Synthesis of high-whiteness zinc sulfide pigments from zinc-containing waste via synergistic crystal growth control and surface modification

Abstract

Zinc sulfide is an important white inorganic pigment widely used in coatings, plastics, fillers, and paints. However, conventional preparation methods often result in high impurity content, low whiteness, and poor weather resistance. To address these issues, a novel synthesis route has been developed. This process uses secondary zinc oxide from zinc-containing waste as the raw material and involves multiple steps, including impurity removal, calcination, doping, and surface modification. After washing, K and Na impurity contents were reduced to 0.0056% and 0.012%, respectively. Optimization of the calcination process, conducted at 650 °C for 30 min, provided guidance for controlling particle size and established a relationship between particle size and whiteness. Cobalt was selected as the dopant due to its suitable ionic radius and electronic structure, which enable effective substitution into the ZnS lattice and regulation of defect states. In addition, aluminum coating enhances reflectance and provides a protective barrier against environmental degradation, while barium-induced nucleation promotes uniform crystallization and suppresses sulfur vacancy formation, jointly improving whiteness. The synthesized zinc sulfide exhibits uniform particle size (∼200 nm), high purity (99.6%), high whiteness (94.51), low light transmittance (16.98%), and excellent optical performance and weather resistance. Compared to the commercial product HD-S, the synthesized zinc sulfide exhibits significantly improved whiteness and weather resistance, which is defined as the ability to resist yellowing, chalking, discoloration, and performance degradation under prolonged exposure to sunlight, oxygen, moisture, and acidic or alkaline environments. These results demonstrate the feasibility of this approach for producing high-performance pigment-grade zinc sulfide.

Keywords

doping / optical property / pigment-grade / weather resistance / zinc sulfide

References

[1] Angelo P D, Farnood R R. Photoluminescent inkjet ink containing ZnS: Mn nanoparticles as pigment. Journal of Experimental Nanoscience, 2011, 6(5): 473-487 J]

[2] Cao L, Huang S, Ren S, et al.. Optical properties of core-shell ZnS: Mn nanoparticles. Spectroscopy and Spectral Analysis, 2003, 23(3): 451-453[J]

[3] Cao L, Zhang J, Ren S, et al.. Luminescence enhancement of core-shell ZnS: Mn/ZnS nanoparticles. Applied Physics Letters, 2002, 80(23): 4300-4302 J]

[4] Chang G, Liu J, Hao Y, et al.. Bifunctional electrolyte additive with redox mediation and capacity contribution for sulfur cathode in aqueous Zn-S batteries. Chemical Engineering Journal, 2023, 457: 141083 J]

[5] Comelli D, Artesani A, Nevin A, et al.. Time-resolved photoluminescence microscopy for the analysis of semiconductor-based paint layers. Materials, 2017, 10(11): 1335 J]

[6] Ummartyotin S, Bunnak N, Juntaro J, et al.. Synthesis and luminescence properties of ZnS and metal (Mn, Cu)-doped-ZnS ceramic powder. Solid State Sciences, 2012, 14(3): 299-304 J]

[7] Chen Y, Hua X, Xu Y, et al.. A highly reflective, hydrophobic, UV resistant, colorful structural color coating. Materials Today Chemistry, 2024, 42: 102360 J]

[8] Ramasamy K, Malik M A, Helliwell M, et al.. Thio- and dithio-biuret precursors for zinc sulfide, cadmium sulfide, and zinc cadmium sulfide thin films. Chemistry of Materials, 2011, 23(6): 1471-1481 J]

[9] Ghosh A, Bakkar A, Momina, et al.. Enhancing solar cell efficiency beyond 27% through the implementation of an efficient charge transport layer utilizing an innovative inorganic perovskite Sr3PI₃. Journal of Physics and Chemistry of Solids, 2024, 190: 112029 J]

[10] Li Y, Hou X, Dai X, et al.. Stoichiometry-controlled InP-based quantum dots: Synthesis, photoluminescence, and electroluminescence. Journal of the American Chemical Society, 2019, 141(16): 6448-6452 J]

[11] Reza M S, Rahman M F, Kuddus A, et al.. Boosting efficiency above 28% using effective charge transport layer with Sr₃ SbI₃ based novel inorganic perovskite. RSC Advances, 2023, 13(45): 31330-31345 J]

[12] Yu P, Cao S, Shan Y, et al.. Highly efficient green InP-based quantum dot light-emitting diodes regulated by inner alloyed shell component. Light: Science & Applications, 2022, 11: 162 J]

[13] Zheng T, Runowski M, Martin I R, et al.. Mechanoluminescence and photoluminescence heterojunction for superior multimode sensing platform of friction, force, pressure, and temperature in fibers and 3D-printed polymers. Advanced Materials, 2023, 35(40): 2304140 J]

