Recent Advances in Rational Design of CO‑Tolerant Anode Electrocatalysts for Durable Direct Formic Acid Fuel Cells

ABSTRACT Direct formic acid fuel cells (DFAFCs) are promising power sources for portable applications, featuring high theoretical energy density, low operational emissions, and simplified system architecture. Their performance is governed by the formic acid oxidation reaction (FAOR), which benefits from a direct oxidation pathway with a two‐electron transfer process. Despite this advantage, the widespread deployment of DFAFCs is hindered by the rapid poisoning of conventional platinum‐ and palladium‐based catalyst surfaces by strongly adsorbed carbon monoxide (CO) intermediates generated during the FAOR. This review systematically summarizes the latest advances (over the past 5 years) in the rational design of CO‑tolerant catalysts. We focus on innovative strategies, including single‐atom engineering, alloying, high‐entropy materials, surface/interface modification, support interactions, and synergistic catalysis, that enhance intrinsic activity, operational stability, and CO resistance. Each approach is discussed in light of the fundamental mechanisms governing FAOR kinetics and CO poisoning. Finally, we outline remaining challenges and future research directions toward commercially viable DFAFCs.