Overpotential

About: Overpotential is a research topic. Over the lifetime, 16474 publications have been published within this topic receiving 616632 citations.

Atomically Transition Metals on Self-Supported Porous Carbon Flake Arrays as Binder-Free Air Cathode for Wearable Zinc-Air Batteries.

Abstract: Metal single-atom materials with their high atom utilization efficiency and unique electronic structures usually show remarkable catalytic performances in many crucial chemical reactions. Herein, a facile and easily scalable "impregnation-carbonization-acidification" strategy for fabricating a class of single-atom-anchored (including cobalt and nickel single atoms) monolith as superior binder-free electrocatalysts for developing high-performance wearable Zn-air batteries is reported. The as-prepared single atoms, supported by N-doped carbon flake arrays grown on carbon nanofibers assembly (M SA@NCF/CNF), demonstrate the dual characteristics of excellent catalytic activity (reversible oxygen overpotential of 0.75 V) and high stability, owing to the greatly improved active sites' accessibility and optimized single-sites/pore-structures correlations. Furthermore, wearable Zn-air battery based on Co SA@NCF/CNF air electrode displays superior stability under deformation, satisfactory energy storage capacity, and good practicality to be utilized as an integrated battery system. Theoretical calculations reveal a mechanism for the promotion of the catalytic performances on single atomic sites by lowering the overall oxygen reduction/evolution reaction barriers comparing to metal cluster co-existing configuration. These findings provide a facile strategy for constructing free-standing single-atom materials as well as the engineering of high-performance binder-free catalytic electrodes.

Determination of Catalyst Unique Parameters for the Oxygen Reduction Reaction in a PEMFC

Abstract: The oxygen reduction reaction (ORR) kinetics of a high-surface-area carbon-supported platinum catalyst (Pt/C) were measured in an operating proton exchange membrane fuel cell (PEMFC). The ORR kinetics of Pt/C can be described over a wide range of temperature, pressure, and current density using four catalyst-specific parameters: transfer coefficient, exchange current density, reaction order with respect to oxygen partial pressure, and activation energy. These parameters were extracted using a combined kinetic and thermodynamic model, either referenced to the reversible cell potential (i.e., using exchange current density as activity parameter) or referenced to a constant ohmic-resistance-corrected (i.e., iR-free) cell voltage. The latter has the advantage of using an activity parameter (activity at 0.9 V iR-free cell voltage) which can be measured explicitly without extrapolation, in contrast to the exchange current density required in the former model. It was found that much of the variation in the published values for these catalyst-specific kinetic parameters derives from applying the same parameter name (e.g., activation energy) without specifying which of its many possible definitions is being used. The obviously significant numerical differences both for "oxygen reaction order" and for "activation energy" due to different definitions (often tacitly assumed and rarely explicitly stated in the literature) are illustrated by the kinetic ORR parameters which we determined for Pt/C: (i) at zero overpotential, where reaction order and activation energy are ∼0.5 and 67 kJ/mol, respectively, and (ii) at 0.9 V iR-free cell voltage, where reaction order and activation energy are ∼0.75 and 10 kJ/mol, respectively.

Large-Scale, Bottom-Up Synthesis of Binary Metal-Organic Framework Nanosheets for Efficient Water Oxidation.

Abstract: Ultrathin metal-organic framework (MOF) nanosheets (NSs) offer potential for many applications, but the synthetic strategies are largely limited to top-down, low-yield exfoliation methods. Herein, Ni-M-MOF (M=Fe, Al, Co, Mn, Zn, and Cd) NSs are reported with a thickness of only several atomic layers, prepared by a large-scale, bottom-up solvothermal method. The solvent mixture of N,N-dimethylacetamide and water plays key role in controlling the formation of these two-dimensional MOF NSs. The MOF NSs can be directly used as efficient electrocatalysts for the oxygen evolution reaction, in which the Ni-Fe-MOF NSs deliver a current density of 10 mA cm-2 at a low overpotential of 221 mV with a small Tafel slope of 56.0 mV dec-1 , and exhibit excellent stability for at least 20 h without obvious activity decay. Density functional theory calculations on the energy barriers for OER occurring at different metal sites confirm that Fe is the active site for OER at Ni-Fe-MOF NSs.

H2 Evolution and Molecular Electrocatalysts: Determination of Overpotentials and Effect of Homoconjugation

Abstract: In an effort to standardize the determination of overpotential values for H2-evolving catalysts in non-aqueous solvents and allow a reliable comparison of catalysts prepared and assayed by different groups, we propose to adopt the half-wave potential as reference potential. We provide a simple method for measuring it from usual stationary cyclic voltammograms, and we derive the formulas to which the measured potential should be compared, taking into account the effect of homoconjugation. We also revisit tabulated values of the standard reduction potential of protons in non-aqueous solvents, EH+/H2°.

Phosphorus-Mo2C@carbon nanowires toward efficient electrochemical hydrogen evolution: composition, structural and electronic regulation

Abstract: To explore high-performance electrocatalysts, electronic regulation on active sites is essentially demanded. Herein, we propose controlled phosphorus doping to effectively modify the electronic configuration of nanostructured Mo2C, accomplishing a benchmark performance of noble-metal-free electrocatalysts in the hydrogen evolution reaction (HER). Employing MoOx–phytic acid–polyaniline hybrids with tunable composition as precursors, a series of hierarchical nanowires composed of phosphorus-doped Mo2C nanoparticles evenly integrated within conducting carbon (denoted as P-Mo2C@C) are successfully obtained via facile pyrolysis under inert flow. Remarkably, P-doping into Mo2C can increase the electron density around the Fermi level of Mo2C, leading to weakened Mo–H bonding toward promoted HER kinetics. Further density functional theory calculations show that the negative hydrogen-binding free energy (ΔGH*) on pristine Mo2C gradually increases with P-doping due to electron transfer and steric hindrance by P on the Mo2C surface, indicating the effectively weakened strength of Mo–H. With optimal doping, a ΔGH* approaching 0 eV suggests a good balance between the Volmer and Heyrovsky/Tafel steps in HER kinetics. As expected, the P-Mo2C@C nanowires with controlled P-doping (P: 2.9 wt%) deliver a low overpotential of 89 mV at a current density of −10 mA cm−2 and striking kinetic metrics (onset overpotential: 35 mV, Tafel slope: 42 mV dec−1) in acidic electrolytes, outperforming most of the current noble-metal-free electrocatalysts. Elucidating feasible electronic regulation and the remarkably enhanced catalysis associated with controlled P-doping, our work will pave the way for developing efficient noble-metal-free catalysts via rational surface engineering.