Electrodeposited-film electrodes derived from a precursor dinitrosyl iron complex for electrocatalytic water splitting

Li, Wei-Liang; Chiou, Tzung-Wen; Chen, Chien‐Hong; Yu, Yi-Ju; Chu, Li‐Kang; Liaw, Wen‐Feng

doi:10.1039/c8dt00601f

Cited by 10 publications

(16 citation statements)

References 60 publications

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“…Complexes 99 , 142 and 153 were incorporated into heterogeneous electrodes to constitute remarkable HER catalysts, capable of reducing protons from water. Liaw and coworkers used the {Fe(NO) 2 } 9 /{Fe(NO) 2 } 10 redox couple in DNICs to design complexes for a solid-state hydrogen evolution cathode. ,, The low-cost PMDTA-bound DNIC 142 , deposited on an electrode, exhibits a low onset potential of -717 mV versus SHE in a neutral 1.0M KCl solution to generate H 2(g) from water . The catalytic activity of DNICs can be further tuned by ligand design.…”

Section: Dinitrosyl Iron Complexes (Dnics)mentioning

confidence: 99%

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

et al. 2021

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Nitric oxide (NO) is an important signaling molecule that is involved in a wide range of physiological and pathological events in biology. Metal coordination chemistry, especially with iron, is at the heart of many biological transformations involving NO. A series of heme proteins, nitric oxide synthases (NOS), soluble guanylate cyclase (sGC), and nitrophorins, are responsible for the biosynthesis, sensing, and transport of NO. Alternatively, NO can be generated from nitrite by heme- and copper-containing nitrite reductases (NIRs). The NO-bearing small molecules such as nitrosothiols and dinitrosyl iron complexes (DNICs) can serve as an alternative vehicle for NO storage and transport. Once NO is formed, the rich reaction chemistry of NO leads to a wide variety of biological activities including reduction of NO by heme or non-heme iron-containing NO reductases and protein post-translational modifications by DNICs. Much of our understanding of the reactivity of metal sites in biology with NO and the mechanisms of these transformations has come from the elucidation of the geometric and electronic structures and chemical reactivity of synthetic model systems, in synergy with biochemical and biophysical studies on the relevant proteins themselves. This review focuses on recent advancements from studies on proteins and model complexes that not only have improved our understanding of the biological roles of NO but also have provided foundations for biomedical research and for bio-inspired catalyst design in energy science.

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Section: Dinitrosyl Iron Complexes (Dnics)mentioning

confidence: 99%

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

et al. 2021

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“…Regarding the biological discovery of the natural [Fe(NO) 2 ] motif as a possible form for the storage and transport of NO, LMW DNIC derived from nitrosylation of the aqueous solution of iron salts, despite the lack of its structural characterization, was adopted to trigger the NO-related function on the activation of soluble guanylate cyclase, , heat-shock protein 70 (HSP70), , nonselective cationic channel, apoptosis, ,, vasodilation, ,,− skin wound healing, , and penile erectile, as well as on the inhibition of Na/K-ATPase, glutathione reductase, glutathione S -transferase, enteroviral rotease A, and platelet aggregation. , To translate this NO-related biological and physiological activity of LMW DNIC into NO-related pharmacology and biomedical application, biomimetic syntheses and crystallographic characterization of mononuclear {Fe(NO) 2 } 9 /{Fe(NO) 2 } 10 DNICs, dinuclear {Fe(NO) 2 } 9 -{Fe(NO) 2 } 9 /{Fe(NO) 2 } 9 -{Fe(NO) 2 } 10 /{Fe(NO) 2 } 10 -{Fe(NO) 2 } 10 DNICs, mononuclear {Fe(NO) 3 } 10 TNICs, and homoleptic {Fe(NO) 4 } 13 iron complexes build up the chemical library of DNICs (Figure ). ,,,,,,− ,− ,− ,,,− ,− ,,− ,− ,,− ...…”

Section: Evolution Of the Functional Model: Redesign Of Natural Dnics...mentioning

confidence: 99%

Bioinorganic Chemistry of the Natural [Fe(NO)₂] Motif: Evolution of a Functional Model for NO-Related Biomedical Application and Revolutionary Development of a Translational Model

Wang

Hung

et al. 2018

Inorg. Chem.

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Identification of the distinctive electron paramagnetic resonance signal at g = 2.03 in the yeast cells and liver of mice treated with carcinogens opened the discovery and investigation of the natural [Fe(NO)2] motif in the form of dinitrosyliron complexes (DNICs). In this Viewpoint, a chronological collection of the benchmark for the study of DNIC demonstrates that the preceding study of its biological synthesis, storage, transport, transformation, and function related to NO physiology inspires the biomimetic study of structural and functional models supported by thiolate ligands to provide mechanistic insight at a molecular level. During the synthetic, spectroscopic, and theoretical investigations on the structure-to-reactivity relationship within DNICs, control of the Fe–NO bonding interaction and of the delivery of NO+/•NO/HNO/NO– by the supporting ligands and nuclearity evolves into the “redesign of the natural [Fe(NO)2] motif” as a strategy to develop DNICs for NO-related biomedical application and therapeutic approach. The revolutionary transformation of covalent a [Fe(NO)2] motif into a translational model for hydrogenase, triggered by the discovery of redox interconversion among [{Fe(NO)2}9-L•] ↔ {Fe(NO)2}9 ↔ {Fe(NO)2}10 ↔ [{Fe(NO)2}10-L•]−, echoes the preceding research journey on [Fe]/[NiFe]-hydrogenase and completes the development of an electrodeposited-film electrode for electrocatalytic water splitting. Through the 50-year journey, bioinorganic chemistry of DNIC containing the covalent [Fe(NO)2] motif and noninnocent/labile NO ligands highlights itself as a unique metallocofactor to join the longitudinal study between biology/chemistry/biomedical application and the lateral study toward multielectron (photo/electro)catalysis for industrial application. This Viewpoint discloses the potential [Fe(NO)2] motif awaiting continued contribution in order to emerge as a novel application in the next 50 years, whereas the parallel development of bioinorganic chemistry, guided by inspirational Nature, moves the science forward to the next stage in order to benefit the immediate needs for human activity.

