A theoretical study on the ORR electrocatalytic activity of axial ligand modified cobalt polyphthalocyanine

Wang, Guilin; Yang, Xiaoli; Wang, Ruiying; Jia, Jianfeng

doi:10.1039/d3cp03707j

Cited by 4 publications

(3 citation statements)

References 56 publications

(104 reference statements)

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“…The Mayer bond order was defined by the density matrix P and the overlapping matrix S, which also was an useful tool for chemical bonding analysis. [ 16 ] The ORR began with *OOH (the first ORR intermediate) occupying the catalytic site, and the entire ORR cycle finished as soon as *OH (the final ORR intermediate) was released. Due to orbital interactions, HfN 4 O exhibits a higher strength of *OOH adsorption (1.12) compared to HfN 4 (1.03) in favor of the start of ORR.…”

Section: Resultsmentioning

confidence: 99%

Regulating d‐Orbital Hybridization of Subgroup‐IVB Single Atoms for Efficient Oxygen Reduction Reaction

Zhao,

Sun,

Wang

et al. 2024

Advanced Materials

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Highly active single‐atom electrocatalysts for the oxygen reduction reaction are crucial for improving the energy conversion efficiency, but they suffer from a limited choice of metal centers and unsatisfactory stabilities. Here we report that optimization of the binding energies for reaction intermediates by tuning the d‐orbital hybridization with axial groups converts inactive subgroup‐IVB (Ti, Zr, Hf) moieties (MN4) into active motifs (MN4O), as confirmed with theoretical calculations. The competition between metal‐ligand covalency and metal‐intermediate covalency affects the d‐p orbital hybridization between the metal site and the intermediates, converting the metal centres into active sites. Subsequently, dispersed single‐atom M sites coordinated by nitrogen/oxygen groups have been prepared on graphene (s‐M‐N/O‐C) catalysts on a large‐scale with high‐energy milling and pyrolysis. Impressively, the s‐Hf‐N/O‐C catalyst with 5.08 wt.% Hf exhibited a half‐wave potential of 0.920 V and encouraging performance in a zinc‐air battery with an extraordinary cycling life of over 1,600 h and a large peak power‐density of 256.9 mW cm−2. This work provides promising single‐atom electrocatalysts and principles for preparing other catalysts for the oxygen reduction reaction.This article is protected by copyright. All rights reserved

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Section: Resultsmentioning

confidence: 99%

Regulating d‐Orbital Hybridization of Subgroup‐IVB Single Atoms for Efficient Oxygen Reduction Reaction

Zhao,

Sun,

Wang

et al. 2024

Advanced Materials

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“…The modified ligands of F, Cl, and CH 3 coordinated axially on Fe–N–C catalysts were found to reduce the orbital hybridization between Fe and *OH and hence promote *OH desorption by improving ORR performance. − CO modified on the Rh site could stabilize *OOH intermediates and promote the two-electron and four-electron ORR processes . The axial NO, HCO 3 , CH 3 , and CN coordination optimized the electronic structure of Fe, which improved U L to 0.72, 0.82, 0.69, and 0.86 V from the original 0.56 V of the pristine Fe–N–C catalyst. − These results indicated that axial ligand engineering is an effective measurement for affecting ORR activities in metal–nitrogen-carbon materials.…”

Section: Introductionmentioning

confidence: 96%

Hierarchical High-Throughput Screening of the Ligand Effect of Electrocatalytic Oxygen Reduction on Dual-Metal Atomic Catalysts (M₁M₂N₆–R): A First-Principles Study

Chen,

Wu,

et al. 2024

ACS Appl. Nano Mater.

