Bond-Energy-Integrated Descriptor for Oxygen Electrocatalysis of Transition Metal Oxides

Wu, Deyan; Dong, Cunku; Zhan, Hongbing; Du, Xi‐Wen

doi:10.1021/acs.jpclett.8b01493

Cited by 35 publications

(41 citation statements)

References 33 publications

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“…Mater. 2022, 5, 157-185 oxides, [310] in which the metal coordinated by six identical ligands in octahedral complexes with O h symmetry. The d orbitals of the center transition metal atom split into low energy t 2g orbitals (d xy d xy , d xz , and d yz ) and high energy antibonding e g orbitals (d x 2 Ày 2 , d z 2 ).…”

Section: E G Orbital Occupationsmentioning

confidence: 99%

Density Functional Theory for Electrocatalysis

Liao

Xia

et al. 2021

Energy & Environ Materials

107

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With the increase in energy demand and worldwide natural environment crises, it is imperative to develop green and sustainable energy systems to produce clean fuels and chemicals, which can replace fossil fuels and reduce carbon dioxide emissions. [1][2][3] A promising strategy is to develop advanced electrochemical technologies that can convert some common molecules (e.g., water, carbon dioxide, and nitrogen) into high-value chemical products (e.g., hydrogen, hydrocarbons, oxygenates, ammonia, and carbonates). [4][5][6][7] The important energy-related electrocatalytic reactions, including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), nitrogen reduction reaction (NRR), carbon dioxide reduction reaction (CO 2 RR), are the key conversion routes. In the complex processes for the electrocatalytic reactions, an efficient, highly selective, and stable electrocatalyst plays a pivotal role in speeding up the reaction kinetics and decreasing the overpotential, [5,8,9] which can enhance the sustainable energy conversion efficiency. Over the past few decades, tremendous progresses have been made in the establishment of electrocatalysts preparation and fundamental catalytic mechanisms. [6,7,[9][10][11][12][13][14][15][16][17][18] Nevertheless, those breakthroughs still stay at the stage of experimental synthesis and lack of indepth understanding of fundamental principles of the active site on the catalyst surface and catalytic reactions mechanisms, which seriously limits the development of efficient catalysts. Researchers are full of enthusiasm about preparation of advanced catalysts with ideal properties, expecting to establish the composition-structure-function relationships. Density functional theory (DFT) calculations are based on quantum mechanics, which can calculate the electronic structure of the whole catalytic system. It is probably the most powerful computational approach to investigate the structure-activity relationships of electrocatalysts at atomic level. With the rapid advances of computer technology, DFT calculations have created tremendous opportunities in shedding light on the electrocatalytic mechanisms and predicting promising catalysts. [19,20] Identification of the active sites and understanding of the reaction mechanisms are the two key aspects for the study of electrocatalytic reactions. [21] For the former, the experimental approach for identifying active sites is indirect by prepared specified catalysts and establishing definite correlations between catalytic performances and controllable factors. [22,23] Actually, many intermediate states of electrocatalytic

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Section: E G Orbital Occupationsmentioning

confidence: 99%

Density Functional Theory for Electrocatalysis

Liao

Xia

et al. 2021

Energy & Environ Materials

107

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“…Theoretically, the calculated adsorption strengths of oxygen species (for OER or ORR) 7,13,14 and hydrogen intermediates (for HER) 15 on active sites are acknowledged as universal descriptors. Lee 16 , Hong 17 , Calle-Vallejo 18 , Wu 19 , Fung 20,21 , and Govindarajan 22 et al also reported the position of the O p -band center, the charge-transfer energy, the bulk formation energy, the bond-energy-integrated coordination number, the adjusted coordination number and the electrochemical-step symmetry index as OER/ORR activity descriptors, respectively. Experimentally, e g occupancy 6 , B-site oxidation state 23 , outer electrons 24 , multi-physicochemical material properties 25 , and electrochemical redox potentials 26 were proposed to elucidate the OER/ORR catalytic activities.…”

Section: Introductionmentioning

confidence: 99%

Screening highly active perovskites for hydrogen-evolving reaction via unifying ionic electronegativity descriptor

et al. 2019

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Facile and reliable screening of cost-effective, high-performance and scalable electrocatalysts is key for energy conversion technologies such as water splitting. ABO 3- δ perovskites, with rich constitutions and structures, have never been designed via activity descriptors for critical hydrogen evolution reaction (HER). Here, we apply coordination rationales to introduce A-site ionic electronegativity (AIE) as an efficient unifying descriptor to predict the HER activities of 13 cobalt-based perovskites. Compared with A-site structural or thermodynamic parameter, AIE endows the HER activity with the best volcano trend. (Gd 0.5 La 0.5 )BaCo 2 O 5.5+ δ predicted from an AIE value of ~2.33 exceeds the state-of-the-art Pt/C catalyst in electrode activity and stability. X-ray absorption and computational studies reveal that the peak HER activities at a moderate AIE value of ~2.33 can be associated with the optimal electronic states of active B-sites via inductive effect in perovskite structure (~200 nm depth), including Co valence, Co-O bond covalency, band gap and O 2 p -band position.

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“…[ 7 , 8 ] Generally, the previously developed descriptors could be classified into two types. One type is associated with surface structures, such as the surface distortion, [ 9 ] coordinatively unsaturated metal cation, [ 10 ] coordination number, [ 11 ] and so on. As OER occurs on the surface of electrocatalysts, the surface descriptors reflecting the local morphology and electronic environments are more accurate.…”

Section: Introductionmentioning

confidence: 99%

Revealing the Correlation of OER with Magnetism: A New Descriptor of Curie/Neel Temperature for Magnetic Electrocatalysts

Bai

Cheng

2021

Advanced Science

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Developing accurate descriptors for oxygen evolution reaction (OER) is of great significance yet challenging, which roots in and also boosts the understanding of its intrinsic mechanisms. Despite various descriptors are reported, it still has limitations in the facile prediction, given that complicated analytical techniques as well as time-consuming modeling and calculations are indispensable. In the present work, strong correlation of magnetic property with OER performance is revealed by in-depth investigations on the crystal and electronic structures. A facile descriptor of Curie/Neel temperature (T C/N ) is developed for La 2−x Sr x Co 2 O 6− perovskite oxides, based on the inference that both magnetism and OER are rooted in the electron exchange interaction. Specifically, both the T C/N and OER activity are proportional to the degree of p-d orbital hybridization, which increases with enlarged bond angle of Co─O─Co and/or increased oxidation of Co. This finding reveals that T C/N from magnetic characterizations is an effective descriptor in designing novel OER electrocatalysts, and interdisciplinary researches are advantageous for revealing the controversial mechanisms of OER process.

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Bond-Energy-Integrated Descriptor for Oxygen Electrocatalysis of Transition Metal Oxides

Cited by 35 publications

References 33 publications

Density Functional Theory for Electrocatalysis

Density Functional Theory for Electrocatalysis

Screening highly active perovskites for hydrogen-evolving reaction via unifying ionic electronegativity descriptor

Revealing the Correlation of OER with Magnetism: A New Descriptor of Curie/Neel Temperature for Magnetic Electrocatalysts

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