PbTe-PbS/TiO2 electrodes are produced via wet chemical routes for splitting water into hydrogen at the ambient temperatures. PbTe nano-crystals are firstly deposited via the successive ionic layer adsorption and reaction (SILAR) treatment onto TiO2 nanotube arrays (TNAs) prepared by anodic oxidation of Ti substrates. Subsequently, linear sweep voltammetry (LSV) is employed to convert the outer PbTe into PbS, producing PbTe-PbSiTiO2 electrodes with a gradient p-n-n band configuration. With the external electric field, the vector charge transfer effect of the TNAs and the gradient energy band structure of PbTe-PbS/TNAs, the two electrode system in which PbTe-PbS/TNAs functions as the anode illustrates excellent hydrogen production activities. The whole electrochemical system consisted of anode, cathode, electrolyte serves as a hot side while the endothermic electrochemical reactions in hydrogen production as an in situ cold side. At 70 degrees C and 1.0 V bath voltage, the system registers 6.1 mL cm(-2) h(-1) rate of hydrogen generation, consuming electric power of 26.2 kW h kg(-1) H-2, with an energy efficiency of 88.5% and a heat efficiency of 49.9%. This method demonstrates a novel pathway to produce chemical energy from low quality waste heat, benefitting from thermoelectric and electrocatalytic coupling. (C) 2016 Elsevier B.V. All rights reserved.