Catalytically Active Oxidized PtOx Species on SnO<sub>2</sub> Supports Synthesized via Anion Exchange Reaction for 4-Nitrophenol Reduction
An anion exchange-assisted technique was used for the synthesis of platinum-decorated SnO<sub>2</sub> supports, providing nanocatalysts with enhanced activity for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). In this study, a series of SnO<sub>2</sub> support...
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MDPI AG
2025-07-01
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| author | Izabela Ðurasović Robert Peter Goran Dražić Fabio Faraguna Rafael Anelić Marijan Marciuš Tanja Jurkin Vlasta Mohaček Grošev Maria Gracheva Zoltán Klencsár Mile Ivanda Goran Štefanić Marijan Gotić |
| author_facet | Izabela Ðurasović Robert Peter Goran Dražić Fabio Faraguna Rafael Anelić Marijan Marciuš Tanja Jurkin Vlasta Mohaček Grošev Maria Gracheva Zoltán Klencsár Mile Ivanda Goran Štefanić Marijan Gotić |
| author_sort | Izabela Ðurasović |
| collection | DOAJ |
| description | An anion exchange-assisted technique was used for the synthesis of platinum-decorated SnO<sub>2</sub> supports, providing nanocatalysts with enhanced activity for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). In this study, a series of SnO<sub>2</sub> supports, namely SnA (synthesized almost at room temperature), SnB (hydrothermally treated at 180 °C), and SnC (annealed at 600 °C), are systematically investigated, all loaded with 1 mol% Pt from H<sub>2</sub>PtCl<sub>6</sub> under identical mild conditions. The chloride ions from the SnCl<sub>4</sub> precursors were efficiently removed via a strong-base anion exchange reaction, resulting in highly dispersed, crystalline ~5 nm cassiterite SnO<sub>2</sub> particles. All Pt/SnO<sub>2</sub> composites displayed mesoporous structures with type IVa isotherms and H<sub>2</sub>-type hysteresis, with SP1a (Pt on SnA) exhibiting the largest surface area (122.6 m<sup>2</sup>/g) and the smallest pores (~3.5 nm). STEM-HAADF imaging revealed well-dispersed PtOx domains (~0.85 nm), while XPS confirmed the dominant Pt<sup>4+</sup> and Pt<sup>2+</sup> species, with ~25% Pt<sup>0</sup> likely resulting from photoreduction and/or interactions with Sn–OH surface groups. Raman spectroscopy revealed three new bands (260–360 cm<sup>−1</sup>) that were clearly visible in the sample with 10 mol% Pt and were due to the vibrational modes of the PtOx species and Pt-Cl bonds introduced due the addition and hydrolysis of H<sub>2</sub>PtCl<sub>6</sub> precursor. TGA/DSC analysis revealed the highest mass loss for SP1a (~7.3%), confirming the strong hydration of the PtOx domains. Despite the predominance of oxidized PtOx species, SP1a exhibited the highest catalytic activity (<i>k</i><sub>app</sub> = 1.27 × 10<sup>−2</sup> s<sup>−1</sup>) and retained 84.5% activity for the reduction of 4-NP to 4-AP after 10 cycles. This chloride-free low-temperature synthesis route offers a promising and generalizable strategy for the preparation of noble metal-based nanocatalysts on oxide supports with high catalytic activity and reusability. |
| format | Article |
| id | doaj-art-1f3eb1c60c3f4ea394f6d1db9315ff20 |
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| publishDate | 2025-07-01 |
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| spelling | doaj-art-1f3eb1c60c3f4ea394f6d1db9315ff202025-08-20T03:02:55ZengMDPI AGNanomaterials2079-49912025-07-011515115910.3390/nano15151159Catalytically Active Oxidized PtOx Species on SnO<sub>2</sub> Supports Synthesized via Anion Exchange Reaction for 4-Nitrophenol ReductionIzabela Ðurasović0Robert Peter1Goran Dražić2Fabio Faraguna3Rafael Anelić4Marijan Marciuš5Tanja Jurkin6Vlasta Mohaček Grošev7Maria Gracheva8Zoltán Klencsár9Mile Ivanda10Goran Štefanić11Marijan Gotić12Laboratory for Molecular Physics and Synthesis of New Materials, Division of Materials Physics, Ruđer Bošković Institute, Bijenička c. 54, 10000 Zagreb, CroatiaDepartment of Physics, University of Rijeka, Radmile Matejčić 2, 51000 Rijeka, CroatiaNational Institute of Chemistry, Hajdrihova 19, SI-1001 Ljubljana, SloveniaPetroleum and Petrochemical Department, Faculty of Chemical Engineering and Technology, University of Zagreb, Trg Marka Marulića Trg 19, 10000 Zagreb, CroatiaPetroleum and Petrochemical Department, Faculty of Chemical Engineering and Technology, University of Zagreb, Trg Marka Marulića Trg 19, 10000 Zagreb, CroatiaDivision of Materials Chemistry, Ruđer Bošković Institute, Bijenička c. 54, 10000 Zagreb, CroatiaRadiation Chemistry and Dosimetry Laboratory, Division of Materials Chemistry, Ruđer Bošković Institute, Bijenička c. 