J. Mor, Anil Boda, S. K. Sharma, Musharaf Ali, Arijit Sengupta
{"title":"了解三、四、六价官能团在金属-有机骨架(MOF) ZIF-67上的吸附行为:实验和理论研究","authors":"J. Mor, Anil Boda, S. K. Sharma, Musharaf Ali, Arijit Sengupta","doi":"10.1080/01496395.2023.2255740","DOIUrl":null,"url":null,"abstract":"ABSTRACTMetal–organic frameworks (MOFs) are a class of compounds with modern-age technological importance due to diverse structural topologies, porosity, and modularity. ZIF-67 has been synthesized for efficient extraction of f cations in different oxidation states (UO22+, Th4+ and Eu3+) from aqueous pH medium exhibiting the trend in sorption efficiency as: KdTh(6.19 × 103) > KdU (5.20 × 103) > KdEu (1.58 × 103) in accordance to their chemical potential. Langmuir isotherm was found to be predominate with sorption capacity 85.9 mg g−1, 137.4 mg g−1 and 50.6 mg g−1 for U, Th and Eu, respectively. The sorption predominantly proceeded via pseudo 2nd order rate kinetics with rate constants: k2U ~0.089 g mg−1 min−1, k2Th ~0.011 g mg−1 min−1 and k2Eu ~0.04 g mg−1 min−1. The processes were found to be spontaneous as revealed from negative ΔG values; and endothermic in nature (ΔHU ~10.5 kJ mol−1; ΔHTh ~12.8 kJ mol−1; ΔHEu ~8.3 kJ mol−1). The sorption proceeded via the formation of an inner sphere complex as indicated from their enhancement in the entropy values on sorption due to the release of water molecules. The Density Functional Theory (DFT) predicted selectivity using binding energy (ZIF-67-Eu3+ ~ -60.90 eV, ZIF-67-Th4+ ~ -70.78 eV, ZIF-67-Th4+ ~ -69.52 eV) is in line with the experimental selectivity of Th4+ > UO22+ > Eu3+. Total density of states (TODS) and Projected density of States (PODS) were estimated in order to understand the interaction between the ZIF-67 and f cations.KEYWORDS: ZIF-67f-cationssorptionisothermradiolytic stability AcknowledgmentsThe authors wish to acknowledge Dr. P. K. Mohapatra, Associate Director, RC & I Group, BARC & Head, Radiochemistry Division.Disclosure statementNo potential conflict of interest was reported by the author(s).Metal-Organic Framework noveltyMetal-Organic Framework (MOF), ZIF-67 has been synthesized for efficient extraction of f-cations in different oxidation states (UO22+, Th4+ and Eu3+) from aqueous pH medium exhibiting the trend in sorption efficiency as: KdTh (6.19 × 103) > KdU (5.20 × 103) > KdEu (1.58 × 103) in accordance to their chemical potential. Langmuir isotherm was found to be predominate with sorption capacity 85.9 mg g−1, 137.4 mg g−1 and 50.6 mg g−1 for U, Th and Eu, respectively. The sorption predominantly proceeded via pseudo 2nd order rate kinetics with rate constants: k2U ~0.089 g mg−1 min−1, k2Th ~0.011 g mg−1 min−1 and k2Eu ~0.04 g mg−1 min−1. The processes were found to be spontaneous as revealed from negative ΔG values, and endothermic in nature (ΔHU ~10.5 kJ mol−1; ΔHTh ~12.8 kJ mol−1 ΔHEu ~8.3 kJ mol−1). The sorption proceeded via the formation of an inner sphere complex as indicated from their enhancement in the entropy values on sorption due to the release of water molecules. The Density Functional Theory (DFT) predicted selectivity using B.E. (ZIF-67-Eu3+ ~ −60.90 eV, ZIF-67-Th4+ ~ −70.78 eV, ZIF-67-Th4+ ~ −69.52 eV) is in line with the experimental selectivity of Th4+ > UO22+ > Eu3+. Total density of states (TODS) and Projected density of states (PODS) were estimated in order to understand the interaction between the ZIF-67 and f-cations.","PeriodicalId":21680,"journal":{"name":"Separation Science and Technology","volume":"41 1","pages":"0"},"PeriodicalIF":2.3000,"publicationDate":"2023-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Understanding the sorption behavior of tri, tetra and hexavalent f cations on metal–organic framework (MOF), ZIF-67: experimental and theoretical investigation\",\"authors\":\"J. Mor, Anil Boda, S. K. Sharma, Musharaf Ali, Arijit Sengupta\",\"doi\":\"10.1080/01496395.2023.2255740\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"ABSTRACTMetal–organic