Anees, M.P.K.Iniyan, S.Pratap Singh, C.Murugavel, M.Krishnamurty, S.Mal, S.S.2026-02-032025Dalton Transactions, 2025, , , pp. -14779226https://doi.org/10.1039/d5dt02621khttps://idr.nitk.ac.in/handle/123456789/20562Recent advancements in pseudocapacitive materials for energy storage and catalytic activities highlight the benefits of incorporating nanostructured active materials. This study investigates the modification of polypyrrole (PPy) surfaces using polyoxometalate H<inf>4</inf>[PVMo<inf>11</inf>O<inf>40</inf>].xH<inf>2</inf>O (PVMo<inf>11</inf>) combined with ionic liquids hexadecyltrimethylammonium chloride (CTAC) and 1-benzyl-3-methylimidazolium chloride (BMI). Among various synthesized nanocomposites, PVMo<inf>11</inf>-BMI-PPy demonstrated superior electrochemical properties in a 0.25 M H<inf>2</inf>SO<inf>4</inf> aqueous electrolyte, achieving a remarkable specific capacitance of 400 F g?1, an energy density of 49.5 W h kg?1 and a power density of 906 W kg?1 at a current density of 1 A g?1. It achieves a capacitive contribution of 94.5% at 10 mV s?1 with an impressive cyclic retention rate of 91.1% and a coulombic efficiency of 98.9% after 10?000 GCD cycles. Additionally, PVMo<inf>11</inf>-BMI-PPy exhibited outstanding electrocatalytic activity for hydrogen evolution reaction (HER), achieving the highest catalytic activity of 19 mV at a current density of 10 mA cm?2, outperforming the benchmark Pt catalyst. Its superior performance is underscored by a high TOF of 6.91 × 10?7 s?1 and excellent long-term stability in 0.5 M H<inf>2</inf>SO<inf>4</inf> over 24 hours. It is a promising candidate for bifunctional activities such as energy storage and catalytic applications. Additionally, density functional theory (DFT) studies were conducted to gain insights into the enhanced performance of PVMo<inf>11</inf>-BMI-PPy. The thermodynamic and electronic characteristics indicate that the V site of PVMo<inf>11</inf>-BMI-PPy offers the most efficient and balanced catalytic environment for hydrogen evolution reaction (HER) compared with all other sites examined. These theoretical findings align well with experimental observations, demonstrating superior HER activity of the PVMo<inf>11</inf>-BMI-PPy catalyst, thereby confirming the computational predictions. This journal is © The Royal Society of Chemistry, 2026Catalyst activityDensity functional theoryElectrolytesHydrogen evolution reactionHydrogen storageIonic liquids'currentEnergyFunctionalsHydrogen evolution reactionsHydrogen-evolutionMethylimidazolium chloridePerformancePhosphomolybdic acidPseudo-capacitive materialsTheoretical studyNanocomposites