{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,15]],"date-time":"2026-05-15T20:18:34Z","timestamp":1778876314246,"version":"3.51.4"},"reference-count":33,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2022,6,2]],"date-time":"2022-06-02T00:00:00Z","timestamp":1654128000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Key Project of Natural Science Foundation of China","award":["41230638"],"award-info":[{"award-number":["41230638"]}]},{"name":"Key Project of Natural Science Foundation of China","award":["B2020019"],"award-info":[{"award-number":["B2020019"]}]},{"name":"Guiding Project of Science and Technology Research of Education Department of Hubei Province","award":["41230638"],"award-info":[{"award-number":["41230638"]}]},{"name":"Guiding Project of Science and Technology Research of Education Department of Hubei Province","award":["B2020019"],"award-info":[{"award-number":["B2020019"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Materials"],"abstract":"<jats:p>Attapulgite (ATP) disaggregated by a ball milling\u2013freezing process was used to support Fe\/Ni bimetallic nanoparticles (nFe\/Ni) to obtain a composite material of D-ATP-nFe\/Ni for the dechlorination degradation of 2,4-dichlorophenol (2,4-DCP), thus improving the problem of agglomeration and oxidation passivation of nanoscale zero-valent iron (nFe) in the dechlorination degradation of chlorinated organic compounds. The results show that Fe\/Ni nanoparticle clusters were dispersed into single spherical particles by the ball milling\u2013freezing-disaggregated attapulgite, in which the average particle size decreased from 423.94 nm to 54.51 nm, and the specific surface area of D-ATP-nFe \/Ni (97.10 m2\/g) was 6.9 times greater than that of nFe\/Ni (14.15 m2\/g). Therefore, the degradation rate of 2,4-DCP increased from 81.9% during ATP-nFe\/Ni application to 96.8% during D-ATP-nFe\/Ni application within 120 min, and the yield of phenol increased from 57.2% to 86.1%. Meanwhile, the reaction rate Kobs of the degradation of 2,4-DCP by D-ATP-nFe\/Ni was 0.0277 min\u22121, which was higher than that of ATP-nFe\/Ni (0.0135 min\u22121). In the dechlorination process of 2,4-DCP by D-ATP-nFe\/Ni, the reaction rate for the direct dechlorination of 2,4-DCP of phenol (k5 = 0.0156 min\u22121) was much higher than that of 4-chlorophenol (4-CP, k2 = 0.0052 min\u22121) and 2-chlorophenol (2-CP, k1 = 0.0070 min\u22121), which suggests that the main dechlorination degradation pathway for the removal of 2,4-DCP by D-ATP-nFe\/Ni was directly reduced to phenol by the removal of two chlorine atoms. In the secondary pathway, the removal of one chlorine atom from 2,4-DCP to generate 2-CP or 4-CP as intermediate was the rate controlling step. The final dechlorination product (phenol) was obtained when the dechlorination rate accelerated with the progress of the reaction. This study contributes to the broad topic of organic pollutant treatment by the application of clay minerals.<\/jats:p>","DOI":"10.3390\/ma15113957","type":"journal-article","created":{"date-parts":[[2022,6,2]],"date-time":"2022-06-02T04:46:23Z","timestamp":1654145183000},"page":"3957","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Performance, Reaction Pathway and Kinetics of the Enhanced Dechlorination Degradation of 2,4-Dichlorophenol by Fe\/Ni Nanoparticles Supported on Attapulgite Disaggregated by a Ball Milling\u2013Freezing Process"],"prefix":"10.3390","volume":"15","author":[{"given":"Hongdan","family":"Wu","sequence":"first","affiliation":[{"name":"College of Resource and Environmental Engineering, Wuhan University of Science and Technology, Wuhan 430081, China"},{"name":"Hubei Key Laboratory for Efficient Utilization and Agglomeration of Metallurgic Mineral Resources, Wuhan University of Science and Technology, Wuhan 430081, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Junwen","family":"Wang","sequence":"additional","affiliation":[{"name":"College of Resource and Environmental Engineering, Wuhan University of Science and Technology, Wuhan 430081, China"},{"name":"Hubei Key Laboratory for Efficient Utilization and Agglomeration of Metallurgic Mineral Resources, Wuhan University of Science and Technology, Wuhan 430081, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hong","family":"Liu","sequence":"additional","affiliation":[{"name":"College of Resource and Environmental Engineering, Wuhan University of Science and Technology, Wuhan 430081, China"},{"name":"Hubei Key Laboratory for Efficient Utilization and Agglomeration of Metallurgic Mineral Resources, Wuhan University of Science and Technology, Wuhan 430081, China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xianyuan","family":"Fan","sequence":"additional","affiliation":[{"name":"College of Resource and Environmental Engineering, Wuhan University of Science and Technology, Wuhan 430081, China"},{"name":"Hubei Key Laboratory for Efficient Utilization and Agglomeration of Metallurgic Mineral Resources, Wuhan University of Science and Technology, Wuhan 430081, China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2022,6,2]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"728","DOI":"10.1021\/acsearthspacechem.8b00204","article-title":"Heterogeneous reduction of 2-chloronitrobenzene by co-substituted magnetite coupled with aqueous Fe2+: Performance, factors, and mechanism","volume":"3","author":"Liang","year":"2019","journal-title":"ACS Earth Space Chem."