frameworks (MOFs) are a class of compounds with modern-age technological importance due to diverse structural topologies, porosity, and modularity. ZIF-67 has been synthesized for efficient extraction of f cations in different oxidation states (UO22+, Th4+ and Eu3+) from aqueous pH medium exhibiting the trend in sorption efficiency as: KdTh(6.19 × 103) > KdU (5.20 × 103) > KdEu (1.58 × 103) in accordance to their chemical potential. Langmuir isotherm was found to be predominate with sorption capacity 85.9 mg g−1, 137.4 mg g−1 and 50.6 mg g−1 for U, Th and Eu, respectively. The sorption predominantly proceeded via pseudo 2nd order rate kinetics with rate constants: k2U ~0.089 g mg−1 min−1, k2Th ~0.011 g mg−1 min−1 and k2Eu ~0.04 g mg−1 min−1. The processes were found to be spontaneous as revealed from negative ΔG values; and endothermic in nature (ΔHU ~10.5 kJ mol−1; ΔHTh ~12.8 kJ mol−1; ΔHEu ~8.3 kJ mol−1). The sorption proceeded via the formation of an inner sphere complex as indicated from their enhancement in the entropy values on sorption due to the release of water molecules. The Density Functional Theory (DFT) predicted selectivity using binding energy (ZIF-67-Eu3+ ~ -60.90 eV, ZIF-67-Th4+ ~ -70.78 eV, ZIF-67-Th4+ ~ -69.52 eV) is in line with the experimental selectivity of Th4+ > UO22+ > Eu3+. Total density of states (TODS) and Projected density of States (PODS) were estimated in order to understand the interaction between the ZIF-67 and f cations.KEYWORDS: ZIF-67f-cationssorptionisothermradiolytic stability AcknowledgmentsThe authors wish to acknowledge Dr. P. K. Mohapatra, Associate Director, RC & I Group, BARC & Head, Radiochemistry Division.Disclosure statementNo potential conflict of interest was reported by the author(s).Metal-Organic Framework noveltyMetal-Organic Framework (MOF), ZIF-67 has been synthesized for efficient extraction of f-cations in different oxidation states (UO22+, Th4+ and Eu3+) from aqueous pH medium exhibiting the trend in sorption efficiency as: KdTh (6.19 × 103) > KdU (5.20 × 103) > KdEu (1.58 × 103) in accordance to their chemical potential. Langmuir isotherm was found to be predominate with sorption capacity 85.9 mg g−1, 137.4 mg g−1 and 50.6 mg g−1 for U, Th and Eu, respectively. The sorption predominantly proceeded via pseudo 2nd order rate kinetics with rate constants: k2U ~0.089 g mg−1 min−1, k2Th ~0.011 g mg−1 min−1 and k2Eu ~0.04 g mg−1 min−1. The processes were found to be spontaneous as revealed from negative ΔG values, and endothermic in nature (ΔHU ~10.5 kJ mol−1; ΔHTh ~12.8 kJ mol−1 ΔHEu ~8.3 kJ mol−1). The sorption proceeded via the formation of an inner sphere complex as indicated from their enhancement in the entropy values on sorption due to the release of water molecules. The Density Functional Theory (DFT) predicted selectivity using B.E. (ZIF-67-Eu3+ ~ −60.90 eV, ZIF-67-Th4+ ~ −70.78 eV, ZIF-67-Th4+ ~ −69.52 eV) is in line with the experimental selectivity of Th4+ > UO22+ > Eu3+. Total density of states (TODS) and Projected density of states (PODS) were estimated in order to understand the interaction between the ZIF-67 and f-cations.\",\"PeriodicalId\":21680,\"journal\":{\"name\":\"Separation Science and Technology\",\"volume\":\"41 1\",\"pages\":\"0\"},\"PeriodicalIF\":2.3000,\"publicationDate\":\"2023-09-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Separation Science and Technology\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1080/01496395.2023.2255740\",\"RegionNum\":4,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Separation Science and Technology","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1080/01496395.2023.2255740","RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Understanding the sorption behavior of tri, tetra and hexavalent f cations on metal–organic framework (MOF), ZIF-67: experimental and theoretical investigation
