Gigantochloa scortechinii-derived microcrystalline cellulose–Ag ₂CO ₃ composite photocatalyst for efficient paracetamol degradation under low-intensity of UVC irradiation

Abstract

This study describes the facile fabrication of microcrystalline cellulose (MCC) from Gigantochloa scortechinii bamboo fibres serving as an electron mediator for Ag₂CO₃ photocatalyst. Comprehensive characterization techniques were used to illustrate the successful integration of Ag₂CO₃ onto MCC surfaces. The SEM images revealed homogeneous distribution of tiny rod-shaped Ag₂CO₃ nanoparticles on MCC’s surfaces. Moreover, XRD verified phase-pure Ag₂CO₃ with crystallinity > 70%, while the PL spectroscopy demonstrated suppressed emission intensity for MCC-Ag₂CO₃ and band gap narrowed from 2.8 to 2.6 eV. As shown by the band gap and PL analyses, the enhanced performance was ascribed to the remarkable rapid separation of electron and holes charge carriers, ease of electron migration, while highlighting the presence of MCC as electron mediators in the composite photocatalyst. The paracetamol (PCM) was used as targeted pollutant for the photocatalytic evaluations assisted by a relatively low UVC light intensity (9 W). With a rate constant of 9.4 × 10⁻³ min⁻¹, which was 1.5 times higher than that of pure Ag₂CO₃, the MCC-Ag₂CO₃ reached a notable 82% percentage of degradation under normal conditions. From DFT calculation, the MCC-Ag₂CO₃ shows orbital hybridization, reducing band gap and recombination while boosting charge separation via conductive channels and localized mid-gap states. The reactivity was dominated by photogenerated holes, followed by superoxide radical anions and hydroxyl radicals (h_vb⁺ >^•O₂⁻ >^•OH) and the degradation was sustained with > 50% efficiency over five consecutive cycles.

Keywords

Density functional theory / Gigantochloa Scortechinii / Microcrystalline cellulose / Paracetamol / Silver carbonate

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

CRediT authorship contribution statement

Nurul Syarima Nadia Sazman: Writing – original draft, Investigation, Formal analysis, Data curation. Nor Husnina Nor Shamsi: Investigation, Formal analysis. Nur Hafiz Hussin: Validation, Software, Investigation, Data curation. Mohamad Syafie Mahmood: Validation, Conceptualization. Fariza Aina Abd Manan: Visualization, Methodology, Conceptualization. Hamizah Mokhtar: Resources, Project administration. Hartini Ahmad Rafaie: Supervision, Methodology. Shaari Daud: Supervision, Resources, Methodology. Zul Adlan Mohd Hir: Writing – review & editing, Supervision, Project administration, Methodology, Funding acquisition, Conceptualization.

Acknowledgements

This research was funded by Ministry of Higher Education, Malaysia under the Fundamental Research Grant Scheme (Project Number: FRGS/1/2024/STG05/UITM/02/12), as well as the services and facilities provided by UiTM Pahang Branch to carry out the laboratory work. The authors further expressed their sincere appreciation to the Ionic Materials and Devices Laboratory, Institute of Science, Universiti Teknologi MARA (UiTM) Shah Alam, for providing access to the computational facilities and CASTEP module used in the Density functional theory (DFT) calculations.

References

[1] W. Alamaw, A.M. Taddesse, A. Adgo, Z. Bezu, E. Teju, Synthesis and characterization of zeolite-supported CdS/TiO₂/Ag₂CO₃ ternary composite for photodegradation of methyl orange , Results Chem. 14 (2025) 102063, doi: 10.1016/j.rechem.2025.102063.

[2] S. Behravesh, N. Mirghaffari, A.A. Alemrajabi, F. Davar, M. Soleimani, Photocatalytic degradation of acetaminophen and codeine medicines using a novel zeolite-supported TiO₂ and ZnO under UV and sunlight irradiation , Environ. Sci. Pollut. Res. 27 (2020) 26929-26942, doi: 10.1007/s11356-020-09038-y.

[3] A. Irshad, M.H.H. Mahmoudb, R.Umer Usman, M. Naeem, I.H. El Azab, Z.M. El-bahy, Investigation of photocatalytic degradation of diclofenac sodium and acetaminophen by Zn-Ag co-doped barium hexaferrite@CNTs composite, Desalin. Water Treat. J. 319 (2024) 100415, doi: 10.1016/j.dwt.2024.100415.

