{"title":"镍修饰的ZIF-67 (Co) MOF衍生双金属催化剂在过硫酸盐活化下微波辐射高效降解四环素:性能评估和预测中间毒性谱","authors":"Saptarshi Bose, Mathava Kumar","doi":"10.1016/j.seppur.2025.132371","DOIUrl":null,"url":null,"abstract":"<div><div>In this study, tetracycline (TC) removal performance evaluation was accomplished alongside the prediction of the eco-toxicological effect of the generated intermediates. The polyhedron shaped nickel (Ni)-decorated ZIF-67 (Co) MOF derived bi-metallic catalyst was synthesized successfully by pyrolysis of the Ni-modified rhombic dodecahedron shaped ZIF-67 template. Therefore, under the following microwave (MW) based operation conditions: catalyst dose 0.6 g/L, initial concentration of TC 10 mg/L, MW input power 450 W, and at unchanged pH, Ni-decorated ZIF-67 (Co) derived catalyst Ni Co /C displayed ∼97.59 % TC removal within only 2 min of MW exposure. Magnetic (i.e., Ni and Co) and dielectric (i.e., carbon) counterparts enhanced better microwave absorption while reducing reflective loss. The absorbed microwave energy was dissipated to form localized ‘hotspots’ for direct decomposition of PS, H<sub>2</sub>O, and TC molecules whereas conductive carbon matrix with Ni doping propagated electronic mobility for free reactive radical generation. The MW induced ‘photo-electric’ effect of electron-hole pair separation and electron transfer via redox couples (i.e., Co<sup>2+</sup>/Co<sup>3+</sup> and Ni<sup>2+</sup>/Ni<sup>3+</sup>) encapsulated in carbon nanocage resulted in the generation of various reactive free radicals including sulfate (SO<sub>4</sub><sup>•−</sup>), hydroxyl (<sup>●</sup>OH), superoxide anion (<sup>●</sup>O<sub>2</sub><sup>–</sup>) radicals and singlet oxygen (<sup>1</sup>O<sub>2</sub>) which were confirmed by EPR. The theoretical eco-toxicological effects of intermediates were analyzed by ECOSAR and T.E.S.T. software, which may highlight the need for stringent rules in the future regarding the discharge of advanced oxidation process-treated wastewater and further research on the mitigation process. Moreover, the reusability study and evaluation of TC degradation in natural water showcased the calibre of this Ni-decorated ZIF-67 (Co) derived catalyst Ni Co /C to become a next-generation MW-responsive catalyst to tackle various emerging contaminants.</div></div>","PeriodicalId":427,"journal":{"name":"Separation and Purification Technology","volume":"364 ","pages":"Article 132371"},"PeriodicalIF":9.0000,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Nickel-decorated ZIF-67 (Co) MOF derived bi-metallic catalyst for efficient degradation of tetracycline under microwave irradiation through persulfate activation route: Performance assessment and predictive intermediate toxicity profile\",\"authors\":\"Saptarshi Bose, Mathava Kumar\",\"doi\":\"10.1016/j.seppur.2025.132371\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>In this study, tetracycline (TC) removal performance evaluation was accomplished alongside the prediction of the eco-toxicological effect of the generated intermediates. The polyhedron shaped nickel (Ni)-decorated ZIF-67 (Co) MOF derived bi-metallic catalyst was synthesized successfully by pyrolysis of the Ni-modified rhombic dodecahedron shaped ZIF-67 template. Therefore, under the following microwave (MW) based operation conditions: catalyst dose 0.6 g/L, initial concentration of TC 10 mg/L, MW input power 450 W, and at unchanged pH, Ni-decorated ZIF-67 (Co) derived catalyst Ni Co /C displayed ∼97.59 % TC removal within only 2 min of MW exposure. Magnetic (i.e., Ni and Co) and dielectric (i.e., carbon) counterparts enhanced better microwave absorption while reducing reflective loss. The absorbed microwave energy was dissipated to form localized ‘hotspots’ for direct decomposition of PS, H<sub>2</sub>O, and TC molecules whereas conductive carbon matrix with Ni doping propagated electronic mobility for free reactive radical generation. The MW induced ‘photo-electric’ effect of electron-hole pair separation and electron transfer via redox couples (i.e., Co<sup>2+</sup>/Co<sup>3+</sup> and Ni<sup>2+</sup>/Ni<sup>3+</sup>) encapsulated in carbon nanocage resulted in the generation of various reactive free radicals including sulfate (SO<sub>4</sub><sup>•−</sup>), hydroxyl (<sup>●</sup>OH), superoxide anion (<sup>●</sup>O<sub>2</sub><sup>–</sup>) radicals and singlet oxygen (<sup>1</sup>O<sub>2</sub>) which were confirmed by EPR. The theoretical eco-toxicological effects of intermediates were analyzed by ECOSAR and T.E.S.T. software, which may highlight the need for stringent rules in the future regarding the discharge of advanced oxidation process-treated wastewater and further research on the mitigation process. Moreover, the reusability study and evaluation of TC degradation in natural water showcased the calibre of this Ni-decorated ZIF-67 (Co) derived catalyst Ni Co /C to become a next-generation MW-responsive catalyst to tackle various emerging contaminants.</div></div>\",\"PeriodicalId\":427,\"journal\":{\"name\":\"Separation and Purification Technology\",\"volume\":\"364 \",\"pages\":\"Article 132371\"},\"PeriodicalIF\":9.0000,\"publicationDate\":\"2025-03-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Separation and Purification Technology\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1383586625009682\",\"RegionNum\":1,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"ENGINEERING, CHEMICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Separation and Purification Technology","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1383586625009682","RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}
Nickel-decorated ZIF-67 (Co) MOF derived bi-metallic catalyst for efficient degradation of tetracycline under microwave irradiation through persulfate activation route: Performance assessment and predictive intermediate toxicity profile
In this study, tetracycline (TC) removal performance evaluation was accomplished alongside the prediction of the eco-toxicological effect of the generated intermediates. The polyhedron shaped nickel (Ni)-decorated ZIF-67 (Co) MOF derived bi-metallic catalyst was synthesized successfully by pyrolysis of the Ni-modified rhombic dodecahedron shaped ZIF-67 template. Therefore, under the following microwave (MW) based operation conditions: catalyst dose 0.6 g/L, initial concentration of TC 10 mg/L, MW input power 450 W, and at unchanged pH, Ni-decorated ZIF-67 (Co) derived catalyst Ni Co /C displayed ∼97.59 % TC removal within only 2 min of MW exposure. Magnetic (i.e., Ni and Co) and dielectric (i.e., carbon) counterparts enhanced better microwave absorption while reducing reflective loss. The absorbed microwave energy was dissipated to form localized ‘hotspots’ for direct decomposition of PS, H2O, and TC molecules whereas conductive carbon matrix with Ni doping propagated electronic mobility for free reactive radical generation. The MW induced ‘photo-electric’ effect of electron-hole pair separation and electron transfer via redox couples (i.e., Co2+/Co3+ and Ni2+/Ni3+) encapsulated in carbon nanocage resulted in the generation of various reactive free radicals including sulfate (SO4•−), hydroxyl (●OH), superoxide anion (●O2–) radicals and singlet oxygen (1O2) which were confirmed by EPR. The theoretical eco-toxicological effects of intermediates were analyzed by ECOSAR and T.E.S.T. software, which may highlight the need for stringent rules in the future regarding the discharge of advanced oxidation process-treated wastewater and further research on the mitigation process. Moreover, the reusability study and evaluation of TC degradation in natural water showcased the calibre of this Ni-decorated ZIF-67 (Co) derived catalyst Ni Co /C to become a next-generation MW-responsive catalyst to tackle various emerging contaminants.
期刊介绍:
Separation and Purification Technology is a premier journal committed to sharing innovative methods for separation and purification in chemical and environmental engineering, encompassing both homogeneous solutions and heterogeneous mixtures. Our scope includes the separation and/or purification of liquids, vapors, and gases, as well as carbon capture and separation techniques. However, it's important to note that methods solely intended for analytical purposes are not within the scope of the journal. Additionally, disciplines such as soil science, polymer science, and metallurgy fall outside the purview of Separation and Purification Technology. Join us in advancing the field of separation and purification methods for sustainable solutions in chemical and environmental engineering.