Summary Recent increase in energy demand and associated environmental degradation concern has triggered more research towards alternative green energy sources. Eco‐friendly energy in facile way has been generated from abundantly available iron oxides using only few microliters of water without any external energy source. Hydroelectric cell (HEC) compatible to environment benign, low cost oxygen‐deficient mesoporous hematite nanoparticles has been used for splitting water molecules spontaneously to generate green electricity. Hematite nanoparticles have been synthesized by coprecipitation method. Chemidissociated hydroxyl group presence on hematite surface has been confirmed by infrared spectroscopy (IR) and X‐ray photoelectron spectroscopy (XPS). Surface oxygen vacancies in nanostructured hematite have been identified by transmission electron microscopy (TEM), XPS, and photoluminescence (PL) measurement. Hematite‐based HEC delivers 30 mA current with 0.92 V emf using approximately 500 μL water. Maximum off‐load output power 27.6 mW delivered by 4.84 cm2 area hematite‐based HEC is 3.52 times higher than reported 7.84 mW power generated by Li‐magnesium ferrite HEC. Electrochemistry of HEC in different irreversible polarization loss regions has been estimated by applying empirical modeling on V‐I polarization curve revealing the reaction and charge transport mechanism of cell. Tafel slope 22.7 mV has been calculated by modeling of activation polarization overvoltage region of 0.11 V. Low activation polarization indicated easy charge/ion diffusion and faster reaction kinetics of Ag/Zn electrode owing to lesser energy barrier at interface. Dissociated H3O+ ions diffuse through surface via proton hopping, while OH− ions migrate through interconnected defective crystallite boundaries resulting into high output cell current.

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There is no signature of the trap filled limit voltage (VTFL) in the J-V characteristics of a sample containing exponentially distributed traps. We show that VTFL and the voltage at which V2 dependence sets in (VMott) can be determined accurately. These voltages are independent of the energy distributions of the traps and depend strongly on the trap density Hb. Contrary to the literature results, it turns out that VTFL is significantly smaller than the VMott. In a specific case with Hb=1.6×1018cm−3 and for a 5% accuracy in the current the value of VMott is about 400V whereas VTFL is 13.5V. Universal J-V curves in reduced units are derived and plotted. The reduced value of VTFL is 0.5. These curves are valid for all organics and inorganic semiconductors and for all energy distributions of traps. It is shown mathematically that all J-V curves approached Mott’s V2 law asymptotically as V increases to infinity. To validate the theory, the experimental J-V curves in polycrystalline undoped and Al doped ZnO thin films are made. The experimental results show good agreement with the theory. In the undoped ZnO films the traps are exponentially distributed and the trap concentration is calculated to be 1.7×1017cm−3. The trap distribution in Al doped ZnO films is found to be discrete at a single level with trap concentration of 8×1016cm−3.

Never before has electricity been generated out of metal oxides without using any light (UV/IR), acid, or alkali, but it has been achieved by adding a few drops of water on nanoporous metal oxide based Hydroelectric cell (HEC) at room temperature. Electricity generation has been validated and unified for six different metal oxides based on the principle of water dissociation at oxygen deficient nonporous pellet. The presence of oxygen vacancies on the surface of all metal oxide samples has been confirmed by Raman and Photoluminescence spectroscopy techniques. Tin oxide (SnO2) based HEC has delivered maximum power ∼16.6 mW in a 4.48 cm2 cell area with highest current 22.2 mA, approximately 2.075 times higher than reported 8 mA current in ferrite based HEC. Water chemidissociation at metal oxide surface was found to be reinforced predominantly by electronegativity of metal cations and oxygen vacancies on nanoporous surface. Divergent peak current values ranging from 22.2 to 1.1 mA were obtained depending on internal resistance, grain boundary nature, water molecule dissociation capability, and nanopores connectivity in different oxides. Slow diffusion of ions in certain metal oxides due to high impedance of grain boundaries has reduced current as confirmed by dielectric and impedance spectroscopy. Metal oxide HEC provides an ecofriendly, cost-effective, and portable green energy source with almost no running cost.