DOI: https://doi.org/10.9767/bcrec.20679

Role of Ni and Zn Dopants in Modulating the Structure and Photocatalytic Activity of Mesoporous Silica–Cu Catalysts for Methylene Blue Degradation

Chemistry Education Study Program, Faculty of Teacher Training and Education, Sebelas Maret University, Jl. Ir. Sutami 36A, Surakarta 57126, Indonesia

Received: 8 Mar 2026; Revised: 4 May 2026; Accepted: 5 May 2026; Available online: 20 May 2026; Published: 30 Oct 2026.
Editor(s): Istadi Istadi
Open Access Copyright (c) 2026 by Authors, Published by BCREC Publishing Group
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Abstract

This study investigates the structural and photocatalytic roles of Ni and Zn dopants in mesoporous silica–Cu catalysts for methylene blue degradation under light irradiation. The materials were synthesized and systematically characterized using FTIR, XRD, BET, SEM–EDS, and UV–DRS to elucidate dopant-dependent structural, textural, and electronic modifications. XRD analysis revealed that Zn doping enhances crystallinity to 90.80% with a crystallite size of 1.97 nm, whereas Ni doping produces lower crystallinity (80.69%) and smaller crystallites (1.82 nm), indicating defect-rich microstructures. BET analysis confirmed mesoporous characteristics in both systems, with Zn incorporation generating broader pore distributions and higher adsorption capacity, while Ni induces more confined pore structures. SEM results showed average particle sizes of 1.49 nm for Zn-doped and 1.67 nm for Ni-doped catalysts. UV–DRS measurements demonstrated pronounced electronic modulation, with Ni doping significantly narrowing the band gap to 1.02–1.11 eV compared with 2.08–2.78 eV for Zn-doped materials. Photocatalytic evaluation at an initial methylene blue concentration of 10 ppm showed superior performance for the Ni-doped catalyst, achieving 79.59% removal efficiency and an adsorption capacity of 19.89 mg g⁻¹, compared with 50.98% removal and 12.74 mg g⁻¹ for the Zn-doped system. Kinetic analysis followed pseudo-first-order behavior, with a higher rate constant for Ni doping (0.01675 min⁻¹) than Zn doping (0.00706 min⁻¹). These findings demonstrate that Ni primarily enhances photocatalytic activity through electronic defect formation and band gap narrowing, while Zn mainly improves structural ordering and pore accessibility. The study highlights the critical role of dopant selection in tailoring structure–activity relationships in mesoporous silica–Cu photocatalysts.

Keywords: Mesoporous silica–Cu; Ni/Zn doping; Photocatalysis; Methylene blue; Band gap tuning; Structure–activity

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Section: Original Research Articles
Language : EN
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  12. Zahoor, S., Muhammad, S., Kashif, M., Shahzad, N., Liu, Y., Celik, C., Ambreen, N., Ali, A., Wu, H., Azizi, S. (2026). Advances in mesoporous nanomaterials for photocatalytic degradation of pollutants : fundamentals , material classifications , challenges and future prospects. Coordination Chemistry Reviews, 549(P1), 217239. DOI: 10.1016/j.ccr.2025.217239
  13. Wei, Y., Yang, W., Yang, Z. (2022). ScienceDirect An excellent universal catalyst support- mesoporous silica : Preparation , modification and applications in energy-related reactions. International Journal of Hydrogen Energy, 47(16), 9537–9565. DOI: 10.1016/j.ijhydene.2022.01.048
