Compounds having scandium yttrium related structures and methods of making and using same

Abstract

The invention discloses a novel compound with a scandium yttrium related structure. These compounds may be colored and may be used as pigments. These compounds are durable in acid stability tests that indicate that the pigment does not substantially discolor when exposed to weak acids such as rainwater. The compounds disclosed herein are generally synthesized from globally rich, environmentally friendly elements or minerals at low cost, thus superior to existing pigments in the art.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to the earlier filing date of U.S. Provisional Patent Application No. 63 / 336,913, filed on April 29, 2022, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present invention relates to a compound having a scandium yttrium structure, in particular to a colored compound, a composition containing the compound, and a method for preparing and using the compound and the composition.

[0004] Acknowledgement of Government Support

[0005] This invention was made with government support under Contract No. DMR-2025615 awarded by the National Science Foundation from the Mathematical and Physical Sciences Directorate. The government has certain rights in this invention. Background Art

[0006] Most of the orange / red inorganic pigments currently used contain heavy metals, such as cadmium, lead and mercury, and thus have environmental problems. There is a need for environmentally friendly, earth-abundant and durable inorganic pigments, especially deep orange / red inorganic pigments. Summary of the invention

[0007] Disclosed herein are embodiments of compounds that are useful as colored pigments but do not contain toxic and / or environmentally problematic heavy metals. In some embodiments, the compound has Formula I: Zn 2-x Ni x V2O7, wherein x is from greater than 0.2 to 0.8, or x is from 1.2 to 1.8. In some embodiments, x is from greater than 0.2 to less than 0.5. The compound may 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, x is from greater than 0.2 to 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, x is 1.2 to 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. And / or the compound may be selected from 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 Ni0.6 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.

[0008] Also disclosed herein are embodiments of compounds having a structure according to Formula II: Zn 2-2x Mn x M x V2O7, wherein x is from greater than 0 to 0.05; M is Mg or Ni. The compound may have L*a*b* values ​​of L* from 22 to 37, a* from 7 to 19, and b* from 3 to 22. 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. And / or the compound may be selected from Zn 1.98 Mn 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.

[0009] Also disclosed are compounds having a structure according to Formula III: In 2-x Znx Ge 2-x V x O7. With respect to Formula I, x is from greater than 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 compound may have L*a*b* values, L* from 48 to 67, a* from -3 to 7, and b* from 26 to 56, and / or is selected from In 1.9 Zn 0.1 Ge 1.9 V 0.1 O7、In 1.7 Zn 0.3 Ge 1.7 V 0.3 O7、In 1.5 Zn 0.5 Ge 1.5 V 0.5 O7, InZnGeVO7, In 0.5 Zn 1.5 Ge 0.5 V 1.5 O7、In 0.3 Zn 1.7 Ge 0.3 V 1.7 O7、In 0.2 Zn 1.8 Ge 0.2 V 1.8 O7、In 0.1 Zn 1.9 Ge 0.1 V 1.9 O7、In 0.07 Zn 1.93 Ge 0.07 V 1.93 O7、In 0.06 Zn 1.94 Ge 0.06 V 1.94 O7、In 0.05 Zn 1.95 Ge 0.05 V 1.95 O7 or In 0.02 Zn 1.98 Ge 0.02 V 1.98 O7.

[0010] Also disclosed are embodiments of compounds having a structure according to Formula IV: InZn 1-x Ni xGeVO7, wherein x is from greater than 0 to 1. x may be 0.1, 0.3, 0.5, 0.7 or 1. The compound may have L*a*b* values ​​of L* from 54 to 59, a* from 4 to 13, and b* from 43 to 46. And / or the compound may be selected from 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 GeVO7 or InNiGeVO7.

[0011] Alternatively, the compound may have a structure according to Formula V: In 1-x Mn x ZnGeVO7, wherein x is from greater than 0 to less than 1. In some embodiments, the compound is In 0.9 Mn 0.1 ZnGeVO7.

[0012] In other embodiments, the compound has a structure according to Formula VI: Zn 1.77-x Ni 0.23 M x V 2-y P y O7, wherein x is from 0 to 0.1; y is from 0 to 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 L* from 35 to 77, a* from -2 to 26, and b* from 23 to 37. And / or the compound may be selected from 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 Ni0.23 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 0.2 O7, 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 O7.

[0013] Also disclosed herein are embodiments of compounds having a structure according to Formula VII: Zn 1.8 Cu 0.1 M 0.1 V2O7, wherein M is Ni, Mn, Mg or Ca. The compound may have L*a*b* values ​​of L* from 40 to 59, a* from 1 to 16, and b* from 26 to 44. In some embodiments, the compound is selected from 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.

[0014] A further embodiment relates to compounds having a structure according to Formula VIII: Zn 1.9 Cu0.1 V x P 2-x O7, wherein x is 0 to 1.8, and may be 0 or 1.8. The compound may have L*a*b* values, L* from 46 to 81, a* from -3 to 4, and b* from 2 to 28, and / or is selected from Zn 1.9 Cu 0.1 P2O7 or Zn 1.9 Cu 0.1 V 1.8 P 0.2 O7.

[0015] Also disclosed are embodiments of compounds having a structure according to Formula IX: Zn 2-x-y Mn x M y V 2-z P z O7. With respect to Formula IX, M is Ni, Mg or Ca; x is from greater than 0 to 0.5, and may be 0.02, 0.1 or 0.5; y is from 0 to 0.1, and may be 0 or 0.1; z is from 0 to 1, and may be 0, 0.2 or 1. The compound may have L*a*b* values, L* from 34 to 37, a* from 20 to 22, and b* from 23 to 24. And / or the compound may be selected from 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 P0.2 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 O7.

[0016] The substituted compound has a structure according to Formula X: Mg 2-x M x V 2-y P y O7, wherein M is Ni or Mn; x is from 0 to 0.2; and y is from 0 to 1. In some embodiments, x is 0 or 0.2 and / or y is 0 or 0.1. The compound may be selected from Mg 1.8 Ni 0.2 V2O7、Mg 1.8 Mn 0.2 V2O7 or Mg2VPO7.

[0017] Also disclosed are embodiments of compounds having a structure according to Formula XI: InZn 1-x Ni x MV 1-y P y O7, wherein M is Si or Ge; x is from 0 to 0.3, for example, 0, 0.1 or 0.3; and y is from 0 to 1, for example, 0, 0.2 or 1. The compound can be selected from 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 O7.

[0018] Also disclosed herein are compounds having a structure according to Formula XII: Zn 2-x-y M x Ni y V 2-x A xO7. With respect to Formula XII, M is Fe, Cr, Sc, Y or La; A is Ge or Si; x is from greater than 0 to 0.1; and y is from 0 to 0.1. In some embodiments, x is 0.1, and / or y is 0 or 0.1. The compound may have L*a*b* values, L* from 28 to 56, a* from 15 to 28, and b* from 34 to 48. And / or the compound may be selected from Zn 1.9 Fe 0.1 V 1.9 Ge 0.1 O7、Zn 1.9 Fe 0.1 V 1.9 Si 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 Si 0.1 O7、Zn 1.9 Sc 0.1 V 1.9 Si 0.1 O7、Zn 1.8 Sc 0.1 Ni 0.1 V 1.9 Si 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 Si 0.1 O7、Zn 1.8 Y 0.1 Ni 0.1 V 1.9 Si 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 Ge 0.1 O7、Zn 1.9 La 0.1 V 1.9 Si 0.1 O7、Zn1.8 La 0.1 Ni 0.1 V 1.9 Si 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 O7.

