Engineered NiO/TiO2 and CuO/NiO/TiO2 heterojunctions for sustainable direct photocatalytic epoxidation of propylene using molecular oxygen

Abstract The selective photocatalytic epoxidation of propylene using molecular oxygen under UV-A irradiation presents a promising sustainable alternative for propylene oxide (PO) production. In this study, NiO/TiO2 and CuO/NiO/TiO2 heterojunction photocatalysts were synthesized via the thermal annea...

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Main Authors: Nicola Morante, Katia Monzillo, Alessandro Padua, Andrea Muscatello, Diana Sannino, Serena Esposito, Vincenzo Vaiano
Format: Article
Language:English
Published: Springer 2025-07-01
Series:Discover Nano
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Online Access:https://doi.org/10.1186/s11671-025-04296-6
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author Nicola Morante
Katia Monzillo
Alessandro Padua
Andrea Muscatello
Diana Sannino
Serena Esposito
Vincenzo Vaiano
author_facet Nicola Morante
Katia Monzillo
Alessandro Padua
Andrea Muscatello
Diana Sannino
Serena Esposito
Vincenzo Vaiano
author_sort Nicola Morante
collection DOAJ
description Abstract The selective photocatalytic epoxidation of propylene using molecular oxygen under UV-A irradiation presents a promising sustainable alternative for propylene oxide (PO) production. In this study, NiO/TiO2 and CuO/NiO/TiO2 heterojunction photocatalysts were synthesized via the thermal annealing of sol-gel-derived TiO2 and tested in a fluidized bed photoreactor. Structural and optical characterizations confirmed the successful deposition of NiO onto TiO2 and highlighted the crucial role of NiO content in optimizing charge separation and catalytic efficiency. Among the NiO/TiO2 series, the NiO(1.1%)/TiO2 composite exhibited the lowest photoluminescence intensity, indicating reduced electron–hole recombination, while UV–Vis DRS analysis revealed a red shift in the absorption onset and a reduction in the band gap energy. These features resulted in enhanced light absorption and facilitated charge transfer, leading to superior photocatalytic performance compared to lower and higher NiO loadings. Under irradiation, NiO(1.1%)/TiO2 achieved a propylene conversion of 52.5%, a selectivity to PO of 83.4%, and a PO yield of 43.8%, confirming its effectiveness in promoting selective epoxidation. The introduction of CuO to form the CuO(1.1%)/NiO(1.1%)/TiO2 heterojunction further enhanced the catalytic performance, reaching 61% propylene conversion, 92% selectivity to PO, and a PO yield of 56%. The improved activity was attributed to the efficient conversion of molecular oxygen into hydrogen peroxide, which acts as a selective oxidant for epoxide formation. Process optimization revealed that water vapor (1000 ppm) significantly enhanced PO selectivity, while incident light intensity played a crucial role in determining conversion rates. The system exhibited excellent stability over 24 h of continuous operation, with no observable deactivation. Furthermore, an energy efficiency analysis demonstrated an exceptionally low energy consumption of 0.019 kWh per mole of propylene converted, significantly outperforming existing photocatalytic systems. These findings highlight the potential of CuO/NiO/TiO2-based photocatalysts, combined with fluidized bed reactors, as an energy-efficient and scalable approach for sustainable PO production.