[4] F.H. Abdullah, N.H.H.A. Bakar, M.A. Bakar, Current advancements on the fabrication, modification, and industrial application of zinc oxide as photocatalyst in the removal of organic and inorganic contaminants in aquatic systems, J. Hazard. Mater. 424 (2022) 127416, doi: 10.1016/j.jhazmat.2021.127416.

[5] Z. Huang, X. Qiu, D. Chen, X. Wu, S. Zhang, P. Zhu, Construction of Ag₂CO₃/ZnFe₂O₄/bentonite Z-type heterojunction photocatalyst and efficient degradation of norfloxacin , Opt. Mater. 143 (2023) 114153, doi: 10.1016/j.optmat.2023.114153.

[6] K. Abhimanyu, H. Singh, S. Sable, V.K. Sonu, P. Singh, A. Kaushik, P. Thakur, V. Chaudhary, Exploring complex silver sulfide nano-systems as efficient photocatalysts for wastewater remediation and clean energy production: Toward sustainable and circular economy, Mater. Today 90 (2025) 681-705, doi: 10.1016/j.mattod.2025.09.004.

[7] N. Thakur, A. Panwar, V. Soni, P. Raizada, P. Singh, A. Aslam, P. Khan, V. Nguyen, C.C. Nguyen, S.J. Yang, Q. Van Le, H. Kim, S. Sonu, Next-generation wastewater treatment with emerging 2D MOF-derived photocatalysts, ACS Omega 10 (2025) 58029-58056, doi: 10.1021/acsomega.5c08223.

[8] N.S.N. Sazman, Z.A.M. Hir, S. Daud, H.A. Rafaie, Charge transport properties and photostability of microcrystalline cellulose derived from Gigantochloa scortechinii-supported ZnO for enhanced acetaminophen degradation, Ind. Crops Prod. 222 (2024) 119558, doi: 10.1016/j.indcrop.2024.119558.

[9] S. Qiu, H. Hao, Z. Liu, Y. Li, X. Liu, T. Liu, Anchoring movable Ag₂CO₃ quantum dots on g-C₃N₄ with rich oxygen vacancies for enhanced simulated-sunlight CO₂ reduction in water medium , Sep. Purif. Technol. 330 (2024) 125330, doi: 10.1016/j.seppur.2023.125330.

[10] H.A. Rafaie, N.I.T. Ramli, Z. Khusaimi, M.A.M. Sarjidan, P. Dulyaseree, Z.M.H. Adlan, Ag₂CO₃-based photocatalyst with enhanced photocatalytic activity for endocrine-disrupting chemicals degradation: A review , Catalysts 13 (2023) 540, doi: 10.3390/catal13030540.

[11] P. Raizada, A. Sudhaik, P. Singh, P. Shandilya, P. Thakur, H. Jung, Visible light assisted photodegradation of 2,4-dinitrophenol using Ag₂CO₃ loaded phosphorus and sulphur co-doped graphitic carbon nitride nanosheets in simulated wastewater , Arab. J. Chem. 13 (2020) 3196-3209, doi: 10.1016/j.arabjc.2018.10.004.

[12] H. Xu, Y. Zhang, Y. Wang, L. Zhang, Z. Zhang, L. Zhong, Z. He, Y. Zheng, Y. Shen, Heterojunction material BiYO₃/g-C₃N₄ modified with cellulose nanofibers for photocatalytic degradation of tetracycline , Carbohydr. Polym. 312 (2023) 120829, doi: 10.1016/j.carbpol.2023.120829.

[13] J. Nie, C. Li, Z. Jin, W. Hu, J. Wang, T. Huang, Y. Wang, Fabrication of MCC/Cu₂O/GO composite foam with high photocatalytic degradation ability toward methylene blue , Carbohydr. Polym. 223 (2019) 115101, doi: 10.1016/j.carbpol.2019.115101.

[14] N.S.N. Sazman, H.A. Rafaie, S. Daud, N.A.M. Shohaimi, M.A.A.A. Bakar, Z.A.M. Hir, Extraction and physicochemical characterization of microcrystalline cellulose from Gigantochloa scortechinii, Malaysian J. Chem. 25 (2023) 323-330, doi: 10.55373/mjchem.v25i3.323.

[15] C. Hua, X. Liu, S. Ren, C. Zhang, W. Liu, Preparation of visible light-responsive photocatalytic paper containing BiVO₄@diatomite/MCC/PVBCFs for degradation of organic pollutants , Ecotoxicol. Environ. Saf. 202 (2020) 110897, doi: 10.1016/j.ecoenv.2020.110897.

