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Rising consumption and cost of fossil fuels invite the researchers to discover the renewable energy sources. Herein, a novel approach to enhance the photocatalytic performances of rutile-TiO 2 has been revealed. To boost the hydrogen generation reactions, Pd/Rb 2 O cocatalysts have been deposited over TiO 2 via chemical reduction. The morphology and optical characteristics of catalysts were demonstrated by XRD, Raman, UV-Vis/DRS, SEM and TEM analysis. Surface properties, particle sizes, and chemical composition were examined via AFM and XPS techniques. The H 2 production activities were monitored by GC-TCD (Shimadzu-2010/Japan). Comparatively, Pd 1.8 /RbO 0.2 @TiO 2 was found most active catalysts that can deliver hydrogen 22.74 mmolg−1h−1. Higher H 2 generation activities were attributed to the presence of Pd and Rb 2 O cocatalysts. Rb 2 O promoted electrons from TiO 2 to Pd active sites by elevation in fermi energy levels to attain the equilibrium during photoreactions. The mechanistic approach for higher electron transportation and better charge separation has been demonstrated and discussed over here. On the basis of results, it can be concluded that the work reported here in is reliable for sustainable energy applications. [Display omitted] [ABSTRACT FROM AUTHOR]