Cyclic Trinickel(II) Clusters in a Metal‐Azolate Framework for Efficient Overall Water Splitting

Herein, a stable metal‐azolate framework with cyclic trinickel(II) clusters, namely [Ni3(μ3‐O)(BTPP)(OH)(H2O)2] (Ni‐BTPP, H3BTPP=1,3,5‐tris((1H‐pyrazol‐4‐yl)phenylene)benzene), achieved a current density of 50 mA cm−2 at a cell voltage of 1.8 V in 1.0 M KOH solution, while the current density of 20%...

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Published inChemistry, an Asian journal Vol. 18; no. 15; pp. e202300281 - n/a
Main Authors Liu, Yan‐Chen, Huang, Jia‐Run, Zhao, Zhen‐Hua, Liao, Pei‐Qin, Chen, Xiao‐Ming
Format Journal Article
LanguageEnglish
Published Germany Wiley Subscription Services, Inc 01.08.2023
Subjects
Benzene
Chemistry
Clusters
Current density
Energy of dissociation
Metal-azolate framework
Nickel(II) cluster
Non-precious metal cluster
Overall water splitting
Oxidation
Water chemistry
Water splitting
Metal-azolate framework
Nickel(II) cluster
Non-precious metal cluster
Overall water splitting
Online AccessGet full text
ISSN1861-4728
1861-471X
1861-471X
DOI10.1002/asia.202300281

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Abstract Herein, a stable metal‐azolate framework with cyclic trinickel(II) clusters, namely [Ni3(μ3‐O)(BTPP)(OH)(H2O)2] (Ni‐BTPP, H3BTPP=1,3,5‐tris((1H‐pyrazol‐4‐yl)phenylene)benzene), achieved a current density of 50 mA cm−2 at a cell voltage of 1.8 V in 1.0 M KOH solution, while the current density of 20%Pt/C@NF||IrO2@NF is just 35.8 mA cm−2 at 2.0 V under the same condition. Moreover, no obvious degradation was observed over 12 hours of continuous operation at a large current density of 50 mA cm−2. Theoretical calculations revealed that the μ3‐O atom in the cyclic trinickel(II) cluster serves as hydrogen‐bonding acceptor to facilitate the dissociation of a H2O molecule adsorbed on the adjacent Ni(II) ion, giving a lower energy barrier of H2O dissociation compared with Pt/C; meanwhile, the μ3‐O atom can also participate in the water oxidation reaction to couple with the adjacent *OH adsorbed on Ni(II) ion, providing a low‐energy coupling pathway, thus Ni‐BTPP achieves a high performance for overall water splitting. A cyclic trinickel(II) cluster‐based metal‐azolate framework is reported as a high‐performance bifunctional catalyst for overall water splitting.
AbstractList Herein, a stable metal-azolate framework with cyclic trinickel(II) clusters, namely [Ni (μ -O)(BTPP)(OH)(H O) ] (Ni-BTPP, H BTPP=1,3,5-tris((1H-pyrazol-4-yl)phenylene)benzene), achieved a current density of 50 mA cm at a cell voltage of 1.8 V in 1.0 M KOH solution, while the current density of 20%Pt/C@NF||IrO @NF is just 35.8 mA cm at 2.0 V under the same condition. Moreover, no obvious degradation was observed over 12 hours of continuous operation at a large current density of 50 mA cm . Theoretical calculations revealed that the μ -O atom in the cyclic trinickel(II) cluster serves as hydrogen-bonding acceptor to facilitate the dissociation of a H O molecule adsorbed on the adjacent Ni(II) ion, giving a lower energy barrier of H O dissociation compared with Pt/C; meanwhile, the μ -O atom can also participate in the water oxidation reaction to couple with the adjacent *OH adsorbed on Ni(II) ion, providing a low-energy coupling pathway, thus Ni-BTPP achieves a high performance for overall water splitting.