[16] N. Amaly, A.Y. El-moghazy, N. Nitin, G. Sun, P.K. Pandey, Synergistic adsorption-photocatalytic degradation of tetracycline by microcrystalline cellulose composite aerogel dopped with montmorillonite hosted methylene blue, Chem. Eng. J. 430 (2022) 133077, doi: 10.1016/j.cej.2021.133077.

[17] X. Li, L. Zhang, Z. Wang, S. Wu, J. Ma, Cellulose controlled zinc oxide nanoparticles with adjustable morphology and their photocatalytic performances, Carbohydr. Polym. 259 (2021) 117752, doi: 10.1016/j.carbpol.2021.117752.

[18] N.S.N. Sazman, N.I. Izhar, N.R.M. Azaludin, S. Daud, H.A. Rafaie, Z.A.M. Hir, Valorization of wood waste as biosorbent for the removal of organic and inorganic contaminants in water, in: S.N. Sarmin, M. Jawaid, R. Elias (Eds.), Wood Waste Management and Products, Sustainable Materials and Technology, Springer, Singapore, 2023, pp. 59-78, doi: 10.1007/978-981-99-1905-5_6.

[19] H. Xi, Q. Kang, D. Liu, H. Wang, W. Lu, Y. Zhao, X. Xu, Z. Yang, Z. Lei, Synthesis of C/BiOCl/Bi₂S₃ heterojunction photocatalyst induced by sodium carboxymethyl cellulose and its photocatalytic performance , Colloids Surf. A 724 (2025) 137498, doi: 10.1016/j.colsurfa.2025.137498.

[20] C.C. Boungou, G.D. Ngantso, B.R. Malonda-Boungou, A.T. Raji, P.S. Moussounda, DFT calculations with and without spin polarization of the adsorption and decomposition of NCO and OCN on the Ag(110) surface, Comput. Condens. Matter 41 (2024) e00975, doi: 10.1016/j.cocom.2024.e00975.

[21] M.F.M. Taib, M.K. Yaakob, O.H. Hassan, M.Z.A. Yahya, Structural, electronic, and lattice dynamics of PbTiO₃, SnTiO₃, and SnZrO₃: A comparative first-principles study , Integr. Ferroelectr. 142 (2013) 119-127, doi: 10.1080/10584587.2013.780528.

[22] W. Kohn, L.J. Sham, Self-consistent equations including exchange and correlation effects, Phys. Rev. 140 (1965) A1133-A1138, doi: 10.1103/PhysRev.140.A1133.

[23] H. Mukhair, A.H. Abdullah, Z.A.M. Hir, N.S. Osman, Z. Zainal, L.H. Ngee, In-depth investigation on the photostability and charge separation mechanism of Ag₃PO₄/g-C₃N₄ photocatalyst towards very low visible light intensity , J. Mol. Liq. 376 (2023) 121494, doi: 10.1016/j.molliq.2023.121494.

[24] M. Chijioke-Okere, A.H. Abdullah, Z.A.M. Hir, J.I. Alinnor, E.E. Oguzie, Efficient photodegradation of paracetamol by integrated PES-ZnO photocatalyst sheets, Inorg. Chem. Commun. 148 (2023) 110377, doi: 10.1016/j.inoche.2022.110377.

[25] M. Zhou, X. Tian, H. Yu, Z. Wang, C. Ren, L. Zhou, Y. Lin, L. Dou, WO₃/Ag₂CO₃ mixed photocatalyst with enhanced photocatalytic activity for organic dye degradation , ACS Omega 6 (2021) 26439-26453, doi: 10.1021/acsomega.1c03694.

[26] A.S. Ganie, S. Hussain, A.A. Bhat, A. Farooq, R.K. Manavalan, A.M. Fouda, G. Qiao, G. Liu, Preparation of bifunctional Ag₂CO₃ decorated BiVO₄ nanospheres for high-performance electrochemical energy storage and photocatalytic activity , Surf. Interfaces 57 (2025) 105756, doi: 10.1016/j.surfin.2025.105756.

[27] H. Sun, P. Qin, Z. Wu, C. Liao, J. Guo, S. Luo, Y. Chai, Visible light-driven photocatalytic degradation of organic pollutants by a novel Ag₃VO₄/Ag₂CO₃ p-n heterojunction photocatalyst: Mechanistic insight and degradation pathways , J. Alloys Compd. 834 (2020) 155211, doi: 10.1016/j.jallcom.2020.15521.