[0019] Also disclosed are embodiments of compounds having a structure according to Formula XIII: Zn 1-x Co x V 1.8 P 0.2 O7, wherein x is from greater than 0 to less than 1, and may be 0.1. The compound may have L*a*b* values, L* from 25 to 26, a* from 1 to 2, and b* from 9 to 10, and / or may be Zn 1.9 Co 0.1 V 1.8 P 0.2 O7.

[0020] A further embodiment relates to a compound having a structure according to Formula XIV: Ni 1-x Mn x V2O7, wherein x is from greater than 0 to less than 1. In one embodiment, the compound is Ni 1.98 Mn 0.02 V2O7.

[0021] Also disclosed herein are embodiments of compositions comprising compounds disclosed herein. The composition may also include at least one additional component, for example, adhesives, solvents, catalysts, thickeners, stabilizers, emulsifiers, texture agents, tackifiers, UV stabilizers, leveling agents, preservatives, polymers, dispersing aids, plasticizers, flame retardants, metal oxides or any combination thereof. The composition may be a paint, ink, dye, glass, plastic, emulsion, fabric or cosmetic preparation. In some embodiments, the composition is glass, and the composition includes metal oxides. Additionally or alternatively, the composition may also include at least one additional compound according to the present disclosure.

[0022] Also disclosed herein is a method for preparing the disclosed compounds. The method may include: selecting a desired metal in the compound; providing a reactant including the selected metal; combining stoichiometric reactants to obtain a desired final ratio of the selected metal in the compound; and heating the reactant combination at an effective temperature for an effective time period to prepare the disclosed compound. The effective temperature may be from 600°C to 1050°C, and / or the time period may be from 6 hours to 12 hours. In some embodiments, heating the reactant combination includes heating for a first time period of 6 hours to 12 hours, grinding the reaction mixture and heating for a second time period of 6 hours to 12 hours.

[0023] The foregoing and other objects, features and advantages of the present invention will become more apparent from the following detailed description made with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 Schematic diagram showing the difference between scandium structure (C2 / m) (left) and scandium-related structure (C2 / c) (right).

[0025] Figure 2 Schematic diagram of the scandium yttrium structure (C2 / m) of an exemplary A2M2O7-type compound, showing trivalent A cations (orange) and tetravalent M cations (cyan), wherein the trivalent A cations are shown as edge-sharing distorted AO6 octahedra forming a 2D hexagonal network perpendicular to the c-axis (left side), the tetravalent M cations are shown as M2O7 diortho groups connecting the AO6 hexagonal sheets to form a 3D structure (right side), and the oxygen ions are shown as red spheres.

[0026] Figure 3 Schematic diagram showing the crystal structure (P21 / c) of ZnMV2O7 (M=Co, Ni), showing a zigzag chain of edge-sharing (Zn / M)O6 octahedra connected by V2O7 diortho groups.

[0027] Figure 4 is a schematic diagram showing how L*a*b* values ​​correspond to different colors.

[0028] Figure 5 is a table showing exemplary compounds according to Formula I.

[0029] Figure 6 is a table showing exemplary compounds according to Formula II.

[0030] Figure 7 is a table showing exemplary compounds according to Formula III.

[0031] Figure 8 is a table showing exemplary compounds according to Formula IV.

[0032] Fig. 9 is a table showing exemplary compounds according to Formula V.

[0033] Fig.10 is a table showing exemplary compounds according to Formula VI.

[0034] Fig.11 is a table showing exemplary compounds according to Formula VII.

[0035] Fig.12 is a table showing exemplary compounds according to Formula VIII.

[0036] Fig.13 is a table showing exemplary compounds according to Formula IX.

[0037] Fig.14 is a table showing exemplary compounds according to Formula X

[0038] Fig.15 is a table showing exemplary compounds according to Formula XI.

[0039] Fig.16 is a table showing exemplary compounds according to Formula XII.

[0040] Fig.17 is a table showing exemplary compounds according to Formula XIII.

[0041] Fig.18 is a table showing exemplary compounds according to Formula XIV.

[0042] Fig.19 is a digital image showing the color of an exemplary solid solution according to the present disclosure.

[0043] Fig. 20 is a graph showing the differences in X-ray diffraction spectra of exemplary compounds according to the present disclosure.

[0044] Fig.21 is a graph of β angle and unit cell volume versus formula, showing β angle and unit cell volume as a function of formula Zn 2- x Ni x Function of x for exemplary compounds of V2O7 (0≤x≤0.3).

[0045] Fig. 22 is a graph of absorbance versus wavelength showing an exemplary Zn 2-x Ni x Diffuse reflectance spectrum of V2O7 (0≤x≤0.3) solid solution.

[0046] Fig.23is a graph of reflectivity versus wavelength showing an exemplary Zn 2-x Ni x NIR reflectance spectra of V2O7 (0≤x≤0.3) samples.

[0047] Fig.24 is a graph of magnetic susceptibility versus temperature, showing that Zn 2-x Ni x Reversed magnetic susceptibility of V2O7 (x = 0.2 and 0.23) phases.

[0048] Fig.25 It shows that Zn 1.77 Ni 0.23 Plot of the X-ray diffraction spectra of V2O7 before and after exposure to dilute aqueous acid. DETAILED DESCRIPTION

[0049] I. Definitions

[0050] The following explanations of terms and methods are provided to better describe the present disclosure and to guide those of ordinary skill in the art to implement the present disclosure. The singular forms "a", "an" and "the" refer to one or more than one, unless the context clearly states otherwise. The term "or" refers to a single element or a combination of two or more elements in the alternative element, unless the context clearly states otherwise. As used herein, "including" means "comprising". Therefore, "including A or B" means "including A, B, or A and B", without excluding additional components. Unless otherwise stated, the entire contents of all references cited herein (including patents and patent applications) are incorporated herein by reference.

[0051] Unless otherwise stated, all numerical values ​​used in the specification or the description indicating the number of components, molecular weights, percentages, temperatures, times, etc. should be understood to be modified by the term "about". Therefore, unless otherwise stated, implicitly or explicitly, the numerical parameters listed are approximate values, which may depend on the desired properties sought and / or the detection limits under standard test conditions / methods. When directly and clearly distinguishing an embodiment from the prior art being discussed, the numbering of the embodiment is not approximate unless the word "about" is explicitly cited.

[0052] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present disclosure belongs. Although methods and materials similar to or equivalent to those described herein may be used in the practice or testing of the present disclosure, suitable methods and materials are described below. The materials, methods, and examples are illustrative only and not restrictive.