Herein, a stable metal‐azolate framework with cyclic trinickel(II) clusters, namely [Ni3(μ3‐O)(BTPP)(OH)(H2O)2] (Ni‐BTPP, H3BTPP=1,3,5‐tris((1H‐pyrazol‐4‐yl)phenylene)benzene), achieved a current density of 50 mA cm−2 at a cell voltage of 1.8 V in 1.0 M KOH solution, while the current density of 20%Pt/C@NF||IrO2@NF is just 35.8 mA cm−2 at 2.0 V under the same condition. Moreover, no obvious degradation was observed over 12 hours of continuous operation at a large current density of 50 mA cm−2. Theoretical calculations revealed that the μ3‐O atom in the cyclic trinickel(II) cluster serves as hydrogen‐bonding acceptor to facilitate the dissociation of a H2O molecule adsorbed on the adjacent Ni(II) ion, giving a lower energy barrier of H2O dissociation compared with Pt/C; meanwhile, the μ3‐O atom can also participate in the water oxidation reaction to couple with the adjacent *OH adsorbed on Ni(II) ion, providing a low‐energy coupling pathway, thus Ni‐BTPP achieves a high performance for overall water splitting. A cyclic trinickel(II) cluster‐based metal‐azolate framework is reported as a high‐performance bifunctional catalyst for overall water splitting.
Herein, a stable metal‐azolate framework with cyclic trinickel(II) clusters, namely [Ni3(μ3‐O)(BTPP)(OH)(H2O)2] (Ni‐BTPP, H3BTPP=1,3,5‐tris((1H‐pyrazol‐4‐yl)phenylene)benzene), achieved a current density of 50 mA cm−2 at a cell voltage of 1.8 V in 1.0 M KOH solution, while the current density of 20%Pt/C@NF||IrO2@NF is just 35.8 mA cm−2 at 2.0 V under the same condition. Moreover, no obvious degradation was observed over 12 hours of continuous operation at a large current density of 50 mA cm−2. Theoretical calculations revealed that the μ3‐O atom in the cyclic trinickel(II) cluster serves as hydrogen‐bonding acceptor to facilitate the dissociation of a H2O molecule adsorbed on the adjacent Ni(II) ion, giving a lower energy barrier of H2O dissociation compared with Pt/C; meanwhile, the μ3‐O atom can also participate in the water oxidation reaction to couple with the adjacent *OH adsorbed on Ni(II) ion, providing a low‐energy coupling pathway, thus Ni‐BTPP achieves a high performance for overall water splitting.
Herein, a stable metal-azolate framework with cyclic trinickel(II) clusters, namely [Ni3 (μ3 -O)(BTPP)(OH)(H2 O)2 ] (Ni-BTPP, H3 BTPP=1,3,5-tris((1H-pyrazol-4-yl)phenylene)benzene), achieved a current density of 50 mA cm-2 at a cell voltage of 1.8 V in 1.0 M KOH solution, while the current density of 20%Pt/C@NF||IrO2 @NF is just 35.8 mA cm-2 at 2.0 V under the same condition. Moreover, no obvious degradation was observed over 12 hours of continuous operation at a large current density of 50 mA cm-2 . Theoretical calculations revealed that the μ3 -O atom in the cyclic trinickel(II) cluster serves as hydrogen-bonding acceptor to facilitate the dissociation of a H2 O molecule adsorbed on the adjacent Ni(II) ion, giving a lower energy barrier of H2 O dissociation compared with Pt/C; meanwhile, the μ3 -O atom can also participate in the water oxidation reaction to couple with the adjacent *OH adsorbed on Ni(II) ion, providing a low-energy coupling pathway, thus Ni-BTPP achieves a high performance for overall water splitting.Herein, a stable metal-azolate framework with cyclic trinickel(II) clusters, namely [Ni3 (μ3 -O)(BTPP)(OH)(H2 O)2 ] (Ni-BTPP, H3 BTPP=1,3,5-tris((1H-pyrazol-4-yl)phenylene)benzene), achieved a current density of 50 mA cm-2 at a cell voltage of 1.8 V in 1.0 M KOH solution, while the current density of 20%Pt/C@NF||IrO2 @NF is just 35.8 mA cm-2 at 2.0 V under the same condition. Moreover, no obvious degradation was observed over 12 hours of continuous operation at a large current density of 50 mA cm-2 . Theoretical calculations revealed that the μ3 -O atom in the cyclic trinickel(II) cluster serves as hydrogen-bonding acceptor to facilitate the dissociation of a H2 O molecule adsorbed on the adjacent Ni(II) ion, giving a lower energy barrier of H2 O dissociation compared with Pt/C; meanwhile, the μ3 -O atom can also participate in the water oxidation reaction to couple with the adjacent *OH adsorbed on Ni(II) ion, providing a low-energy coupling pathway, thus Ni-BTPP achieves a high performance for overall water splitting.
