A molecular-level strategy to boost the mass transport of perovskite electrocatalyst for enhanced oxygen evolution
TL;DR: In this article, the authors proposed a molecular-level strategy with the simultaneous modulation of the ordered pores on the oxygen-deficient sites along with sulfur substitution on oxygen sites at the molecular level to boost the mass transport behavior of perovskite electrocatalyst for enhanced mass activity.
Abstract: Perovskite oxides are of particular interest for the oxygen evolution reaction (OER) due to their high intrinsic activity. However, low surface area and nonpores in bulk phase generally limit the mass transport and thereby result in unsatisfactory mass activity. Herein, we propose a “molecular-level strategy” with the simultaneous modulation of the ordered pores on the oxygen-deficient sites along with sulfur (S) substitution on oxygen sites at the molecular level to boost the mass transport behavior of perovskite electrocatalyst for enhanced mass activity. As a proof of concept, the elaborately designed brownmillerite oxide Sr2Co1.6Fe0.4O4.8S0.2 (S-BM-SCF) shows approximately fourfold mass activity enhancement in 1 M KOH compared with the pristine SrCo0.8Fe0.2O3-δ (SCF) perovskite. Comprehensive experimental results, in combination with theoretical calculations, demonstrate that the intrinsic molecular-level pores in the brownmillerite structure can facilitate reactive hydroxyl ion (OH−) uptake into the oxygen-vacant sites and that S doping further promotes OH− adsorption by electronic structure modulation, thus accelerating mass transport rate. Meanwhile, the S-BM-SCF can significantly weaken the resistance of O2 desorption on the catalyst surface, facilitating the O2 evolution. This work deepens the understanding of how mass transport impacts the kinetics of the OER process and opens up a new avenue to design high-performance catalysts on the molecular level.
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01 Jan 2013
TL;DR: Structurally related Li₂Ru(1-y)Sn(y)O₃ materials that have a single redox cation and exhibit sustainable reversible capacities as high as 230 mA h g(-1) and unambiguously show that the reactivity of these high-capacity materials towards Li entails cumulative cationic and anionic reversible redox processes.
Abstract: Li-ion batteries have contributed to the commercial success of portable electronics and may soon dominate the electric
transportation market provided that major scientific advances including new materials and concepts are developed. Classical
positive electrodes for Li-ion technology operate mainly through an insertion–deinsertion redox process involving cationic
species. However, this mechanism is insufficient to account for the high capacities exhibited by the new generation of Li-rich
(Li1CxNiyCozMn(1
175 citations
TL;DR: In this article , a tensile strain was introduced into various perovskites via a facile thermochemical reduction method, which can greatly improve material performance for the bottleneck oxygen-evolving reaction in water electrolysis.
Abstract: Exploring effective, facile, and universal tuning strategies to optimize material physicochemical properties and catalysis processes is critical for many sustainable energy systems, but still challenging. Herein, we succeed to introduce tensile strain into various perovskites via a facile thermochemical reduction method, which can greatly improve material performance for the bottleneck oxygen-evolving reaction in water electrolysis. As an ideal proof-of-concept, such a chemical-induced tensile strain turns hydrophobic Ba5Co4.17Fe0.83O14- δ perovskite into the hydrophilic one by modulating its solid–liquid tension, contributing to its beneficial adsorption of important hydroxyl reactants as evidenced by fast operando spectroscopy. Both surface-sensitive and bulk-sensitive absorption spectra show that this strategy introduces oxygen vacancies into the saturated face-sharing Co-O motifs of Ba5Co4.17Fe0.83O14- δ and transforms such local structures into the unsaturated edge-sharing units with positive charges and enlarged electrochemical active areas, creating a molecular-level hydroxyl pool. Theoretical computations reveal that this strategy well reduces the thermodynamic energy barrier for hydroxyl adsorption, lowers the electronic work function, and optimizes the charge/electrostatic potential distribution to facilitate the electron transport between active sites and hydroxyl reactants. Also, this strategy is reliable for other single, double, and Ruddlesden–Popper perovskites. We believe that this finding will enlighten rational material design and in-depth understanding for many potential applications.
36 citations
TL;DR: In this article, a perovskite transition metal oxides with ABO3 structure is considered as potential alternative non-precious metal electrocatalysts for designing highly active and durable electrocatalysis for the oxygen evolution reaction (OER).
Abstract: Perovskite transition metal oxides with ABO3 structure are considered as potential alternative non-precious metal electrocatalysts for designing highly active and durable electrocatalysis for the oxygen evolution reaction (OER). Herein, we successfully enable LaFeO3 coated on nickel foam (denoted LFO@NF) perovskite with impressive OER activity by systematically tailoring the Fe cation sites and the introduction of oxygen vacancies. The cationic site involves dual cation modulation with Cr and Mo, which creates lattice distortions inducing strong electronic interaction, while the anionic site entails reduction via a hydrogen-treatment process, creating oxygen vacancy sites to improve the electronic conductivity of the perovskite oxide. As a result, the optimized LFO-based catalyst, specifically hydrogenated LaFe0.75Cr0.15Mo0.10O3-coated on the nickel foam (denoted H-LFCMO@NF), requires the lowest overpotential of 263 mV at 10 mA cm−2, and has superior kinetics and excellent stability, which are superior to its counterparts. Theoretical analysis also confirmed that the tailoring of the LFO@NF perovskite leads to an increase in the exposure of active sites, optimization of the adsorption energy of reaction intermediates and enhanced electronic conductivity. This work may provide a promising concept to enhance the performance of LFO-based perovskite electrocatalysts for alkaline OER and beyond.
26 citations
TL;DR: In this article, a surface defect engineering method is developed for optimizing the electrocatalytic activity of perovskite oxides for water electrolysis, which is found to not only increase the exposure and decrease the coordination of B-site metals but also effectively modulate the electronic structure of these metals.
Abstract: The design of high-performance and cost-effective electrocatalysts for water splitting is of prime importance for efficient and sustainable hydrogen production. In this work, a surface defect engineering method is developed for optimizing the electrocatalytic activity of perovskite oxides for water electrolysis. A typical ferrite-based perovskite oxide material La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) is used and regulated by selective acid etching. The optimal parameters for the surface treatment are identified. An efficient bifunctional perovskite oxide, denoted LSCF-30, is prepared by selectively corroding the A-site Sr element in the surface region, which is found to not only increase the exposure and decrease the coordination of B-site metals but also effectively modulate the electronic structure of these metals. The crystal lattice of the perovskite bulk is kept constant during surface engineering, which ensures the structural stability of the perovskite catalyst. The findings demonstrate an effective strategy of surface defect engineering in enhancing the performance of perovskite oxide electrocatalysts for water splitting.
23 citations
References
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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