[0053] The terms "scandite-related", "scandite-type", "scandite-based", etc. refer to compounds A2M2O7 that have a crystal structure based on the scandite crystal structure, but which may differ from the scandite structure due to atomic displacements and tetrahedral rotations in the M2O7 diorthogroup. This structural change results in the breaking of the AO bond and the formation of a distorted AO5 trigonal bipyramid ( Figure 1 ).

[0054] II. Overview

[0055] Scandite is a granite pegmatite mineral composed of scandium-yttrium silicate (Sc,Y)2Si2O7, usually embedded in spessartine, beryl and magnetite. Scandite occurs in nature in colors ranging from green, gray, yellow to white. The general formula of the scandite structure is A2M2O7. Based on the synthesis conditions, the A2M2O7 family can form a variety of complex structures, for example, pyrochlore, dichromate, ferromagnesianite, scandite and scandite-related structures. The scandite structure (C2 / m) can be described as a combination of a three-dimensional framework of M2O7 diortho groups and a hexagonal network formed by octahedrons sharing the AO6 edges ( Figure 2 ), where the A site can be a rare earth, transition metal or trivalent element (examples: Sc, In, Y, Gd, Fe, etc.), and the M site can be tetravalent silicon or germanium. The coordination numbers of the A site and the M site are 6 and 4, respectively.

[0056] It is reported that the scandite-related solid solution (Zn,M)2V2O7 has different divalent cations (M = Cu, Co, Mg, Ni, Ca, Mn, Cd) in five coordination sites. Based on crystal field theory, transition metals in non-centrosymmetric structures will undergo allowed dd transitions due to crystal field splitting, especially in TBP coordination. The scandite-related structure Zn2V2O7 (C2 / c) consists of a highly distorted TBP site for Zn and a tetrahedral site for vanadium. Figure 1 The differences between scandium (C2 / m) and scandium-related structures (C2 / c) are shown. The distorted M2O7 diortho group in C2 / c destroys one of the bridging oxygens between the diortho group and the hexagonal AO6 network, resulting in the formation of edge-sharing 1D chains of distorted AO5 trigonal bipyramids along the c direction. The structure and magnetic properties of solid solutions of scandium-related (Zn,M)2V2O7 (where M is a divalent cation, such as Cu, Ni and / or Co) were studied, where ZnCoV2O7 and ZnNiV2O7 were found to crystallize in the so-called dichromate structure type, showing monoclinic symmetry, a steric group P21 / c ( Figure 3 ). However, there are no optical studies on Zn2V2O7-based compounds with scandium-related structures.

[0057] The hue (color), chroma (vividness / dullness), and lightness of a powder sample are characterized using the CIE L*a*b* color space. A unique color can be precisely described by the three-dimensional color coordinates L*, a*, and b* ( Figure 4 ). The vertical axis L* gives the lightness from 0 (black) to 100 (white). The a* value shows the color from green to red (- to +), and the b* value shows the color from blue to yellow (- to +), where the neutral gray value is a* = 0 and b* = 0.

[0058] III. Compounds

[0059] Embodiments of compounds having a thortveitite-related structure are disclosed herein. These compounds are colored and can be used as pigments. In some embodiments, these compounds are durable in an acid stability test, which indicates that the pigments do not substantially change color when exposed to weak acids such as rainwater, and thus can be used in weather-exposed applications. The compounds disclosed herein are generally synthesized from earth-abundant, environmentally friendly elements or minerals at low cost and are thus superior to existing pigments in the art.

[0060] Embodiments of the disclosed materials satisfy the general formula A 2-x A’ x M 2-y M' y O7, where A and A’ are divalent or trivalent cations including rare earth elements (e.g., A and A’ can independently be 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 any combination thereof); M and M’ are tetravalent or pentavalent anions (M = V, P, Ge, Si, or a combination thereof); in most cases, x and y are greater than 0.0 but less than or equal to 2. The general formula is a compositional formula and does not necessarily imply chemical structure and / or connectivity.

[0061] A. Formula I

[0062] In some embodiments, the compound has a structure according to Formula I:

[0063] Zn 2-x Ni x V2O7

[0064] Formula I

[0065] Regarding Formula I, x ranges from greater than 0.2 to 0.8 (0.2 < x ≤ 0.8), or x ranges from 1.2 to 1.8 (1.2 ≤ x ≤ 1.8). In some embodiments, x ranges from greater than 0.2 to less than 0.5 (0.2 < x < 0.5).

[0066] The compounds of Formula I may have the following L*a*b* values, where L* ranges from 34 to 60, a* ranges from 10 to 27, and b* ranges from 19 to 60. In some embodiments, 0.2 < x ≤ 0.8, and the compound has the following L*a*b* values, where L* ranges from 34 to 51, a* ranges from 17 to 27, and b* ranges from 19 to 49. In other embodiments, 1.2 ≤ x ≤ 1.8, and the compound has the following L*a*b* values, where L* ranges from 51 to 60, a* ranges from 10 to 14, and b* ranges from 48 to 60.

[0067] Exemplary compounds according to Formula I are shown in Table 1 and Figure 5 are presented below.

[0068] Table 1

[0069] Compound L* a* b* <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 1.77 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.23 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 40.38 26.31 29.73 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 1.76 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.24 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 39.23 25.02 28.29 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 1.75 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.25 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 34.39 22.59 19.51 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 1.7 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.3 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 40.97 17.76 23.8 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 1.4 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.6 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 50.42 19.39 42.7 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 1.2 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.8 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 50.94 17.52 48.6 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 0.8 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 1.2 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 51.98 13.01 48.62 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 0.6 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 1.4 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 54.19 11.5 51.37 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 0.4 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 1.6 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 59.32 10.68 59.26 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 0.2 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 1.8 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 56.35 12.04 55.18

[0070] B. Formula II

[0071] In some embodiments, the compound has the structure according to Formula II:

[0072] Zn 2-2x Mn x M x V2O7

[0073] Formula II

[0074] Regarding Formula II, x ranges from greater than 0 to 0.05 (0 < x ≤ 0.05), and M is a divalent cation Mg or Ni. The compounds of Formula II may have the following L*a*b* values, where L* ranges from 22 to 37, a* ranges from 7 to 19, and b* ranges from 3 to 22.

[0075] In some embodiments, M is Mg, and the compound has the following L*a*b* values, where L* ranges from 32 to 36, a* ranges from 10 to 19, and b* ranges from 11 to 22. In other embodiments, M is Ni, and the compound has the following L*a*b* values, where L* ranges from 22 to 37, a* ranges from 7 to 17, and b* ranges from 3 to 17.

[0076] Exemplary compounds according to Formula II are shown in Table 2 and Figure 6 are presented below.