[28] Y. Li, Z. Chen, Y. Liu, Y. Xu, J. Ma, Y. Guo, Ternary photocatalyst Bi₅O₇I/Bi₂O₂CO₃/Ag₂CO₃ with double Z-scheme heterojunction for the degradation of levofloxacin under visible light: Practical application and DFT calculation , J. Alloys Compd. 1010 (2025) 177294, doi: 10.1016/j.jallcom.2024.177294.

[29] L.V. Bora, R.K. Mewada, Photocatalytic treatment of dye wastewater and parametric study using a novel Z-scheme Ag₂CO₃/SiC photocatalyst under natural sunlight , J. Environ. Chem. Eng. 5 (2017) 5556-5565, doi: 10.1016/j.jece.2017.10.037.

[30] X. Shen, S. Yang, Y. Yang, Z. Yu, S. Liu, S. Shan, X. Wang, Q. Xue, Efficient degradation of norfloxacin by BiOBr/Ag₂CO₃ Z-type semiconductor heterojunction: Mechanistic insights and degradation pathways , Colloids Surf. A 709 (2025) 136135, doi: 10.1016/j.colsurfa.2025.136135.

[31] L. Wang, J. Wang, M. Tang, C. Wang, D. Gao, Y. Zhou, Developing a Z-scheme Ag₂CO₃/ZIF-8 heterojunction for the surface decoration of cotton fabric toward repeatable photocatalytic dye degradation , Appl. Surf. Sci. 610 (2023) 155605, doi: 10.1016/j.apsusc.2022.155605.

[32] A. Rebekah, R.P. V, K.S. Lee, Exploring visible light driven WO₃/Ag₂CO₃ embedded with reduced graphene oxide for enhancement of photocatalytic application , Colloids Surf. A 708 (2025) 136028, doi: 10.1016/j.colsurfa.2024.136028.

[33] C. Teng, Y. Chen, Z. Tang, W. Yuan, L. Zhang, Y. Guo, F. Li, Q. Huang, Synthesis of Ag₂CO₃/TiO₂/SiC with pH stability and chloride ion boosted for efficient photodegrading tetracycline under visible light , Chem. Eng. J. 488 (2024) 150983, doi: 10.1016/j.cej.2024.150983.

[34] R. Cao, H. Yang, X. Deng, S. Zhang, X. Xu, In-situ synthesis of amorphous silver silicate/carbonate composites for selective visible-light photocatalytic decomposition, Sci. Rep. 3 (2017) 15001, doi: 10.1038/s41598-017-15405-6.

[35] N. Wang, L. Shi, L. Yao, C. Lu, Y. Shia, J. Sun, Highly improved visible-light-induced photocatalytic performance over BiOI/Ag₂CO₃ heterojunctions , RSC Adv. 8 (2018) 537-546, doi: 10.1039/c7ra10423e.

[36] A. Moradbak, P.M. Tahir, A.Z. Mohamed, M.M. Abdi, R.L. Razalli, R. Halis, Isolation of cellulose nanocrystals from Gigantochloa scortechinii ASAM pulp, Eur. J. Wood Wood Prod. 76 (2018) 1021-1027, doi: 10.1007/s00107-017-1244-1.

[37] T. Suparanon, S. Kaewchuy, N. Phusunti, V. Suchaiya, W. Phetwarotai, Synergistic effect of microcrystalline cellulose from oil palm empty fruit bunch waste and tricresyl phosphate on the properties of polylactide composites, Int. J. Biol. Macromol. 220 (2022) 1480-1492, doi: 10.1016/j.ijbiomac.2022.09.140.

[38] S. Ventura-Cruz, N. Flores-Alamo, A. Tecante, Preparation of microcrystalline cellulose from residual Rose stems (Rosa spp.) by successive delignification with alkaline hydrogen peroxide, Int. J. Biol. Macromol. 155 (2020) 324-329, doi: 10.1016/j.ijbiomac.2020.03.222.

[39] M.K. Hassan, M. Karim, D. Howlader, M.M. Alam, A. Kukmer, Comparative studies of Ag₃PO₄, Ag₂CO₃, and Ag₃VO₄ as photocatalyst for wastewater treatment: A first-principles calculation , Heliyon 9 (2023) e22757, doi: 10.1016/j.heliyon.2023.e22757.

