Role of Defects in the Interplay between Adsorbate Evolving and Lattice Oxygen Mechanisms of the Oxygen Evolution Reaction in RuO2 and IrO2
TL;DR: The mechanistic interplay between the oxygen evolution reaction (OER) and material degradation during water electrolysis is not yet well understood even for the most studied OER electrocatalysts as mentioned in this paper.
Abstract: The mechanistic interplay between the oxygen evolution reaction (OER) and material degradation during water electrolysis is not yet well understood even for the most studied OER electrocatalysts su...
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TL;DR: In this paper, a generalization of the Local Density Approximation (LDA) method for the systems with strong Coulomb correlations is presented which gives a correct description of the Mott insulators.
Abstract: The generalization of the Local Density Approximation (LDA) method for the systems with strong Coulomb correlations is presented which gives a correct description of the Mott insulators. The LDA+U method is based on the model hamiltonian approach and allows to take into account the non-sphericity of the Coulomb and exchange interactions. parameters. Orbital-dependent LDA+U potential gives correct orbital polarization and corresponding Jahn-Teller distortion. To calculate the spectra of the strongly correlated systems the impurity Anderson model should be solved with a many-electron trial wave function. All parameters of the many-electron hamiltonian are taken from LDA+U calculations. The method was applied to NiO and has shown good agreement with experimental photoemission spectra and with the oxygen Kα X-ray emission spectrum.
376 citations
TL;DR: In this article, the authors provide catalysts and reactor design principles for overcoming OER stability challenges and focus more attention from the field on the great importance of oxygen evolution reaction (OER) stability as well as future large scale electrocatalysis applications.
245 citations
Cites background from "Role of Defects in the Interplay be..."
...More recently, a simulation study proposed that dopants or metal vacancies could promote the LOM over AEM for well-structured surfaces.(108) The authors chose...
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TL;DR: In this article, a review of transition metal-based OER electrocatalysts is presented to reveal the novel design principles and perspectives for further catalytic performance enhancement and deeper understanding of catalyst design.
Abstract: Oxygen evolution reaction (OER) is an important half-reaction involved in many electrochemical applications, such as water splitting and rechargeable metal-air batteries. However, the sluggish kinetics of its four-electron transfer process becomes a bottleneck to the performance enhancement. Thus, rational design of electrocatalysts for OER based on thorough understanding of mechanisms and structure-activity relationship is of vital significance. This review begins with the introduction of OER mechanisms which include conventional adsorbate evolution mechanism and lattice-oxygen-mediated mechanism. The reaction pathways and related intermediates are discussed in detail, and several descriptors which greatly assist in catalyst screen and optimization are summarized. Some important parameters suggested as measurement criteria for OER are also mentioned and discussed. Then, recent developments and breakthroughs in experimental achievements on transition metal-based OER electrocatalysts are reviewed to reveal the novel design principles. Finally, some perspectives and future directions are proposed for further catalytic performance enhancement and deeper understanding of catalyst design. It is believed that iterative improvements based on the understanding of mechanisms and fundamental design principles are essential to realize the applications of efficient transition metal-based OER electrocatalysts for electrochemical energy storage and conversion technologies.
179 citations
TL;DR: In this article, the great achievements and progresses of this flourishing spot are comprehensively reviewed, which are started by a general description of OER to understand the reaction mechanism in detail, followed by proposing many advanced strategies for further promoting the electrocatalytic OER performance of RuO2.
151 citations
TL;DR: Density functional theory calculations revealed co-doping of W and Er tuned electronic structure of RuO2 by charge redistribution, which significantly prohibited formation of soluble Rux>4 and lowered adsorption energies for oxygen intermediates.
Abstract: Designing highly durable and active electrocatalysts applied in polymer electrolyte membrane (PEM) electrolyzer for the oxygen evolution reaction remains a grand challenge due to the high dissolution of catalysts in acidic electrolyte. Hindering formation of oxygen vacancies by tuning the electronic structure of catalysts to improve the durability and activity in acidic electrolyte was theoretically effective but rarely reported. Herein we demonstrated rationally tuning electronic structure of RuO2 with introducing W and Er, which significantly increased oxygen vacancy formation energy. The representative W0.2Er0.1Ru0.7O2-δ required a super-low overpotential of 168 mV (10 mA cm−2) accompanied with a record stability of 500 h in acidic electrolyte. More remarkably, it could operate steadily for 120 h (100 mA cm−2) in PEM device. Density functional theory calculations revealed co-doping of W and Er tuned electronic structure of RuO2 by charge redistribution, which significantly prohibited formation of soluble Rux>4 and lowered adsorption energies for oxygen intermediates. There is an increasing interest in understanding how defect chemistry can alter material reactivity. Here, authors tune the electronic structure of RuO2 by introducing W and Er dopants that boost acidic oxygen evolution performances by limiting oxygen vacancy formation during catalysis.
