{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,15]],"date-time":"2026-10-15T22:13:41Z","timestamp":1792102421862,"version":"4.4.0"},"reference-count":45,"publisher":"MDPI AG","issue":"10","license":[{"start":{"date-parts":[[2025,5,9]],"date-time":"2025-05-09T00:00:00Z","timestamp":1746748800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"National Natural Science Foundation of China","award":["U2067212"],"award-info":[{"award-number":["U2067212"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Nanomaterials"],"abstract":"<jats:p>The separation of palladium from radioactive waste streams represents a critical aspect of the secure handling and disposal of such hazardous materials. Palladium, in addition to its radioactive nature, holds intrinsic value as a resource. Despite the urgency, prevailing adsorbents fall short in their ability to effectively separate palladium under highly acidic environments. To surmount this challenge, our research has pioneered the development of 1,3,5-tris(4-aminophenyl)benzene-2,5-Bis(methylthio)terephthalaldehyde COF (TAPB-BMTTPA-COF), a novel material distinguished by its remarkable stability and an abundance of sulfur-containing functional groups. Leveraging the pronounced affinity of the soft ligands\u2019 nitrogen and sulfur within its molecular architecture, TAPB-BMTTPA-COF demonstrates an exceptional capability for the selective adsorption of palladium. Empirical evidence underscores the material\u2019s swift adsorption kinetics, with equilibrium achieved in as little as ten minutes, and its broad tolerance to varying acidity levels ranging from 0.1 to 3 M HNO3. Furthermore, TAPB-BMTTPA-COF boasts an impressive adsorption capacity, peaking at 343.6 mg\/g, coupled with high selectivity in 13 interfering ions\u2019 environment and the ability to be regenerated, making it a sustainable solution. Comprehensive analyses, including Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS), alongside Density Functional Theory (DFT) calculations, have corroborated the pivotal role played by densely packed nitrogen and sulfur active sites within the framework. These sites exhibit a robust affinity for Pd(II), which is the cornerstone of the material\u2019s outstanding adsorption efficacy. The outcomes of this research underscore the immense potential of COFs endowed with resilient linkers and precisely engineered functional groups. Such COFs can adeptly capture metal ions with high selectivity, even in the face of severe environmental conditions, thereby paving the way for the more effective and environmentally responsible management of radioactive waste.<\/jats:p>","DOI":"10.3390\/nano15100714","type":"journal-article","created":{"date-parts":[[2025,5,9]],"date-time":"2025-05-09T09:56:19Z","timestamp":1746784579000},"page":"714","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Enhanced Separation of Palladium from Nuclear Wastewater by the Sulfur-Rich Functionalized Covalent Organic Framework"],"prefix":"10.3390","volume":"15","author":[{"given":"Junli","family":"Wang","sequence":"first","affiliation":[{"name":"Department of Radiochemistry, China Institute of Atomic Energy, Beijing 102413, China"},{"name":"State Key Laboratory of Chemical Resource Engineering, College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chen","family":"Luo","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering, College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wentao","family":"Wang","sequence":"additional","affiliation":[{"name":"Department of Radiochemistry, China Institute of Atomic Energy, Beijing 102413, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hui","family":"Wang","sequence":"additional","affiliation":[{"name":"Department of Radiochemistry, China Institute of Atomic Energy, Beijing 102413, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yao","family":"Liu","sequence":"additional","affiliation":[{"name":"Department of Radiochemistry, China Institute of Atomic Energy, Beijing 102413, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jianwei","family":"Li","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemical Resource Engineering, College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Taihong","family":"Yan","sequence":"additional","affiliation":[{"name":"Department of Radiochemistry, China Institute of Atomic Energy, Beijing 102413, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2025,5,9]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"565","DOI":"10.1016\/S0165-9936(00)00031-5","article-title":"Platinum group metals (PGM); occurrence, use and recent trends in their determination","volume":"19","author":"Rao","year":"2000","journal-title":"TrAC Trends Anal. Chem."