Photochemically deposited Ir-doped NiCo oxyhydroxide nanosheets provide highly efficient and stable electrocatalysts for the oxygen evolution reaction

Huang, Lican; Shin, Hyungcheol; Goddard, William A.; Wang, Jianming

doi:10.1016/j.nanoen.2020.104885

Cited by 34 publications

(17 citation statements)

References 48 publications

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“…This result is not surprising; previous attempts to isolate the +5 oxidation state of group 9 metals (namely Rh and Ir) has proved difficult and only possible in the presence of strong oxidants. 75,76 These results are consistent with our proposal that the oxidatively induced reductive elimination reactions likely occur through the 1e − oxidation involving Rh IV . Additionally, our findings agree with a previous study by Chang and co-workers in which the Rh IV /Rh II reductive elimination yielded a lower barrier and more exergonic reaction than the Rh III /Rh I reductive elimination.…”

Section: ■ Results and Discussionsupporting

confidence: 91%

Functionalization of Rh^III–Me Bonds: Use of “Capping Arene” Ligands to Facilitate Me–X Reductive Elimination

Chen

Musgrave

et al. 2021

Organometallics

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We show how to improve the yield of MeX from CH 4 activation catalysts from 12% to 90% through the use of "capping arene" ligands. Four (FP)Rh III (Me)(TFA) 2 {FP = "capping arene" ligands, including 8,8′-(1,2-phenylene)diquinoline (6-FP), 8,8′-(1,2naphthalene)diquinoline (6-NP FP), 1,2-bis(N-7-azaindolyl)benzene (5-FP), and 1,2-bis(N-7-azaindolyl)naphthalene (5-NP FP)} complexes. These complexes and (dpe)Rh III (Me)(TFA) 2 (dpe = 1,2-di-2-pyridylethane) were synthesized and tested for their performance in reductive elimination of MeX (X = TFA or halide). The FP ligands were used with the goal of blocking a coordination site to destabilize the Rh III complexes and facilitate MeX reductive elimination. On the basis of single-crystal X-ray diffraction studies, the 6-FP and 6-NP FP ligated Rh complexes have Rh−arene distances shorter than those of the 5-FP and 5-NP FP Rh complexes; thus, it is expected that the Rh−arene interactions are weaker for the 5-FP complexes than for the 6-FP complexes. Consistent with our hypothesis, the 5-FP and 5-NP FP Rh III complexes demonstrate improved performance (from 12% to ∼60% yield) in the reductive elimination of MeX. The reductive elimination of MeX from (FP)Rh III (Me)(TFA) 2 can be further improved by the use of chemical oxidants. For example, the addition of 2 equiv of AgOTf leads to 87(2)% yield of MeTFA and can be achieved in CD 3 CN at 90 °C using (5-FP)Rh(Me)(TFA) 2 .

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Section: ■ Results and Discussionsupporting

confidence: 91%

Functionalization of Rh^III–Me Bonds: Use of “Capping Arene” Ligands to Facilitate Me–X Reductive Elimination

Chen

Musgrave

et al. 2021

Organometallics

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“…Density functional theory (DFT) was used to probe the reaction mechanism. We have previously used this methodology to determine the reaction mechanism and rate constants for the OER on several electrocatalysts: IrO 2 , 89 Fe-doped NiOOH, 90 Ir-doped (Ni,Co)OOH, 91 and Co-doped TiO 2 . 92 The results of the calculations are overviewed in Schemes 3−5.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Electrocatalytic Water Oxidation by a Trinuclear Copper(II) Complex

et al. 2021

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We report a trinuclear copper(II) complex, [(DAM)Cu3(μ3-O)][Cl]4 (1, DAM = dodecaaza macrotetracycle), as a homogeneous electrocatalyst for water oxidation to dioxygen in phosphate-buffered solutions at pH 7.0, 8.1, and 11.5. Electrocatalytic water oxidation at pH 7 occurs at an overpotential of 550 mV with a turnover frequency of ∼19 s–1 at 1.5 V vs NHE. Controlled potential electrolysis (CPE) experiments at pH 11.5 over 3 h at 1.2 V and at pH 8.1 for 40 min at 1.37 V vs NHE confirm the evolution of dioxygen with Faradaic efficiencies of 81% and 45%, respectively. Rinse tests conducted after CPE studies provide evidence for the homogeneous nature of the catalysis. The linear dependence of the current density on the catalyst concentration indicates a likely first-order dependence on the Cu precatalyst 1, while kinetic isotope studies (H2O versus D2O) point to involvement of a proton in or preceding the rate-determining step. Rotating ring-disk electrode measurements at pH 8.1 and 11.2 show no evidence of H2O2 formation and support selectivity to form dioxygen. Freeze-quench electron paramagnetic resonance studies during electrolysis provide evidence for the formation of a molecular copper intermediate. Experimental and computational studies support a key role of the phosphate as an acceptor base. Moreover, density functional theory calculations highlight the importance of second-sphere interactions and the role of the nitrogen-based ligands to facilitate proton transfer processes.