  14. Kankala, R.K., Zhang, H., Liu, C., Kanubaddi, K.R., Lee, C., Wang, S., Cui, W., Santos, H.A., Lin, K., Chen, A. (2019). Metal Species – Encapsulated Mesoporous Silica Nanoparticles : Current Advancements and Latest Breakthroughs. 1902652, 1–42. DOI: 10.1002/adfm.201902652
  15. Jovita, S., Tata, A., Santoso, E., Subagyo, R., Tamim, R., Asikin-mijan, N., Holilah, H., Bahruji, H., Edra, R. (2025). Mesoporous aluminosilicate from nanocellulose template : effect of porosity , morphology and catalytic activity for biofuel production. Renewable Energy, 250(May), 123293. DOI: 10.1016/j.renene.2025.123293
  16. Hao, Y., Zhao, D., Liu, W., Zhang, M., Lou, Y., Wang, Z., Tang, Q., Yang, J. (2022). Uniformly Dispersed Cu Nanoparticles over Mesoporous Silica as a Highly Selective and Recyclable Ethanol Dehydrogenation Catalyst. Catalyst, 12, 1049. DOI: 10.3390/catal12091049
  17. Zhou, S., Yang, F., Wang, B., Su, H., Lu, K., Ding, Y., Lei, K., Xu, M., Shao, B., Wang, Y., Kong, Y. (2018). Ordered Mesoporous Silicas and Their Catalytic Applications in the Oxidation of Aromatic Compounds. https://doi.org/10.3390/catal8020080
  18. Yang, H., Fang, J., Liu, L., Du, H. (2024). Research progress on photocatalytic degradation performance of CuS and its composite materials. Materials Today Communications, 40(May), 109988. DOI: 10.1016/j.mtcomm.2024.109988
  19. Porcu, S., Secci, F., Ricci, P.C. (2022). Advances in Hybrid Composites for Photocatalytic Applications : A Review. Molecules, 27, 6828. DOI: 10.3390/molecules27206828
  20. Gao, S., Li, W., Dai, J., Wang, Q., Suo, Z. (2021). Effect of transition metals doping on electronic structure and optical properties of β-Ga 2 O 3 Effect of transition metals doping on electronic structure and optical properties of β -Ga 2 O 3. Materials Research Express, 8, 025904. DOI: 10.1088/2053-1591/abde10
  21. Patnaik, S., Sahoo, D.P., Parida, K. (2021). Recent advances in anion doped g-C 3 N 4 photocatalysts : A review. Carbon, 172, 682–711. DOI: 10.1016/j.carbon.2020.10.073
  22. Characteristics, O. morphological , optical and magnetic The impact of nickel doping on the structural , morphological , optical and magnetic characteristics of zinc oxide nanorods. https://doi.org/10.1088/1742-6596/2974/1/012018
  23. Wang, Z., Wang, Z., Wang, J., Shi, H., Wang, C., Fan, Y., Bai, Z., Zhu, C. (2023). ScienceDirect Ni , Zn Co-doping ZIF-67-derived electrocatalyst based on CNT film for efficient overall water splitting. International Journal of Hydrogen Energy, 48(75), 29189–29197. DOI: 10.1016/j.ijhydene.2023.04.082
  24. Chang, W., Jhan, D., Lu, J., Chen, S., Huang, Y., Chang, Y., Lu, M. (2025). Synergistic enhancement of photocatalytic hydrogen evolution via Ni doping and Mo ₂ C co-catalysis in ZnIn ₂ S ₄. Journal of Alloys and Compounds, 1039(June), 183242. DOI: 10.1016/j.jallcom.2025.183242
  25. Guo, B., Liu, L., Li, A., Li, X., Chang, Y., Jiao, Z., Han, M. (2024). Insights into the effect of Ni doping on In 2 S 3 for enhanced activity and selectivity of photocatalytic CO 2 reduction. 995(May) DOI: 10.1016/j.jallcom.2024.174741
  26. Ranjan, N., Prakash, S., Sahu, D. (2026). Nickel ion doping induced enhancement in photocatalytic degradation efficiency of tin oxide nanoparticles towards mineralization of Reactive Blue 19 textile dye. Next Materials, 10(October 2025), 101362. DOI: 10.1016/j.nxmate.2025.101362
