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| Main Authors: | , , , , , |
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| Format: | Preprint |
| Published: |
2025
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| Subjects: | |
| Online Access: | https://arxiv.org/abs/2510.24176 |
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| _version_ | 1866914342967967744 |
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| author | Nizkaia, Tatiana Groppe, Philipp Müller, Valentin Harting, Jens Wintzheimer, Susanne Malgaretti, Paolo |
| author_facet | Nizkaia, Tatiana Groppe, Philipp Müller, Valentin Harting, Jens Wintzheimer, Susanne Malgaretti, Paolo |
| contents | The reduction of 4-nitrophenol (4-NiP) with sodium borohydride is widely used to benchmark heterogeneous catalysts, yet its kinetics are commonly oversimplified as pseudo-first-order. In reality, borohydride hydrolysis and hydrogenation by dissolved hydrogen proceed concurrently, making hydrogen transport a decisive factor in shaping apparent activity. Re-examining data on Pt-SiO2 supraparticles with different pore structures, we attribute contrasting kinetic behavior to distinct regimes of hydrogen transport: diffusive transport sustains pseudo-first-order kinetics, while bubble-mediated escape causes hydrogen loss and incomplete conversion. We propose a kinetic model that captures this transition and enables consistent interpretation of experimental data. More broadly, our analysis shows that apparent differences in activity during 4-NiP benchmarking can arise from hydrogen transport rather than intrinsic properties of the catalyst, underscoring the need to account for transport effects when comparing catalyst performance. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2510_24176 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Effects of Hydrogen Transport on the Kinetic Regimes of 4-Nitrophenol Reduction by Sodium Borohydride Nizkaia, Tatiana Groppe, Philipp Müller, Valentin Harting, Jens Wintzheimer, Susanne Malgaretti, Paolo Chemical Physics The reduction of 4-nitrophenol (4-NiP) with sodium borohydride is widely used to benchmark heterogeneous catalysts, yet its kinetics are commonly oversimplified as pseudo-first-order. In reality, borohydride hydrolysis and hydrogenation by dissolved hydrogen proceed concurrently, making hydrogen transport a decisive factor in shaping apparent activity. Re-examining data on Pt-SiO2 supraparticles with different pore structures, we attribute contrasting kinetic behavior to distinct regimes of hydrogen transport: diffusive transport sustains pseudo-first-order kinetics, while bubble-mediated escape causes hydrogen loss and incomplete conversion. We propose a kinetic model that captures this transition and enables consistent interpretation of experimental data. More broadly, our analysis shows that apparent differences in activity during 4-NiP benchmarking can arise from hydrogen transport rather than intrinsic properties of the catalyst, underscoring the need to account for transport effects when comparing catalyst performance. |
| title | Effects of Hydrogen Transport on the Kinetic Regimes of 4-Nitrophenol Reduction by Sodium Borohydride |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2510.24176 |