[14] Lin Z, Wang G, Li L, et al.. Preparation and protection of ZnS surface sub-wavelength structure for infrared window. Applied Surface Science, 2019, 470: 395-404 J]

[15] Jing G, Khan S, Cho S H, et al.. Preparation and immobilization of zinc sulfide (ZnS) nanoparticles on polyvinylidene fluoride pellets for photocatalytic degradation of methylene blue in wastewater. Applied Surface Science, 2019, 473: 425-432 J]

[16] Chen D, Huang F, Ren G, et al.. ZnS nanoarchitectures: Photocatalysis, deactivation and regeneration. Nanoscale, 2010, 2(10): 2062 J]

[17] Fu Y, Wang Y, Zhao H, et al.. Synthesis of ternary ZnO/ZnS/MoS₂ piezoelectric nanoarrays for enhanced photocatalytic performance by conversion of dual heterojunctions. Applied Surface Science, 2021, 556: 149695 J]

[18] Hu J, Ren L, Guo Y, et al.. Mass production and high photocatalytic activity of ZnS nanoporous nanoparticles. Angewandte Chemie International Edition, 2005, 44(8): 1269-1273 J]

[19] Lange T, Reichenberger S, Ristig S, et al.. Zinc sulfide for photocatalysis: White angel or black sheep. Progress in Materials Science, 2022, 124: 100865 J]

[20] Luo W, Li A, Yang B, et al.. Synthesis of a hexagonal phase ZnS photocatalyst for high CO selectivity in CO₂ reduction reactions. ACS Applied Materials & Interfaces, 2023, 15(12): 15387-15395 J]

[21] Praus P, Svoboda L, Tokarsky J, et al.. Core/shell CdS/ZnS nanoparticles: Molecular modelling and characterization by photocatalytic decomposition of Methylene Blue. Applied Surface Science, 2014, 292: 813-822 J]

[22] Knowles K E, Hartstein K H, Kilburn T B, et al.. Luminescent colloidal semiconductor nanocrystals containing copper: Synthesis, photophysics, and applications. Chemical Reviews, 2016, 116(18): 10820-10851 J]

[23] Li H, Zhang W, Bian Y, et al.. ZnF₂-assisted synthesis of highly luminescent InP/ZnSe/ZnS quantum dots for efficient and stable electroluminescence. Nano Letters, 2022, 22(10): 4067-4073 J]

[24] Liu M, Zhong G, Yin Y, et al.. Aluminum-doped cesium lead bromide perovskite nanocrystals with stable blue photoluminescence used for display backlight. Advanced Science, 2017, 4(11): 1700335 J]

[25] Sobhanan J, Rival J V, Anas A, et al.. Luminescent quantum dots: Synthesis, optical properties, bioimaging and toxicity. Advanced Drug Delivery Reviews, 2023, 197: 114830 J]

[26] Li L, Xie R, Gu Y, et al.. Preparation and characterization of ZnS: Fe/MX (M=Cd, Zn; X=S, Se) core – shell nanocrystals. Applied Surface Science, 2012, 258(16): 5992-5995 J]

[27] Pfaff G. Zinc sulfide pigments. Physical Sciences Reviews, 2021, 6(8): 369-373 J]

[28] Gu J, Wang X, Xu C, et al.. Polythiourethane composite film with high transparency, high refractive index and low dispersion containing ZnS nanoparticle via thiol-ene click chemistry. Macromolecular Research, 2023, 31(6): 603-613 J]

[29] Kumar S, Verma N K, Singla M L. Reflective properties of ZnS nanoparticle coatings. Journal of Coatings Technology and Research, 2011, 8(2): 223-228 J]

[30] Bercu V, Duliu O G, Manea B, et al.. Electron paramagnetic resonance and discriminant analysis of white pigment used by Early Neolithic potters in the Eastern Romanian Plain. Journal of Archaeological Science: Reports, 2024, 60: 104810[J]

[31] Gueli A M, Gallo S, Pasquale S. Optical and colorimetric characterization on binary mixtures prepared with coloured and white historical pigments. Dyes and Pigments, 2018, 157: 342-350 J]

[32] Koci K, Matějová L, Kozák O, et al.. ZnS/MMT nanocomposites: The effect of ZnS loading in MMT on the photocatalytic reduction of carbon dioxide. Applied Catalysis B: Environmental, 2014, 158–159: 410-417 J]

[33] Pecchioni E, Ricci M, Vaselli O, et al.. Chemical and mineralogical characterization and ¹⁴C dating of white and red pigments in the rock paintings from Nyero (Uganda). Microchemical Journal, 2019, 144: 329-338 J]