[0077] Table 2

[0078] Compound L* a* b* <![CDATA[Zn 1.98 Mn 0.01 Mg 0.01 V2O7]]> 35.06 18.5 21.47 <![CDATA[Zn 1.96 Mn 0.02 Mg 0.02 V2O7]]> 32.12 15.61 13.78 <![CDATA[Zn 1.94 Mn 0.03 Mg 0.03 V2O7]]> 35.12 13.17 13.71 <![CDATA[Zn 1.92 Mn 0.04 Mg 0.04 V2O7]]> 34.17 10.28 11.53 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 1.96 <h2 style=";text-align:left;direction:ltr"> Mn<h2 style=";text-align:left;direction:ltr"> 0.02 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.02 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 34.91 16.53 16.75 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 1.96 <h2 style=";text-align:left;direction:ltr"> Mn<h2 style=";text-align:left;direction:ltr"> 0.02 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.02 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 36.5 14.66 15.42 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 1.94 <h2 style=";text-align:left;direction:ltr"> Mn<h2 style=";text-align:left;direction:ltr"> 0.03 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.03 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 32.07 11.93 11.12 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 1.92 <h2 style=";text-align:left;direction:ltr"> Mn<h2 style=";text-align:left;direction:ltr"> 0.04 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.04 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 22.8 10.17 5.27 <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 1.9 <h2 style=";text-align:left;direction:ltr"> Mn<h2 style=";text-align:left;direction:ltr"> 0.05 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.05 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 22.96 7.54 3.95

[0079] C. Formula III

[0080] In some embodiments, the compound has the structure according to Formula III:

[0081] In 2-x Zn x Ge 2-x V x O7

[0082] Formula III

[0083] Regarding Formula III, x ranges from greater than 0 to less than 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 from 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.

[0084] In some embodiments, the compound of Formula III has the following L*a*b* values, L* ranges from 48 to 67, a* ranges from -3 to 7, and b* ranges from 26 to 56.

[0085] Exemplary compounds according to Formula III are shown in Table 3 and Figure 7 are shown below.

[0086] Table 3

[0087] Compound L* a* b* <![CDATA[In 1.9 Zn 0.1 Ge 1.9 V 0.1 O7]]> 51.06 8.48 22.11 <![CDATA[In 1.7 Zn 0.3 Ge 1.7 V 0.3 O7]]> 54.36 -1.2 24.2 <![CDATA[In 1.5 Zn 0.5 Ge 1.5 V 0.5 O7]]> 49.56 5.41 26.68 <![CDATA[InZnGeVO7]]> 49.56 5.41 26.68 <![CDATA[In 0.5 Zn 1.5 Ge 0.5 V 1.5 O7]]> 57.79 0.8 45.33 <![CDATA[In 0.3 Zn 1.7 Ge 0.3 V 1.7 O7]]> 56.11 1.89 49.33 <![CDATA[In 0.2 Zn 1.8 Ge 0.2 V 1.8 O7]]> 58.24 -0.03 51.19 <![CDATA[In 0.1 Zn 1.9 Ge 0.1 V 1.9 O7]]> 48.61 5.99 40.77 <![CDATA[In 0.07 Zn 1.93 Ge 0.07 V 1.93 O7]]> 65.93 -1.79 55.11 <![CDATA[In 0.06 Zn 1.94 Ge 0.06 V 1.94 O7]]> 59.24 6.68 40.6 <![CDATA[In 0.05 Zn 1.95 Ge 0.05 V 1.95 O7]]> 66.53 -2.06 30.14 <![CDATA[In 0.02 Zn 1.98 Ge 0.02 V 1.98 O7]]> 64.29 -0.79 26.97

[0088] D. Formula IV

[0089] In some embodiments, the compound has the formula IV:

[0090] InZn 1-x Ni x GeVO7

[0091] Formula IV

[0092] Regarding Formula IV, x ranges from greater than 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 the following L*a*b* values, L* ranges from 48 to 59, a* ranges from 1 to 13, and b* ranges from 31 to 46.

[0093] Exemplary compounds according to Formula IV are shown in Table 4 and Figure 8 are shown below.

[0094] Table 4

[0095] Compound L* a* b* <![CDATA[InZn 0.9 It is 0.1 GeVO7]]> 59.71 4.81 43.25 <![CDATA[InZn 0.7 It is 0.3 GeVO7]]> 54.07 12.65 45.19 <![CDATA[InZn 0.5 It is 0.5 GeVO7]]> ND ND ND <![CDATA[InZn 0.3 It is 0.7 GeVO7]]> 48.27 1.61 31.99 <![CDATA[InNiGeVO7]]> ND ND ND

[0096] ND = Not Determined

[0097] E. Formula V

[0098] In some embodiments, the compound has the formula V:

[0099] In 1-x Mn x ZnGeVO7

[0100] Formula V

[0101] Regarding Formula V, x ranges from greater than 0 to less than 1 (0 < x < 1), for example, from greater than 0 to 0.5. In some embodiments, x is 0.1.

[0102] An exemplary compound according to Formula V is In 0.9 Mn 0.1 ZnGeVO7( Fig. 9 ).

[0103] F. Formula VI

[0104] In some embodiments, the compound has Formula VI:

[0105] Zn 1.77-x Ni 0.23 M x V 2-y P y O7

[0106] Formula VI

[0107] Regarding Formula VI, x ranges from 0 to 0.1 (0 ≤ x ≤ 0.1), and y ranges from 0 to 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.

[0108] In some embodiments, the compound of Formula VI has the following L*a*b* values, L* ranges from 35 to 77, a* ranges from -2 to 26, and b* ranges from 23 to 37.

[0109] Exemplary compounds according to Formula VI are shown in Table 5 and Fig.10 are presented below.

[0110] Table 5

[0111] Compound L* a* b* <![CDATA[Zn 1.67 Ni 0.23 Mg 0.1 V2O7]]> 37.35 24.55 27.56 <![CDATA[Zn 1.67 us 0.23 That 0.1 V2O7]]> 47.59 22.7 36.73 <![CDATA[Zn 1.67 In 0.23 (NaAl) 0.1 V2O7]]> ND ND ND <![CDATA[Zn 1.67 Ni 0.23 (NaGa) 0.1 V2O7]]> ND ND ND <![CDATA[Zn 1.67 Be 0.23 (Go) 0.1 V2O7]]> ND ND ND <![CDATA[Zn 1.67 What? 0.23 (KGa) 0.1 V2O7]]> ND ND ND <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 1.77 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.23 <h2 style=";text-align:left;direction:ltr"> P2O7]]><h2 style=";text-align:left;direction:ltr"> 75.07 -1.44 23.96 <![CDATA[Zn 1.77 Ni 0.23 V 1.8 P 0.2 O7]]> 40.93 25.38 33.34 <![CDATA[Zn 1.67 Ni 0.23 Mg 0.1 V 1.8 Q 0.2 O7]]> 35.53 20.82 27.65 <![CDATA[Zn 1.67 Neither 0.23 AC 0.1 V 1.8 P 0.2 O7]]> 44.48 22.58 31.48 <![CDATA[Zn 1.67 Then 0.23 (NaAl) 0.1 V 1.8 P 0.2 O7]]> ND ND ND <![CDATA[Zn 1.67 Ni 0.23 (NaGa) 0.1 V 1.8 P.S 0.2 O7]]> ND ND ND <![CDATA[Zn 1.67 Ni 0.23 (KAl) 0.1 V 1.8 P 0.2 O7]]> ND ND ND <![CDATA[Zn 1.67 What? 0.23 (KGa) 0.1 V 1.8 P 0.2 O7]]> ND ND ND

[0112] ND = Not Determined

[0113] G. Formula VII

[0114] In some embodiments, the compound has Formula VII:

[0115] Zn 1.8 Cu 0.1 M 0.1 V2O7

[0116] Formula VII

[0117] With respect to 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 L* from 40 to 59, a* from 1 to 16, and b* from 26 to 44.

