Reaction of Al metal with water is a well-known technique for large scale production of hydrogen. However, this method suffers from kinetic limitations due to formation of a passivation layer on Al, preventing optimal operations. Using high resolution Scanning Kelvin Probe Force Microscopy (SKPFM), we show the origin of formation of ‘nano-galvanic couple’ on in situ formed nano-aluminum amalgam surfaces in a water splitting system; passivation based limitations are completely bypassed in this approach. Furthermore, they offer an opportunity to beneficiate and recover mercury in contaminated water. The nano-galvanic corrosion due to substantial lateral variation in surface contact potential is responsible for the observed high throughput of hydrogen production (720 mL/min per 0.5 g Al salt). It may be noted that this process fares better than in situ prepared nano-Al based hydrogen production, wherein 600 mL/min of hydrogen is obtained for 0.5 g Al salt. Investigations using Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) provide evidence for passivation-bypassed hydrolysis and favourable kinetics for in situ derived nano-AlHg hydrolytic agents (when compared to nano-Al). This study, to the best of our knowledge, reports the first direct proof of nano-galvanic couple formation on in-situ prepared nanoaluminum amalgam surface; paving a direct way to overcome the long standing passivation problem in Al hydrolysis. It is found that the hydrogen production rate and standard deviation (SD) of the contact potential of nanoaluminum amalgam are directly related to the rate of addition of the reducing agent, offering an opportunity for kinetic control for the in situ hydrolytic process. © 2018 Hydrogen Energy Publications LLC