0.05 and M is Mg or Ni. The compounds can have L*a*b values ​​of 22-37, a* of 7-19, and b* of 3-22. In some embodiments, M is Mg and the compounds have L*a*b values ​​of 32-36, a* of 10-19, and b* of 11-22. In other embodiments, M is Ni and the compounds have L*a*b values ​​of 22-37, a* of 7-17, and b* of 3-17. And / or the compounds have Zn 1.98Mn 0.01 Mg 0.01 V2O7, Zn 1.96 Mn 0.02 Mg 0.02 V2O7, Zn 1.94 Mn 0.03 Mg 0.03 V2O7, Zn 1.92 Mn 0.04 Mg 0.04 V2O7, Zn 1.96 Mn 0.02 Ni 0.02 V2O7, Zn 1.96 Mn 0.02 Ni 0.02 V2O7, Zn 1.94 Mn 0.03 Ni 0.03 V2O7, Zn 1.92 Mn 0.04 Ni 0.04 V2O7, or Zn 1.9 Mn 0.05 Ni 0.05 V2O7 can be selected.

[0007] Chemical formula III:In 2-x Zinc x Ge 2-x V x Also disclosed are compounds having the structure according to formula I. With respect to formula I, x is 0 to less than 2, and may be 0.1, 0.3, 0.5, 1, 1.5, 1.7, 1.8, 1.90, 1.93, 1.94, 1.95, or 1.98. The compounds have L*a*b values ​​of L* from 48 to 67, a* from -3 to 7, and b* from 26 to 56, and / or In 1.9 Zinc 0.1 Ge 1.9 V 0.1 O7, In 1.7 Zinc 0.3 Ge 1.7 V 0.3 O7, In 1.5 Zinc 0.5 Ge 1.5 V 0.5 O7, InZnGeVO7, In 0.5 Zinc 1.5 Ge 0.5 V 1.5 O7, In 0.3 Zinc 1.7 Ge0.3 V 1.7 O7, In 0.2 Zinc 1.8 Ge 0.2 V 1.8 O7, In 0.1 Zinc 1.9 Ge 0.1 V 1.9 O7, In 0.07 Zinc 1.93 Ge 0.07 V 1.93 O7, In 0.06 Zinc 1.94 Ge 0.06 V 1.94 O7, In 0.05 Zinc 1.95 Ge 0.05 V 1.95 O7, or In 0.02 Zinc 1.98 Ge 0.02 V 1.98 You can choose from O7.

[0008] Also, the chemical formula IV: InZn 1-x Ni x Also disclosed are embodiments of compounds having a structure according to GeVO7, where x is 0.1, 0.3, 0.5, 0.7, or 1. The compounds can have L*a*b values ​​of 54-59, a* of 4-13, and b* of 43-46. And / or the compounds can have InZn 0.9 Ni 0.1 GeVO7, InZn 0.7 Ni 0.3 GeVO7, InZn 0.5 Ni 0.5 GeVO7, InZn 0.3 Ni 0.7 You can choose from GeVO7 or InNiGeVO7.

[0009] Alternatively, the chemical formula V:In 1-x Mn x The compound has a structure according to ZnGeVO7, where x is 0 to less than 1. In one embodiment, the compound is In 0.9 Mn 0.1 It is ZnGeVO7.

[0010] In another embodiment, the compound has the formula VI:Zn 1.77-x Ni 0.23 M x V 2-y P y O7, where x is 0-0.1, y is 0-2, and M is Mg, Ca, (NaAl), (NaGa), (KAl), or (KGa). x may be 0 or 0.1, and / or y may be 0, 0.2, or 2. The compound may have L*a*b values ​​of 35-77, a* of -2-26, and b* of 23-37. And / or the compound may have Zn 1.67 Ni 0.23 Mg 0.1 V2O7, Zn 1.67 Ni 0.23 Ca 0.1 V2O7, Zn 1.67 Ni 0.23 (NaAl) 0.1 V2O7, Zn 1.67 Ni 0.23 (Naga) 0.1 V2O7, Zn 1.67 Ni 0.23 (KAl) 0.1 V2O7, Zn 1.67 Ni 0.23 (KGa) 0.1 V2O7, Zn 1.77 Ni 0.23 P2O7, Zn 1.77 Ni 0.23 V 1.8 P 0.2 O7, Zn 1.67 Ni 0.23 Mg 0.1 V 1.8 P 0.2 O7, Zn 1.67 Ni 0.23 Ca 0.1 V 1.8 P 0.2 O7, Zn 1.67 Ni 0.23 (NaAl) 0.1 V 1.8 P 0.2 O7, Zn 1.67 Ni 0.23 (Naga) 0.1 V 1.8 P 0.2O7, Zn 1.67 Ni 0.23 (KAl) 0.1 V 1.8 P 0.2 O7, or Zn 1.67 Ni 0.23 (KGa) 0.1 V 1.8 P 0.2 You can choose from O7.

[0011] Also, in this specification, the compound of formula VII:Zn 1.8 Cu 0.1 M 0.1 Also disclosed are embodiments of compounds having a structure according to V2O7, where M is Ni, Mn, Mg, or Ca. The compounds can have L*a*b values ​​of 40-59, a* of 1-16, and b* of 26-44. In some embodiments, the compounds can have Zn 1.8 Cu 0.1 Ni 0.1 V2O7, Zn 1.8 Cu 0.1 Mn 0.1 V2O7, Zn 1.8 Cu 0.1 Mg 0.1 V2O7, or Zn 1.8 Cu 0.1 Ca 0.1 V2O7 can be selected.

[0012] Further embodiments include compounds of formula VIII:Zn 1.9 Cu 0.1 V x P 2-x O7, where x is 0 to 1.8 and may be 0 or 1.8. The compound has L*a*b* values ​​of 46 to 81, a* of -3 to 4, and b* of 2 to 28, and / or Zn 1.9 Cu 0.1 P2O7 or Zn 1.9 Cu 0.1 V 1.8 P 0.2 You can choose from O7.

[0013] Also, the chemical formula IX: Zn 2-x-yMn x M y V 2-z P z Also disclosed are embodiments of compounds having the structure according to O7. With respect to formula IX, M is Ni, Mg, or Ca, x is 0-0.5 and may be 0.02, 0.1, or 0.5, y is 0-0.1 and may be 0 or 0.1, and z is 0-1 and may be 0, 0.2, or 1. The compounds may have L*a*b values ​​of 34-37, a* of 20-22, and b* of 23-24. And / or the compounds may have Zn 1.88 Mn 0.02 Ni 0.1 V2O7, Zn 1.88 Mn 0.02 Mg 0.1 V2O7, Zn 1.88 Mn 0.02 Ca 0.1 V2O7, Zn 1.98 Mn 0.02 V 1.8 P 0.2 O7, Zn 1.88 Mn 0.02 Ni 0.1 V 1.8 P 0.2 O7, Zn 1.88 Mn 0.02 Mg 0.1 V 1.8 P 0.2 O7, Zn 1.88 Mn 0.02 Ca 0.1 V 1.8 P 0.2 O7, Zn 1.9 Mn 0.1 VPO7, Zn 1.9 Mn 0.1 V 1.8 P 0.2 O7, Zn 1.9 Mn 0.1 V 1.5 P 0.5 O7, or Zn 1.5 Mn 0.5 V 1.5 P 0.5 You can choose from O7.