  27. Li, Z., Zhang, L., Wang, L., Yu, W., Zhang, S., Li, X. (2023). Engineering the electronic structure of two-dimensional MoS 2 by Ni dopants for pollutant degradation. Separation and Purification Technology, 314(January), 123637. DOI: 10.1016/j.seppur.2023.123637
  28. Morante, N., Monzillo, K., Padua, A., Muscatello, A., Sannino, D., Esposito, S., Vaiano, V. (2025). Engineered NiO / TiO 2 and CuO / NiO / TiO 2 heterojunctions for sustainable direct photocatalytic epoxidation of propylene using molecular oxygen. Discover Nano, 20, 104. DOI: 10.1186/s11671-025-04296-6
  29. Belloni, C., Korving, L., Witkamp, G.J., Brück, E., Dugulan, A.I. (2024). Colloids and Surfaces A : Physicochemical and Engineering Aspects Zn induced surface modification of stable goethite nanoparticles for improved regenerative phosphate adsorption. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 687(January), 133476. DOI: 10.1016/j.colsurfa.2024.133476
  30. Alhamdu, I., Chidera, E., Mustapha, S., Saka, A., Oladejo, J. (2026). Adsorption kinetics , isotherm , and thermodynamics studies of phytochemical-assisted synthesized ZnO nanoparticles for the removal of selected heavy metals from abattoir wastewater. Desalination and Water Treatment, 325(December 2025), 101628. DOI: 10.1016/j.dwt.2025.101628
  31. Liu, C., Zhu, Y., Di, S., He, J., Niu, P., Kelarakis, A., Krysmann, M., Wang, S., Li, L. (2024). coating for ultra ‐ stable Zn metal anodes. https://doi.org/10.1002/elt2.29
  32. Dadi, D.G., Shura, M.W., Gochole, F. (2025). OPEN DFT analysis of structural , electronic and optical properties of Ni and Zn doped CoS counter electrode for dye sensitized solar cells. Scientific Reports, 15, 35486. DOI: 10.1038/s41598-025-19663-71
  33. Maria, L., Anna, S., Aravind, A., Ma, Y., Anil, S. (2023). Effect of Ni doping on the adsorption and visible light photocatalytic activity of ZnO hexagonal nanorods. Inorganic Chemistry Communications, 147(May 2022), 110208. DOI: 10.1016/j.inoche.2022.110208
  34. Khan, S., Sadiq, M., Muhammad, N., Noor, A., Qayyum, S. (2026). NiCd / ZnO nanocomposites : novel materials for photocatalytic degradation of Allura Red dye. Scientific Reports, 16, 5204. DOI: 10.1038/s41598-026-36010-61
  35. Rao, S., Shilpa, M.P., Shetty, S.J., Bhat, S.S., Gummagol, N.B., Surabhi, S., Gurumurthy, S.C. (2025). Zn ‑ doped ­ TiO 2 nanoparticles : enhanced catalytic and nonlinear optical properties. Journal of Materials Science: Materials in Electronics, 36(19), 1–13. DOI: 10.1007/s10854-025-15182-3
  36. Harsono, H., Nurhuda, M., Utami, T.S., Dardiri, A.A., Engge, Y., Maulana, F. (2023). EFFECT OF ADDITIONAL Ni METAL DOPANTS ON OPTICAL ABSORPTION PROPERTIES AND CRYSTAL STRUCTURE OF ZnO PHOTOCATALYST MATERIALS. Jurnal Neutrino:Jurnal Fisika dan Aplikasinya, 15(2), 52–61. DOI: 10.18860/neu.v15i2.17514
  37. Li, Z., Yao, Y., Gao, X., Bai, H., Meng, X. (2021). Interfacial charge transfer and enhanced photocatalytic mechanisms for Pt nanoparticles loaded onto sulfur-doped g-C 3 N 4 in H 2 evolution. Materials Today Energy, 22, 100881. DOI: 10.1016/j.mtener.2021.100881
  38. Vento-lujano, E., Gonz, L.A. (2021). Applied Surface Science Defect-induced modification of band structure by the insertion of Ce 3 + and Ce 4 + in SrTiO 3 : A high-performance sunlight-driven photocatalyst. 569(June) DOI: 10.1016/j.apsusc.2021.151044
  39. Zhao, Y., Cui, H., Xu, J., Shi, J., Yan, R., Yan, N. (2025). Synthesis of biomimetic N-doped porous carbons from gelatin using salt template coupled with chemical activation strategy for CO 2 capture. Chemical Engineering Journal, 505(January), 159241. DOI: 10.1016/j.cej.2025.159241
