{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,18]],"date-time":"2026-08-18T17:24:20Z","timestamp":1787073860921,"version":"build-2736575974"},"reference-count":47,"publisher":"American Chemical Society (ACS)","issue":"32","license":[{"start":{"date-parts":[[2026,8,5]],"date-time":"2026-08-05T00:00:00Z","timestamp":1785888000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/100012964","name":"Enseignement Sup?rieur et de la Recherche Scientifique","doi-asserted-by":"publisher","id":[{"id":"10.13039\/100012964","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,18]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>This study examines the removal of the azo dye dark blue (DB) using natural raw clay as an iron-bearing material in a clay-based Fenton system. Characterization of the natural mineral via XRD, FTIR, and SEM\/EDX confirmed a quartz-rich structure containing native iron. The main objectives were to evaluate the effect of pH on color removal efficiency over time, to assess the contribution of adsorption on the clay surface, and to clarify the molecular interactions between DB and the clay. Optimization of the initial pH showed that the highest color and COD removal efficiencies were achieved at a pH of 4. Comparative experiments involving conventional Fenton reactions at pH 3 and pH 4, together with ultrasound-assisted clay-based Fenton oxidation under identical molar ratios, showed that the presence of clay improved dye removal at pH 4, whereas adsorption accounted for only 8% of the overall removal under the investigated conditions. To gain deeper insights into the adsorption step, density functional theory (DFT) calculations based on the cluster approximation were performed to model the molecular and electronic interactions between DB and the clay surface. The calculations, carried out at the B3LYP-D3(BJ)\/6\u2013311G(d,p) level with CPCM water solvation, indicate that adsorption is mainly governed by weak noncovalent interactions and suggest two distinct adsorption modes: DB is stabilized on the CLAY(Si\u2013O) surface primarily through localized hydrogen bonds, whereas its stabilization on the CLAY(Al\u2013O) surface results from the cumulative contribution of weaker and more diffuse noncovalent interactions.<\/jats:p>","DOI":"10.1021\/acsomega.6c05177","type":"journal-article","created":{"date-parts":[[2026,8,6]],"date-time":"2026-08-06T03:11:47Z","timestamp":1785985907000},"page":"48450-48462","source":"Crossref","is-referenced-by-count":0,"title":["Raw Clay-Assisted\nFenton Removal of Dark Blue Reactive\nDye: Experimental Assessment Supported by DFT Insights"],"prefix":"10.1021","volume":"11","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4236-2224","authenticated-orcid":true,"given":"Ghazza","family":"Masmoudi","sequence":"first","affiliation":[{"name":"University of Monastir , , ,","place":["Monastir, Tunisia, 5019"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sahar","family":"Mazgar","sequence":"additional","affiliation":[{"name":"University of Monastir , , ,","place":["Monastir, Tunisia, 5019"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hatem","family":"Dhaouadi","sequence":"additional","affiliation":[{"name":"University of Monastir , , ,","place":["Monastir, Tunisia, 5019"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,5]]},"reference":[{"issue":"5","key":"2026081811093396900_cit1","doi-asserted-by":"publisher","first-page":"633","DOI":"10.1016\/j.biortech.2004.06.004","article-title":"Effects of Alkalinity and Co-Substrate on the Performance\nof an Upflow Anaerobic Sludge Blanket (UASB) Reactor through Decolorization\nof Congo Red Azo Dye","volume":"96","author":"ISIK","year":"2005","journal-title":"Bioresour. Technol."},{"key":"2026081811093396900_cit2","doi-asserted-by":"publisher","first-page":"227","DOI":"10.1016\/j.jes.2015.06.013","article-title":"Removal of C.I. Reactive\nRed 2 by Low Pressure UV\/Chlorine Advanced Oxidation","volume":"41","author":"Wu","year":"2016","journal-title":"J. Environ. Sci."