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Herein, we report the synthesis of titania supported Rh(0) nanoparticles (Rh0/TiO2) as electrocatalyst for hydrogen evolution reaction (HER) in acidic medium. Rhodium nanoparticles with an average particle size of 2.54 nm are found to be well-dispersed on TiO2 surface. Rh0/TiO2 with very low loading density (3.79 μg cm−2) was attached on the glassy carbon electrode (GCE) by drop-casting method. Electrocatalytic performance of modified GCE was investigated via linear sweep voltammetry (LSV) in 0.5 M aqueous H2SO4 solution after 2000 cycle treatment (Rh0/TiO2-2000) and it was found that Rh0/TiO2-2000 on GCE exhibits superior electrocatalytic activity (TOF: 11.45 s−1 at η = 100 mV, η 0:−28 mV, η 10 mA cm −2: −37 mV, j0: 0.686 mA cm−2 and Tafel slope: 32 Mv dec−1). More importantly, it provides outstanding long-term stability (10000 cycles) at room temperature for HER, which makes Rh0/TiO2-2000 a promising electrocatalyst for hydrogen generation.

High Durability and Electrocatalytic Activity Toward Hydrogen Evolution Reaction with Ultralow Rhodium Loading on Titania