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Article

Copper-Enhanced NiMo/TiO2 Catalysts for Bifunctional Green Hydrogen Production and Pharmaceutical Pollutant Removal

by
Nicolás Alejandro Sacco
1,
Fernanda Albana Marchesini
1,
Ilaria Gamba
2 and
Gonzalo García
2,*
1
Instituto de Investigaciones en Catálisis y Petroquímica, INCAPE (UNL-CONICET), Facultad de Ingeniería Química, Santa Fe 3000, Argentina
2
Instituto Universitario de Materiales y Nanotecnología, Departamento de Química, Universidad de La Laguna, 38200 La Laguna, Santa Cruz de Tenerife, Spain
*
Author to whom correspondence should be addressed.
Catalysts 2025, 15(8), 737; https://doi.org/10.3390/catal15080737 (registering DOI)
Submission received: 8 June 2025 / Revised: 26 July 2025 / Accepted: 30 July 2025 / Published: 1 August 2025
(This article belongs to the Section Electrocatalysis)

Abstract

This study presents the development of Cu-doped NiMo/TiO2 photoelectrocatalysts for simultaneous green hydrogen production and pharmaceutical pollutant removal under simulated solar irradiation. The catalysts were synthesized via wet impregnation (15 wt.% total metal loading with 0.6 wt.% Cu) and thermally treated at 400 °C and 900 °C to investigate structural transformations and catalytic performance. Comprehensive characterization (XRD, BET, SEM, XPS) revealed phase transitions, enhanced crystallinity, and redistribution of redox states upon Cu incorporation, particularly the formation of NiTiO3 and an increase in oxygen vacancies. Crystallite sizes for anatase, rutile, and brookite ranged from 21 to 47 nm at NiMoCu400, while NiMoCu900 exhibited only the rutile phase with 55 nm crystallites. BET analysis showed a surface area of 44.4 m2·g−1 for NiMoCu400, and electrochemical measurements confirmed its higher electrochemically active surface area (ECSA, 2.4 cm2), indicating enhanced surface accessibility. In contrast, NiMoCu900 exhibited a much lower BET surface area (1.4 m2·g−1) and ECSA (1.4 cm2), consistent with its inferior photoelectrocatalytic performance. Compared to previously reported binary NiMo/TiO2 systems, the ternary NiMoCu/TiO2 catalysts demonstrated significantly improved hydrogen production activity and more efficient photoelectrochemical degradation of paracetamol. Specifically, NiMoCu400 showed an anodic peak current of 0.24 mA·cm−2 for paracetamol oxidation, representing a 60% increase over NiMo400 and a cathodic current of –0.46 mA·cm−2 at –0.1 V vs. RHE under illumination, nearly six times higher than the undoped counterpart (–0.08 mA·cm−2). Mott–Schottky analysis further revealed that NiMoCu400 retained n-type behavior, while NiMoCu900 exhibited an unusual inversion to p-type, likely due to Cu migration and rutile-phase-induced realignment of donor states. Despite its higher photosensitivity, NiMoCu900 showed negligible photocurrent, confirming that structural preservation and surface redox activity are critical for photoelectrochemical performance. This work provides mechanistic insight into Cu-mediated photoelectrocatalysis and identifies NiMoCu/TiO2 as a promising bifunctional platform for integrated solar-driven water treatment and sustainable hydrogen production.
Keywords: green hydrogen production; photoelectrochemical oxidation of paracetamol; NiMoCu; TiO2 supported photocatalysts; electrocatalysis; catalysis; photoelectrocatalysis green hydrogen production; photoelectrochemical oxidation of paracetamol; NiMoCu; TiO2 supported photocatalysts; electrocatalysis; catalysis; photoelectrocatalysis

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MDPI and ACS Style

Sacco, N.A.; Marchesini, F.A.; Gamba, I.; García, G. Copper-Enhanced NiMo/TiO2 Catalysts for Bifunctional Green Hydrogen Production and Pharmaceutical Pollutant Removal. Catalysts 2025, 15, 737. https://doi.org/10.3390/catal15080737

AMA Style

Sacco NA, Marchesini FA, Gamba I, García G. Copper-Enhanced NiMo/TiO2 Catalysts for Bifunctional Green Hydrogen Production and Pharmaceutical Pollutant Removal. Catalysts. 2025; 15(8):737. https://doi.org/10.3390/catal15080737

Chicago/Turabian Style

Sacco, Nicolás Alejandro, Fernanda Albana Marchesini, Ilaria Gamba, and Gonzalo García. 2025. "Copper-Enhanced NiMo/TiO2 Catalysts for Bifunctional Green Hydrogen Production and Pharmaceutical Pollutant Removal" Catalysts 15, no. 8: 737. https://doi.org/10.3390/catal15080737

APA Style

Sacco, N. A., Marchesini, F. A., Gamba, I., & García, G. (2025). Copper-Enhanced NiMo/TiO2 Catalysts for Bifunctional Green Hydrogen Production and Pharmaceutical Pollutant Removal. Catalysts, 15(8), 737. https://doi.org/10.3390/catal15080737

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