[0014] The alternative compound has the formula X:Mg 2-x Mx V 2-y P y O7, where M is Ni or Mn, x is 0 to 0.2, and y is 0 to 1. In some embodiments, x is 0 or 0.2 and / or y is 0 or 0.1. The compound has the structure Mg 1.8 Ni 0.2 V2O7, Mg 1.8 Mn 0.2 V2O 7、または Mg2VPO7.

[0015] Also, the chemical formula XI: InZn 1-x Ni x Music Video 1-y P y Also disclosed are embodiments of compounds having the structure according to the invention, InZnSiVO7, InZn 0.9 Ni 0.1 SiVO7, InZnGePO7, InZn 0.9 Ni 0.1 GePO7, InZnSiPO7, InZn 0.9 Ni 0.1 SiPO7, InZn 0.9 Ni 0.1 GeV 0.8 P 0.2 O7, or InZn 0.9 Ni 0.1 SiV 0.8 P 0.2 You can choose from O7.

[0016] The compound has the formula XII:Zn 2-x-y M x Ni y V 2-x A xAlso disclosed herein are compounds having a structure according to O7. With respect to formula XII, M is Fe, Cr, Sc, Y, or La; A is Ge or Si, x is 0-0.1; and y is 0-0.1. In some embodiments, x is 0.1, and / or y is 0 or 0.1. The compounds can have L*a*b values ​​of L* of 28-56, a* of 15-28, and b* of 34-48. And / or the compounds can have Zn 1.9 Fe 0.1 V 1.9 Ge 0.1 O7, Zn 1.9 Fe 0.1 V 1.9 S 0.1 O7, Zn 1.9 Cr 0.1 V 1.9 Ge 0.1 O7, Zn 1.9 Cr 0.1 V 1.9 S 0.1 O7, Zn 1.9 Sc 0.1 V 1.9 S 0.1 O7, Zn 1.8 Sc 0.1 Ni 0.1 V 1.9 S 0.1 O7, Zn 1.9 Sc 0.1 V 1.9 Ge 0.1 O7, Zn 1.8 Sc 0.1 Ni 0.1 V 1.9 Ge 0.1 O7, Zn 1.9 Y 0.1 V 1.9 S 0.1 O7, Zn 1.8 Y 0.1 Ni 0.1 V 1.9 S 0.1 O7, Zn 1.9 Y 0.1 V 1.9 Ge 0.1 O7, Zn 1.8 Y 0.1 Ni 0.1 V 1.9 Ge0.1 O7, Zn 1.9 La 0.1 V 1.9 S 0.1 O7, Zn 1.8 La 0.1 Ni 0.1 V 1.9 S 0.1 O7, Zn 1.9 La 0.1 V 1.9 Ge 0.1 O7, or Zn 1.8 La 0.1 Ni 0.1 V 1.9 Ge 0.1 You can choose from O7.

[0017] Also, the chemical formula XIII:Zn 1-x Co x V 1.8 P 0.2 Also disclosed are embodiments of compounds having a structure according to O7, where x is 0 to less than 1, and may be 0.1. The compounds have L*a*b* values ​​of 25 to 26, a* of 1 to 2, and b* of 9 to 10, and / or Zn 1.9 Co 0.1 V 1.8 P 0.2 It could be O7.

[0018] Further embodiments include compounds of formula XIV: 1-x Mn x In one embodiment, the compound has the structure according to V2O7, where x is 0 to less than 1. 1.98 Mn 0.02 It is V2O7.

[0019] Also disclosed herein are embodiments of compositions comprising the compounds disclosed herein. The compositions may further comprise at least one additional component, such as binders, solvents, catalysts, thickeners, stabilizers, emulsifiers, texturizers, adhesion promoters, UV stabilizers, leveling agents, preservatives, polymers, dispersing aids, plasticizers, flame retardants, oxides of metals, or any combination thereof. The compositions may be paints, inks, dyes, glass, plastics, emulsions, fabrics, or cosmetic preparations. In some embodiments, the composition is glass and the composition comprises a metal oxide. Additionally or alternatively, the compositions may further comprise at least one additional compound according to the present disclosure.

[0020] Also disclosed herein are methods of making the disclosed compounds. The methods may include selecting a metal desired in the compound, preparing reactants containing the selected metal, combining the reactants in stoichiometric amounts to achieve a desired final ratio of the selected metal in the compound, and heating the combination of reactants at an effective temperature for an effective time to produce the disclosed compounds. The effective temperature is between 600° C. and 1050° C., and / or the effective time is between 6 hours and 12 hours. In some embodiments, heating the combination of reactants includes heating for a first time of between 6 hours and 12 hours, grinding the reaction mixture, and reheating for a second time of between 6 hours and 12 hours.

[0021] The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description which proceeds with reference to the accompanying drawings. [Brief description of the drawings]

[0022] [Figure 1] Schematic diagram showing the difference between the sortobaitite-type structure (C2 / m) (left) and the sortobaitite-related structure (C2 / c) (right). [Diagram 2]Schematic diagram of the sortobeitite-type structure (C2 / m) of an exemplary A2M2O7 versatile compound, showing trivalent A cations (orange) (left) shown as edge-sharing distorted AO6 octahedra that form a two-dimensional hexagonal network perpendicular to the c-axis, and tetravalent M cations (cyan) (right) shown as M2O7 di-orthogonal groups that connect the AO6 hexagonal sheets to form a three-dimensional structure; oxygen ions are shown as small red spheres. [Diagram 3] Schematic diagram showing the crystal structure (P21 / c) of ZnMV2O7 (M = Co, Ni), showing zigzag chains of edge-sharing (Zn / M)O6 octahedra connected by tandem V2O7 groups. [Figure 4] FIG. 2 is a schematic diagram showing how L*a*b* values ​​correspond to different colors. [Diagram 5] 1 is a table showing exemplary compounds according to Formula I. [Figure 6] 1 is a table showing exemplary compounds according to Formula II. [Figure 7] 1 is a table illustrating exemplary compounds according to Formula III. [Figure 8] 1 is a table illustrating exemplary compounds according to Formula IV. [Figure 9] 1 is a table illustrating exemplary compounds according to Formula V. [Figure 10] 1 is a table illustrating exemplary compounds according to Formula VI. [Figure 11] 1 is a table illustrating exemplary compounds according to Formula VII. [Figure 12] 1 is a table illustrating exemplary compounds according to Formula VIII. [Figure 13] 1 is a table illustrating exemplary compounds according to Formula IX. [Figure 14] 1 is a table illustrating exemplary compounds according to formula X. [Figure 15] 1 is a table illustrating exemplary compounds according to Formula XI. [Figure 16] 1 is a table illustrating exemplary compounds according to Formula XII. [Figure 17]1 is a table illustrating exemplary compounds according to Formula XIII. [Figure 18] 1 is a table illustrating exemplary compounds according to formula XIV. [Figure 19] 1 is a digital image illustrating the color of an exemplary solid solution according to the present disclosure. [Figure 20] 1 is a graph showing differences in X-ray diffraction spectra of exemplary compounds according to the present disclosure. [Figure 21] 1 is a graph of β angle and cell volume versus formulation illustrating β angle and cell volume as a function of x for example compounds having the chemical formula Zn2-xNixV2O7 (0≦x≦0.3). [Figure 22] 1 is a graph of absorbance versus wavelength showing the diffuse reflectance spectrum of an exemplary Zn2-xNixV2O7 (0≦x≦0.3) solid solution. [Diagram 23] 1 is a graph of reflectance versus wavelength illustrating the near-infrared reflectance spectrum of an exemplary Zn2-xNixV2O7 (0≦x≦0.3) sample. [Figure 24] 1 is a graph of magnetic susceptibility versus temperature showing the inverse magnetic susceptibility of the Zn2-xNixV2O7 (x=0.2 and 0.23) phase. [Diagram 25] 1 is a graph showing X-ray diffraction spectra of Zn1.77Ni0.23V2O7 before and after exposure to dilute acid.