[0118] Exemplary compounds according to Formula VII are listed in Table 6 and Fig.11 Shown in.

[0119] Table 6

[0120] Compound L* a* b* <![CDATA[Zn 1.8 With 0.1 us 0.1 V2O7]]> 40.77 15.84 26 <![CDATA[Zn 1.8 With 0.1 min 0.1 V2O7]]> ND ND ND <![CDATA[Zn 1.8 With 0.1 Mg 0.1 V2O7]]> 52.81 6.96 36.31 <![CDATA[Zn 1.8 With 0.1 That 0.1 V2O7]]> 58.7 1.92 43.97

[0121] ND = Not Determined

[0122] H. Formula VIII

[0123] In some embodiments, the compound has Formula VIII:

[0124] Zn 1.9 Cu 0.1 V x P 2-x O7

[0125] Formula VIII

[0126] With respect to Formula VIII, x is from 0 to 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 the following L*a*b* values, L* is from 46 to 81, a* is from -3 to 4, and b* is from 2 to 28.

[0127] Exemplary compounds according to Formula VIII are listed in Table 7 and Fig.12 Shown in.

[0128] Table 7

[0129] Compound L* a* b* <![CDATA[Zn 1.9 With 0.1 P2O7]]> 80.68 -2.32 2.38 <![CDATA[Zn 1.9 With 0.1 V 1.8 P 0.2 O7]]> 46.24 3.36 27.61

[0130] I. Formula IX

[0131] In some embodiments, the compound has Formula IX:

[0132] Zn 2-x-y Mn x M y V 2-z P z O7

[0133] Formula IX

[0134] With respect to Formula IX, M is a divalent cation Ni, Mg or Ca.

[0135] x ranges from greater than 0 to 0.5 (0≤x≤0.5).

[0136] y ranges from 0 to 0.1 (0≤y≤0.1).

[0137] z ranges from 0 to 1 (0≤z≤1).

[0138] In some embodiments, x = 0.02, 0.1 or 0.5.

[0139] In some embodiments, y=0 or y=0.1.

[0140] In some embodiments, z=0, z=0.2, or z=1.

[0141] In some embodiments, the compound of Formula IX has L*a*b* values ​​of L* from 33 to 41, a* from 17 to 22, and b* from 21 to 24.

[0142] Exemplary compounds according to Formula IX are listed in Table 8 and Fig.13 Shown in.

[0143] Table 8

[0144]

[0145]

[0146] ND = Not Determined

[0147] J. Type X

[0148] In some embodiments, the compound has Formula X:

[0149] Mg 2-x M x V 2-y P y O7

[0150] Formula X

[0151] With respect to formula X, M is a divalent cation Ni or Mn. x is from 0 to 0.2 (0≤x≤0.2), and y is from 0 to 1 (0≤y≤1).

[0152] In some embodiments, x=0 or x=0.2.

[0153] In some embodiments, y=0 or y=1.

[0154] In some embodiments, the compound of Formula X has L*a*b* values ​​of L* from 36 to 67, a* from 4 to 14, and b* from 15 to 46.

[0155] Exemplary compounds according to Formula X are listed in Table 9 and Fig.14 Shown in.

[0156] Table 9

[0157] Compound L* a* b* <h2 style=";text-align:left;direction:ltr"><![CDATA[Mg <h2 style=";text-align:left;direction:ltr"> 1.8 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.2 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 66.92 4.36 45.95 <h2 style=";text-align:left;direction:ltr"><![CDATA[Mg <h2 style=";text-align:left;direction:ltr"> 1.8 <h2 style=";text-align:left;direction:ltr"> Mn<h2 style=";text-align:left;direction:ltr"> 0.2 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 36.54 13.45 15.73 <![CDATA[Mg2VPO7]]> ND ND ND

[0158] ND = Not Determined

[0159] K. Type XI

[0160] In some embodiments, the compound has Formula XI:

[0161] InZ 1-x Ni x MV 1-y P y O7

[0162] Formula XI

[0163] With respect to Formula XI, M is Si or Ge.

[0164] x ranges from 0 to 0.3 (0≤x≤0.3).

[0165] y ranges from 0 to 1 (0≤y≤1).

[0166] In some embodiments, x = 0 or 0.1.

[0167] In some embodiments, y=0, 0.2 or 1.

[0168] In some embodiments, the compound of Formula XI has L*a*b* values ​​of L* from 45 to 77, a* from 2 to 7, and b* from 24 to 46.

[0169] Exemplary compounds according to Formula XI are listed in Table 10 and Fig.15 Shown in.

[0170] Table 10

[0171] Compound L* a* b* <![CDATA[InZnSiVO7]]> ND ND ND <![CDATA[InZn 0.9 It is 0.1 Not VO7]]> 45.92 3.01 27.99 <![CDATA[InZnGePO7]]> ND ND ND <![CDATA[InZn 0.9 Ni 0.1 GePO7]]> 71.19 6.36 34.22 <![CDATA[InZnSiPO7]]> ND ND ND <![CDATA[InZn 0.9 It is 0.1 Not PO7]]> 76.48 2.88 24.68 <![CDATA[InZn 0.9 There is no 0.1 GeV 0.8 P 0.2 O7]]> ND ND ND <![CDATA[InZn 0.9 You 0.1 SiV 0.8 P 0.2 O7]]> 54.86 6.23 45.43

[0172] ND = Not Determined

[0173] L. Formula XII

[0174] In some embodiments, the compound has Formula XII:

[0175] Zn 2-x-y M x Ni y V 2-x A x O7

[0176] Formula XII

[0177] Regarding Formula XII, M is a trivalent cation Fe, Cr, Sc, Y, or La.

[0178] A is Ge or Si.

[0179] x ranges from greater than 0 to 0.1 (0 < x ≤ 0.1). In some embodiments, x is 0.1.

[0180] y ranges from 0 to 0.1. In some embodiments, y is 0, but in other embodiments, y is 0.1.

[0181] In some embodiments, the compound of Formula XII has the following L*a*b* values, L* from 28 to 56, a* from 15 to 28, and b* from 34 to 48.

[0182] Exemplary compounds according to Formula XII are shown in Table 11 and Fig.16 are presented below.