},{"key":"ref_2","first-page":"433","article-title":"Remediation of 2,4-dichlorophenol contaminated water by visible light-enhanced WO3 photoelectrocatalysis","volume":"123\u2013124","author":"Kruth","year":"2012","journal-title":"Appl. Catal. B Environ."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"219","DOI":"10.1016\/j.apcatb.2003.09.010","article-title":"Degradation of chlorophenols by means of advanced oxidation processes: A general review","volume":"47","author":"Baos","year":"2004","journal-title":"Appl. Catal. B Environ."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"1022","DOI":"10.1016\/S0043-1354(00)00347-X","article-title":"Photocatalytic degradation of trichloroethylene in water using TiO2 pellets","volume":"35","author":"Suzuko","year":"2001","journal-title":"Water Res."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"3109","DOI":"10.1016\/S0045-6535(98)00516-5","article-title":"Microbial degradation of 4-chlorophenol by microorganisms entrapped in carrageenan-chitosan gels","volume":"38","author":"Wang","year":"1999","journal-title":"Chemosphere"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"335","DOI":"10.1016\/j.cej.2016.11.154","article-title":"Clay-supported nanoscale zero-valent iron composite materials for the remediation of contaminated aqueous solutions: A review","volume":"312","author":"Ezzatahmadi","year":"2017","journal-title":"Chem. Eng. J."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"102955","DOI":"10.1016\/j.jece.2019.102955","article-title":"Simultaneous adsorption and degradation of 2,4-dichlorophenol on sepiolite-supported bimetallic Fe\/Ni nanoparticles","volume":"7","author":"Ezzatahmadi","year":"2019","journal-title":"J. Environ. Chem. Eng."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"10","DOI":"10.1016\/j.jclepro.2013.12.026","article-title":"Nanoscale zerovalent iron particles for groundwater remediation: A review","volume":"77","author":"Tosco","year":"2014","journal-title":"J. Clean. Prod."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"56","DOI":"10.1111\/j.1745-6592.2008.00203.x","article-title":"Mineral precipitation upgradient from a zero-valent iron permeable reactive barrier","volume":"28","author":"Johnson","year":"2008","journal-title":"Ground Water Monit. R."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"443","DOI":"10.1080\/10643389.2015.1103832","article-title":"A review on synthesis, characterization, and applications of nano zero valent iron (nZVI) for environmental remediation","volume":"46","author":"Mukherjee","year":"2015","journal-title":"Environ. Sci. Technol."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"194","DOI":"10.1016\/j.jhazmat.2013.12.062","article-title":"The use of zero-valent iron for groundwater remediation and wastewater treatment: A review","volume":"267","author":"Fu","year":"2014","journal-title":"J. Hazard. Mater."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.watres.2015.02.034","article-title":"The limitations of applying zero-valent iron technology in contaminants sequestration and the corresponding countermeasures: The development in zero-valent iron technology in the last two decades (1994\u20132014)","volume":"75","author":"Guan","year":"2015","journal-title":"Water Res."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"284","DOI":"10.1021\/es061349a","article-title":"Aggregation and sedimentation of aqueous nanoscale zerovalent iron dispersions","volume":"41","author":"Phenrat","year":"2007","journal-title":"Environ. Sci. Technol."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"109","DOI":"10.1111\/j.1745-6592.1997.tb01270.x","article-title":"Remediating ground water with zero-valent metals: Chemical considerations in barrier design","volume":"17","author":"Tratnyek","year":"1997","journal-title":"Ground Water Monit. R."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"886","DOI":"10.1016\/j.watres.2010.09.025","article-title":"Removal of Chromium (VI) from wastewater using bentonite-supported nanoscale zero-valent iron","volume":"45","author":"Shi","year":"2011","journal-title":"Water Res."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"14","DOI":"10.1016\/j.cej.2013.12.049","article-title":"Montmorillonite-supported nanoscale zero-valent iron for removal of arsenic from aqueous solution: Kinetics and mechanism","volume":"243","author":"Bhowmick","year":"2014","journal-title":"Che. Eng. J."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"3261","DOI":"10.1021\/acssuschemeng.6b00306","article-title":"Homogeneously dispersed zerovalent iron nanoparticles supported on hydrochar-derived porous carbon: Simple, in situ synthesis and use for dechlorination of PCBs","volume":"4","author":"Llu","year":"2016","journal-title":"ACS Sustai. Chem. Eng."