This study presents the development of Cu-doped NiMo/TiO
2 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 NiTiO
3 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 m
2·g
−1 for NiMoCu400, and electrochemical measurements confirmed its higher electrochemically active surface area (ECSA, 2.4 cm
2), indicating enhanced surface accessibility. In contrast, NiMoCu900 exhibited a much lower BET surface area (1.4 m
2·g
−1) and ECSA (1.4 cm
2), consistent with its inferior photoelectrocatalytic performance. Compared to previously reported binary NiMo/TiO
2 systems, the ternary NiMoCu/TiO
2 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/TiO
2 as a promising bifunctional platform for integrated solar-driven water treatment and sustainable hydrogen production.
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