Gaining insight into the impact of electronic property and interface electrostatic field on ORR kinetics in alloy engineering via theoretical prognostication and experimental validation.

Alloy engineering has been utilized as a potent strategy to modulate the oxygen reduction reaction （ORR） activity. However, the regulatory mechanism underpinning the ORR kinetics by means of alloy engineering is still shrouded in ambiguity. This work places emphasis on the kinetics of the ORR concerning Pt3M (M = Cr, Co, Cu, Pd, Sn, and Ir) catalysts, and integrates theoretical prognostication and experimental validation to illuminate the fundamental principles of alloy engineering. The ORR kinetic activity, as prognosticated by theory, shows significant agreement with experimental results, provided that the rate-determining step (RDS) accounts for a dominant role in the potential-independent kinetic mechanism. In essence, alloy engineering manipulates electronic properties through electron transfer to modulate intermediate adsorption and adjusts the interface electric field (Efield) to regulate hydrogen atom transport, ultimately influencing kinetics. The Efield holds greater significance in ORR kinetics compared to the intermediate adsorption (EadsO), the corresponding degrees of correlation with free energy barriers (Ea) of RDS are -0.89, and 0.75, respectively. This work highlights the nature of alloy engineering for ORR kinetics modulation and assists in the design of efficient catalysts.

Micromodification of the Catalyst Layer by CO to Increase Pt Utilization for Proton-Exchange Membrane Fuel Cells.

Improving the utilization of platinum in proton-exchange membrane (PEM) fuel cells is critical to reducing their cost. In the past decade, numerous Pt-based oxygen reduction reaction catalysts with high specific and mass activities have been developed. However, the high activities are mostly achieved in rotating disk electrode (RDE) measurement and have rarely been accomplished at the membrane electrode assembly (MEA) level. The failure of these direct translations from RDE to MEA has been well documented with several key reasons having been previously identified. One of them is the resistance caused by complex mass transport pathways in the MEA. Herein, we improve the proton and oxygen transportations in the MEA by building a thin and uniform distribution of ionomer on the catalyst surface. As a result, a PEM fuel cell design is capable of showing a current density improvement of 38% at the same voltage (0.6 V) under the H2/air operation.

Elucidating the Correlation between ORR Polarization Curves and Kinetics at Metal-Electrolyte Interfaces.

The metal-vacuum models used to analyze the thermodynamics of the oxygen reduction reaction (ORR) completely overlook the role of electrolytes in the electrochemical process and thus cannot reflect the actual kinetic process occurring at the metal-electrolyte interface. Therefore, based on the real experimental process, the current work elucidates the chemical interactions between the electrolyte and the chemical species for the ORR via a novel metal-electrolyte model for the first time by effectively elucidating the correlation between ORR kinetics and polarization curves. Our simulation model analysis comprises the study of all possible ORR mechanisms on different Pt surfaces (Pt(111), Pt(110), and Pt(100)) and PtNi alloys with different compositions (Pt3Ni(111), Pt2Ni2(111), and PtNi3(111)). The obtained results demonstrate that the hydrogenation of adsorbed oxygen to form adsorbed hydroxyl (R8), whose immense control weight is reflected by a coverage of adsorbed oxygen (θO*) of about 1, is the rate-determining step (RDS) in the four-electron-dominated ORR process. A direct correlation has been established by the great fitting of polarization curves from theoretical ORR kinetics obtained via both the metal-electrolyte model and experimental measurement. This study reveals that among the different Pt surfaces and PtNi alloys, Pt3Ni(111) exhibits the highest ORR activity with the lowest free energy barrier of Ea (0.74 eV), the smallest value of |ΔGO* - 2.46| (0.80 eV), the highest reaction rate r (9.98 × 105 s-1 per site), and a more positive half-wave potential U1/2 (0.93 V). In contrast to previous model studies, this work provides a more accurate theoretical system for catalyst screening, which will help researchers to better understand the experimental phenomena and will be a guiding piece of work for catalyst design and development.