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“…As reported in the previous study on the implementation of DNICs as homogeneous HER electrocatalysts in aqueous solution, the subsequent deposition of the amount of iron (oxy)hydroxide on graphite electrode during the electrocatalytic HER process demonstrated that DNICs act as a precursor of the heterogeneous HER catalyst . After the extended electrolysis of 1.0 M Na 2 SO 4 aqueous solution with DNICs 1 / 3 – 6 (1 mM) at an applied potential of −1.20 V (vs. SHE) for 1 hr, DNICs 1 / 3 – 6 were reduced to generate catalytically active film on the glassy carbon electrodes that act as the heterogeneous electrodeposited‐film electrodes for HER.…”

Section: Resultsmentioning

confidence: 99%

“…Alternatively, {Fe(NO) 2 } 10 DNIC [(PMDTA)Fe(NO) 2 ] was employed as a precursor to derive the electrodeposited solid‐state HER catalysts . It is demonstrated that the components of the electrodeposited catalyst are the mixture of the metallic iron and iron oxides . In addition, the surface area of electrodeposited catalyst is larger than that of iron salts‐derived catalyst .…”

Section: Introductionmentioning

confidence: 99%

“…It is demonstrated that the components of the electrodeposited catalyst are the mixture of the metallic iron and iron oxides . In addition, the surface area of electrodeposited catalyst is larger than that of iron salts‐derived catalyst . Despite easy fabrication of the micro/nanostructures on the supports by electrodeposition, controlling the shapes and sizes of micro/nanostructures is still challenged .…”

Section: Introductionmentioning

confidence: 99%

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Dinitrosyl iron complexes: From molecular electrocatalysts to electrodeposited‐film electrodes for hydrogen evolution reaction

Chiang

Chiou

et al. 2019

J Chinese Chemical Soc

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Clean and large‐scale production of hydrogen via water splitting triggered by active, robust, and low‐cost electrocatalysts is a promising and sustainable strategy for energy conversion and storage. In this study, a series of four‐coordinated chelating amine‐bound {Fe(NO)2}10 dinitrosyl iron complexes (DNICs) [(L)Fe(NO)2] were synthesized to investigate how the electronic structure of [Fe(NO)2] unit of DNICs was tailored to promote the electrocatalytic hydrogen evolution reaction (HER) triggered by the homogeneous DNICs' molecular catalysts and the heterogeneous DNIC‐derived electrodeposited‐film electrodes. The electrochemical studies demonstrate that HER onset potentials of those DNICs in neutral sodium sulfate aqueous solution are dependent on their IR ν(NO) stretching frequencies, indicating that the electron‐rich [Fe(NO)2] core modulated by the synergistic cooperation of the electron‐donating ability and steric effect of methyl‐/hydrogen‐substituted diamine‐coordinated ligands, presumably, benefits the formation of metal‐hydride intermediate to reduce the required onset potential. In contrast with homogeneous catalyst retaining its molecular integrity during the catalytic HER process, it is noticed that DNICs [(L)Fe(NO)2] act as the precursor of the active heterogeneous HER catalyst during the electrocatalytic HER process. It is presumed that the intermolecular hydrogen‐bonding interactions among DNICs [(L)Fe(NO)2] may control the particle sizes of DNIC‐derived electrodeposited film to modulate HER efficiency.

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Electrodeposited-film electrodes derived from a precursor dinitrosyl iron complex for electrocatalytic water splitting

Cited by 10 publications

References 60 publications

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

Bioinorganic Chemistry of the Natural [Fe(NO)₂] Motif: Evolution of a Functional Model for NO-Related Biomedical Application and Revolutionary Development of a Translational Model

Dinitrosyl iron complexes: From molecular electrocatalysts to electrodeposited‐film electrodes for hydrogen evolution reaction

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Electrodeposited-film electrodes derived from a precursor dinitrosyl iron complex for electrocatalytic water splitting

Cited by 10 publications

References 60 publications

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

The Biologically Relevant Coordination Chemistry of Iron and Nitric Oxide: Electronic Structure and Reactivity

Bioinorganic Chemistry of the Natural [Fe(NO)2] Motif: Evolution of a Functional Model for NO-Related Biomedical Application and Revolutionary Development of a Translational Model

Dinitrosyl iron complexes: From molecular electrocatalysts to electrodeposited‐film electrodes for hydrogen evolution reaction

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Bioinorganic Chemistry of the Natural [Fe(NO)₂] Motif: Evolution of a Functional Model for NO-Related Biomedical Application and Revolutionary Development of a Translational Model