  40. Rahmani, M., Pourmadadi, M., Abdouss, M., Rahdar, A. (2024). Industrial Crops & Products Gelatin / polyethylene glycol / g-C 3 N 4 hydrogel with olive oil as a sustainable and biocompatible nanovehicle for targeted delivery of 5-fluorouracil. Industrial Crops & Products, 208(December 2023), 117912. DOI: 10.1016/j.indcrop.2023.117912
  41. Ulfa, M., Rohmah, I.S. (2025). Thermal-induced structural evolution of mesoporous oxides Fe – Co – Ni for enhanced visible-light dye degradation. Next Materials, 9(August), 101024. DOI: 10.1016/j.nxmate.2025.101024
  42. Hasan, R., Muhammadi, F.M., Solihat, I., Listianti, E., Putri, Y.R., Alfiani, P. (2025). ARTICLE ORIGINAL Nano-silica Derived from Coal Fly Ash : A Sustainable Iron ( III ) Ion Adsorbent. 10(3), 331–338. DOI: 10.22090/jwent.2025.03.008
  43. Ulfa, M., Aziza, H., Amalia, N. (2025). Results in Engineering In-situ sulfonated mesoporous silica as ZnO nanomaterial support for enhanced dyes photodegradation. Results in Engineering, 26(October 2024), 104381. DOI: 10.1016/j.rineng.2025.104381
  44. Jabkhiro, H., Naitana, M.L., Marconi, E., Bertel, F., Iucci, G., Carlomagno, I., Battocchio, C., Meneghini, C., Tortora, L. (2025). One-Pot Synthesis of Zinc-Doped Mesoporous Silica. Crystals, 15, 100. DOI: 10.3390/cryst15020100
  45. Zhao, Q., Hu, W., Li, S., Gu, Z., Zhang, Y., Yao, Y., Zhang, Y. (2023). Microporous and Mesoporous Materials Incorporation of metal organic framework into mesoporous silica nanoparticles with high contents. Microporous and Mesoporous Materials, 360(June), 112707. DOI: 10.1016/j.micromeso.2023.112707
  46. Evdokimenko, N.D., Kapustin, G.I., Tkachenko, O.P., Kalmykov, K.B., Kustov, A.L. (2022). Zn Doping Effect on the Performance of Fe-Based Catalysts for the Hydrogenation of CO 2 to Light Hydrocarbons. Molecules, 27, 1065. DOI: 10.3390/molecules27031065
  47. Guo, B., Liu, L., Li, A., Li, X., Chang, Y., Jiao, Z., Han, M. (2024). Insights into the effect of Ni doping on In 2 S 3 for enhanced activity and selectivity of photocatalytic CO 2 reduction. 995(April) DOI: 10.1016/j.jallcom.2024.174741
  48. Mostafa, M., Khalifa, A., Hemeda, O.M., El, M.I.A., Sorory, H.A.-, Shalaby, R.M., Abdelhakim, N.A. (2025). A Comparative study of the influence of Zn ions as a growth catalyst on the physical and mechanical properties of MnFe 2 O 4. Journal of Crystal Growth, 653(December 2024), 128073. DOI: 10.1016/j.jcrysgro.2025.128073
  49. Ahmed, W., Iqbal, J. (2021). Effect of Ni doping on structural , optical and magnetic characteristics of ZrO 2 nanoparticles with efficient visible light driven photocatalytic activity. Ceramics International, 47(17), 24895–24905. DOI: 10.1016/j.ceramint.2021.05.216
  50. Ashokkumar, M., Muthukumaran, S. (2014). Microstructure , optical and FTIR studies of Ni , Cu co-doped ZnO nanoparticles by co-precipitation method. Optical Materials, 37, 671–678. DOI: 10.1016/j.optmat.2014.08.012
  51. Tsai, J., Lee, T., Chiang, H. (2023). Nitrogen Adsorption and Characteristics of Iron , Cobalt , and Nickel Oxides Impregnated on SBA-15 Mesoporous Silica. Nanomaterials, 13, 1015. DOI: 10.3390/nano13061015
  52. Zhuang, J., Lu, B., Gu, F., Zhong, Z., Su, F. (2018). Ordered mesoporous Cu – Ca – Zr : A superior catalyst for direct synthesis of methyl formate from syngas. Carbon Resources Conversion, 1(2), 174–182. DOI: 10.1016/j.crcon.2018.05.005