},{"key":"2026081811093396900_cit3","doi-asserted-by":"publisher","first-page":"332","DOI":"10.1016\/j.jhazmat.2014.05.047","article-title":"Aquatic Toxicity of Dyes before and after Photo-Fenton\nTreatment","volume":"276","author":"de Luna","year":"2014","journal-title":"J. Hazard. Mater."},{"key":"2026081811093396900_cit4","doi-asserted-by":"publisher","DOI":"10.1016\/j.cej.2021.133002","article-title":"Advanced Oxidation\nProcesses (AOPs) Based Wastewater Treatment - Unexpected Nitration\nSide Reactions - a Serious Environmental Issue: A Review","volume":"430","author":"Rayaroth","year":"2022","journal-title":"Chem. Eng. J."},{"issue":"24","key":"2026081811093396900_cit5","doi-asserted-by":"publisher","first-page":"10867","DOI":"10.3390\/su162410867","article-title":"Environmental Impacts and Biological Technologies Toward\nSustainable Treatment of Textile Dyeing Wastewater: A Review","volume":"16","author":"Liu","year":"2024","journal-title":"Sustainability"},{"issue":"2","key":"2026081811093396900_cit6","doi-asserted-by":"publisher","first-page":"495","DOI":"10.3390\/su16020495","article-title":"Recent\nAdvances in the Remediation of Textile-Dye-Containing Wastewater:\nPrioritizing Human Health and Sustainable Wastewater Treatment","volume":"16","author":"Periyasamy","year":"2024","journal-title":"Sustainability"},{"key":"2026081811093396900_cit7","doi-asserted-by":"publisher","first-page":"11","DOI":"10.1016\/j.jes.2022.01.042","article-title":"Fe2O3\/TiO2\/Reduced\nGraphene Oxide-Driven Recycled Visible-Photocatalytic Fenton Reactions\nto Mineralize Organic Pollutants in a Wide pH Range","volume":"134","author":"Zheng","year":"2023","journal-title":"J. Environ. Sci."},{"issue":"4","key":"2026081811093396900_cit8","doi-asserted-by":"publisher","first-page":"2245","DOI":"10.1021\/acs.est.4c10348","article-title":"Probing the Photochemical\nFormation\nof Hydroxyl Radical from Dissolved Organic Matter: Insights into the\nH2 O2 -Dependent Pathway","volume":"59","author":"Cheng","year":"2025","journal-title":"Environ. Sci. Technol."},{"key":"2026081811093396900_cit9","doi-asserted-by":"publisher","DOI":"10.1016\/j.jhazmat.2023.131926","article-title":"H2O2 Activation and Contaminants\nRemoval in Heterogeneous Fenton-like Systems","volume":"458","author":"Li","year":"2023","journal-title":"J. Hazard. Mater."},{"key":"2026081811093396900_cit10","doi-asserted-by":"publisher","DOI":"10.3389\/fchem.2022.892424","article-title":"Enhanced Heterogeneous\nFenton Degradation of Organic Pollutants by CRC\/Fe3O4 Catalyst at\nNeutral pH","volume":"10","author":"Wang","year":"2022","journal-title":"Front. Chem."},{"issue":"3","key":"2026081811093396900_cit11","doi-asserted-by":"publisher","first-page":"344","DOI":"10.3390\/catal12030344","article-title":"Heterogeneous Advanced\nOxidation Processes: Current Approaches for Wastewater Treatment","volume":"12","author":"Lama","year":"2022","journal-title":"Catalysts"},{"issue":"10","key":"2026081811093396900_cit12","doi-asserted-by":"publisher","first-page":"2188","DOI":"10.3390\/molecules29102188","article-title":"Polymer-Supported Heterogeneous Fenton\nCatalysts for the Environmental Remediation of Wastewater","volume":"29","author":"Bouzayani","year":"2024","journal-title":"Molecules"},{"issue":"08","key":"2026081811093396900_cit13","doi-asserted-by":"publisher","first-page":"490","DOI":"10.4236\/ajac.2014.58058","article-title":"Heterogeneous\nFenton Catalyst for the Efficient Removal of Azo Dyes in Water","volume":"05","author":"Blanco","year":"2014","journal-title":"Am. J. Anal. Chem."},{"key":"2026081811093396900_cit14","doi-asserted-by":"publisher","first-page":"432","DOI":"10.1016\/j.clay.2017.06.034","article-title":"Ni-Exchanged Cationic Clays as Novel\nHeterogeneous Catalysts for Selective Ethylene Oligomerization","volume":"146","author":"Aid","year":"2017","journal-title":"Appl. Clay Sci."