[0023] [Problem to be solved by the invention] [I.Definition] The following explanations of terms and methods are provided to better explain the present disclosure and to guide those skilled in the art in the practice of the present disclosure. The singular forms "a", "an", and "the" refer to one or more, unless the context clearly dictates otherwise. The term "or" refers to a single element or a combination of two or more elements of the listed alternative elements, unless the context clearly dictates otherwise. As used herein, "comprises" means "includes". Thus, "comprising A or B" means "including A, B, or A and B," without excluding additional elements. All references cited herein, including patents and patent applications, are incorporated by reference in their entirety, unless otherwise indicated.

[0024] Unless otherwise indicated, all numerical values ​​expressing amounts, molecular weights, percentages of ingredients, temperatures, times, and the like used in the specification or claims are understood to be modified by the term "about". Thus, unless otherwise indicated, either implicitly or explicitly, the numerical parameters recited are approximations that may depend on the desired properties sought and / or detection limits under standard testing conditions / methods. In cases where the embodiments are directly and explicitly distinguished from the prior art discussed, the numerical values ​​of the embodiments are not approximations unless the word "about" is explicitly recited.

[0025] Unless otherwise explained, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this disclosure pertains.In carrying out or testing this disclosure, methods and materials similar or equivalent to those described herein can be used, but suitable methods and materials are described below.Materials, methods, and examples are illustrative only and are not intended to be limiting.

[0026] The terms "thortveitite-related," "thortveitite-type," "thortveitite-base," etc. refer to the compound A2M2O7, which has a crystal structure based on the sortveitite crystal structure, but whose structure may differ from the sortveitite structure due to the displacement of atoms present in the compound and the rotation of the tetrahedron in the M2O7 diortho group. This structural change results in the breaking of the A-O bond and the formation of a distorted AO5 trigonal pyramid (Figure 1).

[0027] [II. Overview] Sortbeitite is a granitic pegmatite mineral composed of scandium-yttrium-silicate (Sc,Y)2Si2O7, commonly embedded in spessartite, beryl, and magnetite. It is naturally green, gray, yellow to white in color. Its general formula is A2M2O7. The A2M2O7 family can form various complex structures based on synthesis conditions, such as pyrochlore, dichromate, weberite, sortbeitite, and sortbeitite-related structures. The sortbeitite structure (C2 / m) has rare earths, transition metals, or trivalent elements (e.g. Sc, In, Y, Gd, Fe, etc.) at the A site, and potentially tetravalent silicon or germanium at the M site. The coordination numbers of the A and M sites are 6 and 4, respectively.

[0028] Solid solutions of (Zn,M)2V2O7, a sortovaitite-related structure with five-coordinated divalent cations (M=Cu, Co, Mg, Ni, Ca, Mn, Cd), have been reported. Based on crystal field theory, transition metals in non-centrosymmetric structures are allowed to undergo dd transitions due to crystal field splitting, especially in the TBP coordination. The sortovaitite-related structure, Zn2V2O7(C2 / c), consists of highly distorted TBP sites for Zn and tetrahedral sites for vanadium. The difference between sortovaitite (C2 / m) and sortovaitite-related structures (C2 / c) is shown in Figure 1. The twisted M2O7 di-tandem group in C2 / c breaks one of the bridging oxygens between the di-tandem group and the hexagonal AO6 network, resulting in the formation of distorted AO5 trigonal pyramids forming edge-sharing one-dimensional chains along the c direction. Solid solutions of (Zn,M)2V2O7 (where M is a divalent cation such as Cu, Ni, or Co) related to sotoveitite have been explored for their structural and magnetic properties, in which ZnCoV2O7 and ZnNiV2O7 were found to crystallize in the so-called dichromate structure type, exhibiting monoclinic symmetry and space group P21 / c (Figure 3). However, there have been no optical studies on compounds based on Zn2V2O7 with a sotoveitite-related structure.

[0029] The hue (color), saturation (brightness / dullness) and lightness of the powder samples are characterized using the CIE L*a*b* color space. The specific color can be precisely described by the three-dimensional color coordinates L*, a* and b* (Figure 4). The vertical axis L* indicates lightness ranging from 0 (black) to 100 (white). The a* value indicates the color from green to red (- to +), while b* indicates the color from blue to yellow (- to +), with a*=0, b*=0 being the neutral gray value.

[0030] [III. Compound] Disclosed herein are embodiments of compounds having a sort of beta - type zeolite - related structure that are chromogenic and may be useful as pigments. In some embodiments, the compounds are durable with respect to acid stability tests, which indicates that the pigments do not substantially change color even when exposed to weak acids such as rain, and thus may be useful in applications exposed to the elements. The compounds disclosed herein are typically synthesized from environmentally friendly elements or minerals that are abundant on Earth at low cost, and are thus more advantageous than existing pigments in the art.

[0031] Embodiments of the disclosed materials have the general formula A 2-x A’ x M 2-y M’ y satisfy O7, where A and A’ are divalent or trivalent cations including rare earth elements (for example, A and A’ are each independently Zn, Ni, Fe, Mn, Cr, Co, Mg, Cu, Ca, Sr, Ba, Al, Ga, or In, or rare earth elements such as Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, or combinations thereof). M and M’ are tetravalent or pentavalent anions (M = V, P, Ge, Si, or combinations thereof), and in most cases, x and y are greater than 0. The general formula is a compositional formula and does not necessarily imply chemical structure and / or connectivity.

[0032] [A. Chemical formula I] In some embodiments, the compound has a structure according to the following Chemical formula I. Zn 2-x Ni x V2O7 Chemical formula I

[0033] Regarding Chemical formula I, x is 0.2 - 0.8 (0.2 < x ≤ 0.8) or x is 1.2 - 1.8 (1.2 ≤ x ≤ 1.8). In some embodiments, x is less than 0.2 - 0.5 (0.2 < x < 0.5).

[0034] The compound of Formula I can have L*a*b* values of L* from 34 to 60, a* from 10 to 27, and b* from 19 to 60. In some embodiments, 0.2 < x ≦ 0.8, and the compound has L*a*b* values of L* from 34 to 51, a* from 17 to 27, and b* from 19 to 49. In other embodiments, 1.2 ≦ x ≦ 1.8, and the compound has L*a*b* values of L* from 51 to 60, a* from 10 to 14, and b* from 48 to 60.

[0035] Exemplary compounds according to Formula I are also shown in Table 1 and Figure 5.

[0036]

Table 1

[0037] [B. Formula II] In some embodiments, the compound has a structure according to the following Formula II Zn 2-2x Mn x M x V2O7 Formula II

[0038] Regarding Formula II, x is from 0 to 0.05 (0 < x ≦ 0.05), and M is a divalent cation Mg or Ni. The compound of Formula II can have L*a*b* values of L* from 22 to 37, a* from 7 to 19, and b* from 3 to 22.