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spelling doaj-art-71fb395b9f0e468eab8342680f3bf3dd2025-08-20T03:06:02ZengSpringerDiscover Nano2731-92292025-07-0120113010.1186/s11671-025-04296-6Engineered NiO/TiO2 and CuO/NiO/TiO2 heterojunctions for sustainable direct photocatalytic epoxidation of propylene using molecular oxygenNicola Morante0Katia Monzillo1Alessandro Padua2Andrea Muscatello3Diana Sannino4Serena Esposito5Vincenzo Vaiano6Department of Industrial Engineering, University of SalernoDepartment of Industrial Engineering, University of SalernoDepartment of Applied Science and Technology and INSTM Unit of Turin– Politecnico, Politecnico Di TorinoDepartment of Applied Science and Technology and INSTM Unit of Turin– Politecnico, Politecnico Di TorinoDepartment of Industrial Engineering, University of SalernoDepartment of Applied Science and Technology and INSTM Unit of Turin– Politecnico, Politecnico Di TorinoDepartment of Industrial Engineering, University of SalernoAbstract The selective photocatalytic epoxidation of propylene using molecular oxygen under UV-A irradiation presents a promising sustainable alternative for propylene oxide (PO) production. In this study, NiO/TiO2 and CuO/NiO/TiO2 heterojunction photocatalysts were synthesized via the thermal annealing of sol-gel-derived TiO2 and tested in a fluidized bed photoreactor. Structural and optical characterizations confirmed the successful deposition of NiO onto TiO2 and highlighted the crucial role of NiO content in optimizing charge separation and catalytic efficiency. Among the NiO/TiO2 series, the NiO(1.1%)/TiO2 composite exhibited the lowest photoluminescence intensity, indicating reduced electron–hole recombination, while UV–Vis DRS analysis revealed a red shift in the absorption onset and a reduction in the band gap energy. These features resulted in enhanced light absorption and facilitated charge transfer, leading to superior photocatalytic performance compared to lower and higher NiO loadings. Under irradiation, NiO(1.1%)/TiO2 achieved a propylene conversion of 52.5%, a selectivity to PO of 83.4%, and a PO yield of 43.8%, confirming its effectiveness in promoting selective epoxidation. The introduction of CuO to form the CuO(1.1%)/NiO(1.1%)/TiO2 heterojunction further enhanced the catalytic performance, reaching 61% propylene conversion, 92% selectivity to PO, and a PO yield of 56%. The improved activity was attributed to the efficient conversion of molecular oxygen into hydrogen peroxide, which acts as a selective oxidant for epoxide formation. Process optimization revealed that water vapor (1000 ppm) significantly enhanced PO selectivity, while incident light intensity played a crucial role in determining conversion rates. The system exhibited excellent stability over 24 h of continuous operation, with no observable deactivation. Furthermore, an energy efficiency analysis demonstrated an exceptionally low energy consumption of 0.019 kWh per mole of propylene converted, significantly outperforming existing photocatalytic systems. These findings highlight the potential of CuO/NiO/TiO2-based photocatalysts, combined with fluidized bed reactors, as an energy-efficient and scalable approach for sustainable PO production.https://doi.org/10.1186/s11671-025-04296-6PropylenePhotoepoxidationPropylene oxidePhotocatalysisNiO/TiO2CuO/NiO/TiO2
spellingShingle Nicola Morante
Katia Monzillo
Alessandro Padua
Andrea Muscatello
Diana Sannino
Serena Esposito
Vincenzo Vaiano
Engineered NiO/TiO2 and CuO/NiO/TiO2 heterojunctions for sustainable direct photocatalytic epoxidation of propylene using molecular oxygen
Discover Nano
Propylene
Photoepoxidation
Propylene oxide
Photocatalysis
NiO/TiO2
CuO/NiO/TiO2
title Engineered NiO/TiO2 and CuO/NiO/TiO2 heterojunctions for sustainable direct photocatalytic epoxidation of propylene using molecular oxygen
title_full Engineered NiO/TiO2 and CuO/NiO/TiO2 heterojunctions for sustainable direct photocatalytic epoxidation of propylene using molecular oxygen
title_fullStr Engineered NiO/TiO2 and CuO/NiO/TiO2 heterojunctions for sustainable direct photocatalytic epoxidation of propylene using molecular oxygen
title_full_unstemmed Engineered NiO/TiO2 and CuO/NiO/TiO2 heterojunctions for sustainable direct photocatalytic epoxidation of propylene using molecular oxygen
title_short Engineered NiO/TiO2 and CuO/NiO/TiO2 heterojunctions for sustainable direct photocatalytic epoxidation of propylene using molecular oxygen
title_sort engineered nio tio2 and cuo nio tio2 heterojunctions for sustainable direct photocatalytic epoxidation of propylene using molecular oxygen
topic Propylene
Photoepoxidation
Propylene oxide
Photocatalysis
NiO/TiO2
CuO/NiO/TiO2
url https://doi.org/10.1186/s11671-025-04296-6
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