[34] Ruiqi Z, Gethin P. Provenance of the cobalt pigment used for Jingdezhen Minyao blue-and-white porcelain in the early Qing dynasty. Ceramics International, 2021, 47(18): 25763-25768 J]

[35] Tom E, Velluva A, Joseph A, et al.. Tailoring the electrochemical properties of ZnS electrodes via cobalt doping for improved supercapacitor application. Journal of Electronic Materials, 2025, 54(1): 451-461 J]

[36] Poornaprakash B, Poojitha P T, Chalapathi U, et al.. Synthesis, structural, optical, and magnetic properties of Co doped, Sm doped and Co+Sm Co-doped ZnS nanoparticles. Physica E: Low-Dimensional Systems and Nanostructures, 2016, 83: 180-185 J]

[37] Ullah A, Javaid N, Rafiq A, et al.. Outstanding performance of Co-doped ZnS nanoparticles used as nanocatalyst for synthetic dye degradation. Results in Materials, 2024, 24: 100628 J]

[38] Sonkar R, Mondal N J, Thakur S, et al.. Cobalt-substituted ZnS QDs: A diluted magnetic semiconductor and efficient photocatalyst. Nanoscale Advances, 2023, 5(24): 7042-7056 J]

[39] Godavarti U D, Nagaraju P, Yelsani V, et al.. Synthesis and characterization of ZnS-based quantum dots to trace low concentration of ammonia. Journal of Semiconductors, 2021, 42(12): 122901 J]

[40] Lange T, Reichenberger S, Rohe M, et al.. Alumina-protected, durable and photostable zinc sulfide particles from scalable atomic layer deposition. Advanced Functional Materials, 2021, 31(14): 2009323 J]

[41] Li J, Liu Y, Wang Y, et al.. Hydrous alumina/silica double-layer surface coating of TiO₂ pigment. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2012, 407: 77-84 J]

[42] Butanovs E, Kuzmin A, Zolotarjovs A, et al.. The role of Al₂O₃ interlayer in the synthesis of ZnS/Al₂O₃/MoS₂ core-shell nanowires. Journal of Alloys and Compounds, 2022, 918: 165648 J]

[43] George J, Manikuttan P K, Shaju I K. High silica-alumina-coated TiO₂ pigment with improved dry hiding for flat paints. Journal of Coatings Technology and Research, 2022, 19(6): 1665-1672 J]

[44] Kim Y, Lee J. Leaching kinetics of zinc from metal oxide varistors (MOVs) with sulfuric acid. Metals, 2016, 6(8): 192 J]

[45] Zheng X, Li S, Liu B, et al.. A study on the mechanism and kinetics of ultrasound-enhanced sulfuric acid leaching for zinc extraction from zinc oxide dust. Materials, 2022, 15(17): 5969 J]

[46] Wang G, Du P, Zhang L, et al.. Stepwise extraction of zinc, indium and lead from secondary zinc oxide dusts experimental study. Scientific Reports, 2024, 14: 30153 J]

[47] Li S, Lu Y, Wang Y, et al.. Effects of Co²⁺ doping on the chroma, crystal form, and morphology of zinc sulfide pigment: An experimental and theoretical study. Materials Chemistry and Physics, 2026, 348: 131708 J]

[48] Li J, Zhou Y, Wang J, et al.. Manipulation of morphology, particle size of barium sulfate and the interacting mechanism of methyl glycine diacetic acid. Molecules, 2023, 28(2): 726 J]

[49] Cheng G, Guo R, Gao P, et al.. Research on surface hydrophobic modification and flotation decarbonization of coal gasification fine slag. Chemical Engineering Journal, 2026, 529: 172241 J]

[50] Sarkar R, Tiwary C S, Kumbhakar P, et al.. Enhanced visible light emission from Co²⁺ doped ZnS nanoparticles. Physica B: Condensed Matter, 2009, 404(21): 3855-3858 J]

[51] Thanh N T K, MacLean N, Mahiddine S. Mechanisms of nucleation and growth of nanoparticles in solution. Chemical Reviews, 2014, 114(15): 7610-7630 J]

[52] Erdemir D, Lee A Y, Myerson A S. Nucleation of crystals from solution: Classical and two-step models. Accounts of Chemical Research, 2009, 42(5): 621-629 J]

[53] De Yoreo J J, Gilbert P U P A, Sommerdijk N A J M, et al.. Crystallization by particle attachment in synthetic, biogenic, and geologic environments. Science, 2015, 349(6247): aaa6760 J]

[54] Hafeez M, Ali Al-Asbahi B, Hj Jumali M H, et al.. Critical role of defect states on visible luminescence from ZnS nanostructures doped with Au, Mn and Ga. Materials Science in Semiconductor Processing, 2020, 117: 105193 J]

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