144 citations
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TL;DR: A simple derivation of a simple GGA is presented, in which all parameters (other than those in LSD) are fundamental constants, and only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked.
Abstract: Generalized gradient approximations (GGA’s) for the exchange-correlation energy improve upon the local spin density (LSD) description of atoms, molecules, and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental constants. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential. [S0031-9007(96)01479-2] PACS numbers: 71.15.Mb, 71.45.Gm Kohn-Sham density functional theory [1,2] is widely used for self-consistent-field electronic structure calculations of the ground-state properties of atoms, molecules, and solids. In this theory, only the exchange-correlation energy EXC › EX 1 EC as a functional of the electron spin densities n"srd and n#srd must be approximated. The most popular functionals have a form appropriate for slowly varying densities: the local spin density (LSD) approximation Z d 3 rn e unif
146,533 citations
TL;DR: An efficient scheme for calculating the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set is presented and the application of Pulay's DIIS method to the iterative diagonalization of large matrices will be discussed.
Abstract: We present an efficient scheme for calculating the Kohn-Sham ground state of metallic systems using pseudopotentials and a plane-wave basis set. In the first part the application of Pulay's DIIS method (direct inversion in the iterative subspace) to the iterative diagonalization of large matrices will be discussed. Our approach is stable, reliable, and minimizes the number of order ${\mathit{N}}_{\mathrm{atoms}}^{3}$ operations. In the second part, we will discuss an efficient mixing scheme also based on Pulay's scheme. A special ``metric'' and a special ``preconditioning'' optimized for a plane-wave basis set will be introduced. Scaling of the method will be discussed in detail for non-self-consistent and self-consistent calculations. It will be shown that the number of iterations required to obtain a specific precision is almost independent of the system size. Altogether an order ${\mathit{N}}_{\mathrm{atoms}}^{2}$ scaling is found for systems containing up to 1000 electrons. If we take into account that the number of k points can be decreased linearly with the system size, the overall scaling can approach ${\mathit{N}}_{\mathrm{atoms}}$. We have implemented these algorithms within a powerful package called VASP (Vienna ab initio simulation package). The program and the techniques have been used successfully for a large number of different systems (liquid and amorphous semiconductors, liquid simple and transition metals, metallic and semiconducting surfaces, phonons in simple metals, transition metals, and semiconductors) and turned out to be very reliable. \textcopyright{} 1996 The American Physical Society.
81,985 citations
IBM1
TL;DR: An approach for electronic structure calculations is described that generalizes both the pseudopotential method and the linear augmented-plane-wave (LAPW) method in a natural way and can be used to treat first-row and transition-metal elements with affordable effort and provides access to the full wave function.
Abstract: An approach for electronic structure calculations is described that generalizes both the pseudopotential method and the linear augmented-plane-wave (LAPW) method in a natural way. The method allows high-quality first-principles molecular-dynamics calculations to be performed using the original fictitious Lagrangian approach of Car and Parrinello. Like the LAPW method it can be used to treat first-row and transition-metal elements with affordable effort and provides access to the full wave function. The augmentation procedure is generalized in that partial-wave expansions are not determined by the value and the derivative of the envelope function at some muffin-tin radius, but rather by the overlap with localized projector functions. The pseudopotential approach based on generalized separable pseudopotentials can be regained by a simple approximation.
61,450 citations
TL;DR: In this paper, the formal relationship between US Vanderbilt-type pseudopotentials and Blochl's projector augmented wave (PAW) method is derived and the Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional.
Abstract: The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Bl\"ochl's projector augmented wave (PAW) method is derived. It is shown that the total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addition, critical tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed core all electron methods. These tests include small molecules $({\mathrm{H}}_{2}{,\mathrm{}\mathrm{H}}_{2}{\mathrm{O},\mathrm{}\mathrm{Li}}_{2}{,\mathrm{}\mathrm{N}}_{2}{,\mathrm{}\mathrm{F}}_{2}{,\mathrm{}\mathrm{BF}}_{3}{,\mathrm{}\mathrm{SiF}}_{4})$ and several bulk systems (diamond, Si, V, Li, Ca, ${\mathrm{CaF}}_{2},$ Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.
57,691 citations
TL;DR: A detailed description and comparison of algorithms for performing ab-initio quantum-mechanical calculations using pseudopotentials and a plane-wave basis set is presented in this article. But this is not a comparison of our algorithm with the one presented in this paper.
47,666 citations