Guofeng Wang

Design and synthesis of bimetallic electrocatalyst with multilayered Pt-skin surfaces.

Advancement in heterogeneous catalysis relies on the capability of altering material structures at the nanoscale, and that is particularly important for the development of highly active electrocatalysts with uncompromised durability. Here, we report the design and synthesis of a Pt-bimetallic catalyst with multilayered Pt-skin surface, which shows superior electrocatalytic performance for the oxygen reduction reaction (ORR). This novel structure was first established on thin film extended surfaces with tailored composition profiles and then implemented in nanocatalysts by organic solution synthesis. Electrochemical studies for the ORR demonstrated that after prolonged exposure to reaction conditions, the Pt-bimetallic catalyst with multilayered Pt-skin surface exhibited an improvement factor of more than 1 order of magnitude in activity versus conventional Pt catalysts. The substantially enhanced catalytic activity and durability indicate great potential for improving the material properties by fine-tuning of the nanoscale architecture.

Multimetallic Au/FePt3 Nanoparticles as Highly Durable Electrocatalyst

We report the design and synthesis of multimetallic Au/Pt-bimetallic nanoparticles as a highly durable electrocatalyst for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. This system was first studied on well-defined Pt and FePt thin films deposited on a Au(111) surface, which has guided the development of novel synthetic routes toward shape-controlled Au nanoparticles coated with a Pt-bimetallic alloy. It has been demonstrated that these multimetallic Au/FePt(3) nanoparticles possess both the high catalytic activity of Pt-bimetallic alloys and the superior durability of the tailored morphology and composition profile, with mass-activity enhancement of more than 1 order of magnitude over Pt catalysts. The reported synergy between well-defined surfaces and nanoparticle synthesis offers a persuasive approach toward advanced functional nanomaterials.

Monodisperse Pt3Co nanoparticles as electrocatalyst: the effects of particle size and pretreatment on electrocatalytic reduction of oxygen

Monodisperse Pt(3)Co nanoparticles have been synthesized with size control via an organic solvothermal approach. The obtained nanoparticles were incorporated into a carbon matrix and applied as electrocatalysts for the oxygen reduction reaction to investigate the effects of particle size and pretreatment on their catalytic performance. It has been found that the optimal conditions for maximum mass activity were with particles of approximately 4.5 nm and a mild annealing temperature of about 500 degrees C. While the particle size effect can be correlated to the average surface coordination number, Monte Carlo simulations have been introduced to depict the nanoparticle structure and segregation profile, which revealed that the annealing temperature has a direct influence on the particle surface relaxation, segregation and adsorption/catalytic properties. The obtained fundamental understanding of activity enhancement in Pt-bimetallic alloy catalysts could be utilized to guide the development of advanced nanomaterials for catalytic applications.

Rational Development of Ternary Alloy Electrocatalysts

Improving the efficiency of electrocatalytic reduction of oxygen represents one of the main challenges for the development of renewable energy technologies. Here, we report the systematic evaluation of Pt-ternary alloys (Pt3(MN)1 with M, N = Fe, Co, or Ni) as electrocatalysts for the oxygen reduction reaction (ORR). We first studied the ternary systems on extended surfaces of polycrystalline thin films to establish the trend of electrocatalytic activities and then applied this knowledge to synthesize ternary alloy nanocatalysts by a solvothermal approach. This study demonstrates that the ternary alloy catalysts can be compelling systems for further advancement of ORR electrocatalysis, reaching higher catalytic activities than bimetallic Pt alloys and improvement factors of up to 4 versus monometallic Pt.

Surface faceting and elemental diffusion behaviour at atomic scale for alloy nanoparticles during in situ annealing

The catalytic performance of nanoparticles is primarily determined by the precise nature of the surface and near-surface atomic configurations, which can be tailored by post-synthesis annealing effectively and straightforwardly. Understanding the complete dynamic response of surface structure and chemistry to thermal treatments at the atomic scale is imperative for the rational design of catalyst nanoparticles. Here, by tracking the same individual Pt3Co nanoparticles during in situ annealing in a scanning transmission electron microscope, we directly discern five distinct stages of surface elemental rearrangements in Pt3Co nanoparticles at the atomic scale: initial random (alloy) elemental distribution; surface platinum-skin-layer formation; nucleation of structurally ordered domains; ordered framework development and, finally, initiation of amorphization. Furthermore, a comprehensive interplay among phase evolution, surface faceting and elemental inter-diffusion is revealed, and supported by atomistic simulations. This work may pave the way towards designing catalysts through post-synthesis annealing for optimized catalytic performance.