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"3009","DOI":"10.1021\/cr9903048","article-title":"The heck reaction as a sharpening stone of palladium catalysis","volume":"100","author":"Beletskaya","year":"2000","journal-title":"Chem. Rev."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"13","DOI":"10.1595\/003214087X3111319","article-title":"The Development and Application of Palladium Contact Materials","volume":"31","author":"Antler","year":"1987","journal-title":"Platin. Met. Rev."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"405","DOI":"10.1126\/science.aac6153","article-title":"Pharmaceutical diversification via palladium oxidative addition complexes","volume":"363","author":"Uehling","year":"2019","journal-title":"Science"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1637","DOI":"10.1016\/j.surfcoat.2009.10.048","article-title":"The preparation of corrosion resistant palladium films on 316L stainless steel by brush plating","volume":"204","author":"Tang","year":"2010","journal-title":"Surf. Coat. Technol."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"108239","DOI":"10.1016\/j.radphyschem.2019.03.043","article-title":"Palladium analysis in gold items from Punic jewellery (C\u00e1diz, Spain)","volume":"167","author":"Scrivano","year":"2020","journal-title":"Radiat. Phys. Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"417","DOI":"10.1016\/j.gca.2017.08.025","article-title":"Anthrobiogeochemical platinum, palladium and rhodium cycles of earth: Emerging environmental contamination","volume":"216","author":"Mitra","year":"2017","journal-title":"Geochim. Cosmochim. Acta"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"113","DOI":"10.1016\/0920-5861(94)80096-0","article-title":"Development of automotive palladium three-way catalysts","volume":"22","author":"Sekiba","year":"1994","journal-title":"Catal. Today"},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Micha\u0142ek, T., Hessel, V., and Wojnicki, M. (2024). Production, Recycling and Economy of Palladium: A Critical Review. Materials, 17.","DOI":"10.3390\/ma17010045"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"614","DOI":"10.1016\/j.scitotenv.2017.11.350","article-title":"Global platinum group element resources, reserves and mining\u2014A critical assessment","volume":"622\u2013623","author":"Mudd","year":"2018","journal-title":"Sci. Total Environ."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"127767","DOI":"10.1016\/j.colsurfa.2021.127767","article-title":"Functional novel ligand based palladium(II) separation and recovery from e-waste using solvent-ligand approach","volume":"632","author":"Islam","year":"2022","journal-title":"Colloids Surf. A"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"394","DOI":"10.1016\/j.hydromet.2017.06.014","article-title":"Recovery of palladium from a spent industrial catalyst through leaching and solvent extraction","volume":"171","author":"Paiva","year":"2017","journal-title":"Hydrometallurgy"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"74","DOI":"10.1595\/003214003X4727487","article-title":"Recovery of value fission platinoids from spent nuclear fuel","volume":"47","author":"Kolarik","year":"2003","journal-title":"Platin. Met. Rev."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"270","DOI":"10.1134\/S106636222203002X","article-title":"Prospects for the use of Palladium from NPP spent nuclear fuel and ways to design the technology of its recovery at a radiochemical enterprise","volume":"64","author":"Pokhitonov","year":"2022","journal-title":"Radiochemistry"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"135","DOI":"10.1023\/A:1019663027481","article-title":"Study of extraction of palladium from nitric acid solutions with nitrogen-containing compounds, as applied to recovery of fission palladium from spent nuclear fuel of nuclear power plants: 1. Extraction and backwashing conditions","volume":"44","author":"Mezhov","year":"2002","journal-title":"Radiochemistry"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"124","DOI":"10.1016\/j.jnucmat.2011.12.029","article-title":"The ternary system palladium\u2013rhodium\u2013tellurium: A Study to understand phase formation in the vitrification process of high-level waste concentrates (HLWC)","volume":"422","author":"Hartmann","year":"2012","journal-title":"Nucl. Mater."