},{"issue":"1\u20132","key":"2026081811093396900_cit15","doi-asserted-by":"publisher","first-page":"10","DOI":"10.1016\/j.apcatb.2010.05.004","article-title":"Heterogeneous Photo-Fenton\nOxidation\nwith Pillared Clay-Based Catalysts for Wastewater Treatment: A Review","volume":"98","author":"Herney-Ramirez","year":"2010","journal-title":"Appl. Catal., B"},{"issue":"47","key":"2026081811093396900_cit16","doi-asserted-by":"publisher","first-page":"29537","DOI":"10.1039\/D1RA05416C","article-title":"Iron-Containing\nPalygorskite Clay as Fenton Reagent for the Catalytic Degradation\nof Phenol in Water","volume":"11","author":"Xu","year":"2021","journal-title":"RSC Adv."},{"key":"2026081811093396900_cit17","doi-asserted-by":"publisher","DOI":"10.1016\/j.colsurfa.2023.132630","article-title":"Raw Clays\nfrom Morocco for Degradation of Pollutants by Fenton-like Reaction\nfor Water Treatment","volume":"679","author":"Assila","year":"2023","journal-title":"Colloids Surf., A"},{"issue":"8","key":"2026081811093396900_cit18","doi-asserted-by":"publisher","first-page":"1215","DOI":"10.1016\/S0008-6223(98)00317-0","article-title":"On the Characterization\nof Acidic and Basic Surface Sites on Carbons by Various Techniques","volume":"37","author":"Lopez-Ramon","year":"1999","journal-title":"Carbon"},{"issue":"1","key":"2026081811093396900_cit19","doi-asserted-by":"publisher","first-page":"406","DOI":"10.3390\/su16010406","article-title":"Purification\nof Pesticide-Contaminated\nWater Using Activated Carbon from Prickly Pear Seeds for Environmentally\nFriendly Reuse in a Circular Economy","volume":"16","author":"Zgolli","year":"2024","journal-title":"Sustainability"},{"issue":"8","key":"2026081811093396900_cit20","doi-asserted-by":"publisher","first-page":"4425","DOI":"10.1007\/s11696-023-02792-6","article-title":"Optimization of Dark Blue Reactive\nDye Degradation\nwith Fenton Reaction Based on Experimental Design Methodology and\nDFT Calculations","volume":"77","author":"Slama","year":"2023","journal-title":"Chem. Pap."},{"issue":"16","key":"2026081811093396900_cit21","doi-asserted-by":"publisher","first-page":"4503","DOI":"10.1080\/03067319.2021.1928105","article-title":"Chemical and Thermal\nActivation of Clay Sample for\nImprovement Adsorption Capacity of Methylene Blue","volume":"103","author":"Teg\u0306in","year":"2023","journal-title":"Int. J. Environ. Anal. Chem."},{"key":"2026081811093396900_cit22","doi-asserted-by":"publisher","first-page":"83","DOI":"10.1016\/B978-0-12-814837-2.00004-4","article-title":"4 - Application\nof Nanotechnology\nin the Removal of Heavy Metal From Water","volume-title":"Nanomaterials for the Removal of Pollutants and Resource Reutilization","author":"Liu","year":"2019"},{"key":"2026081811093396900_cit23","doi-asserted-by":"publisher","first-page":"381","DOI":"10.1016\/j.molliq.2014.11.006","article-title":"Agricultural Peels\nfor Dye Adsorption: A Review of\nRecent Literature","volume":"200","author":"Anastopoulos","year":"2014","journal-title":"J. Mol. Liq."},{"issue":"3\u20134","key":"2026081811093396900_cit24","doi-asserted-by":"publisher","first-page":"325","DOI":"10.1080\/09593330.2010.499545","article-title":"Removal of Lead and Yellow 44 Acid\nDye in Single and Binary Component Systems by Raw Posidonia Oceanica\nand the Cellulose Extracted from the Raw Biomass","volume":"32","author":"Dridi-Dhaouadi","year":"2011","journal-title":"Environ. Technol."},{"key":"2026081811093396900_cit25","doi-asserted-by":"publisher","first-page":"16","DOI":"10.1016\/j.comptc.2013.09.025","article-title":"The DFT Study\nof Adsorption of 2,4-Dinitrotoluene on Kaolinite Surfaces","volume":"1025","author":"Wang","year":"2013","journal-title":"Comput. Theor. Chem."},{"issue":"5","key":"2026081811093396900_cit26","doi-asserted-by":"publisher","first-page":"580","DOI":"10.1002\/jcc.22885","article-title":"Multiwfn: A Multifunctional Wavefunction Analyzer","volume":"33","author":"Lu","year":"2012","journal-title":"J. Comput. Chem."},{"issue":"4","key":"2026081811093396900_cit27","doi-asserted-by":"publisher","first-page":"553","DOI":"10.1080\/00268977000101561","article-title":"The Calculation of\nSmall Molecular Interactions by\nthe Differences of Separate Total Energies. Some Procedures with Reduced\nErrors","volume":"19","author":"Boys","year":"1970","journal-title":"Mol. Phys."