[0039] In some embodiments, M is Mg, and the compound has L*a*b* values of L* from 32 to 36, a* from 10 to 19, and b* from 11 to 22. In other embodiments, M is Ni, and the compound has L*a*b* values of L* from 22 to 37, a* from 7 to 17, and b* from 3 to 17.

[0040] Exemplary compounds according to Formula II are shown in Table 2 and Figure 6.

[0041]

Table 2

[0042] [c. Chemical Formula III] In some embodiments, the compound has a structure according to the following Chemical Formula III. In 2-x Zn x Ge 2-x V x O7 Chemical Formula III

[0043] With respect to Chemical Formula III, x is less than 0 to 2 (0 < x < 2). In certain embodiments, x is selected from 0.1, 0.3, 0.5, 1, 1.5, 1.7, 1.8, or 1.90 to 1.98, for example 0.1, 0.3, 0.5, 1, 1.5, 1.7, 1.8, 1.90, 1.93, 1.94, 1.95, or 1.98.

[0044] In some embodiments, the compound of Chemical Formula III has L*a*b values of 48 to 67 for L*, -3 to 7 for a*, and 26 to 56 for b*.

[0045] Exemplary compounds according to Chemical Formula III are shown in Table 3 and in FIG. 7.

[0046] [Table 3]

[0047] [D. Chemical Formula IV] In some embodiments, the compound has a structure according to the following Chemical Formula IV. InZn 1-x Ni x GeVO7 Chemical Formula IV

[0048] Regarding Chemical Formula IV, x is from 0 to 1 (0 < x ≤ 1). In certain embodiments, x is selected from 0.1, 0.3, 0.5, 0.7, or 1.0. In some embodiments, the compound has L*a*b values of 48 - 59 for L*, 1 - 13 for a*, and 31 - 46 for b*.

[0049] Exemplary compounds according to Chemical Formula IV are shown in Table 4 and also in Figure 8.

[0050]

Table 4

[0051] [E. Chemical Formula V] In some embodiments, the compound has a structure according to Chemical Formula V. In 1-x Mn x ZnGeVO7 Chemical Formula V

[0052] Regarding Chemical Formula V, x is from 0 to 1 (0 < x < 1), for example, from 0 to 0.5. In certain embodiments, x is 0.1.

[0053] An exemplary compound according to Chemical Formula V is In 0.9 Mn 0.1 ZnGeVO7 (Figure 9).

[0054] [F. Chemical Formula VI] In some embodiments, the compound has a structure according to Chemical Formula VI. Zn 1.77-x Ni 0.23 M x V 2-y P y O7 Chemical Formula VI

[0055] With respect to Formula VI, x is 0-0.1 (0≦x≦0.1) and y is 0-2 (0≦y≦2). M is Mg, Ca, (NaAl), (NaGa), (KAl), or (KGa). In some embodiments, x is 0 or x is 0.1. In certain embodiments, y is 0, 0.2, or 2.

[0056] In some embodiments, the compound of formula VI has L*a*b values ​​of 35-77, a*-2-26, and b*-23-37.

[0057] Exemplary compounds according to Formula VI are shown in Table 5 and in FIG.

[0058] [Table 5]

[0059] [G.Formula VII] In some embodiments, the compound has formula VII. Zinc 1.8 Cu 0.1 M 0.1 V2O7 Chemical formula VII

[0060] For formula VII, M is a divalent cation Ni, Mn, Mg, or Ca. In some embodiments, the compound of formula VII has L*a*b* values ​​of 40-59, a* of 1-16, and b* of 26-44.

[0061] Exemplary compounds according to Formula VII are shown in Table 6 and in FIG.

[0062] [Table 6]

[0063] [H.Formula VIII] In some embodiments, the compound has the following formula VIII: Zinc 1.9 Cu 0.1 V x P 2-x O7 Chemical formula VIII

[0064] With respect to formula VIII, x is 0-1.8 (0≦x≦1.8). In certain embodiments, x is 0 or x is 1.8. In some embodiments, the compound of formula VII has L*a*b* values ​​of 46-81, a* of −3-4, and b* of 2-28.

[0065] Exemplary compounds according to Formula VIII are shown in Table 7 and in FIG.

[0066] [Table 7]

[0067] [H. Formula IX] In some embodiments, the compound has the following formula IX: Zinc 2-x-y Mn x M y V 2-z P z O7 Chemical formula IX

[0068] With respect to formula IX, M is a divalent cation Ni, Mg, or Ca.

[0069] x is 0 to 0.5 (0≦x≦0.5).

[0070] y is 0 to 0.1 (0≦y≦0.1).

[0071] z is 0 to 1 (0≦z≦1).

[0072] In some embodiments, x=0.02, 0.1, or 0.5.

[0073] In some embodiments, y=0 or y=0.1.

[0074] In some embodiments, z=0, z=0.2, or z=1.

[0075] In some embodiments, the compound of formula IX has L*a*b values ​​of L* from 33-41, a* from 17-22, and b* from 21-24.

[0076] Exemplary compounds according to Formula IX are shown in Table 8 and in FIG.

[0077] [Table 8]

[0078] [J.Chemical formula X] In some embodiments, the compound has the following formula X: Mg 2-x M x V 2-y P y O7 chemical formula x

[0079] For the chemical formula X, M is a divalent cation Ni or Mn, x is zero to 0.2 (0≦x≦0.2), and y is 0-1 (0≦y≦1).

[0080] In some embodiments, x=0 or x=0.2.

[0081] In some embodiments, y=0 or y=1.

[0082] In some embodiments, the compound of formula X has L*a*b values ​​of L* from 36-67, a* from 4-14, and b* from 15-46.

[0083] Exemplary compounds according to Formula X are shown in Table 9 and in FIG.

[0084] [Table 9]

[0085] [K.Formula XI] In some embodiments, the compound has the following formula XI: InZn 1-x Ni x Music Video 1-y P y O7 Chemical formula XI

[0086] With respect to formula XI, M is Si or Ge.

[0087] x is 0 to 0.3 (0≦x≦0.3).

[0088] y is 0 to 1 (0≦y≦1).

[0089] In some embodiments, x=0 or 0.1.

[0090] In some embodiments, y=0, 0.2, or 1.

[0091] In some embodiments, the compound of formula XI has L*a*b values ​​of 45-77, a*-2-7, and b*-24-46.

[0092] Exemplary compounds according to Formula XI are shown in Table 10 and in FIG.

[0093] [Table 10]

[0094] [L.Formula XII] In some embodiments, the compound has the following formula XII: Zinc 2-x-y M x Ni y V 2-x A x O7 Chemical formula XII

[0095] Regarding Chemical formula XII, M is a trivalent cation Fe, Cr, Sc, Y, or La.

[0096] A is Ge or Si.

[0097] x is from 0 to 0.1 (0 < x ≤ 0.1). In some embodiments, x is 0.1.

[0098] y is from 0 to 0.1. In some embodiments, y is 0, while in other embodiments, y is 0.1.

[0099] In some embodiments, the compound of Chemical formula XII has L*a*b values of 28 to 56 for L*, 15 to 28 for a*, and 34 to 48 for b*.

[0100] Exemplary compounds according to Chemical formula XII are shown in Table 11 and also in Figure 16.

[0101]

Table 11

[0102] [M. Chemical formula XIII] In some embodiments, the compound has the following Chemical formula XIII. Zn 1-x Co x V 1.8 P 0.2 O7 Chemical formula XIII

[0103] Regarding Chemical formula XIII, x is from 0 to 1 (0 < x < 1), for example, from 0 to 0.5. In certain embodiments, x is 0.1.