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"24344","DOI":"10.1039\/c4ra02024c","article-title":"Separation of palladium from high level liquid waste\u2014A review","volume":"4","author":"Ruhela","year":"2014","journal-title":"RSC Adv."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"514","DOI":"10.1016\/j.pnucene.2007.11.036","article-title":"Vitrification of high-level radioactive waste considering the behavior of platinum group metals","volume":"50","author":"Uruga","year":"2008","journal-title":"Prog. Nucl. Energy"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"6","DOI":"10.1016\/j.hydromet.2015.05.002","article-title":"Extraction of palladium (II) from nitric acid solutions with diglycolthioamide","volume":"156","author":"Huang","year":"2015","journal-title":"Hydrometallurgy"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"106127","DOI":"10.1016\/j.hydromet.2023.106127","article-title":"Highly efficient and selective adsorption of palladium (II) from simulated nuclear waste solution using Amberlite XAD-7 resin impregnated with a phenanthroline-derived diamide","volume":"221","author":"Xiao","year":"2023","journal-title":"Hydrometallurgy"},{"key":"ref_21","doi-asserted-by":"crossref","unstructured":"Herbst, R.S., Baron, P., and Nilsson, M. (2011). Advanced Separation Techniques for Nuclear Fuel Reprocessing and Radioactive Waste Treatment, Elsevier.","DOI":"10.1533\/9780857092274.2.141"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"592","DOI":"10.1016\/S1004-9541(11)60027-X","article-title":"Adsorptive recovery of uranium from nuclear fuel industrial wastewater by titanium loaded collagen fiber","volume":"19","author":"Cheng","year":"2011","journal-title":"Chin. J. Chem. Eng."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"76","DOI":"10.1016\/j.seppur.2017.03.019","article-title":"Development of adsorption and solidification process for decontamination of Cs-contaminated radioactive water in Fukushima through silica-based AMP hybrid adsorbent","volume":"181","author":"Wu","year":"2017","journal-title":"Sep. Purif. Technol."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"292","DOI":"10.1016\/j.trechm.2019.02.010","article-title":"Opportunities of porous organic polymers for radionuclide sequestration","volume":"1","author":"Sun","year":"2019","journal-title":"Trends Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"110161","DOI":"10.1016\/j.micromeso.2020.110161","article-title":"Functional porous organic polymer with high S and N for reversible iodine capture","volume":"300","author":"Pan","year":"2020","journal-title":"Microporous Mesoporous Mater."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"132618","DOI":"10.1016\/j.cej.2021.132618","article-title":"High acidity-and radiation-resistant triazine-based POPs for recovery of Pd (II) from nuclear fission products","volume":"430","author":"Yuan","year":"2022","journal-title":"Chem. Eng. J."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"1166","DOI":"10.1126\/science.1120411","article-title":"Porous, crystalline, covalent organic frameworks","volume":"310","author":"Benin","year":"2005","journal-title":"Science"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"10558","DOI":"10.1002\/chem.201803510","article-title":"Cover Feature: Adsorption of Pharmaceutical Pollutants from Water Using Covalent Organic Frameworks (Chem. Eur. J. 42\/2018)","volume":"24","author":"Mellah","year":"2018","journal-title":"Chem.\u2014Eur. J."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"131","DOI":"10.1146\/annurev-chembioeng-112019-084830","article-title":"Covalent organic frameworks in separation","volume":"11","author":"Das","year":"2020","journal-title":"Annu. Rev. Chem. Biomol. Eng."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"6871","DOI":"10.1039\/D0CS01569E","article-title":"Covalent organic frameworks (COFs) for electrochemical applications","volume":"50","author":"Zhao","year":"2021","journal-title":"Chem. Soc. Rev."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"1705553","DOI":"10.1002\/adfm.201705553","article-title":"Covalent organic frameworks: Structures, synthesis, and applications","volume":"28","author":"Lohse","year":"2018","journal-title":"Adv. Funct. Mater."