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“…These two broad peaks were separated into five individual components that can be identified at 438, 470, 480, 550, and 561 cm −1 (Figure 7c). The observed Raman bands at 438, 561 cm −1 and 480, 550 cm −1 , were attributed to the Ni−O vibrations in the nickel oxides and nickel oxyhydroxides, respectively [39–42] . The Ni−OH symmetric mode (A 1g(T) ) from the Ni(OH) 2 was found at 470 cm −1 [43] .…”

Section: Resultsmentioning

confidence: 93%

Boosting Oxygen Evolution Reaction on Metallocene‐based Transition Metal Sulfides Integrated with N‐doped Carbon Nanostructures

Thangasamy

Nam

et al. 2021

ChemSusChem

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In this study, utilizing metallocene and organosulfur chelating agent, an innovative synthetic route was developed towards electrochemically activated transition metal sulfides entrapped in pyridinic nitrogen‐incorporated carbon nanostructures for superior oxygen evolution reaction (OER). Most importantly, the preferential electrochemical activation process, which consisted of both anodic and cathodic pre‐treatment steps, strikingly enhanced OER and long‐lasting cyclic stability. The substantial increase in OER electrocatalytic activity of Ni9S8/Ni3S2−NC and Co9S8−NC during the activation process was mainly attributed to the increase of faradaic active site density on the catalytic layer resulting from the reconstruction of catalytic interfaces. It was also found that Fe‐based metallocene [ferrocene (Fc)]‐incorporation in the Co9S8−NC and Ni9S8/Ni3S2−NC nanostructures significantly boosted the OER activity. Thus, the combined effects of Fc‐incorporation and the electrochemical activation process reduced the overpotential to about 115 and 95 mV on the Ni9S8/Ni3S2−NC and Co9S8−NC nanostructures to derive a current density of 10 mA cm−2, respectively. Notably, Fc−Ni9S8/Ni3S2−NC electrocatalysts required very small overpotentials of around 222, 244, and 280 mV to acquire the current densities of 10, 20, and 50 mA cm−2, respectively. This work opens up a new avenue for superior OER electrocatalysts by the utilization of metallocene and the preferential electrochemical activation process.

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Photochemically deposited Ir-doped NiCo oxyhydroxide nanosheets provide highly efficient and stable electrocatalysts for the oxygen evolution reaction

Cited by 34 publications

References 48 publications

Functionalization of Rh^III–Me Bonds: Use of “Capping Arene” Ligands to Facilitate Me–X Reductive Elimination

Functionalization of Rh^III–Me Bonds: Use of “Capping Arene” Ligands to Facilitate Me–X Reductive Elimination

Electrocatalytic Water Oxidation by a Trinuclear Copper(II) Complex

Boosting Oxygen Evolution Reaction on Metallocene‐based Transition Metal Sulfides Integrated with N‐doped Carbon Nanostructures

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Photochemically deposited Ir-doped NiCo oxyhydroxide nanosheets provide highly efficient and stable electrocatalysts for the oxygen evolution reaction

Cited by 34 publications

References 48 publications

Functionalization of RhIII–Me Bonds: Use of “Capping Arene” Ligands to Facilitate Me–X Reductive Elimination

Functionalization of RhIII–Me Bonds: Use of “Capping Arene” Ligands to Facilitate Me–X Reductive Elimination

Electrocatalytic Water Oxidation by a Trinuclear Copper(II) Complex

Boosting Oxygen Evolution Reaction on Metallocene‐based Transition Metal Sulfides Integrated with N‐doped Carbon Nanostructures

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Product

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Functionalization of Rh^III–Me Bonds: Use of “Capping Arene” Ligands to Facilitate Me–X Reductive Elimination

Functionalization of Rh^III–Me Bonds: Use of “Capping Arene” Ligands to Facilitate Me–X Reductive Elimination