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The design of low-cost and high-activity oxygen reduction catalysts on the cathode is important to improve the conversion efficiency in proton exchange membrane fuel cells. A series of nonprecious 3d-TM-combined M 1 M 2 N 6 /C candidates are constructed within high-throughput screening to find out highefficient oxygen reduction reaction (ORR) catalysts through axially coordinating with 13 kinds of potentially accompanied ligands by first-principles calculation. Among the fabricated 55 pristine M 1 M 2 N 6 structures, some pre-3d metals (d e ≤ 5) of Sc-, Ti-, and V-contained M 1 M 2 N 6 /C are excluded due to poor ORR activities with too low negative limiting potentials (U L ) values (U L < −1.0 V). The screening results of three common ligands (R = −OH, −F, and −NH 2 ) coordination indicate that axial ligand modification could significantly enlarge the U L of M 1 M 2 N 6 −R. A volcano relationship between U L and ΔG of OH* intermediate is helpful to select four excellent ORR candidates of NiNi-, CoNi-, FeCo-, and CoCo-combinations to further perform 10 kinds of axial ligand engineering. More applicable ligands of −CO, −COH, −NH, −NO, -Cl, and -CH 2 are identified to enhance ORR activity for certain pristine M 1 M 2 N 6 catalysts. Totally, 16 different candidates exhibit good ORR activity with U L > 0.80 V of Pt(111) by ligand modification screening. The increased moderate positive charge on central metals is ascribed to the weakened interaction between catalysts and OH* in *OH-intermediates. Our work provides valuable insights into understanding ligand engineering on dual-metal catalysts, which is helpful for designing highly efficient, nonprecious single-atom catalysts by tuning the metal bonding environment.

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“…59 Wang et al reported that cobalt polyphthalocyanine with an axially coordinated azide showed much better catalytic performance for the ORR than that of pristine cobalt polyphthalocyanine. 71…”

Section: Introductionmentioning

confidence: 99%

First-principle calculations study of the ORR/OER electrocatalytic activity of ruthenium polyphthalocyanine axially modified with aliphatic thiol groups

Wang,

Ren,

Feng

et al. 2024

Phys. Chem. Chem. Phys.

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A theoretical study on the ORR electrocatalytic activity of axial ligand modified cobalt polyphthalocyanine

Abstract: In this work, the catalytic activity of the oxygen reduction reaction (ORR) of cobalt polyphthalocyanine whose central Co atom coordinated at the axial position by the ligands (L= -F, -OH,...

Cited by 4 publications

References 56 publications

Regulating d‐Orbital Hybridization of Subgroup‐IVB Single Atoms for Efficient Oxygen Reduction Reaction

Regulating d‐Orbital Hybridization of Subgroup‐IVB Single Atoms for Efficient Oxygen Reduction Reaction

Hierarchical High-Throughput Screening of the Ligand Effect of Electrocatalytic Oxygen Reduction on Dual-Metal Atomic Catalysts (M₁M₂N₆–R): A First-Principles Study

First-principle calculations study of the ORR/OER electrocatalytic activity of ruthenium polyphthalocyanine axially modified with aliphatic thiol groups

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A theoretical study on the ORR electrocatalytic activity of axial ligand modified cobalt polyphthalocyanine

Abstract: In this work, the catalytic activity of the oxygen reduction reaction (ORR) of cobalt polyphthalocyanine whose central Co atom coordinated at the axial position by the ligands (L= -F, -OH,...

Cited by 4 publications

References 56 publications

Regulating d‐Orbital Hybridization of Subgroup‐IVB Single Atoms for Efficient Oxygen Reduction Reaction

Regulating d‐Orbital Hybridization of Subgroup‐IVB Single Atoms for Efficient Oxygen Reduction Reaction

Hierarchical High-Throughput Screening of the Ligand Effect of Electrocatalytic Oxygen Reduction on Dual-Metal Atomic Catalysts (M1M2N6–R): A First-Principles Study

First-principle calculations study of the ORR/OER electrocatalytic activity of ruthenium polyphthalocyanine axially modified with aliphatic thiol groups

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Hierarchical High-Throughput Screening of the Ligand Effect of Electrocatalytic Oxygen Reduction on Dual-Metal Atomic Catalysts (M₁M₂N₆–R): A First-Principles Study