{"title":"Ag-NiFe₂O₄在介孔二氧化硅上高效还原4-硝基苯酚:纳米催化剂的开发、动力学研究和反应优化","authors":"Nail Saleh Al Sailah , Binitha N Narayanan","doi":"10.1016/j.materresbull.2025.113455","DOIUrl":null,"url":null,"abstract":"<div><div>An innovative magnetic ternary catalyst, silver-doped nickel ferrite integrated into the nanoreactor mesoporous silica (Ag-NiFe<sub>2</sub>O<sub>4</sub>/meso-SiO<sub>2</sub>), has been synthesized, offering a promise in the catalytic transformation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). This design synergistically combines the exceptional catalytic activity of ∼3 nm silver nanoparticles (AgNPs) with the structural advantages of ordered mesoporous silica (meso-SiO<sub>2</sub>), effectively stabilizing the nanoparticles and preventing agglomeration. The incorporation of a magnetic NiFe<sub>2</sub>O<sub>4</sub> not only enhances reusability but also facilitates efficient magnetic recovery, addressing key challenges in catalyst reusability. Comprehensive characterization using XRD, FTIR spectroscopy, UV-vis DRS spectroscopy, XPS, FESEM, HRTEM, and VSM analyses confirms the material's structural integrity, mesoporosity, and robust magnetic properties. BET-BJH suface area-porosity analysis reveals a 262.18 m<sup>2</sup>/g surface area for meso-SiO<sub>2</sub>, with pore size in the range of 7.13 nm, which can accommodate both AgNPs (3 nm) and NiFe<sub>2</sub>O<sub>4</sub> (∼15-18 nm) enabling reaction inside the channels and thereby meso-SiO<sub>2</sub> acting as a nanoreactor for conversion of 4-NP. Employing a Box-Behnken design under response surface methodology, the catalyst achieved optimal reduction conditions; i.e., 0.2 mmol/L 4-NP, 5.3 mg catalyst, 49.1 mg NaBH<sub>4</sub>, and a reaction time of 12 minutes. The Ag-NiFe<sub>2</sub>O<sub>4</sub>/meso-SiO<sub>2</sub> system demonstrated first order kinetics with exceptional catalytic efficiency, operational stability over five repeated cycles, and rapid magnetic separation, showcasing its potential as a model platform for sustainable nanocatalysis. This study pioneers the integration of noble-metal nanoparticles with magnetic materials inside the mesoporous nanoreactors, setting new dimensions of advanced catalytic systems in green and efficient chemical processes.</div></div>","PeriodicalId":18265,"journal":{"name":"Materials Research Bulletin","volume":"189 ","pages":"Article 113455"},"PeriodicalIF":5.3000,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Ag-NiFe₂O₄ over Mesoporous Silica for Efficient 4-Nitrophenol Reduction: Nanocatalyst Development, Kinetics Studies and Reaction Optimization\",\"authors\":\"Nail Saleh Al Sailah , Binitha N Narayanan\",\"doi\":\"10.1016/j.materresbull.2025.113455\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>An innovative magnetic ternary catalyst, silver-doped nickel ferrite integrated into the nanoreactor mesoporous silica (Ag-NiFe<sub>2</sub>O<sub>4</sub>/meso-SiO<sub>2</sub>), has been synthesized, offering a promise in the catalytic transformation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). This design synergistically combines the exceptional catalytic activity of ∼3 nm silver nanoparticles (AgNPs) with the structural advantages of ordered mesoporous silica (meso-SiO<sub>2</sub>), effectively stabilizing the nanoparticles and preventing agglomeration. The incorporation of a magnetic NiFe<sub>2</sub>O<sub>4</sub> not only enhances reusability but also facilitates efficient magnetic recovery, addressing key challenges in catalyst reusability. Comprehensive characterization using XRD, FTIR spectroscopy, UV-vis DRS spectroscopy, XPS, FESEM, HRTEM, and VSM analyses confirms the material's structural integrity, mesoporosity, and robust magnetic properties. BET-BJH suface area-porosity analysis reveals a 262.18 m<sup>2</sup>/g surface area for meso-SiO<sub>2</sub>, with pore size in the range of 7.13 nm, which can accommodate both AgNPs (3 nm) and NiFe<sub>2</sub>O<sub>4</sub> (∼15-18 nm) enabling reaction inside the channels and thereby meso-SiO<sub>2</sub> acting as a nanoreactor for conversion of 4-NP. Employing a Box-Behnken design under response surface methodology, the catalyst achieved optimal reduction conditions; i.e., 0.2 mmol/L 4-NP, 5.3 mg catalyst, 49.1 mg NaBH<sub>4</sub>, and a reaction time of 12 minutes. The Ag-NiFe<sub>2</sub>O<sub>4</sub>/meso-SiO<sub>2</sub> system demonstrated first order kinetics with exceptional catalytic efficiency, operational stability over five repeated cycles, and rapid magnetic separation, showcasing its potential as a model platform for sustainable nanocatalysis. This study pioneers the integration of noble-metal nanoparticles with magnetic materials inside the mesoporous nanoreactors, setting new dimensions of advanced catalytic systems in green and efficient chemical processes.