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Understanding and Optimizing Ultra‐Thin Coordination Polymer Derivatives with High Oxygen Evolution Performance


Zhao, Yonggui; Wan, Wenchao; Chen, Yi; Erni, Rolf; Triana, Carlos A; Li, Jingguo; Mavrokefalos, Christos K; Zhou, Ying; Patzke, Greta R (2020). Understanding and Optimizing Ultra‐Thin Coordination Polymer Derivatives with High Oxygen Evolution Performance. Advanced Energy Materials, 10(37):2002228.

Abstract

Engineering low‐crystalline and ultra‐thin nanostructures into coordination polymer assemblies is a promising strategy to design efficient electrocatalysts for energy conversion and storage. However, the rational utilization of coordination polymers (CPs) or their derivatives as electrocatalysts has been hindered by a lack of insight into their underlying catalytic mechanisms. Herein, a convenient approach is presented where a series of Ni10‐xFex‐CPs (0 ≤ x ≤ 5) is first synthesized, followed by the introduction of abundant structural deficiencies using a facile reductive method (R‐Ni10‐xFex‐CPs). The representative low‐crystalline R‐Ni8Fe2‐CPs (R‐NiFe‐CPs) with a thickness of sub‐2 nm display promising oxygen evolution reaction (OER) performance with a very low overpotential of 225 mV at 10 mA cm−2 and high long‐term durability over 120 h. Comprehensive investigations including X‐ray absorption spectroscopy, density functional theory, and mass diffusion theory reveal strong synergistic effects of structural deficiencies on the OER activity. A super‐Nernstian pH‐dependence of 85.15 mV pH−1 suggests that the catalytic OER mechanism of R‐NiFe‐CPs involved a decoupled proton‐electron transfer (PT/ET) pathway, leading to notably higher OER activity compared to the concerted coupled proton‐electron transfer pathway. New insights into the catalytic reaction mechanisms of CP‐related materials open up new approaches to expedite the design of efficient electrocatalysts.

Abstract

Engineering low‐crystalline and ultra‐thin nanostructures into coordination polymer assemblies is a promising strategy to design efficient electrocatalysts for energy conversion and storage. However, the rational utilization of coordination polymers (CPs) or their derivatives as electrocatalysts has been hindered by a lack of insight into their underlying catalytic mechanisms. Herein, a convenient approach is presented where a series of Ni10‐xFex‐CPs (0 ≤ x ≤ 5) is first synthesized, followed by the introduction of abundant structural deficiencies using a facile reductive method (R‐Ni10‐xFex‐CPs). The representative low‐crystalline R‐Ni8Fe2‐CPs (R‐NiFe‐CPs) with a thickness of sub‐2 nm display promising oxygen evolution reaction (OER) performance with a very low overpotential of 225 mV at 10 mA cm−2 and high long‐term durability over 120 h. Comprehensive investigations including X‐ray absorption spectroscopy, density functional theory, and mass diffusion theory reveal strong synergistic effects of structural deficiencies on the OER activity. A super‐Nernstian pH‐dependence of 85.15 mV pH−1 suggests that the catalytic OER mechanism of R‐NiFe‐CPs involved a decoupled proton‐electron transfer (PT/ET) pathway, leading to notably higher OER activity compared to the concerted coupled proton‐electron transfer pathway. New insights into the catalytic reaction mechanisms of CP‐related materials open up new approaches to expedite the design of efficient electrocatalysts.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
08 Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Renewable Energy, Sustainability and the Environment
Physical Sciences > General Materials Science
Uncontrolled Keywords:Renewable Energy, Sustainability and the Environment, General Materials Science
Language:English
Date:1 October 2020
Deposited On:04 Feb 2021 10:02
Last Modified:05 Feb 2021 21:05
Publisher:Wiley-VCH Verlag
ISSN:1614-6832
OA Status:Closed
Publisher DOI:https://doi.org/10.1002/aenm.202002228
Project Information:
  • : FunderSNSF
  • : Grant IDCRSII2_160801
  • : Project TitlePhotocatalytic Processes at Solvated Interfaces

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Embargo till: 2021-09-01