[0104] In some embodiments, the compound of Chemical formula XIII has L*a*b* values of 25 to 26 for L*, 1 to 2 for a*, and 9 to 10 for b*.

[0105] An exemplary compound according to Chemical Formula XIII is Zn 1.9 Co 0.1 V 1.8 P 0.2 O7 (Figure 17).

[0106] [N. Chemical Formula XIV] In some embodiments, the compound has Chemical Formula XIV. Ni 2-x Mn x V2O7 Chemical Formula XIV

[0107] With respect to Chemical Formula XIV, x is from 0 to 1 (0 < x < 1), for example, from 0 to 0.1. In certain embodiments, x is 0.02.

[0108] An exemplary compound according to Chemical Formula XIV is Ni 1.98 Mn 0.02 V2O7 (Figure 18).

[0109] [IV. Synthesis] The disclosed compounds are manufactured by standard techniques known to those skilled in the art. In some embodiments, conventional solid reactions are used. However, other synthetic routes such as sol-gel solution methods and hydrothermal low-temperature preparation methods can also be used, but are not limited thereto.

[0110] In some embodiments, stoichiometric amounts of appropriate starting materials are weighed, mixed, ground, and pelletized. Suitable starting materials include, but are not limited to, compounds having the formula ACO3, where A=Mg, Ca, Sr, or Ba; compounds having the formula MO3, where M=Al, Ga, In, Mn, Fe, Cr, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; compounds having the formula MO2, where M'=Si, or Ge; compounds having the formula MO2, where M''=Ni, Mn, Cu, Zn, or Fe; compounds having the formula MO5, where M''=V, or P; and Co3O4. One skilled in the art will know how to select a particular combination of starting materials to provide the stoichiometric amounts of each desired metal and oxygen required to produce the desired final compound.

[0111] The resulting pellets are then heated to a suitable temperature, for example, below 500°C to above 1200°C, for example, between 600°C and 1050°C, for a suitable time to facilitate the formation of the desired compounds. The heating time can be from below 4 hours to above 18 hours, for example, between 6 hours and 12 hours. Heating may be carried out in air (i.e., ambient atmosphere). Additionally, the reaction mixture is heated to the reaction temperature multiple times, for example, once, twice, three times or more, and intermediate grinding is performed. Heating is ramped at a suitable rate to facilitate the progress of the reaction, for example, at a ramp rate of 300°C / hour.

[0112] The compounds are analyzed by X-ray diffraction, near infrared reflectance spectroscopy, magnetic susceptibility, and stability to acid exposure. Diffuse reflectance spectroscopy is used to determine the spectral properties of the compounds, and L*a*b* color coordinates are determined for each compound.

[0113] [V. Composition] The present disclosure also relates to compositions comprising at least one of the disclosed compounds or compounds according to any one of formulas I-XIV and at least one additional ingredient. Such compositions include paints, inks, dyes, glass, plastics, emulsions, fabrics, or cosmetic preparations. Additional ingredients suitable for use in paint, ink dye, or emulsion products include, but are not limited to, binders, solvents, and additives such as catalysts, thickeners, stabilizers, emulsifiers, texturizers, adhesion promoters, UV stabilizers, leveling agents (i.e., gloss removers), preservatives, and other additives known to those skilled in the art.

[0114] Additional materials suitable for use in glass products include, for example, network formers (e.g., oxides of silicon, boron, germanium) to form highly crosslinked networks of chemical bonds, modifiers that change the network structure (e.g., calcium, lead, lithium, sodium, potassium), intermediates that can act as both network formers and modifiers (e.g., titanium, aluminum, zirconium, beryllium, magnesium, zinc), and combinations thereof.

[0115] Additional materials suitable for use in plastic products include, for example, dispersing aids (e.g., zinc stearate, calcium stearate, ethylene bisstearamide), plasticizers, flame retardants, internal mold release agents, slip agents, and combinations thereof.

[0116] When coloring a ceramic product, the material is usually added to a ceramic glaze composition. Other materials used in glazes include, for example, silica, metal oxides (e.g., sodium, potassium, calcium), alumina, opacifiers (e.g., tin oxide, zirconium oxide), and combinations thereof.

[0117] [VI. Examples] Example 1 Colored sotobeitite-based pigments were prepared by traditional solid-state reactions. Stoichiometric amounts of ACO3 (A=Mg, Ca, Sr, Ba), M2O3 (M=Al, Ga, In, Mn, Fe, Cr, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb.Lu), M'O2 (M'=Si, Ge), M''O (M''=Ni, Mn, Cu, Zn, Fe), M'''2O5 (M'''=V, P), and Co3O4 were weighed, mixed, ground, and pelletized. The resulting pellets were heated in air for the appropriate time and temperature range. The ramp rate was 300°C / h. Specific heating conditions used for certain disclosed embodiments are provided in Figures 5-18.

[0118] The properties of the calcined powders were measured with a Rigaku Miniflex X-ray diffractometer using Cu Kα radiation and a graphite monochromator on the diffraction beam. Diffuse reflectance spectra of the powder samples were obtained up to 2500 nm with a JASCO V-770 spectrophotometer. Data in the UV-Visible region were converted to absorbance using the Kubelka-Munk function. L*a*b* color coordinates were measured with a Konica Minolta CM-700d spectrophotometer (standard illuminance D65). Zn 2-x Ni x Magnetic measurements of the V2O7 (x = 0.2 and 0.23) samples were carried out in the temperature range of 5–300 K using a Quantum Design MPMS instrument.

[0119] Exemplary compounds made by the disclosed methods, along with reaction conditions and exemplary starting materials, are shown in Table 12. One of ordinary skill in the art would know how to adjust the amounts of the disclosed starting materials to make alternative compositions.

[0120] [Table 12-1] [Table 12-2] [Table 12-3] [Table 12-4] [Table 12-5] [Table 12-6] [Table 12-7] [Table 12-8] [Table 12-9] [Table 12-10]

[0121] [Results and Discussion] Materials characterization results are presented using the following exemplary solid solution systems: Zn 2-x Ni x V2O7(0≦x≦0.3) The orange powder colors for selected compositions are shown in Figure 19. Powders of various colors with different compositions are shown in Figures 5-18.

[0122] Solid solution Zn 2-x Ni x The X-ray diffraction pattern of V2O7 (0≦x≦0.3) is shown in Fig. 20. The lattice constants of the unit cell calculated by full pattern fitting are shown in Fig. 21. The decrease in the volume of the unit cell is due to the large Zn 2+ Ni ions are small 2+ This is consistent with the substitution of ions.

[0123] Zinc 2-x Ni xThe diffuse reflectance spectrum of the V2O7 (0≦x≦0.3) solid solution is shown in Figure 22. Strong absorption in the blue / green spectral region combined with absorption in the high energy region is responsible for the bright orange / red color observed. In pure Zn2V2O7, almost no absorption occurs in the entire visible range, except for a weak absorption near the violet spectral region, resulting in a pale yellow color. As the Ni content x increases, the intensity of the absorption peak near 480 nm increases, consistent with the sample gradually darkening towards a strong orange / red color. We found that the Ni content in the oxide 2+ I am not aware of any precedent for the intense orange / red color caused by this.

