Exposing Fe–N–C catalysts to H2O2-byproduct leaves their catalytic sites untouched but decreases the turnover frequency via oxidation of the carbon surface.

Polymer coatings are widely used to protect metals from corrosion. Coating adhesion to the base material is critical for good protection, but coatings may fail because of cathodic delamination. Most of the experimental studies on cathodic delamination use polymers to study the corrosion behavior under conditions where the interfacial chemistry at the metal(oxide)/polymer interface is not well-defined. Here, ultrathin linear and cross-linked poly(methyl methacrylate) [PMMA] coatings that are covalently bound to oxide-covered zinc via a silane linker have been prepared. For preparation, zinc was functionalized with vinyltrimethoxysilane (VTS), yielding a vinyl monomer-covered surface. These samples were subjected to thermally initiated free radical polymerization in the presence of methyl methacrylate (MMA) to yield surface-bound ultrathin PMMA films of 10-20 nm thickness, bound to the surface via Zn-O-Si bonds. A similar preparation was also carried out in the presence of different amounts of the cross-linkers ethylene glycol diacrylate and hexanediol diacrylate. Functionalized and polymer-coated zinc samples were characterized by infrared (IR) spectroscopy, secondary ion mass spectrometry (SIMS), ellipsometry, and X-ray photoelectron spectroscopy (XPS). Coating stability toward cathodic delamination has been evaluated by scanning Kelvin probe (SKP) experiments. In all cases, the covalently linked coatings show lower delamination rates of 0.02-0.2 mm h(-1) than coatings attached to the surface without covalent bonds (rates ∼10 mm h(-1)). Samples with a higher fraction of cross-linker delaminate slower, with rates down to 0.03-0.04 mm h(-1), compared to ∼0.3 mm h(-1) without cross-linker. Samples with longer hydrophobic alkyl chains also delaminate slower, with the lowest observed delamination rate of 0.028 mm h(-1) using hexanediol diacrylate. For the coatings studied here, delamination kinetics is not diffusion limited, but the rate is controlled by a chemical reaction. Several possibilities for the nature of this reaction are discussed; radical side reactions of the oxygen reduction are the most likely path of deadhesion.

Fuel cells efficiently convert chemical into electric energy, with promising application for clean transportation. In proton-exchange membrane fuel cells (PEMFCs), rare platinum metal catalyzes today the oxygen reduction reaction (ORR) while iron(cobalt)-nitrogen-carbon materials (Fe(Co)-N-C) are a promising alternative. Their active sites can be classified as atomically dispersed metal-ions coordinated to nitrogen atoms (MeNxCy moieties) or nitrogen functionalities (possibly influenced by sub-surface metallic particles). While their durability is a recognized challenge, its rational improvement is impeded by insufficient understanding of operando degradation mechanisms. Here, we show that FeNxCy moieties in a representative Fe-N-C catalyst are structurally stable but electrochemically unstable when exposed in acidic medium to H2O2, the main ORR byproduct. We reveal that exposure to H2O2 leaves iron-based catalytic sites untouched but decreases their turnover frequency (TOF) via oxidation of the carbon surface, leading to weakened O2 binding on iron-based sites. Their TOF is recovered upon electrochemical reduction of the carbon surface, demonstrating the proposed deactivation mechanism. Our results reveal a hitherto unsuspected deactivation mechanism during ORR in acidic medium. This study identifies the N-doped carbon surface as Achilles' heel during ORR catalysis in PEMFCs. Observed in acidic but not in alkaline electrolyte, these insights suggest that durable iron-nitrogen-carbon catalysts are within reach for PEMFCs if rational strategies minimizing the amount of H2O2 or reactive oxygen species (ROS) produced during ORR are developed.

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