[0183] Table 11

[0184]

[0185]

[0186] ND = Not Determined

[0187] M. Formula XIII

[0188] In some embodiments, the compound has Formula XIII:

[0189] Zn 1-x Co x V 1.8 P 0.2 O7

[0190] Formula XIII

[0191] Regarding Formula XIII, x ranges from greater than 0 to less than 1 (0 < x < 1), for example, from greater than 0 to 0.5. In certain embodiments, x is 0.1.

[0192] In some embodiments, the compound of Formula XIII has the following L*a*b* values, L* from 25 to 26, a* from 1 to 2, and b* from 9 to 10.

[0193] Exemplary compounds according to Formula XIII are Zn 1.9 Co 0.1 V 1.8 P 0.2 O7( Fig.17 )

[0194] N. Formula XIV

[0195] In some embodiments, the compound has Formula XIV:

[0196] Ni 2-x Mn x V2O7

[0197] Formula XIV

[0198] With respect to Formula XIV, x ranges from greater than 0 to less than 1 (0 < x < 1), for example, from greater than 0 to less than 0.1. In certain embodiments, x is 0.02.

[0199] Exemplary compounds according to Formula XIV are Ni 1.98 Mn 0.02 V2O7( Fig.18 ).

[0200] IV. Synthesis

[0201] The disclosed compounds are made by standard techniques known to those of ordinary skill in the art. In some embodiments, traditional solid-state reactions are used. However, other synthetic routes can also be used, such as but not limited to sol-gel solution methods and hydrothermal low-temperature preparations.

[0202] In some embodiments, stoichiometrically 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 M2O3, 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 M’O2, where M’ = Si or Ge; compounds having the formula M”O, where M” = Ni, Mn, Cu, Zn, or Fe; compounds having the formula M’”2O5, where M’” = V or P; and Co3O4. Those of ordinary skill in the art understand how to select a particular combination of starting materials to provide the stoichiometry required for each desired metal and oxygen, thereby producing the desired final compound.

[0203] Then, the resulting pellets are heated to a suitable temperature, for example, a temperature from 500 °C or lower to 1200 °C or higher, for example, from 600 °C to 1050 °C, for a suitable time to promote the formation of the desired compound. The heating time can range from 4 hours or less to 18 hours or more, for example, from 6 hours to 12 hours. The heating can be carried out in air (i.e., ambient atmosphere). In addition, the reaction mixture is heated to the reaction temperature multiple times, for example, 1, 2, 3, or more times, with intermediate grinding. The heating is carried out at a suitable rate of temperature increase to promote the reaction, for example, a heating rate of 300 °C / hour.

[0204] The compounds were analyzed by X-ray diffraction, NIR reflectance spectroscopy, magnetic susceptibility, and stability to acid exposure. Diffuse reflectance spectroscopy was used to determine the spectral characteristics of the compounds and to determine the L*a*b* color coordinates for each compound.

[0205] V. Composition

[0206] The disclosure also relates to compositions comprising at least one disclosed compound or a compound according to any one of formulas I-XIV and at least one other component. Such compositions include paints, inks, dyes, glass, plastics, emulsions, fabrics or cosmetic preparations. Other components suitable for use in paints, inks, dyes or emulsion products include, but are not limited to, adhesives, solvents and additives, for example, catalysts, thickeners, stabilizers, emulsifiers, texture agents, tackifiers, UV stabilizers, leveling agents (i.e., matting agents), preservatives and other additives known to those of ordinary skill in the art.

[0207] Additional materials suitable for use in glass products include, for example: network formers (e.g., oxides of silicon, boron, germanium), which are used to form a highly cross-linked network of chemical bonds; modifiers (e.g., calcium, lead, lithium, sodium, potassium), which are used to change the network structure; intermediates (e.g., titanium, aluminum, zirconium, beryllium, magnesium, zinc), which can act as both network formers and modifiers; and combinations thereof.

[0208] Additional materials suitable for use in plastic products include, for example, dispersing aids (eg, zinc stearate, calcium stearate, ethylene bis(amide), plasticizers, flame retardants, internal mold release agents, slip agents, and combinations thereof.

[0209] When coloring ceramic products, this material is typically added to the ceramic glaze composition.Other materials used in glazes include, for example, silica, metal (e.g., sodium, potassium, calcium) oxides, alumina, opacifiers (e.g., tin oxide, zirconium oxide), and combinations thereof.

[0210] VI. Examples

[0211] Example 1

[0212] Colored scandium yttrium-based pigments are prepared via a conventional solid phase reaction. 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), Co3O4 are weighed, mixed, ground and granulated. The resulting granules are then heated in air to a suitable temperature range for a suitable time, optionally with multiple heating stages and intermediate grinding. The heating rate is 300°C / h. Figures 5 to 18 Specific heating conditions for certain disclosed embodiments are provided in.

[0213] The calcined powders were characterized by a Rigaku Miniflex X-ray diffractometer using Cu Kα radiation and a graphite monochromator on the diffracted beam. Diffuse reflectance spectra of the powder samples were obtained using a JASCO V-770 spectrophotometer up to 2500 nm. The data in the UV-vis range were converted to absorbance using the Kubelka-Munk function. The L*a*b* color coordinates were measured by a Konica Minolta CM-700d spectrophotometer (standard illuminant D65). Zn 2-x Ni x The magnetic properties of V2O7 (x = 0.2 and 0.23) samples were measured using a Quantum Design MPMS instrument in the temperature range of 5 to 300 K.

[0214] Exemplary compounds prepared by the disclosed methods are shown in Table 12 along with reaction conditions and exemplary starting materials. One of ordinary skill in the art understands how to adjust the amounts of the disclosed starting materials to produce alternative compositions.

[0215] Table 12

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224] Results and discussion

[0225] The following exemplary solid solution system is used here to illustrate the results of the material characterization: Zn 2-x Ni x V2O7(0≤x≤0.3).

[0226] Fig.19 The color of the orange powder of the selected composition is shown. Figures 5 to 18 Powders of various colors with different compositions are shown.

[0227] Solid solution Zn 2-x Ni x The X-ray diffraction pattern of V2O7 (0≤x≤0.3) is Fig. 20 The lattice parameters of the unit cell calculated by overall pattern fitting are shown in Fig.21 The decrease in unit cell volume is related to the larger Zn 2+ ions are replaced by smaller Ni 2+ The ionic substitution is consistent.

[0228] Zn 2-x Ni x The diffuse reflectance spectrum of V2O7 (0≤x≤0.3) solid solution is Fig. 22 The strong absorption in the blue / green spectral region is combined with the absorption in the higher energy range, resulting in the observed bright orange / red color. In pure Zn2V2O7, there is almost no absorption in the entire visible range, except for weak absorption near the near-violet spectral region, producing a light yellow color. As the Ni content x increases, the intensity of the absorption peak near 480nm increases, which is consistent with the gradual darkening of the sample towards the intense orange / red color. The inventors are not aware of the Ni content in the oxide. 2+ ions produce any precedent of intense orange / red colors.

[0229] Zn 2-x Ni x The NIR reflectance spectrum of V2O7 (0≤x≤0.3) solid solution is Fig.23 The NIR reflectivity decreases with increasing Ni content.