[0124] Zinc 2-x Ni x The NIR reflectance spectrum of the V2O7 (0≦x≦0.3) solid solution is shown in Figure 23. The NIR reflectance decreases with increasing Ni content.

[0125] A plot of the magnetic susceptibility is shown in Figure 24. The Curie and Weiss constants were derived from the slope and intercept of the linear region of 1 / χ vs. χ. Zn 2-x Ni x The magnetic susceptibility data for V2O7 (x=0.2, 0.23) suggest near paramagnetic behavior. The experimental moments are 2+ The results show reasonable agreement with the moments predicted by

[0126] Example 2 [Acid test] The compounds were tested to see if they would change color when exposed to acids in a similar pH range as normal rain. Since normal rain has a pH of about 5.6, the compounds were exposed to two dilute acid samples, HCl and HNO3, at pH=5. The results are shown below before and after the acid test. The results show that exposure to acid causes very little, if any, color change (Table 12) as seen from the L*, a*, and b* values. Additionally, the X-ray diffraction patterns show very little, if any, change in the crystal structure (Figure 25).

[0127] [Table 13]

[0128] In view of the many possible embodiments to which the principles of the disclosed invention may be applied, it should be recognized that the illustrated embodiments are merely preferred examples of the invention and should not be taken as limiting the scope of the invention. Rather, the scope of the invention is defined by the following claims. We therefore claim as our invention all that comes within the scope and spirit of these claims.

Claims

1. A compound having a structure represented by any of the chemical formulas I to XIV, Chemical formula I is Zn ２－ｘ Ni ｘ V ２ O ７ Here, x is between 0.2 and 0.8, or x is between 1.2 and 1.

8. Chemical formula II is Zn ２－２ｘ Mn ｘ M ｘ V ２ O ７ where x is from 0 to 0.05, M is Mg or Ni, Chemical formula III is In ２－ｘ Zn ｘ Ge ２－ｘ V ｘ O ７ Here, x is between 0 and less than 2, Chemical formula IV is InZn １－ｘ Ni ｘ GeVO ７ Here, x is between 0 and 1, Chemical formula V is In １－ｘ Mn ｘ ZnGeVO ７ Here, x is between 0 and less than 1, Chemical formula VI is Zn １．７７－ｘ Ni ０．２３ M ｘ V ２－ｙ P ｙ O ７ Here, x is between 0 and 0.1, y is between 0 and 2, and M is Mg, Ca, (NaAl), (NaGa), (KAl), or (KGa). Chemical formula VII is Zn １．８ Cu ０．１ M ０．１ V ２ O ７ Here, M is Ni, Mn, Mg, or Ca. Chemical formula VIII is Zn １．９ Cu ０．１ V ｘ P ２－ｘ O ７ Here, x is between 0 and 1.

8. Chemical formula IX is Zn ２－ｘ－ｙ Mn ｘ M ｙ V ２－ｚ P ｚ O ７ Here, M is Ni, Mg, or Ca, x is between 0 and 0.5, y is between 0 and 0.1, and z is between 0 and 1. Chemical formula X is Mg ２－ｘ M ｘ V ２－ｙ P ｙ O ７ Here, M is Ni or Mn, x is between 0 and 0.2, and y is between 0 and 1. Chemical formula XI is InZn １－ｘ Ni ｘ MV １－ｙ P ｙ O ７ Here, M is Si or Ge, x is between 0 and 0.3, and y is between 0 and 1. Chemical formula XII is Zn ２－ｘ－ｙ M ｘ Ni ｙ V ２－ｘ A ｘ O ７ Here, M is Fe, Cr, Sc, Y, or La, A is Ge, or Si, x is between 0 and 0.1, and y is between 0 and 0.

1. Chemical formula XIII is Zn １－ｘ Co ｘ V １．８ P ０．２ O ７ And here x is between 0 and less than 1, or Chemical formula XIV is Ni １－ｘ Mn ｘ V ２ O ７ A compound where x is between 0 and less than 1.

2. The following chemical formula I, that is, Zn ２－ｘ Ni ｘ V ２ O ７ Chemical formula I A compound of chemical formula 1 having the structure of, Here, x is between 0.2 and 0.8, or A compound in which x is between 1.2 and 1.

8.

3. A compound according to claim 2, wherein x is 0.2 to less than 0.

5.

4. A compound according to claim 2 or claim 3, wherein the L*a*b* values ​​of the compound are 34 to 60 for L*, 10 to 27 for a*, and 19 to 60 for b*.

5. The compound according to claim 4, wherein x is 0.2 to 0.8, and the L*a*b* values ​​of the compound are L* of 34 to 51, a* of 17 to 27, and b* of 19 to 49.

6. The compound according to claim 4, wherein x is 1.2 to 1.8, and the L*a*b values ​​of the compound are 51 to 60 for L*, 10 to 14 for a*, and 48 to 60 for b*.

7. In the compound according to claim 2 or claim 3, the compound is Zn １．７７ Ni ０．２３ V ２ O ７ Zn １．７６ Ni ０．２４ V ２ O ７ Zn １．７５ Ni ０．２５ V ２ O ７ Zn １．７ Ni ０．３ V ２ O ７ Zn １．４ Ni ０．６ V ２ O ７ [[ID=4|0]]Zn １．２ Ni ０．８ V ２ O ７ Zn ０．８ Ni １．２ V ２ O ７ Zn ０．６ Ni １．４ V ２ O ７ Zn ０．４ Ni １．６ V ２ O <{\| ７ or Zn ０．２ Ni １．８ V ２ O ７ selected from, a compound.

8. The following chemical formula II, that is, Zn ２－２ｘ Mn ｘ M ｘ V ２ O ７ Chemical formula II A compound of chemical formula 1 having the structure of, Here, x is between 0 and 0.05, and A compound in which M is either Mg or Ni.

9. The compound according to claim 8, wherein the L*a*b* values ​​of the compound are 22 to 37 for L*, 7 to 19 for a*, and 3 to 22 for b*.

10. The compound according to claim 8, wherein M is Mg, and the L*a*b* values ​​of the compound are L* of 32 to 36, a* of 10 to 19, and b* of 11 to 22.

11. The compound according to claim 8, wherein M is Ni, and the L*a*b* values ​​of the compound are L* of 22 to 37, a* of 7 to 17, and b* of 3 to 17.

12. In the compound according to any one of claims 8 to 11, the compound is Zn １．９８ Mn ０．０１ Mg ０．０１ V ２ O ７ , Zn １．９６ Mn ０．０２ Mg ０．０２ V ２ O ７ , Zn １．９４ Mn ０．０３ Mg ０．０３ V ２ O ７ , Zn １．９２ Mn ０．０４ Mg ０．０４ V ２ O ７ , Zn １．９６ Mn ０．０２ Ni ０．０２ V ２ O ７ , Zn １．９６ Mn ０．０２ Ni ０．０２ V ２ O ７ , Zn １．９４ Mn ０．０３ Ni ０．０３ V ２ O ７ , Zn １．９２ Mn ０．０４ Ni ０．０４ V ２ O ７ , or Zn １．９ Mn ０．０５ Ni ０．０５ V ２ O ７ A compound selected from among them.

13. The following chemical formula III, that is, In ２－ｘ Zn ｘ Ge ２－ｘ V ｘ O ７ Chemical formula III A compound according to claim 1 having the structure, Here, x is a compound between 0 and less than 2.