Herein, a stable metal‐azolate framework with cyclic trinickel(II) clusters, namely [Ni 3 ( μ 3 ‐O)(BTPP)(OH)(H 2 O) 2 ] ( Ni‐BTPP , H 3 BTPP=1,3,5‐tris((1 H ‐pyrazol‐4‐yl)phenylene)benzene), achieved a current density of 50 mA cm −2 at a cell voltage of 1.8 V in 1.0 M KOH solution, while the current density of 20%Pt/C@NF||IrO 2 @NF is just 35.8 mA cm −2 at 2.0 V under the same condition. Moreover, no obvious degradation was observed over 12 hours of continuous operation at a large current density of 50 mA cm −2 . Theoretical calculations revealed that the μ 3 ‐O atom in the cyclic trinickel(II) cluster serves as hydrogen‐bonding acceptor to facilitate the dissociation of a H 2 O molecule adsorbed on the adjacent Ni(II) ion, giving a lower energy barrier of H 2 O dissociation compared with Pt/C; meanwhile, the μ 3 ‐O atom can also participate in the water oxidation reaction to couple with the adjacent *OH adsorbed on Ni(II) ion, providing a low‐energy coupling pathway, thus Ni‐BTPP achieves a high performance for overall water splitting.
Author Liao, Pei‐Qin
Zhao, Zhen‐Hua
Chen, Xiao‐Ming
Liu, Yan‐Chen
Huang, Jia‐Run
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Keywords Metal-azolate framework
Nickel(II) cluster
Non-precious metal cluster
Overall water splitting
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Snippet Herein, a stable metal‐azolate framework with cyclic trinickel(II) clusters, namely [Ni3(μ3‐O)(BTPP)(OH)(H2O)2] (Ni‐BTPP,...
Herein, a stable metal‐azolate framework with cyclic trinickel(II) clusters, namely [Ni 3 ( μ 3 ‐O)(BTPP)(OH)(H 2 O) 2 ] ( Ni‐BTPP , H 3 BTPP=1,3,5‐tris((1 H...
Herein, a stable metal-azolate framework with cyclic trinickel(II) clusters, namely [Ni (μ -O)(BTPP)(OH)(H O) ] (Ni-BTPP, H...
Herein, a stable metal-azolate framework with cyclic trinickel(II) clusters, namely [Ni3 (μ3 -O)(BTPP)(OH)(H2 O)2 ] (Ni-BTPP, H3...
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StartPage e202300281
SubjectTerms Benzene
Chemistry
Clusters
Current density
Energy of dissociation
Metal-azolate framework
Nickel(II) cluster
Non-precious metal cluster
Overall water splitting
Oxidation
Water chemistry
Water splitting
Title Cyclic Trinickel(II) Clusters in a Metal‐Azolate Framework for Efficient Overall Water Splitting
URI https://onlinelibrary.wiley.com/doi/abs/10.1002%2Fasia.202300281
https://www.ncbi.nlm.nih.gov/pubmed/37147935
https://www.proquest.com/docview/2844023489
https://www.proquest.com/docview/2810917351
Volume 18
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