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1137","DOI":"10.1016\/j.chemosphere.2006.04.012","article-title":"Reductive dechlorination of 1,2,4-trichlorobenzene with palladized nanoscale Fe0 particles supported on chitosan and silica","volume":"65","author":"Zhu","year":"2006","journal-title":"Chemosphere"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"289","DOI":"10.1002\/ep.10072","article-title":"Arsenate remediation using nanosized modified zerovalent iron particles","volume":"24","author":"Jegadeesan","year":"2005","journal-title":"Environ. Prog."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"121","DOI":"10.1016\/j.ces.2019.02.024","article-title":"Continuous rapid dechlorination of p-chlorophenol by Fe-Pd nanoparticles promoted by procyanidin","volume":"201","author":"Liu","year":"2019","journal-title":"Che. Eng. Sci."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"157","DOI":"10.1016\/j.powtec.2013.08.002","article-title":"A novel approach for dispersion palygorskite aggregates into nanorods via adding freezing process into extrusion and homogenization treatment","volume":"249","author":"Xu","year":"2013","journal-title":"Powder Technol."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"60","DOI":"10.1016\/j.powtec.2017.03.044","article-title":"Novel environment friendly inorganic red pigments based on attapulgite","volume":"315","author":"Tian","year":"2017","journal-title":"Powder Technol."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"328","DOI":"10.1016\/j.jhazmat.2015.05.032","article-title":"Debromination of polybrominated diphenyl ethers by attapulgite-supported Fe\/Ni bimetallic nanoparticles: Influencing factors, kinetics and mechanism","volume":"298","author":"Liu","year":"2015","journal-title":"J. Hazard. Mater."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"541","DOI":"10.1016\/j.jhazmat.2006.09.088","article-title":"Adsorption studies of a water soluble dye, Reactive Red MF-3B, using sonication-surfactant-modified attapulgite clay","volume":"143","author":"Huang","year":"2007","journal-title":"J. Hazard. Mater."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"118","DOI":"10.1016\/j.clay.2011.07.020","article-title":"Disaggregation of palygorskite crystal bundles via high-pressure homogenization","volume":"54","author":"Xu","year":"2011","journal-title":"Appl. Clay Sci."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"6","DOI":"10.1109\/TNANO.2009.2033675","article-title":"A new approach to efficiently disperse aggregated palygorskite into single crystals via adding freeze process into traditional extrusion treatment","volume":"9","author":"Chen","year":"2010","journal-title":"IEEE Trans. Nanotechnol."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"327","DOI":"10.1016\/j.biortech.2005.12.026","article-title":"Utilization of starch and clay for the preparation of superabsorbent composite","volume":"98","author":"Li","year":"2007","journal-title":"Bioresour. Technol."},{"key":"ref_28","first-page":"163","article-title":"Synthesis and properties of clay-based superabsorbent composite","volume":"41","author":"An","year":"2005","journal-title":"Eur. Polym. J."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1904","DOI":"10.1016\/j.eurpolymj.2009.04.004","article-title":"Mechanical properties of attapulgite clay reinforced polyurethane shape-memory nanocomposites","volume":"45","author":"Xu","year":"2009","journal-title":"Eur. Polym. J."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"2014","DOI":"10.1021\/es991129f","article-title":"Dechlorination of pentachlorophenol by zero valent iron and modified zero valent irons","volume":"34","author":"Kim","year":"2000","journal-title":"Environ. Sci. Technol."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"92","DOI":"10.1016\/j.jes.2015.10.033","article-title":"Enhanced dechlorination of 2,4-dichlorophenol by recoverable Ni\/Fe-Fe3O4 nanocomposites","volume":"48","author":"Xu","year":"2016","journal-title":"J. Environ. Sci. China"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"133996.1","DOI":"10.1016\/j.scitotenv.2019.133996","article-title":"A new insight into the main mechanism of 2,4-dichlorophenol dechlorination by Fe\/Ni nanoparticles","volume":"697","author":"Ruan","year":"2019","journal-title":"Sci. Total Environ."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"5079","DOI":"10.1021\/es903278e","article-title":"Characterization and reactivity of iron nanoparticles prepared with added Cu, Pd, and Ni","volume":"44","author":"Chun","year":"2010","journal-title":"Environ. Sci. Technol."}],"container-title":["Materials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1996-1944\/15\/11\/3957\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T23:23:39Z","timestamp":1760138619000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1996-1944\/15\/11\/3957"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,6,2]]},"references-count":33,"journal-issue":{"issue":"11","published-online":{"date-parts":[[2022,6]]}},"alternative-id":["ma15113957"],"URL":"https:\/\/doi.org\/10.3390\/ma15113957","relation":{},"ISSN":["1996-1944"],"issn-type":[{"value":"1996-1944","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,6,2]]}}}