14. A compound according to claim 13, wherein x is 0.1, 0.3, 0.5, 1, 1.5, 1.7, 1.8, 1.90, 1.93, 1.94, 1.95, or 1.

98.

15. A compound according to claim 13 or claim 14, wherein the L*a*b values ​​of the compound of chemical formula III are L* of 48 to 67, a* of -3 to 7, and b* of 26 to 56.

16. In the compound according to claim 13 or claim 14, the compound is In １．９ Zn ０．１ Ge １．９ V ０．１ O ７ In １．７ Zn ０．３ Ge １．７ V ０．３ O ７ In １．５ Zn ０．５ Ge １．５ V ０．５ O ７ InZnGeVO ７ In ０．５ Zn １．５ Ge ０．５ V １．５ O ７ In ０．３ Zn １．７ Ge ０．３ V １．７ O ７ In ０．２ Zn １．８ Ge ０．２ V １．８ O ７ In ０．１ Zn １．９ Ge ０．１ V １．９ O ７ In ０．０７ Zn １．９３ Ge ０．０７ V １．９３ O ７ In ０．０６ Zn １．９４ Ge ０．０６ V １．９４ O ７ In ０．０５ Zn １．９５ Ge ０．０５ V １．９５ O ７ , or In ０．０２ Zn １．９８ Ge ０．０２ V １．９８ O ７ A compound selected from among them.

17. The following chemical formula IV, that is, 9000 １－ｘ ii ｘ 1169 ７ Chemical formula IV A compound according to claim 1 having the structure, Here, x is a compound between 0 and 1.

18. A compound according to claim 17, wherein x is 0.1, 0.3, 0.5, 0.7, or 1.

19. A compound according to claim 17 or claim 18, wherein the L*a*b values ​​of the compound are 54 to 59 for L*, 4 to 13 for a*, and 43 to 46 for b*.

20. In the compound according to claim 17 or claim 18, the compound is InZn ０．９ Ni ０．１ GeVO ７ InZn ０．７ Ni ０．３ GeVO ７ InZn ０．５ Ni ０．５ GeVO ７ InZn ０．３ Ni ０．７ GeVO ７ , or InNiGeVO ７ A compound selected from among them.

21. The following chemical formula V, that is, In １－ｘ Mn ｘ ZnGeVO ７ Chemical formula V A compound according to claim 1 having the structure, Here, x is a compound between 0 and less than 1.

22. In the compound according to claim 21, the compound is In ０．９ Mn ０．１ ZnGeVO ７ It is a compound.

23. The following chemical formula VI, that is, Zn １．７７－ｘ Ni ０．２３ M ｘ V ２－ｙ P ｙ O ７ Chemical formula VI A compound according to claim 1 having the structure, Here, x is between 0 and 0.

1. y is between 0 and 2, and A compound in which M is Mg, Ca, (NaAl), (NaGa), (KAl), or (KGa).

24. A compound according to claim 23, wherein x is 0 or 0.

1.

25. A compound according to claim 23 or claim 24, wherein y is 0, 0.2, or 2.

26. A compound according to claim 23 or claim 24, wherein the L*a*b values ​​of the compound are L* from 35 to 77, a* from -2 to 26, and b* from 23 to 37.

27. In the compound according to claim 23 or claim 24, the compound is Zn １．６７ Ni ０．２３ Mg ０．１ V ２ O ７ , Zn １．６７ Ni ０．２３ Ca ０．１ V ２ O ７ , Zn １．６７ Ni ０．２３ (NaAl) ０．１ V ２ O ７ , Zn １．６７ Ni ０．２３ (NaGa) ０．１ V ２ O ７ , Zn １．６７ Ni ０．２３ (KAl) ０．１ V ２ O ７ , Zn １．６７ Ni ０．２３ (KGa) ０．１ V ２ O ７ , Zn １．７７ Ni ０．２３ P ２ O ７ , Zn １．７７ Ni ０．２３ V １．８ P ０．２ O ７ , Zn １．６７ Ni ０．２３ Mg ０．１ V １．８ P ０．２ O ７ , Zn １．６７ Ni ０．２３ Ca ０．１ V １．８ P ０．２ O ７ , Zn １．６７ Ni ０．２３ (NaAl) ０．１ V １．８ P ０．２ O ７ , Zn １．６７ Ni ０．２３ (NaGa) ０．１ V １．８ P ０．２ O ７ , Zn １．６７ Ni ０．２３ (KAl) ０．１ V １．８ P ０．２ O ７ , or Zn １．６７ Ni ０．２３ (KGa) ０．１ V １．８ P ０．２ O ７ A compound selected from among them.

28. The following chemical formula VII, that is, Zn １．８ Cu ０．１ M ０．１ V ２ O ７ Chemical formula VII A compound according to claim 1 having the structure, Here, M is a compound where M is Ni, Mn, Mg, or Ca.

29. The compound according to claim 28, wherein the L*a*b* values ​​of the compound are 40 to 59 for L*, 1 to 16 for a*, and 26 to 44 for b*.

30. In the compound according to any one of claims 28 to 29, the compound is Zn １．８ Cu ０．１ Ni ０．１ V ２ O ７ , Zn １．８ Cu ０．１ Mn ０．１ V ２ O ７ , Zn １．８ Cu ０．１ Mg ０．１ V ２ O ７ , or Zn １．８ Cu ０．１ Ca ０．１ V ２ O ７ A compound selected from among them.

31. The following chemical formula VIII, that is, Zn １．９ Cu ０．１ V ｘ P ２－ｘ O ７ Chemical formula VIII A compound according to claim 1 having the structure, Here, x is a compound between 0 and 1.

8.

32. A compound according to claim 31, wherein x is 0 or 1.

8.

33. A compound according to claim 31 or claim 32, wherein the L*a*b* values ​​of the compound are 46 to 81 for L*, -3 to 4 for a*, and 2 to 28 for b*.

34. In the compound according to claim 31 or claim 32, the compound is Zn １．９ Cu ０．１ P ２ O ７ , or Zn １．９ Cu ０．１ V １．８ P ０．２ O ７ A compound selected from among them.

35. The following chemical formula IX, that is, Zn ２－ｘ－ｙ Mn ｘ M ｙ V ２－ｚ P ｚ O ７ Chemical formula IX A compound according to claim 1 having the structure, Here, M is Ni, Mg, or Ca. x is between 0 and 0.

5. y is between 0 and 0.1, and A compound where z is between 0 and 1.

36. A compound according to claim 35, wherein x = 0.02, 0.1, or 0.

5.

37. A compound according to claim 35 or claim 36, wherein Y is 0 or 0.

1.

38. A compound according to claim 35 or claim 36, wherein z is 0, 0.2, or 1.

39. A compound according to claim 35 or claim 36, wherein the L*a*b values ​​of the compound are 34 to 37 for L*, 20 to 22 for a*, and 23 to 24 for b*.

40. In the compound according to claim 35 or claim 36, the compound is Zn １．８８ Mn ０．０２ Ni ０．１ V ２ O ７ , Zn １．８８ Mn ０．０２ Mg ０．１ V ２ O ７ , Zn １．８８ Mn ０．０２ Ca ０．１ V ２ O ７ , Zn １．９８ Mn ０．０２ V １．８ P ０．２ O ７ , Zn １．８８ Mn ０．０２ Ni ０．１ V １．８ P ０．２ O ７ , Zn １．８８ Mn ０．０２ Mg ０．１ V １．８ P ０．２ O ７ , Zn １．８８ Mn ０．０２ Ca ０．１ V １．８ P ０．２ O ７ , Zn １．９ Mn ０．１ VPO ７ , Zn １．９ Mn ０．１ V １．８ P ０．２ O ７ , Zn １．９ Mn ０．１ V １．５ P ０．５ O ７ , or Zn １．５ Mn ０．５ V １．５ P ０．５ O ７ A compound selected from among them.