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"133215","DOI":"10.1016\/j.chemosphere.2021.133215","article-title":"Functionalized dual modification of covalent organic framework for efficient and rapid trace heavy metals removal from drinking water","volume":"290","author":"Yang","year":"2022","journal-title":"Chemosphere"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"122","DOI":"10.1016\/j.jtice.2020.07.005","article-title":"Facile synthesis of sulfonated covalent organic framework for the adsorption of heavy metal ions","volume":"112","author":"Wang","year":"2020","journal-title":"Taiwan Inst. Chem. E"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"2428","DOI":"10.1021\/jacs.6b12328","article-title":"Stable covalent organic frameworks for exceptional mercury removal from aqueous solutions","volume":"139","author":"Huang","year":"2017","journal-title":"Am. Chem. Soc."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"4914","DOI":"10.1021\/ol302243t","article-title":"Largely \u03c0-extended thienoacenes with internal thieno [3, 2-b] thiophene substructures: Synthesis, characterization, and organic field-effect transistor applications","volume":"14","author":"Yamamoto","year":"2012","journal-title":"Org. Lett."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"15","DOI":"10.1016\/0927-0256(96)00008-0","article-title":"Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set","volume":"6","author":"Kresse","year":"1996","journal-title":"Comput. Mater. Sci."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"11169","DOI":"10.1103\/PhysRevB.54.11169","article-title":"Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set","volume":"54","author":"Kresse","year":"1996","journal-title":"Phys. Rev. B"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"1758","DOI":"10.1103\/PhysRevB.59.1758","article-title":"From ultrasoft pseudopotentials to the projector augmented-wave method","volume":"59","author":"Kresse","year":"1999","journal-title":"Phys. Rev. B"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"17953","DOI":"10.1103\/PhysRevB.50.17953","article-title":"Projector augmented-wave method","volume":"50","author":"Blochl","year":"1994","journal-title":"Phys. Rev. B"},{"key":"ref_40","first-page":"154104","article-title":"A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu","volume":"132","author":"Grimme","year":"2010","journal-title":"Chem. Phys."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"5188","DOI":"10.1103\/PhysRevB.13.5188","article-title":"Special points for Brillouin-zone integrations","volume":"13","author":"Monkhorst","year":"1976","journal-title":"Phys. Rev. B"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"795","DOI":"10.1021\/acs.accounts.1c00693","article-title":"2D conjugated covalent organic frameworks: Defined synthesis and tailor-made functions","volume":"55","author":"Zhang","year":"2022","journal-title":"Acc. Chem. Res."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"129","DOI":"10.1021\/ed074p129","article-title":"X-ray diffraction and the Bragg equation","volume":"74","author":"Pope","year":"1997","journal-title":"J. Chem. Educ."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"10513","DOI":"10.1021\/acsami.0c17748","article-title":"Theoretical screening and experimental synthesis of ultrahigh-iodine capture covalent organic frameworks","volume":"13","author":"Song","year":"2021","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"905","DOI":"10.1038\/nchem.2352","article-title":"Stable, crystalline, porous, covalent organic frameworks as a platform for chiral organocatalysts","volume":"7","author":"Xu","year":"2015","journal-title":"Nat. Chem."}],"container-title":["Nanomaterials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2079-4991\/15\/10\/714\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,9]],"date-time":"2025-10-09T17:30:18Z","timestamp":1760031018000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2079-4991\/15\/10\/714"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,5,9]]},"references-count":45,"journal-issue":{"issue":"10","published-online":{"date-parts":[[2025,5]]}},"alternative-id":["nano15100714"],"URL":"https:\/\/doi.org\/10.3390\/nano15100714","relation":{},"ISSN":["2079-4991"],"issn-type":[{"value":"2079-4991","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,5,9]]}}}