Molecular Mimics of Heterogeneous Metal Phosphides: Thermochemistry, Hydride‐Proton Isomerism, and HER Reactivity

Buss, Joshua A.; Hirahara, Masanari; Ueda, Yohei; Agapie, Theodor

doi:10.1002/ange.201808307

Cited by 5 publications

(1 citation statement)

References 65 publications

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“…To date, various noble metals and semiconductors prove to be promising HER catalysts. Phosphides [44,45], sulfides, and manganese have shown good performance in HER. Hydroxides/oxides of nickel [46], iron [46,47], and cobalt [48] have shown good performance in OER.…”

Section: Introductionmentioning

confidence: 99%

Laser-induced graphene electrodes for electrochemical ion sensing, pesticide monitoring, and water splitting

et al. 2021

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Laser-induced graphene (LIG) has shown to be a scalable manufacturing route to create graphene electrodes that overcome the expense associated with conventional graphene electrode fabrication. Herein, we expand upon initial LIG reports by functionalizing the LIG with metallic nanoparticles for ion sensing, pesticide monitoring, and water splitting. The LIG electrodes were converted into ion-selective sensors by functionalization with poly(vinyl chloride)-based membranes containing K + and H + ionophores. These ion-selective sensors exhibited a rapid response time (10-15 s), near-Nernstian sensitivity (53.0 mV/dec for the K + sensor and − 56.6 mV/pH for the pH sensor), and long storage stability for 40 days, and were capable of ion monitoring in artificial urine. The pesticide biosensors were created by functionalizing the LIG electrodes with the enzyme horseradish peroxidase and displayed a high sensitivity to atrazine (28.9 nA/μM) with negligible inference from other common herbicides (glyphosate, dicamba, and 2,4-dichlorophenoxyacetic acid). Finally, the LIG electrodes also exhibited a small overpotential for hydrogen evolution reaction and oxygen evolution reaction. The oxygen evolution reaction tests yielded overpotentials of 448 mV and 995 mV for 10 mA/cm 2 and 100 mA/cm 2 , respectively. The hydrogen evolution reaction tests yielded 35 mV and 281 mV for the corresponding current densities. Such a versatile LIG platform paves the way for simple, efficient electrochemical sensing and energy harvesting applications.

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Section: Introductionmentioning

confidence: 99%

Laser-induced graphene electrodes for electrochemical ion sensing, pesticide monitoring, and water splitting

et al. 2021

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Homolytic versus Heterolytic Hydrogen Evolution Reaction Steered by a Steric Effect

Guo

Wang

et al. 2020

Angewandte Chemie

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Several H−H bond forming pathways have been proposed for the hydrogen evolution reaction (HER). Revealing these HER mechanisms is of fundamental importance for the rational design of catalysts and is also extremely challenging. Now, an unparalleled example of switching between homolytic and heterolytic HER mechanisms is reported. Three nickel(II) porphyrins were designed and synthesized with distinct steric effects by introducing bulky amido moieties to ortho‐ or para‐positions of the meso‐phenyl groups. These porphyrins exhibited different catalytic HER behaviors. For these Ni porphyrins, although their 1e‐reduced forms are active to reduce trifluoroacetic acid, the resulting Ni hydrides (depending on the steric effects of porphyrin rings) have different pathways to make H2. Understanding HER processes, especially controllable switching between homolytic and heterolytic H−H bond formation pathways through molecular engineering, is unprecedented in electrocatalysis.

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Homolytic versus Heterolytic Hydrogen Evolution Reaction Steered by a Steric Effect

et al. 2020

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+ ] These authors contributed equally to this work. Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.1002/anie.202002311.Figure 1. a) Proposed homolytic and heterolytic HER pathways. b) Calculated transition state of the bimetallic homolysis for the HÀH bond formation mediated by Ni TPFP. Bond lengths are given in . Angewandte Chemie Communications

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Molecular Mimics of Heterogeneous Metal Phosphides: Thermochemistry, Hydride‐Proton Isomerism, and HER Reactivity

Cited by 5 publications

References 65 publications

Laser-induced graphene electrodes for electrochemical ion sensing, pesticide monitoring, and water splitting

Laser-induced graphene electrodes for electrochemical ion sensing, pesticide monitoring, and water splitting

Homolytic versus Heterolytic Hydrogen Evolution Reaction Steered by a Steric Effect

Homolytic versus Heterolytic Hydrogen Evolution Reaction Steered by a Steric Effect

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