},{"issue":"29","key":"2026081811093396900_cit28","doi-asserted-by":"publisher","first-page":"13561","DOI":"10.1080\/19443994.2015.1061953","article-title":"Application\nof Modified Clays as an Adsorbent for the Removal of Basic Red 46\nand Reactive Yellow 181 from Aqueous Solution","volume":"57","author":"Bouatay","year":"2016","journal-title":"Desalin. Water Treat."},{"issue":"15","key":"2026081811093396900_cit29","doi-asserted-by":"publisher","first-page":"9349","DOI":"10.1007\/s12633-021-01637-9","article-title":"Rapid Adsorption\nof Cationic Methylene Blue Dye onto Volcanic Ash-Metakaolin Based\nGeopolymers","volume":"14","author":"Shikuku","year":"2022","journal-title":"Silicon"},{"issue":"4","key":"2026081811093396900_cit30","doi-asserted-by":"publisher","DOI":"10.1617\/s11527-020-01531-7","article-title":"EDX\/XRD-Based\nIdentification of Micrometer-Sized Domains\nin Scanning Electron Micrographs of Fired Clay","volume":"53","author":"Kariem","year":"2020","journal-title":"Mater. Struct."},{"key":"2026081811093396900_cit31","doi-asserted-by":"publisher","DOI":"10.1016\/j.jwpe.2020.101320","article-title":"Stability of Iron Chelates during Photo-Fenton Process:\nThe Role of pH, Hydroxyl Radical Attack and Temperature","volume":"36","author":"Ahile","year":"2020","journal-title":"J. Water Process Eng."},{"issue":"11","key":"2026081811093396900_cit32","doi-asserted-by":"publisher","first-page":"6771","DOI":"10.1021\/acs.est.0c01257","article-title":"Influence of pH\non the Kinetics and\nMechanism of Photoreductive Dissolution of Amorphous Iron Oxyhydroxide\nin the Presence of Natural Organic Matter: Implications to Iron Bioavailability\nin Surface Waters","volume":"54","author":"Garg","year":"2020","journal-title":"Environ. Sci. Technol."},{"issue":"12","key":"2026081811093396900_cit33","doi-asserted-by":"publisher","first-page":"1825","DOI":"10.1007\/s11426-020-9885-3","article-title":"A Novel Heterogeneous Co(II)-Fenton-like\nCatalyst for Efficient Photodegradation by Visible Light over Extended\npH","volume":"63","author":"Chen","year":"2020","journal-title":"Sci. China Chem."},{"key":"2026081811093396900_cit34","doi-asserted-by":"publisher","DOI":"10.1016\/j.apcatb.2023.123667","article-title":"Surface Structure Regulation of Sulfidated Zero-Valent\nIron by H2O2\nfor Efficient pH Self-Regulation and Proton Cycle to Boost Heterogeneous\nFenton-like Reaction for Pollutant Control","volume":"345","author":"Feng","year":"2024","journal-title":"Appl. Catal., B"},{"issue":"5","key":"2026081811093396900_cit35","doi-asserted-by":"publisher","first-page":"744","DOI":"10.1016\/S1001-0742(10)60470-6","article-title":"Production\nand Contribution\nof Hydroxyl Radicals between the DSA Anode and Water Interface","volume":"23","author":"Li","year":"2011","journal-title":"J. Environ. Sci."},{"key":"2026081811093396900_cit36","doi-asserted-by":"publisher","first-page":"390","DOI":"10.1016\/j.actbio.2022.04.004","article-title":"Aqueous Decomposition\nBehavior of\nSolid Peroxides: Effect of pH and Buffer Composition on Oxygen and\nHydrogen Peroxide Formation","volume":"145","author":"Rastinfard","year":"2022","journal-title":"Acta Biomater."},{"issue":"2","key":"2026081811093396900_cit37","doi-asserted-by":"publisher","first-page":"1278","DOI":"10.1021\/acs.est.1c05722","article-title":"pH Dependence\nof Hydroxyl Radical,\nFerryl, and\/or Ferric Peroxo Species Generation in the Heterogeneous\nFenton Process","volume":"56","author":"Chen","year":"2022","journal-title":"Environ. Sci. Technol."},{"issue":"11","key":"2026081811093396900_cit38","doi-asserted-by":"publisher","first-page":"2598","DOI":"10.2166\/wst.2018.221","article-title":"Adsorption\nof Reactive Dyes onto Chitosan\/Montmorillonite Intercalated Composite:\nMulti-Response Optimization, Kinetic, Isotherm and Thermodynamic Study","volume":"77","author":"Li","year":"2018","journal-title":"Water Sci. Technol."