54, 10000 Zagreb, CroatiaLaboratory for Molecular Physics and Synthesis of New Materials, Division of Materials Physics, Ruđer Bošković Institute, Bijenička c. 54, 10000 Zagreb, CroatiaBudapest Neutron Centre, HUN-REN Centre for Energy Research, Konkoly-Thege Miklós út 29-33, 1121 Budapest, HungaryBudapest Neutron Centre, HUN-REN Centre for Energy Research, Konkoly-Thege Miklós út 29-33, 1121 Budapest, HungaryLaboratory for Molecular Physics and Synthesis of New Materials, Division of Materials Physics, Ruđer Bošković Institute, Bijenička c. 54, 10000 Zagreb, CroatiaLaboratory for Molecular Physics and Synthesis of New Materials, Division of Materials Physics, Ruđer Bošković Institute, Bijenička c. 54, 10000 Zagreb, CroatiaLaboratory for Molecular Physics and Synthesis of New Materials, Division of Materials Physics, Ruđer Bošković Institute, Bijenička c. 54, 10000 Zagreb, CroatiaAn anion exchange-assisted technique was used for the synthesis of platinum-decorated SnO<sub>2</sub> supports, providing nanocatalysts with enhanced activity for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). In this study, a series of SnO<sub>2</sub> supports, namely SnA (synthesized almost at room temperature), SnB (hydrothermally treated at 180 °C), and SnC (annealed at 600 °C), are systematically investigated, all loaded with 1 mol% Pt from H<sub>2</sub>PtCl<sub>6</sub> under identical mild conditions. The chloride ions from the SnCl<sub>4</sub> precursors were efficiently removed via a strong-base anion exchange reaction, resulting in highly dispersed, crystalline ~5 nm cassiterite SnO<sub>2</sub> particles. All Pt/SnO<sub>2</sub> composites displayed mesoporous structures with type IVa isotherms and H<sub>2</sub>-type hysteresis, with SP1a (Pt on SnA) exhibiting the largest surface area (122.6 m<sup>2</sup>/g) and the smallest pores (~3.5 nm). STEM-HAADF imaging revealed well-dispersed PtOx domains (~0.85 nm), while XPS confirmed the dominant Pt<sup>4+</sup> and Pt<sup>2+</sup> species, with ~25% Pt<sup>0</sup> likely resulting from photoreduction and/or interactions with Sn–OH surface groups. Raman spectroscopy revealed three new bands (260–360 cm<sup>−1</sup>) that were clearly visible in the sample with 10 mol% Pt and were due to the vibrational modes of the PtOx species and Pt-Cl bonds introduced due the addition and hydrolysis of H<sub>2</sub>PtCl<sub>6</sub> precursor. TGA/DSC analysis revealed the highest mass loss for SP1a (~7.3%), confirming the strong hydration of the PtOx domains. Despite the predominance of oxidized PtOx species, SP1a exhibited the highest catalytic activity (<i>k</i><sub>app</sub> = 1.27 × 10<sup>−2</sup> s<sup>−1</sup>) and retained 84.5% activity for the reduction of 4-NP to 4-AP after 10 cycles. This chloride-free low-temperature synthesis route offers a promising and generalizable strategy for the preparation of noble metal-based nanocatalysts on oxide supports with high catalytic activity and reusability.https://www.mdpi.com/2079-4991/15/15/1159platinumSnO<sub>2</sub>anion exchangeDowex 550catalyst4-nitrophenol |
| spellingShingle | Izabela Ðurasović Robert Peter Goran Dražić Fabio Faraguna Rafael Anelić Marijan Marciuš Tanja Jurkin Vlasta Mohaček Grošev Maria Gracheva Zoltán Klencsár Mile Ivanda Goran Štefanić Marijan Gotić Catalytically Active Oxidized PtOx Species on SnO<sub>2</sub> Supports Synthesized via Anion Exchange Reaction for 4-Nitrophenol Reduction Nanomaterials platinum SnO<sub>2</sub> anion exchange Dowex 550 catalyst 4-nitrophenol |
| title | Catalytically Active Oxidized PtOx Species on SnO<sub>2</sub> Supports Synthesized via Anion Exchange Reaction for 4-Nitrophenol Reduction |
| title_full | Catalytically Active Oxidized PtOx Species on SnO<sub>2</sub> Supports Synthesized via Anion Exchange Reaction for 4-Nitrophenol Reduction |
| title_fullStr | Catalytically Active Oxidized PtOx Species on SnO<sub>2</sub> Supports Synthesized via Anion Exchange Reaction for 4-Nitrophenol Reduction |
| title_full_unstemmed | Catalytically Active Oxidized PtOx Species on SnO<sub>2</sub> Supports Synthesized via Anion Exchange Reaction for 4-Nitrophenol Reduction |
| title_short | Catalytically Active Oxidized PtOx Species on SnO<sub>2</sub> Supports Synthesized via Anion Exchange Reaction for 4-Nitrophenol Reduction |
| title_sort | catalytically active oxidized ptox species on sno sub 2 sub supports synthesized via anion exchange reaction for 4 nitrophenol reduction |
| topic | platinum SnO<sub>2</sub> anion exchange Dowex 550 catalyst 4-nitrophenol |
| url | https://www.mdpi.com/2079-4991/15/15/1159 |
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