The Impact of Ligand Carboxylates on Electrocatalyzed Water Oxidation

Das, Biswanath; Rahaman, Ahibur; Shatskiy, Andrey; Verho, Oscar; Kärkäs, Markus D.

doi:10.1021/acs.accounts.1c00298

Cited by 48 publications

(47 citation statements)

References 43 publications

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“…[ 9 ] It has been confirmed that the carboxylate group in the ruthenium complexes can improve water oxidation in three ways: 1) accelerating the CPET process; 2) stabilizing the high oxidation states of the metal center; 3) improving the stability of catalysts by the strong coordination with metal centers. [ 6b,10 ] Similar results were also observed for metal‐organic frameworks. [ 6b,9a ] These findings inspire us to upgrade the design of NiFe LDH through a biomimetic process to accelerate the sluggish kinetics.…”

Section: Introductionsupporting

confidence: 70%

Two Birds with One Stone: Contemporaneously Boosting OER Activity and Kinetics for Layered Double Hydroxide Inspired by Photosystem II

Lin

Cao

Chen

et al. 2022

Adv Funct Materials

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The poor catalytic kinetics together with unsatisfied activity of nonprecious metal electrocatalysts for oxygen evolution reaction hamper their applications in industrial water electrolysis. Inspired by the oxygen evolution cluster of photosystem II in nature, Li + -doped NiFe layered double hydroxide modified with carboxylate is constructed by in situ growth on Ni foam (NFCL(70)-LDH @ NF) via one-pot redox synthesis. Herein, lithium acetate is introduced to regulate the electronic structure and improve proton transfer kinetics, thus "Two birds with one stone". The targeted product exhibits highly improved OER performance in 1 M KOH at room temperature (159 and 224 mV at 10 and 100 mA cm −2 ), as well as dramatically decreased Tafel slope (47.9 mV dec -1 ). Control experiments and theoretical calculations uncover that the presence of Li + modulates the local electronic structure and stabilizes the OOH* intermediate. Specifically, the carboxylate ligands serve as relays to promote proton transfer efficiency, which is similar to the concerted proton electrons transfer in photosystem II. Moreover, NFCL(70)-LDH @ NF maintains the excellent performance over a month under the simulated industrial condition. The exploration of high performance, triggered synergistically by Li + doping and acetate-modifying, sheds light on the design of organic-inorganic hybrid electrocatalysts for highly efficient OER.

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Section: Introductionsupporting

confidence: 70%

Two Birds with One Stone: Contemporaneously Boosting OER Activity and Kinetics for Layered Double Hydroxide Inspired by Photosystem II

Lin

Cao

Chen

et al. 2022

Adv Funct Materials

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“…As shown in Scheme 2, the calculated p K a of 3 2 is around 11, while the calculated H 2 O→OH − ligand exchange has an exothermicity of 7.2 kcal mol −1 , indicating both pathways are feasible, but the latter pathway could be more favorable at the experimental pH of 11.5. In the third pathway (III), the formation of .+ L−Cu II −OH − may transpire via the proton‐coupled electron transfer, a prevalent process in electrochemical reactions [91–98] . However, such a process is associated with a redox potential of 1.39 V and thus less unfavorable compared to the pathway 3 2 → 3 3′ .…”

Section: Resultsmentioning

confidence: 99%

“…In the third pathway (III), the formation of * + LÀ Cu II À OH À may transpire via the proton-coupled electron transfer, a prevalent process in electrochemical reactions. [91][92][93][94][95][96][97][98] However, such a process is associated with a redox potential of 1.39 V and thus less unfavorable compared to the pathway 3 2! 3 3'.…”

Section: Formation Of Active Speciesmentioning

confidence: 99%

Molecular Mechanism of the Mononuclear Copper Complex‐Catalyzed Water Oxidation from Cluster‐Continuum Model Calculations

Yan

Fang

et al. 2022

ChemSusChem

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Cluster-continuum model calculations were conducted to decipher the mechanism of water oxidation catalyzed by a mononuclear copper complex. Among various OÀ O bond formation mechanisms investigated in this study, the most favorable pathway involved the nucleophilic attack of OH À onto the * + LÀ Cu II À OH À intermediate. During such process, the initial binding of OH À to the proximity of * + LÀ Cu II À OH À would result in the spontaneous oxidation of OH À , leading to OH * radical and Cu II À OH À species. The further OÀ O coupling between OH * radical and Cu II À OH À was associated with a barrier of 14.8 kcal mol À 1 , leading to the formation of H 2 O 2 intermediate. Notably, the formation of "Cu III À O *À " species, a widely proposed active species for OÀ O bond formation, was found to be thermodynamically unfavorable and could be bypassed during the catalytic reactions. On the basis the present calculations, a catalytic cycle of the mononuclear copper complex-catalyzed water oxidation was proposed.

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“…[13] The abovementioned negatively charged groups also contribute to lower the overpotentials once directly coordinated to the catalytic sites. [14] However, it is challenging to simultaneously incorporate these groups in the inner and outer coordination environments, and complete protonation of more basic groups such as pyridines and more basic oxygenated bases also prevents their wide applications under acidic conditions. [15] Alternatively, the ubiquitous hydrophobic interactions have been shown to significantly influence activities in enzymatic catalysis and molecular devices through stabilizing the intermediates.…”

Section: Introductionmentioning

confidence: 99%

Promoting Proton Transfer and Stabilizing Intermediates in Catalytic Water Oxidation via Hydrophobic Outer Sphere Interactions

Liu

Shen

et al. 2022

Chemistry A European J

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The outer coordination sphere of metalloenzyme often plays an important role in its high catalytic activity, however, this principle is rarely considered in the design of man‐made molecular catalysts. Herein, four Ru‐bda (bda=2,2′‐bipyridine‐6,6′‐dicarboxylate) based molecular water oxidation catalysts with well‐defined outer spheres are designed and synthesized. Experimental and theoretical studies showed that the hydrophobic environment around the Ru center could lead to thermodynamic stabilization of the high‐valent intermediates and kinetic acceleration of the proton transfer process during catalytic water oxidation. By this outer sphere stabilization, a 6‐fold rate increase for water oxidation catalysis has been achieved.

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The Impact of Ligand Carboxylates on Electrocatalyzed Water Oxidation

Abstract: orientation of two ruthenium centers encapsulating the carboxylate containing noninnocent ligand f ramework in electro-and photochemical WO was reported. Two wellcharacterized ruthenium complexes (cis and trans) with very similar ligand scaf folds were investigated.

Cited by 48 publications

References 43 publications

Two Birds with One Stone: Contemporaneously Boosting OER Activity and Kinetics for Layered Double Hydroxide Inspired by Photosystem II

Two Birds with One Stone: Contemporaneously Boosting OER Activity and Kinetics for Layered Double Hydroxide Inspired by Photosystem II

Molecular Mechanism of the Mononuclear Copper Complex‐Catalyzed Water Oxidation from Cluster‐Continuum Model Calculations

Promoting Proton Transfer and Stabilizing Intermediates in Catalytic Water Oxidation via Hydrophobic Outer Sphere Interactions

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