First-principles studies on vacancy-modified interstitial diffusion mechanism of oxygen in nickel, associated with large-scale atomic simulation techniques

This paper is concerned with the prediction of oxygen diffusivities in fcc nickel from first-principles calculations and large-scale atomic simulations. Considering only the interstitial octahedral to tetrahedral to octahedral minimum energy pathway for oxygen diffusion in fcc lattice, greatly underestimates the migration barrier and overestimates the diffusivities by several orders of magnitude. The results indicate that vacancies in the Ni-lattice significantly impact the migration barrier of oxygen in nickel. Incorporation of the effect of vacancies results in predicted diffusivities consistent with available experimental data. First-principles calculations show that at high temperatures the vacancy concentration is comparable to the oxygen solubility, and there is a strong binding energy and a redistribution of charge density between the oxygen atom and vacancy. Consequently, there is a strong attraction between the oxygen and vacancy in the Ni lattice, which impacts diffusion.

Bivalence Mn5O8 with hydroxylated interphase for high-voltage aqueous sodium-ion storage

Aqueous electrochemical energy storage devices have attracted significant attention owing to their high safety, low cost and environmental friendliness. However, their applications have been limited by a narrow potential window (∼1.23u2009V), beyond which the hydrogen and oxygen evolution reactions occur. Here we report the formation of layered Mn5O8 pseudocapacitor electrode material with a well-ordered hydroxylated interphase. A symmetric full cell using such electrodes demonstrates a stable potential window of 3.0u2009V in an aqueous electrolyte, as well as high energy and power performance, nearly 100% coulombic efficiency and 85% energy efficiency after 25,000 charge–discharge cycles. The interplay between hydroxylated interphase on the surface and the unique bivalence structure of Mn5O8 suppresses the gas evolution reactions, offers a two-electron charge transfer via Mn2+/Mn4+ redox couple, and provides facile pathway for Na-ion transport via intra-/inter-layer defects of Mn5O8.

Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes

Oxygen adsorption energy is directly relevant to the catalytic activity of electrocatalysts for oxygen reduction reaction (ORR). In this study, we established the correlation between the O2 adsorption energy and the electronic structure of transition metal macrocyclic complexes which exhibit activity for ORR. To this end, we have predicted the molecular and electronic structures of a series of transition metal macrocyclic complexes with planar N4 chelation, as well as the molecular and electronic structures for the O2 adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O2 on the transition metal macrocyclic complexes was linearly related to the average position (relative to the lowest unoccupied molecular orbital of the macrocyclic complexes) of the non-bonding d orbitals (d(z(2)), d(xy), d(xz), and d(yz)) which belong to the central transition metal atom. Importantly, our results suggest that varying the energy level of the non-bonding d orbitals through changing the central transition metal atom and/or peripheral ligand groups could be an effective way to tuning their O2 adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.

Quantifying solvation energies at solid/liquid interfaces using continuum solvation methods

Abstract To investigate the degree that efficient computational methods can be used for modelling adsorbates at solid/liquid interfaces, we have benchmarked gas phase and solvated energetics for H, O and OH adsorbates on the Pt(1u20091u20091) surface calculated from periodic slab and surface cluster models. We have found that absolute solvation energies using the VASPsol continuum solvation model under periodic boundary conditions are typically much smaller in magnitude compared to solvation energies computed using COSMO using a surface cluster model. Although the two models provide quite different absolute solvation energies, the relative energy contributions between the different models are generally similar with one notable exception being the OH adsorbate when bound at top sites on this surface. We provide recommendations for reliable computational quantum chemistry modelling of adsorption energies on solid/liquid interfaces.

Charged vacancy diffusion in chromium oxide crystal: DFT and DFT+U predictions

In this work, we computationally studied the lattice diffusion through the ion-vacancy exchange mechanism in α-Cr2O3 crystal using the first-principles density functional theory (DFT) and DFT+U calculation methods. For both O and Cr vacancies, we have identified four elementary diffusion paths in α-Cr2O3 crystal. Our DFT+U calculations predict that the O vacancy with charge +2 ( VO2+) is stable when Fermi energy is near to valence band maximum, whereas the Cr vacancy with charge −3 ( VCr3−) is stable when Fermi energy is close to conduction band minimum. Moreover, the DFT+U calculations predict that the migration energy for VO2+u2009 diffusion varies from 1.18 to 2.98u2009eV, whereas that for VCr3− diffusion varies from 2.02 to 2.59u2009eV, close to experimental data. Both DFT and DFT+U results indicate that the migration energy of neutral vacancies ( VO0 and VCr0) is higher than that of the charged vacancies ( VO2+ and VCr3−) along any diffusive path. Importantly, it is found that the DFT+U method describes α-Cr2O3 ...