[0230] The magnetic susceptibility curve is Fig.24 The Curie constant and the Weiss constant are derived from the slope and intercept of the straight line area of ​​1 / χ versus T. Zn 2-x Ni x The magnetic susceptibility data of V2O7 (x = 0.2, 0.23) show near paramagnetic behavior. Experimental magnetic moment and high spin Ni 2+ The expected magnetic moment is quite consistent with that of .

[0231] Example 2

[0232] Acid Test

[0233] The compound was tested to determine if its color would be affected by acids in a pH range similar to normal rainwater. Normal rainwater has a pH of approximately 5.6, so the compound was exposed to two dilute acid samples at pH = 5, HCl and HNO3. The results before and after the acid test are shown below. The results indicate that the color change due to the acid exposure is very slight, if any, based on the L*, a*, and b* values ​​(Table 12). In addition, the X-ray diffraction pattern indicates that any crystal structure changes are also very small, if any ( Fig.25 ).

[0234] Table 12

[0235] Compound L* a* b* <h2 style=";text-align:left;direction:ltr"><![CDATA[Zn <h2 style=";text-align:left;direction:ltr"> 1.77 <h2 style=";text-align:left;direction:ltr"> Ni<h2 style=";text-align:left;direction:ltr"> 0.23 <h2 style=";text-align:left;direction:ltr"> V2O7]]><h2 style=";text-align:left;direction:ltr"> 40.38 26.31 29.73 pH 5 HCl 38.90 25.52 28.83 <![CDATA[pH5 HNO3]]> 37.60 25.95 28.40

[0236] Given that the principles of the disclosed invention can be applied to many possible embodiments, it should be recognized that the illustrated embodiments are merely preferred examples of the invention and should not be considered to limit the scope of the invention. Instead, the scope of the invention is defined by the following claims. Therefore, we claim as our invention all that comes within the scope and spirit of these claims.

Claims

1. A compound having a structure according to one of formulas I-XIV: Formula I Zn 2-x Ni x V2O7, among which x is from greater than 0.2 to 0.8, or x is from 1.2 to 1.8; Formula II Zn 2-2x Mn x M x V2O7, wherein x is from greater than 0 to 0.05, and M is Mg or Ni; Formula III In 2-x Zn x Ge 2-x V x O7, where x ranges from greater than 0 to less than 2; Formula IV InZn 1-x Ni x GeVO7, where x ranges from greater than 0 to 1; V In 1-x Mn x ZnGeVO7, wherein x ranges from greater than 0 to less than 1; Formula VI Zn 1.77-x Ni 0.23 M x V 2-y P y O7, wherein x is from 0 to 0.1, y is from 0 to 2, and M is Mg, Ca, (NaAl), (NaGa), (KAl) or (KGa); Formula VII Zn 1.8 Cu 0.1 M 0.1 V2O7, wherein M is Ni, Mn, Mg or Ca; Formula VIII Zn 1.9 Cu 0.1 V x P 2-x O7, where x ranges from 0 to 1.8; Formula IX Zn 2-x-y Mn x M y V 2-z P z O7, wherein M is Ni, Mg or Ca, x is from greater than 0 to 0.5, y is from 0 to 0.1, and z is from 0 to 1; Formula X Mg 2-x M x V 2-y P y O7, wherein M is Ni or Mn, x is from 0 to 0.2, and y is from 0 to 1; Formula XI InZn 1-x Ni x MV 1-y P y O7, wherein M is Si or Ge, x is from 0 to 0.3, and y is from 0 to 1; Formula XII Zn 2-x-y M x Ni y V 2-x A x O7, wherein M is Fe, Cr, Sc, Y or La, A is Ge or Si, x is from greater than 0 to 0.1, and y is from 0 to 0.1; Formula XIII Zn 1-x Co x V 1.8 P 0.2 O7, wherein x ranges from greater than 0 to less than 1; or Formula XIV Ni 1-x Mn x V2O7, wherein x ranges from greater than 0 to less than 1.

2. The compound according to claim 1, having a structure according to formula I, Zn 2-x No x V2O7 Formula I in: x is from greater than 0.2 to 0.8; or x ranges from 1.2 to 1.

8.

3. The compound according to claim 2, wherein x ranges from greater than 0.2 to less than 0.

5.

4. The compound according to claim 2 or 3, wherein The compounds have L*a*b* values ​​of L* from 34 to 60, a* from 10 to 27, and b* from 19 to 60.

5. The compound according to claim 4, wherein x ranges from greater than 0.2 to 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.

6. The compound according to claim 4, wherein x is from 1.2 to 1.8, and the compound has the following L*a*b* values, L* is from 51 to 60, a* is from 10 to 14, and b* is from 48 to 60.

7. A compound according to any one of claims 2 to 6, wherein Selected compound 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 V2O7orZn 0.2 Ni 1.8 V2O7.

8. The compound according to claim 1, having a structure according to formula II, Zn 2-2x Mn x M x V2O7 Formula II in: x is from greater than 0 to 0.05; and M is Mg or Ni.

9. The compound according to claim 8, wherein The compounds have L*a*b* values ​​of L* from 22 to 37, a* from 7 to 19, and b* from 3 to 22.

10. The compound according to claim 8, wherein 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.

11. The compound according to claim 8, wherein 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.

12. A compound according to any one of claims 8 to 11, wherein The compound is selected from Zn 1.98 Mn 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.

13. The compound according to claim 1, having a structure according to formula III, In 2-x Zn x Ge 2-x V x O7 Formula III in, x ranges from greater than 0 to less than 2.

14. The 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. The compound according to claim 13 or 14, wherein The compounds of Formula III have L*a*b* values ​​of L* from 48 to 67, a* from -3 to 7, and b* from 26 to 56.

16. A compound according to any one of claims 13 to 15, wherein The compound is selected from In 1.9 Zn 0.1 Ge 1.9 V 0.1 O7, In 1.7 Zn 0.3 Ge 1.7 V 0.3 O7, In 1.5 Zn 0.5 Ge 1.5 V 0.5 O7, InZnGeVO7, In 0.5 Zn 1.5 Ge 0.5 V 1.5 O7, In 0.3 Zn 1.7 Ge 0.3 V 1.7 O7, In 0.2 Zn 1.8 Ge 0.2 V 1.8 O7, In 0.1 Zn 1.9 Ge 0.1 V 1.9 O7, In 0.07 Zn 1.93 Ge 0.07 V 1.93 O7, In 0.06 Zn 1.94 Ge 0.06 V 1.94 O7, In 0.05 Zn 1.95 Ge 0.05 V 1.95 O7 or In 0.02 Zn 1.98 Ge 0.02 V 1.98 O7.

17. The compound according to claim 1, having a structure according to Formula IV, InZn 1-x It is x GeVO7 Formula IV in, x ranges from greater than 0 to 1.

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

19. The compound according to claim 17 or 18, wherein The compounds have L*a*b* values ​​of L* from 54 to 59, a* from 4 to 13, and b* from 43 to 46.

