The electro reduction of nitric oxide on bulk platinum in acid solutions

Elucidation of Pathways for NO Electroreduction on Pt(111) from First Principles

“…[5][6][7] Recent DFT calculations by Mavrikakis and co-workers [15] have indirectly supported this argument, demonstrating that, with increasing coverage,N Ow ill occupy both three-fold and top sites,w ith high coverage NO showing higher barriers to chemical NÀO bond activation. [5][6][7] Recent DFT calculations by Mavrikakis and co-workers [15] have indirectly supported this argument, demonstrating that, with increasing coverage,N Ow ill occupy both three-fold and top sites,w ith high coverage NO showing higher barriers to chemical NÀO bond activation.…”

“…[1] In particular, investigations of the electrochemical reduction of NO and nitrates on Pt-based electrodes have been an important focus of fundamental experimental studies. [3][4][5][6][7][8][9] Them ain products of NO electroreduction on single-crystal platinum electrode surfaces are ammonia (NH 3 /NH 4 + ), dinitrogen (N 2 ), and nitrous oxide (N 2 O) ( Figure 1). [1] Forr eductive stripping at modest coverages (< 0.45 ML;M L = monolayer) and relatively low potentials (< 0.4 V SHE ), it has been well-established that ammonia is produced:…”

Carbon-supported iron complexes as electrocatalysts for the cogeneration of hydroxylamine and electricity in a NO-H2 fuel cell: A combined electrochemical and density functional theory study

“…6.A). [13,69] The pyrolysis treatment of the FeSalen/AC led to a poorer LSV performance of the GDE, suggesting that the structure of the complex plays a relevant role in the electrocatalytic behaviour. The GDEs prepared using FeSalen supported on graphite showed poor performances compared to their counterparts based on activated carbon (Fig.…”

Elucidation of Pathways for NO Electroreduction on Pt(111) from First Principles

“…5 Interestingly, although the mechanistic pathways differ, both of these mechanisms suggest an (electro)chemical step for NO bond activation, a hypothesis that will be further evaluated below. Concerning N 2 O formation, early studies on platinum suggested that in order to form N 2 O, NN bonds could form by a Langmuir–Hinshelwood (L‐H) mechanism, yielding dimers such as ONNO, NOHNO, and HONNOH, and eventually leading to formation of N 2 O 7. Koper and co‐workers, in contrast, proposed an Eley–Rideal‐like (E‐R) mechanism, whereby a solvated NO could form (NO) 2 and eventually produce N 2 O 3…”

“…As mentioned briefly above, experiments have observed that the primary product for electrochemical reduction of NO is NH 3 /NH 4 + at coverages up to 0.5 ML and potentials less than 0.4 V. Additionally, it has been suggested that, in the case of reductive stripping, the observed voltammetric features are a result of NO* occupying different sites on the Pt(111) surface, with the higher voltage peaks corresponding to stripping from top sites and the lowest voltage peaks being associated with NO at threefold sites 5–7. Recent DFT calculations by Mavrikakis and co‐workers15 have indirectly supported this argument, demonstrating that, with increasing coverage, NO will occupy both three‐fold and top sites, with high coverage NO showing higher barriers to chemical NO bond activation.…”