  53. Zienkiewicz-strzalka, M., Blachnio, M., Derylo-marczewska, A., Winter, S. (2024). Mesoporous Carbons and Highly Cross-Linking Polymers for Removal of Cationic Dyes from Aqueous Solutions — Studies on Adsorption Equilibrium and Kinetics. Materials, 17, 1374. DOI: 10.3390/ma17061374
  54. Shen, J., Wu, C., Song, J., Yu, J., Li, Y. (2023). Adsorption and capillary condensation transitions on nanostructures : Mechanisms of atomic evolution and meniscus growth. International Communications in Heat and Mass Transfer, 148, 107064. DOI: 10.1016/j.icheatmasstransfer.2023.107064
  55. Zhao, Y., Liu, X., Liu, Y., Chen, Y., Gao, S. (2022). ScienceDirect Favorable pore size distribution of biomass-derived N , S dual-doped carbon materials for advanced oxygen reduction reaction. International Journal of Hydrogen Energy, 47(26), 12964–12974. DOI: 10.1016/j.ijhydene.2022.02.064
  56. Kumar, M., Ramulu, B., Yu, J.S. (2023). Nanoarchitectonic Ni-doped edge dislocation defect-rich MoS 2 boosting catalytic activity in electrochemical hydrogen production. Journal of Cleaner Production, 414(February), 137589. DOI: 10.1016/j.jclepro.2023.137589
  57. Ungureanu, A., Dragoi, B., Chirieac, A., Ciotonea, C., Duprez, D., Mamede, A.S., Dumitriu, E. (2013). Composition-Dependent Morphostructural Properties of Ni − Cu Oxide Nanoparticles Con fi ned within the Channels of Ordered Mesoporous SBA-15 Silica. Applied Maters & Interfaces, 5, 3010−3025. DOI: 10.1021/am302733m
  58. Song, T., Du, X., Xia, T., Liu, Y., Zhu, J., Zhang, X. (2026). Effect of Fe / Ni Microalloying on Interface Regulation of SiC / Al Composites : Molecular Dynamics Simulation and Experiments. Materials, 19, 283. DOI: 10.3390/ma19020283
  59. Ranjan, N., Prakash, S., Sahu, D. (2026). Nickel ion doping induced enhancement in photocatalytic degradation efficiency of tin oxide nanoparticles towards mineralization of Reactive Blue 19 textile dye. Next Materials, 10, 101362. DOI: 10.1016/j.nxmate.2025.101362
  60. Shi, Y., Chu, W., Zhang, L., Wang, B., Saidi, W.A., Zhao, J., Prezhdo, O. V (2025). Band Gap Narrowing in Lead-Halide Perovskites by Dynamic Defect Self-Doping for Enhanced Light Absorption and Energy Upconversion. https://doi.org/10.1021/acs.chemmater.4c02530
  61. Sadiq, M. (2022). Applied Surface Science Advances Ni 2 + grafted Ag 3 PO 4 : Enhanced photocatalytic performance under visible light. 11(June) DOI: 10.1016/j.apsadv.2022.100288
  62. Kamarulzaman, N., Diyana, N., Aziz, A., Firdaus, M., Fadilah, N., Hanum, R., Subban, Y., Badar, N. (2019). Journal of Solid State Chemistry Anomalies in wide band gap SnO 2 nanostructures. 277(May), 271–280. DOI: 10.1016/j.jssc.2019.05.035
  63. Zerjav, G., Zava, J. (2022). Journal of Environmental Chemical Engineering The influence of synthesis conditions on the visible-light triggered photocatalytic activity of g-C 3 N 4 / TiO 2 composites used in AOPs skari ˇ. 10(April) DOI: 10.1016/j.jece.2022.107656
  64. Ishikawa, T., Matsuda, M., Inagaki, S., Fukushimab, T., Kondo, S. (1985). Surface silanol groups of mesoporous silica FSM-16. Faraday, 92. DOI: 10.1039/FT9969201985
  65. Ai, L., Liu, Z., Zhang, X., Wang, L., Jia, D., Guo, N., Zha, M., Tan, C. (2025). Journal of Colloid And Interface Science Engineering cycling of Cu 2 + / Cu + pairs in Bi 2 WO 6 nanoflowers for boosting photocatalytic CO 2 reduction. Journal of Colloid And Interface Science, 692(December 2024), 137480. DOI: 10.1016/j.jcis.2025.137480

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