41. The following chemical formula X, that is, Mg ２－ｘ M ｘ V ２－ｙ P ｙ O ７ chemical formula A compound according to claim 1 having the structure, Here, M is either Ni or Mn, x is between 0 and 0.2, and A compound in which y is between 0 and 1.

42. A compound according to claim 41, wherein x is 0 or 0.

2.

43. A compound according to claim 41 or claim 42, wherein y is 0 or 0.

1.

44. In the compound according to claim 41 or claim 42, the compound is Mg １．８ Ni ０．２ V ２ O ７ Mg １．８ Mn ０．２ V ２ O ７ , or Mg ２ VPO ７ A compound selected from among them.

45. The following chemical formula XI, that is, InZn １－ｘ Yes ｘ MV １－ｙ P ｙ Oh ７ Chemical formula XI A compound according to claim 1 having the structure, Here, M is Si or Ge, x is between 0 and 0.3, and A compound in which y is between 0 and 1.

46. A compound according to claim 45, wherein x is 0, 0.1, or 0.

3.

47. A compound according to claim 45 or claim 46, wherein y is 0, 0.2, or 1.

48. In the compound according to claim 45 or claim 46, the compound is InZnSiVO ７ InZn ０．９ Ni ０．１ SiVO ７ InZnGePO ７ InZn ０．９ Ni ０．１ GePO ７ InZnSiPO ７ InZn ０．９ Ni ０．１ SiPO ７ InZn ０．９ Ni ０．１ GeV ０．８ P ０．２ O ７ , or InZn ０．９ Ni ０．１ SiV ０．８ P ０．２ O ７ A compound selected from among them.

49. The following chemical formula XII, that is, Zn ２－ｘ－ｙ M ｘ Ni ｙ V ２－ｘ A ｘ O ７ Chemical formula XII A compound according to claim 1 having the structure, Here, M is Fe, Cr, Sc, Y, or La. A is Ge or Si, x is between 0 and 0.1, and A compound in which y is between 0 and 0.

1.

50. A compound according to claim 49, wherein x is 0.

1.

51. A compound according to claim 49 or claim 50, wherein y is 0 or 0.

1.

52. A compound according to claim 49 or claim 50, wherein the L*a*b values ​​of the compound are L* of 28 to 56, a* of 15 to 28, and b* of 34 to 48.

53. In the compound according to claim 49 or claim 50, the compound is Zn １．９ Fe ０．１ V １．９ Ge ０．１ O ７ , Zn １．９ Fe ０．１ V １．９ Si ０．１ O ７ , Zn １．９ Cr ０．１ V １．９ Ge ０．１ O ７ , Zn １．９ Cr ０．１ V １．９ Si ０．１ O ７ , Zn １．９ Sc ０．１ V １．９ Si ０．１ O ７ , Zn １．８ Sc ０．１ Ni ０．１ V １．９ Si ０．１ O ７ , Zn １．９ Sc ０．１ V １．９ Ge ０．１ O ７ , Zn １．８ Sc ０．１ Ni ０．１ V １．９ Ge ０．１ O ７ , Zn １．９ Y ０．１ V １．９ Si ０．１ O ７ , Zn １．８ Y ０．１ Ni ０．１ V １．９ Si ０．１ O ７ , Zn １．９ Y ０．１ V １．９ Ge ０．１ O ７ , Zn １．８ Y ０．１ Ni ０．１ V １．９ Ge ０．１ O ７ , Zn １．９ La ０．１ V １．９ Si ０．１ O ７ , Zn １．８ La ０．１ Ni ０．１ V １．９ Si ０．１ O ７ , Zn １．９ La ０．１ V １．９ Ge ０．１ O ７ , or Zn １．８ La ０．１ Ni ０．１ V １．９ Ge ０．１ O ７ A compound selected from among them.

54. The following chemical formula XIII, that is, Zn １－ｘ Co ｘ V １．８ P ０．２ O ７ Chemical formula XIII A compound according to claim 1 having the structure, Here, x is a compound between 0 and less than 1.

55. A compound according to claim 54, wherein x is 0.

1.

56. A compound according to claim 54 or claim 55, wherein the L*a*b* values ​​of the compound are 25 to 26 for L*, 1 to 2 for a*, and 9 to 10 for b*.

57. In the compound according to claim 54 or claim 55, the compound is Zn １．９ Co ０．１ V １．８ P ０．２ O ７ It is a compound.

58. Chemical formula XIV, that is, Ni １－ｘ Mn ｘ V ２ O ７ Chemical formula XIV A compound according to claim 1 having the structure, Here, x is a compound between 0 and less than 1.

59. In the compound according to claim 58, the compound is Ni １．９８ Mn ０．０２ V ２ O ７ It is a compound.

60. A composition comprising any one of the compounds described in claim 1, claim 2, claim 3, claim 8, claim 9, claim 10, claim 11, claim 13, claim 14, claim 17, claim 18, claim 21, claim 22, claim 23, claim 24, claim 28, claim 29, claim 31, claim 32, claim 35, claim 36, claim 41, claim 42, claim 45, claim 46, claim 49, claim 50, claim 54, claim 55, claim 58, and claim 59, A composition comprising at least one additional component.

61. The composition according to claim 60, wherein the composition is a paint, ink, dye, glass, plastic, emulsion, cloth, or cosmetic preparation.

62. A composition according to claim 60, wherein at least one additional component is a binder, a solvent, a catalyst, a thickener, a stabilizer, an emulsifier, a texturizer, an adhesion promoter, a UV stabilizer, a planarizer, a preservative, a polymer, a dispersion aid, a plasticizer, a flame retardant, a metal oxide, or any combination thereof.

63. The composition according to claim 60, wherein the composition is glass, and at least one additional component is a metal oxide.

64. A composition according to claim 60, further comprising at least one additional compound according to any one of claims 1, 2, 3, 8, 9, 10, 11, 13, 14, 17, 18, 21, 22, 23, 24, 28, 29, 31, 32, 35, 36, 41, 42, 45, 46, 49, 50, 54, 55, 58, and 59.

65. A method for producing a compound according to any one of claims 1, 2, 3, 8, 9, 10, 11, 13, 14, 17, 18, 21, 22, 23, 24, 28, 29, 31, 32, 35, 36, 41, 42, 45, 46, 49, 50, 54, 55, 58, and 59, wherein the method is: The steps include selecting a desired metal in the compound, A step of preparing a reactant containing the selected metal, The steps include combining reactants in stoichiometric amounts to achieve the desired final ratio of the selected metal in the compound, and The steps include heating the combination of reactants at an effective temperature for an effective time to produce a compound, and A method that includes [a certain feature].

66. A method according to claim 65, wherein the effective temperature is 600°C to 1050°C.

67. A method according to claim 65, wherein the time is 6 to 12 hours.

68. A method according to claim 65, wherein the step of heating the combination of reactants comprises a step of heating over a first period of 6 to 12 hours, a step of grinding the mixture of reactants, and a step of reheating over a second period of 6 to 12 hours.

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