},{"issue":"10","key":"2026081811093396900_cit39","doi-asserted-by":"publisher","DOI":"10.1007\/s10661-024-13035-w","article-title":"Reactive Blue\nMEBF 222 Dye and Textile Wastewater Treatment Using Metal-Doped Cobalt\nand Nickel Perovskites by Batch and Column Adsorption Process","volume":"196","author":"Sherin","year":"2024","journal-title":"Environ. Monit. Assess."},{"issue":"5","key":"2026081811093396900_cit40","doi-asserted-by":"publisher","DOI":"10.1007\/s11274-024-03949-5","article-title":"Adsorption\nof Azo Dye by Biomass and Immobilized Yarrowia Lipolytica; Equilibrium,\nKinetic and Thermodynamic Studies","volume":"40","author":"Hassan Ibrahim","year":"2024","journal-title":"World J.\nMicrobiol. Biotechnol."},{"issue":"6","key":"2026081811093396900_cit41","doi-asserted-by":"publisher","first-page":"2057","DOI":"10.55730\/1300-0527.3502","article-title":"Kinetic, Isotherm,\nand Thermodynamic Studies for Adsorptive\nRemoval of Basic Violet 14 from Aqueous Solution","volume":"46","author":"Tamer","year":"2022","journal-title":"Turk. J. Chem."},{"issue":"2","key":"2026081811093396900_cit42","doi-asserted-by":"publisher","first-page":"579","DOI":"10.1039\/D4MA00818A","article-title":"Unraveling\nthe Sorption Mechanism of Industrial Dyes\nonto Zr-Based MOFs: Computational and Experimental Modelling for Highly\nEfficient Removal","volume":"6","author":"Nguena","year":"2025","journal-title":"Mater. Adv."},{"issue":"Pt B","key":"2026081811093396900_cit43","doi-asserted-by":"publisher","DOI":"10.1016\/j.jhazmat.2020.124082","article-title":"Heterogeneous Fenton Catalysts: A\nReview of Recent Advances","volume":"404","author":"Thomas","year":"2021","journal-title":"J. Hazard. Mater."},{"key":"2026081811093396900_cit44","doi-asserted-by":"publisher","DOI":"10.1016\/j.chemosphere.2023.141024","article-title":"Ultrasonic\nCavitation: Tackling\nOrganic Pollutants in Wastewater","volume":"350","author":"Song","year":"2024","journal-title":"Chemosphere"},{"key":"2026081811093396900_cit45","doi-asserted-by":"publisher","DOI":"10.3389\/fchem.2018.00012","article-title":"Iron Based Catalysts\nUsed in Water Treatment Assisted by Ultrasound:\nA Mini Review","volume":"6","author":"Zhang","year":"2018","journal-title":"Front. Chem."},{"key":"2026081811093396900_cit46","doi-asserted-by":"publisher","first-page":"426","DOI":"10.1016\/j.rser.2015.10.139","article-title":"Review on the Recent Improvements\nin Sonochemical and Combined Sonochemical Oxidation Processes \u2013\nA Powerful Tool for Destruction of Environmental Contaminants","volume":"55","author":"Sathishkumar","year":"2016","journal-title":"Renewable. Sustainable Energy Rev."},{"issue":"37","key":"2026081811093396900_cit47","doi-asserted-by":"publisher","first-page":"16369","DOI":"10.1039\/D4NJ02367F","article-title":"Dark Blue Azo Dye Degradation\nby the Electro-Fenton\nProcess and Reaction Mechanism Prediction via Theoretical\nFukui Function Analysis","volume":"48","author":"Slama","year":"2024","journal-title":"New J. Chem."}],"container-title":["ACS Omega"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acsomega.6c05177","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/acsodf\/article-pdf\/11\/32\/48450\/66426841\/acsomega.6c05177.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/acsodf\/article-pdf\/11\/32\/48450\/66426841\/acsomega.6c05177.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,18]],"date-time":"2026-08-18T16:25:40Z","timestamp":1787070340000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/acsodf\/article\/11\/32\/48450\/5247103\/Raw-Clay-Assisted-Fenton-Removal-of-Dark-Blue"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,5]]},"references-count":47,"journal-issue":{"issue":"32","published-online":{"date-parts":[[2026,8,5]]},"published-print":{"date-parts":[[2026,8,18]]}},"URL":"https:\/\/doi.org\/10.1021\/acsomega.6c05177","relation":{},"ISSN":["2470-1343"],"issn-type":[{"value":"2470-1343","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,5]]}}}