20. The compound according to any one of claims 17 to 19, wherein The compound is selected from 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 GeVO7 or InNiGeVO7.

21. The compound according to claim 1, having a structure according to Formula V, In 1-x Mn x ZnGeVO7 Formula V in, x ranges from greater than 0 to less than 1.

22. The compound according to claim 21, wherein The compound is In 0.9 Mn 0.1 ZnGeVO7.

23. The compound according to claim 1, having a structure according to Formula VI, Zn 1.77-x No 0.23 M x V 2-y P y O7 Formula VI in: x from 0 to 0.1; y ranges from 0 to 2; and M is Mg, Ca, (NaAl), (NaGa), (KAl) or (KGa).

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

1.

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

26. A compound according to any one of claims 23 to 25, wherein The compounds have L*a*b* values ​​of L* from 35 to 77, a* from -2 to 26, and b* from 23 to 37.

27. A compound according to any one of claims 23 to 26, wherein Selected compound 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 0.2 O7, 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 O7.

28. The compound according to claim 1, having a structure according to Formula VII, Zn 1.8 With 0.1 M 0.1 V2O7 Formula VII in, M is Ni, Mn, Mg or Ca.

29. The compound according to claim 28, wherein The compounds have L*a*b* values ​​as follows: L* from 40 to 59, a* from 1 to 16, and b* from 26 to 44.

30. The compound according to claim 28 or 29, wherein The compound is selected from 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.

31. The compound according to claim 1, having a structure according to Formula VIII, Zn 1.9 Cu 0.1 V x Q 2-x O7 Formula VIII in, x ranges from 0 to 1.

8.

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

8.

33. The compound according to claim 31 or 32, wherein The compounds have L*a*b* values ​​as follows: L* from 46 to 81, a* from -3 to 4, and b* from 2 to 28.

34. A compound according to any one of claims 31 to 33, wherein The compound is selected from Zn 1.9 Cu 0.1 P2O7 or Zn 1.9 Cu 0.1 V 1.8 P 0.2 O7.

35. The compound according to claim 1, having a structure according to Formula IX, Zn 2-x-y Mn x M y V 2-z P z O7 Formula IX in: M is Ni, Mg or Ca; x from greater than 0 to 0.5; y ranges from 0 to 0.1; and z ranges from 0 to 1.

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

5.

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

1.

38. A compound according to any one of claims 35 to 37, wherein z is 0, 0.2 or 1.

39. A compound according to any one of claims 35 to 38, wherein The compounds have L*a*b* values ​​of L* from 34 to 37, a* from 20 to 22, and b* from 23 to 24.

40. A compound according to any one of claims 35 to 39, wherein The compound is selected from 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 O7.

41. The compound according to claim 1, having a structure according to Formula X, Mg 2-x M x V 2-y Q y O7 Formula X in: M is Ni or Mn; x ranges from 0 to 0.2; and y ranges from 0 to 1.

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

2.

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

1.

44. A compound according to any one of claims 41 to 43, wherein The compound is selected from Mg 1.8 Ni 0.2 V2O7、Mg 1.8 Mn 0.2 V2O7 or Mg2VPO7.

45. The compound according to claim 1, having a structure according to Formula XI, InZn 1-x Ni x MV 1-y P.S y O7 Formula XI in: M is Si or Ge; x ranges from 0 to 0.3; and y ranges from 0 to 1.

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

3.

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

48. A compound according to any one of claims 45 to 47, wherein The compound is selected from 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 O7.

49. The compound according to claim 1, having a structure according to Formula XII, Zn 2-x-y M x No y V 2-x AND x O7 Formula XII in: M is Fe, Cr, Sc, Y or La; A is Ge or Si; x is from greater than 0 to 0.1; and y ranges from 0 to 0.

1.

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

1.

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

1.

52. A compound according to any one of claims 49 to 51, wherein The compounds have L*a*b* values ​​of L* from 28 to 56, a* from 15 to 28, and b* from 34 to 48.

53. A compound according to any one of claims 49 to 52, wherein The compound is selected from Zn 1.9 Fe 0.1 V 1.9 Ge 0.1 O7, Zn 1.9 Fe 0.1 V 1.9 Si 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 Si 0.1 O7, Zn 1.9 Sc 0.1 V 1.9 Si 0.1 O7, Zn 1.8 Sc 0.1 Ni 0.1 V 1.9 Si 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 Si 0.1 O7, Zn 1.8 Y 0.1 Ni 0.1 V 1.9 Si 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 Ge 0.1 O7, Zn 1.9 La 0.1 V 1.9 Si 0.1 O7, Zn 1.8 La 0.1 Ni 0.1 V 1.9 Si 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 O7.

54. The compound according to claim 1, having a structure according to Formula XIII, Zn 1-x What x V 1.8 P 0.2 O7 Formula XIII in, x ranges from greater than 0 to less than 1.

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

1.

56. The compound according to claim 54 or 55, wherein The compounds have L*a*b* values ​​of L* from 25 to 26, a* from 1 to 2, and b* from 9 to 10.

57. A compound according to any one of claims 54 to 56, wherein The compound is Zn 1.9 Co 0.1 V 1.8 P 0.2 O7.

58. The compound according to claim 1, having a structure according to Formula XIV, <h2 style=";text-align:left;direction:ltr">Ni<h2 style=";text-align:left;direction:ltr"> 1-x <h2 style=";text-align:left;direction:ltr"> Mn<h2 style=";text-align:left;direction:ltr"> x <h2 style=";text-align:left;direction:ltr"> V2O7 Formula XIV in, x ranges from greater than 0 to less than 1.

59. The compound according to claim 58, wherein The compound is Ni 1.98 Mn 0.02 V2O7.

60. A composition comprising: A compound according to any one of claims 1 to 59; and At least one additional component.

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

62. The composition according to claim 60 or 61, wherein The at least one additional component is a binder, a solvent, a catalyst, a thickener, a stabilizer, an emulsifier, a texturizing agent, a tackifier, a UV stabilizer, a leveling agent, a preservative, a polymer, a dispersing aid, a plasticizer, a flame retardant, a metal oxide, or any combination thereof.

63. A composition according to any one of claims 60-62, wherein The composition is a glass and the at least one additional component is a metal oxide.

64. The composition of any one of claims 60-63, further comprising at least one additional compound of any one of claims 1-59.

65. A method for preparing a compound according to any one of claims 1-59, comprising: selecting a desired metal in the compound; providing a reactant including a selected metal; combining stoichiometric amounts of said reactants to obtain a desired final ratio of the selected metals in said compound; as well as The combination of reactants is heated at an effective temperature for an effective period of time to produce a compound according to any one of claims 1-59.

66. The method of claim 65, wherein: The effective temperature is from 600°C to 1050°C.

67. The method of claim 65 or 66, wherein: The time period is from 6 hours to 12 hours.

68. The method according to any one of claims 65 to 67, wherein: The combination of heating the reactants includes heating for a first period of time of 6 hours to 12 hours, grinding the reaction mixture and heating for a second period of time of 6 hours to 12 hours.

Images