In this work, we report heterogeneous catalysis of bicarbonate reduction to formate (FA) using silver nanoparticles (Ag NP) and silver nanoclusters (Ag NC) supported on multi-wall carbon nanotubes (MWCNT). FA detection was performed by substrate generation/tip collection (SG/TC) mode of scanning electrochemical microscopy (SECM) using Pt UME in 100 mM HCO3 at pH 8. The Ag NP and Ag NC showed high carbonate reduction current, and similar activity as massive gold electrode targets them as alternative catalysts for FA production. Prior to bicarbonate reduction, the electrochemical activity of Ag NP and Ag NC was evaluated using carbon fiber ultra microelectrodes (UME), these carbon UME were fabricated and characterized for use in SCEM mapping; carbon UME provided an excellent feedback response and are dispensable electrodes with renewable surfaces. Also, a carbon UME enables the fabrication of an enzymatic sensor which was designed for NAD(+) (Nicotine amide dinucleotide) dependent formate dehydrogenase immobilization. The enzymatic reaction coupled with the redox mediator 2,2V-Azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) allowed a sensitive FA detection. The production of FA on silver particles and the FA detection methods presented in this work will be the target of further investigation for energy storage molecules. (C) 2017 Elsevier Ltd. All rights reserved.