ABSTRACTMetal–organic frameworks (MOFs) are a class of compounds with modern-age technological importance due to diverse structural topologies, porosity, and modularity. ZIF-67 has been synthesized for efficient extraction of f cations in different oxidation states (UO22+, Th4+ and Eu3+) from aqueous pH medium exhibiting the trend in sorption efficiency as: KdTh(6.19 × 103) > KdU (5.20 × 103) > KdEu (1.58 × 103) in accordance to their chemical potential. Langmuir isotherm was found to be predominate with sorption capacity 85.9 mg g−1, 137.4 mg g−1 and 50.6 mg g−1 for U, Th and Eu, respectively. The sorption predominantly proceeded via pseudo 2nd order rate kinetics with rate constants: k2U ~0.089 g mg−1 min−1, k2Th ~0.011 g mg−1 min−1 and k2Eu ~0.04 g mg−1 min−1. The processes were found to be spontaneous as revealed from negative ΔG values; and endothermic in nature (ΔHU ~10.5 kJ mol−1; ΔHTh ~12.8 kJ mol−1; ΔHEu ~8.3 kJ mol−1). The sorption proceeded via the formation of an inner sphere complex as indicated from their enhancement in the entropy values on sorption due to the release of water molecules. The Density Functional Theory (DFT) predicted selectivity using binding energy (ZIF-67-Eu3+ ~ -60.90 eV, ZIF-67-Th4+ ~ -70.78 eV, ZIF-67-Th4+ ~ -69.52 eV) is in line with the experimental selectivity of Th4+ > UO22+ > Eu3+. Total density of states (TODS) and Projected density of States (PODS) were estimated in order to understand the interaction between the ZIF-67 and f cations.KEYWORDS: ZIF-67f-cationssorptionisothermradiolytic stability AcknowledgmentsThe authors wish to acknowledge Dr. P. K. Mohapatra, Associate Director, RC & I Group, BARC & Head, Radiochemistry Division.Disclosure statementNo potential conflict of interest was reported by the author(s).Metal-Organic Framework noveltyMetal-Organic Framework (MOF), ZIF-67 has been synthesized for efficient extraction of f-cations in different oxidation states (UO22+, Th4+ and Eu3+) from aqueous pH medium exhibiting the trend in sorption efficiency as: KdTh (6.19 × 103) > KdU (5.20 × 103) > KdEu (1.58 × 103) in accordance to their chemical potential. Langmuir isotherm was found to be predominate with sorption capacity 85.9 mg g−1, 137.4 mg g−1 and 50.6 mg g−1 for U, Th and Eu, respectively. The sorption predominantly proceeded via pseudo 2nd order rate kinetics with rate constants: k2U ~0.089 g mg−1 min−1, k2Th ~0.011 g mg−1 min−1 and k2Eu ~0.04 g mg−1 min−1. The processes were found to be spontaneous as revealed from negative ΔG values, and endothermic in nature (ΔHU ~10.5 kJ mol−1; ΔHTh ~12.8 kJ mol−1 ΔHEu ~8.3 kJ mol−1). The sorption proceeded via the formation of an inner sphere complex as indicated from their enhancement in the entropy values on sorption due to the release of water molecules. The Density Functional Theory (DFT) predicted selectivity using B.E. (ZIF-67-Eu3+ ~ −60.90 eV, ZIF-67-Th4+ ~ −70.78 eV, ZIF-67-Th4+ ~ −69.52 eV) is in line with the experimental selectivity of Th4+ > UO22+ > Eu3+. Total density of states (TODS) and Projected density of states (PODS) were estimated in order to understand the interaction between the ZIF-67 and f-cations.
期刊介绍:
This international journal deals with fundamental and applied aspects of separation processes related to a number of fields. A wide range of topics are covered in the journal including adsorption, membranes, extraction, distillation, absorption, centrifugation, crystallization, precipitation, reactive separations, hybrid processes, continuous separations, carbon capture, flocculation and magnetic separations. The journal focuses on state of the art preparative separations and theoretical contributions to the field of separation science. Applications include environmental, energy, water, and biotechnology. The journal does not publish analytical separation papers unless they contain new fundamental contributions to the field of separation science.