[40] A. Sudhaik, P. Raizada, T. Ahamad, S.M. Alshehri, V. Nguyen, Q. Van Le, S. Thakur, V. Kumar, R. Selvasembian, P. Singh, Recent advances in cellulose supported photocatalysis for pollutant mitigation: A review, Int. J. Biol. Macromol. 226 (2023) 1284-1308, doi: 10.1016/j.ijbiomac.2022.11.241.

[41] H. Dong, G. Chen, J. Sun, C. Li, Y. Yu, D. Chen, A novel high-efficiency visible-light sensitive Ag₂CO₃ photocatalyst with universal photodegradation performances: Simple synthesis, reaction mechanism and first-principles study , Appl. Catal. B Environ. 134 (2013) 46-54, doi: 10.1016/j.apcatb.2012.12.041.

[42] S. Li, X. Li, Y. Liu, P. Zhang, J. Zhang, B. Zhang, Interfacial engineering of a plasmonic Ag/Ag₂CO₃/C₃N₅ S-scheme heterojunction for high-performance photocatalytic degradation of antibiotics , Chinese J. Catal. 72 (2025) 130-142, doi: 10.1016/S1872-2067(25)64652-3.

[43] I. Rouibah, S. Hakimi, N. Khellaf, H. Ben Mansour, A.A. Assadi, Photoactivity performance of TiO₂/cellulose and ZnO/polystyrene; intensified effect of oxidants on degradation efficiency of acetaminophen , Phys. Chem. Res. 9 (2021) 413-426, doi: 10.22036/pcr.2020.243655.1810.

[44] C. Shi, L. Zhang, H. Bian, Z. Shi, J. Ma, Z. Wang, Construction of Ag-ZnO/cellulose nanocomposites via tunable cellulose size for improving photocatalytic performance, J. Clean. Prod. 288 (2021) 125089, doi: 10.1016/j.jclepro.2020.125089.

[45] M.F.H. Hashim, Z.A.M. Hir, S. Daud, H.A. Rafaie, H. Mokhtar, M.A. Mohamed, Microcrystalline cellulose from kapok fiber (Ceiba pentandra) as carbon interstitial dopant in ZnO: Physicochemical characteristics and photocatalytic activity, Environ. Qual. Manag. 35 (2025) e70199, doi: 10.1002/tqem.70199.

[46] J. Li, R. Guan, J. Zhang, Z. Zhao, H. Zhai, D. Sun, Y. Qi, Preparation and photocatalytic performance of dumbbell Ag₂CO₃-ZnO heterojunctions , ACS Omega 5 (2020) 570-577, doi: 10.1021/acsomega.9b03131.

[47] M.O. Chijioke-Okere, Z.A.M. Hir, C.E. Ogukwe, P.C. Njoku, A.H. Abdullah, E.E. Oguzie, TiO₂/polyethersulphone films for photocatalytic degradation of acetaminophen in aqueous solution , J. Mol. Liq. 338 (2021) 116692, doi: 10.1016/j.molliq.2021.116692.

[48] S. Qiu, H. Hao, Z. Liu, Y. Li, X. Liu, T. Liu, Anchoring movable Ag₂CO₃ quantum dots on g-C₃N₄ with rich oxygen vacancies for enhanced simulated-sunlight CO₂ reduction in water medium , Sep. Purif. Technol. 330 (2024) 125330, doi: 10.1016/j.seppur.2023.125330.

[49] N. Pan, S. Liu, Y. Han, D. Li, J. Chai, A comparison study of the performance of Ag₂CO₃ photocatalysts synthesized respectively in a surfactant-free microemulsion, water, and a water/propan-2-ol mixture , J. Mater. 8 (2022) 781-789, doi: 10.1016/j.jmat.2022.02.006.

[50] M. Hasanpour, M. Hatami, Photocatalytic performance of aerogels for organic dyes removal from wastewaters: Review study, J. Mol. Liq. 309 (2020) 113094, doi: 10.1016/j.molliq.2020.113094.

[51] E. Moctezuma, E. Leyva, C.A. Aguilar, R.A. Luna, C. Montalvo, Photocatalytic degradation of paracetamol: Intermediates and total reaction mechanism, J. Hazard. Mater. 243 (2012) 130-138, doi: 10.1016/j.jhazmat.2012.10.010.

[52] V.H.T. Thi, B.K. Lee, Effective photocatalytic degradation of paracetamol using La-doped ZnO photocatalyst under visible light irradiation, Mater. Res. Bull. 96 (2017) 171-182, doi: 10.1016/j.materresbull.2017.04.028.