Effects of alloying on oxidation and dissolution corrosion of the surface of γ-Fe(111): a DFT study

Han, Cheng; Zhang, Caili; Liu, Xinglong; Huang, Hui; Zhuang, Shengyi; Han, Peide; Wu, Xiaolei

doi:10.1007/s00894-015-2719-9

Cited by 20 publications

(9 citation statements)

References 44 publications

(47 reference statements)

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“…We explain the role of formal charges, geometry, and surface electronic and mechanical properties on the BEs. Such knowledge can then be used to predict the water interaction with a wide range of surfaces and has applications in electrocatalysis and electrochemistry, − surface wetting, − solid–water interfaces beyond TMs, − solids corrosion, ,, biological systems, , etc. As a consequence of the material-independent scaling relations we find between the N and O 2p lone-pair species, such knowledge is transferrable to other molecules in this class.…”

Section: Introductionmentioning

confidence: 99%

Nature of Lone-Pair–Surface Bonds and Their Scaling Relations

et al. 2018

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We investigate the (surface) bonding of a class of industrially and biologically important molecules in which the chemically active orbital is a 2 p electron lone pair located on an N or O atom bound via single bonds to H or alkyl groups. This class includes water, ammonia, alcohols, ethers, and amines. Using extensive density functional theory (DFT) calculations, we discover scaling relations (correlations) among molecular binding energies of different members of this class: the bonding energetics of a single member can be used as a descriptor for other members. We investigate the bonding mechanism for a representative (HO) and find the most important physical surface properties that dictate the strength and nature of the bonding through a combination of covalent and noncovalent electrostatic effects. We describe the importance of surface intrinsic electrostatic, geometric, and mechanical properties in determining the extent of the lone-pair-surface interactions. We study systems including ionic materials in which the surface positive and negative centers create strong local surface electric fields, which polarize the dangling lone pair and lead to a strong "electrostatically driven bond". We emphasize the importance of noncovalent electrostatic effects and discuss why a fully covalent picture, common in the current first-principles literature on surface bonding of these molecules, is not adequate to correctly describe the bonding mechanism and energy trends. By pointing out a completely different mechanism (charge transfer) as the major factor for binding N- and O-containing unsaturated (radical) adsorbates, we explain why their binding energies can be tuned independently from those of the aforementioned species, having potential implications in scaling-driven catalyst discovery.

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Section: Introductionmentioning

confidence: 99%

Nature of Lone-Pair–Surface Bonds and Their Scaling Relations

et al. 2018

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“…The difference between RDE and MEA is that the diffusion of the dissolved base metals in MEA is much slower than that in RDE, resulting in much slower dealloying kinetics. This insight parallels the technology on "stainless" alloys 46 , fills a knowledge gap between the structure and durability of alloy catalysts under fuel cell operating conditions while reducing Pt-content in the catalysts. The findings demonstrate a paradigm shift from the traditional perception of dealloying-induced phase segregation to the design and preparation of alloy catalysts that are commercially viable.…”

Section: Resultsmentioning

confidence: 66%

Alloying–Realloying Enabled High Durability for Pt–Pd–3d-Transition Metal Nanoparticle Fuel Cell Catalysts

Maswadeh

Wen

et al. 2020

Preprint

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Alloying noble metals with non-noble metals enables high activity while reducing the cost of electrocatalysts in fuel cells. However, under fuel cell operating conditions, state-of-the-art oxygen reduction reaction alloy catalysts either feature high atomic percentages of noble metals (>70%) with limited durability or show poor durability when lower percentages of noble metals (<50%) are used. Here we demonstrate a highly-durable alloy catalyst derived by alloying PtPd (<50%) with 3d-transition metals (Cu, Ni or Co) in ternary compositions. The origin of the high durability is probed by in-situ/operando high-energy synchrotron X-ray diffraction coupled with pair distribution function analysis of atomic phase structures and strains, revealing an important role of realloying in the compressively-strained single-phase alloy state despite the occurrence of dealloying. The implication of the finding, a striking departure from previous perceptions of phase-segregated noble metal skin or complete dealloying of non-noble metals, is the fulfilling of the promise of alloy catalysts for mass commercialization of fuel cells.

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“…According to Fermi-Dirac function, a lower work function implies a lower corrosion potential. Han, et al, [139][140] calculated the work function associated with water adsorption on γ-Fe(111) surface with 10 different alloy elements, and found that most of the alloying elements-especially Cr, Mo, and Si, but not Ti and Nb-can mitigate dissolution corrosion of the γ-Fe substrate in an aqueous environment. They also found that when Cr combines with interstitial atoms, especially in 2Cr-N and 4Cr-C co-doped surfaces, it leads to a weakening of the surface corrosion resistance.…”

Section: Modeling Dissolution Of Metallic Materialsmentioning

confidence: 99%

Density Functional Theory: An Essential Partner in the Integrated Computational Materials Engineering Approach to Corrosion

Taylor

2019

CORROSION

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The utility of density functional theory (DFT) for modeling in materials science and engineering with a focus on corrosion, is broadly introduced, along with an introduction to the technique, its inputs and outputs, and the risks and benefits. Case studies from the literature in which DFT is applied to problems such as the simulation of the properties of corrosion inhibitors, oxidation of metallic surfaces, localized corrosion, and the dissolution of metallic materials are then reviewed. Some speculations as to the future utility of DFT to further corrosion science and engineering are then made.

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Effects of alloying on oxidation and dissolution corrosion of the surface of γ-Fe(111): a DFT study

Cited by 20 publications

References 44 publications

Nature of Lone-Pair–Surface Bonds and Their Scaling Relations

Nature of Lone-Pair–Surface Bonds and Their Scaling Relations

Alloying–Realloying Enabled High Durability for Pt–Pd–3d-Transition Metal Nanoparticle Fuel Cell Catalysts

Density Functional Theory: An Essential Partner in the Integrated Computational Materials Engineering Approach to Corrosion

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