</div></div>\",\"PeriodicalId\":18265,\"journal\":{\"name\":\"Materials Research Bulletin\",\"volume\":\"189 \",\"pages\":\"Article 113455\"},\"PeriodicalIF\":5.3000,\"publicationDate\":\"2025-03-31\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Materials Research Bulletin\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0025540825001631\",\"RegionNum\":3,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Materials Research Bulletin","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0025540825001631","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Ag-NiFe₂O₄ over Mesoporous Silica for Efficient 4-Nitrophenol Reduction: Nanocatalyst Development, Kinetics Studies and Reaction Optimization
An innovative magnetic ternary catalyst, silver-doped nickel ferrite integrated into the nanoreactor mesoporous silica (Ag-NiFe2O4/meso-SiO2), has been synthesized, offering a promise in the catalytic transformation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). This design synergistically combines the exceptional catalytic activity of ∼3 nm silver nanoparticles (AgNPs) with the structural advantages of ordered mesoporous silica (meso-SiO2), effectively stabilizing the nanoparticles and preventing agglomeration. The incorporation of a magnetic NiFe2O4 not only enhances reusability but also facilitates efficient magnetic recovery, addressing key challenges in catalyst reusability. Comprehensive characterization using XRD, FTIR spectroscopy, UV-vis DRS spectroscopy, XPS, FESEM, HRTEM, and VSM analyses confirms the material's structural integrity, mesoporosity, and robust magnetic properties. BET-BJH suface area-porosity analysis reveals a 262.18 m2/g surface area for meso-SiO2, with pore size in the range of 7.13 nm, which can accommodate both AgNPs (3 nm) and NiFe2O4 (∼15-18 nm) enabling reaction inside the channels and thereby meso-SiO2 acting as a nanoreactor for conversion of 4-NP. Employing a Box-Behnken design under response surface methodology, the catalyst achieved optimal reduction conditions; i.e., 0.2 mmol/L 4-NP, 5.3 mg catalyst, 49.1 mg NaBH4, and a reaction time of 12 minutes. The Ag-NiFe2O4/meso-SiO2 system demonstrated first order kinetics with exceptional catalytic efficiency, operational stability over five repeated cycles, and rapid magnetic separation, showcasing its potential as a model platform for sustainable nanocatalysis. This study pioneers the integration of noble-metal nanoparticles with magnetic materials inside the mesoporous nanoreactors, setting new dimensions of advanced catalytic systems in green and efficient chemical processes.
期刊介绍:
Materials Research Bulletin is an international journal reporting high-impact research on processing-structure-property relationships in functional materials and nanomaterials with interesting electronic, magnetic, optical, thermal, mechanical or catalytic properties. Papers purely on thermodynamics or theoretical calculations (e.g., density functional theory) do not fall within the scope of the journal unless they also demonstrate a clear link to physical properties. Topics covered include functional materials (e.g., dielectrics, pyroelectrics, piezoelectrics, ferroelectrics, relaxors, thermoelectrics, etc.); electrochemistry and solid-state ionics (e.g., photovoltaics, batteries, sensors, and fuel cells); nanomaterials, graphene, and nanocomposites; luminescence and photocatalysis; crystal-structure and defect-structure analysis; novel electronics; non-crystalline solids; flexible electronics; protein-material interactions; and polymeric ion-exchange membranes.