Direct formic acid fuel cells (DFAFCs) are potential candidates as power sources for various applications, especially in portable electronics and medical diagnostic devices. Though they have been the subject of considerable research, commercial prototypes of DFAFCs are rudimentary compared to other liquid fuel cells, particularly the widespread methanol‐based direct methanol fuel cells. Various strategies for rationally engineering the electrocatalysts for enhancing DFAFC performance have been explored in the last few years, such as alloying noble metals with earth‐abundant transition metals, designing specific morphological and structural arrangements, decorating the surface with corrosion‐tolerant cocatalysts, and providing better catalyst support for effective catalyst dispersion. An overall approach may be necessary and should include (i) understanding the underlying mechanism, which will guide the direction of catalyst engineering, (ii) employing morphological, compositional, and structural control of the electrocatalysts to improve catalyst utilization and enhance the intrinsic activity for real‐world applications, and (iii) integrating these in a proficiently designed cell architecture suitable for targeted applications. In this review, we focus on the recent advances in electrocatalysts, formic acid electrooxidation mechanisms, and DFAFC cell architectures, which could help address the opportunities and challenges of commercializing DFAFC as a prospective alternative power source for portable applications. This article is categorized under: Fuel Cells and Hydrogen > Science and Materials Energy Research & Innovation > Science and Materials

Pd catalyst with dendritic morphology was synthesized on ordered and uniformly distributed titania nanotubes (TNT/Ti), and bare Ti by a simple electrochemical deposition process. The influence of support morphology was studied in relation to Pd deposition and its electro catalytic oxidation of formic acid. The structural property of Pd dendrites was characterized by scanning electron microscopy and X‐ray diffraction. The electrochemical study showed the activity and durability of Pd/TNT/Ti catalyst for formic acid oxidation was enhanced compared to Pd/Ti electro catalyst. The synergetic contribution from TNT/Ti as support for Pd and its enhanced catalytic activity is discussed.

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The electrodeposition of platinum-based catalysts (PtPd, PtRu, and PtSn) using the pulse current deposition technique was carried out on titanium substrate to prepare electrodes of different compositions to identify a possible catalyst offering high catalytic activity towards methanol oxidation (MOR). Characterization by XRD, SEM, and EDX confirmed the deposition of catalysts with the desired composition with various morphologies of dendritic, spherical, and irregular deposits for PtPd, PtRu, and PtSn, respectively. Among the various compositions and binary metals studied, electrochemical results indicate PtRu/Ti with Pt to Ru ratio of 1:1 (Pt50Ru50/Ti) to be most active with lower onset potentials for CO oxidation (0.381 V) and methanol oxidation (0.545 V) along with higher peak current density of ∼90 mA cm−2 compared to Pt/Ti (with onset potentials of 0.601 V for CO oxidation, 0.659 V for methanol oxidation and ∼68 mA cm−2 peak current density). Moreover, the MOR catalytic activity retention after 1000 accelerated durability test cycles was the highest for Pt50Ru50/Ti at 55% compared to Pt/Ti and commercial Pt/C.