Preparation and Electrochemistry of Iron, Ruthenium, and Cobalt(II) Hexaphenanthrene Clathrochelates Designed for Efficient Electrocatalytic Hydrogen Production and Their Physisorption on Carbon Materials

Voloshin, Yan Z.; Chornenka, Nina V.; Belov, Alexander S.; Grigoriev, S.A.; Pushkarev, Artem S.; Millet, Pierre; Kalinichenko, Valery N.; Oranskiy, Dmitriy A.; Дедов, А. Г.

doi:10.1149/2.0391913jes

Cited by 7 publications

(5 citation statements)

References 21 publications

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“…An original method of using graphene as a support of molecular electrocatalysts for hydrogen evolution was demonstrated in the studies of Russian researchers, including those performed at the National Research Center Kurchatov Institute [ 126 ]. The clathrochelate complexes of Fe, Co, and Ru can be adsorbed on the developed RGO surface, which makes it possible to significantly increase the efficiency and productivity of the cathode of a PEM water electrolyzer [ 127 , 128 ]. A similar approach can be used in the case of molecular electrocatalysts of the ORR, etc.…”

Section: Application Of Graphene In Electrocatalytic Layers Of Polmentioning

confidence: 99%

Graphene and Graphene-Like Materials for Hydrogen Energy

et al. 2020

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The review is devoted to current and promising areas of application of graphene and materials based on it for generating environmentally friendly hydrogen energy. Analysis of the results of theoretical and experimental studies of hydrogen accumulation in graphene materials confirms the possibility of creating on their basis systems for reversible hydrogen storage, which combine high capacity, stability, and the possibility of rapid hydrogen evolution under conditions acceptable for practical use. Recent advances in the development of chemically and heat-resistant graphene-based membrane materials make it possible to create new gas separation membranes that provide high permeability and selectivity and are promising for hydrogen purification in processes of its production from natural gas. The characteristics of polymer membranes that are currently used in industry for the most part can be significantly improved with small additions of graphene materials. The use of graphene-like materials as a support of nanoparticles or as functional additives in the composition of the electrocatalytic layer in polymer electrolyte membrane fuel cells makes it possible to improve their characteristics and to increase the activity and stability of the electrocatalyst in the reaction of oxygen evolution.

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Section: Application Of Graphene In Electrocatalytic Layers Of Polmentioning

confidence: 99%

Graphene and Graphene-Like Materials for Hydrogen Energy

et al. 2020

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“…Specifically, they can be adsorbed onto highsurface-area electrode materials and used as an alternative to metallic Pt-containing electrocatalysts. 13,22 However, the exact catalytic mechanism of the d-metal-electrocatalyzed HER in the case of the cobalt and iron complexes of this type remains an open question. 24,25,33 Theoretical studies of the resting cobalt(II) clathrochelates are essential to shed light on the role of these complexes toward the HER.…”

Section: Introductionmentioning

confidence: 99%

“…Cage complexes with encapsulated transition d -metal ion containing the derivatives of Fe, Ni or Co (e.g., clathrochelates , ) were synthesized, − among which, the macrobicyclic cobalt(II) tris-α-dioximates (Scheme ) allow the fabrication of a broad and interesting family of metal complexes. Such complexes have been highlighted , due to their efficiency as both homogeneous − and immobilized − electrocatalysts for hydrogen production. They are also reported to be good precatalysts for the deposition of highly catalytically active metal nanoparticles. − Their three-dimensional macropolycyclic ligands with suitable electron-withdrawing substituents (especially halogen atoms) in their ribbed chelating ligand are able to stabilize the low (probably, catalytically active) oxidation states of their encapsulated transition metal ions (in particular, iron(I) and cobalt(I) oxidation states ,− ), which makes them unique candidates to be applied as molecular electrocatalysts for the HER. , …”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Transition d-metal clathrochelates with encapsulated iron, ruthenium, or cobalt(II) ion are especially promising electrocatalysts for the HER, when they are immobilized on the surface of the cathode of a given water electrolyzer . Surface functionalization via physisorption is reported to be the easiest way to implement these macrobicyclic electrocatalysts, and this process can be improved by increasing the number of terminal polyaromatic groups per cage molecule of these complexes. Specifically, they can be adsorbed onto high-surface-area electrode materials and used as an alternative to metallic Pt-containing electrocatalysts. , However, the exact catalytic mechanism of the d - metal-electrocatalyzed HER in the case of the cobalt and iron complexes of this type remains an open question. ,, …”

Section: Introductionmentioning

confidence: 99%

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Precise Fingerprint Determination of Vibrational Infrared Spectra in a Series of Co(II) Clathrochelates through Experimental and Theoretical Analyses

Corcho-Valdes,

Ponce de Leon-Cabrera,

Padron-Ramirez

et al. 2023

J. Phys. Chem. A

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The energetic demands of modern society for clean energy vectors, such as H 2 , have caused a surge in research associated with homogeneous and immobilized electrocatalysts that may replace Pt. In particular, clathrochelates have shown excellent electrocatalytic properties for the hydrogen evolution reaction (HER). However, the actual mechanism for the HER catalyzed by these d-metal complexes remains an open debate, which may be addressed via Operando spectroelectrochemistry. The prediction of electrochemical properties via density functional theory (DFT) needs access to thermodynamic functions, which are only available after Hessian calculations. Unfortunately, there is a notable lack in the current literature regarding the precise evaluation of vibrational spectra of such complexes, given their structural complexity and the associated tangled IR spectra. In this work, we have performed a detailed theoretical and experimental analysis in a family of Co(II) clathrochelates, in order to establish univocally their IR pattern, and also the calculation methodology that is adequate for such predictions. In summary, we have observed the presence of multiple common bands shared by this clathrochelate family, using the B3LYP functional, the LANL2DZ basis, and effective core potentials (ECP) for heavy atoms. The most important issue addressed in this article was therefore related to the detailed assignment of the fingerprint associated with cobalt(II) clathrochelates, which is a challenging endeavor due to the crowded nature of their spectra.

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