Enhancement of Oxygen Evolution Activity of Nickel Oxyhydroxide by Electrolyte Alkali Cations

Garcia, Amanda C.; Touzalin, Thomas; Nieuwland, Celine; Perini, Nickson; Koper, Marc T. M.

doi:10.1002/ange.201905501

Cited by 43 publications

(35 citation statements)

References 54 publications

(76 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…38). The broad signals at the range of 850-1150 cm −1 can be assignable to active oxygen species in Ni (OO)species 54,55 , whose emergence in EA-FCN and EA-FCCN strengthens the preferential step of intramolecular LOC. Then, we simulated the OER cycling at Fe-Ni dual-site and determined the first OH − adsorption as RLS with an energy barrier of 1.43 eV for (FeCoCrNi)OOH model (Fig.…”

Section: Resultsmentioning

confidence: 93%

Lattice oxygen activation enabled by high-valence metal sites for enhanced water oxidation

et al. 2020

View full text Add to dashboard Cite

Anodic oxygen evolution reaction (OER) is recognized as kinetic bottleneck in water electrolysis. Transition metal sites with high valence states can accelerate the reaction kinetics to offer highly intrinsic activity, but suffer from thermodynamic formation barrier. Here, we show subtle engineering of highly oxidized Ni 4+ species in surface reconstructed (oxy) hydroxides on multicomponent FeCoCrNi alloy film through interatomically electronic interplay. Our spectroscopic investigations with theoretical studies uncover that Fe component enables the formation of Ni 4+ species, which is energetically favored by the multistep evolution of Ni 2+ →Ni 3+ →Ni 4+. The dynamically constructed Ni 4+ species drives holes into oxygen ligands to facilitate intramolecular oxygen coupling, triggering lattice oxygen activation to form Fe-Ni dual-sites as ultimate catalytic center with highly intrinsic activity. As a result, the surface reconstructed FeCoCrNi OER catalyst delivers outstanding mass activity and turnover frequency of 3601 A g metal −1 and 0.483 s −1 at an overpotential of 300 mV in alkaline electrolyte, respectively.

show abstract

Section: Resultsmentioning

confidence: 93%

Lattice oxygen activation enabled by high-valence metal sites for enhanced water oxidation

et al. 2020

View full text Add to dashboard Cite

show abstract

“…[42][43] The absence of charge transfer barrier in FeOOH-NiOOH would be consistent with surface-dominated catalysis. The significant cation effect for NiFe LDH also indicates bulk sites are involved in OER, [44][45][46] although the origin of this effect is under debate. [44][45][46] The small cation effect observed for FeOOH-NiOOH is again consistent with surface catalysis.…”

Section: Discussion 31 Raman Spectroscopic Analysismentioning

confidence: 99%

Spectroscopic and Electrokinetic Evidence for a Bifunctional Mechanism of the Oxygen Evolution Reaction

Bai¹,

Lee²,

2020

Preprint

View full text Add to dashboard Cite

The oxygen evolution reaction (OER) is an essential anodic reaction in many energy storage processes. OER is most often proposed to occur via a mechanism involving four consecutive proton-coupled electron transfer (PCET) steps, which imposes a performance limit due to the scaling relationship of various oxygen intermediates. A bifunctional OER mechanism, in which the energetically demanding step of the attack of hydroxide on a metal oxo unit is facilitated by a hydrogen atom transfer to a second site, has the potential to circumvent the scaling relationship. However, the bifunctional mechanism has hitherto only been supported by theoretical computations. Here we describe an operando Raman spectroscopic and electrokinetic study of two highly active OER catalysts, FeOOH-NiOOH and NiFe layered double hydroxide (LDH). The data support two distinct mechanisms for the two catalysts: FeOOH-NiOOH operates by a bifunctional mechanism where the rate-determining O-O bond forming step is the OH- attack on a Fe=O coupled with a hydrogen atom transfer to a NiIII-O site, whereas NiFe LDH operates by a conventional mechanism of four consecutive PCET steps. The experimental validation of the bifunctional mechanism enhances the understanding of OER catalysts.<br>

show abstract

“…Transition metals such as Ni, Co, Mn, Ta or Fe and their oxides have demonstrated appropriate properties as catalysts for OER [13][14][15][16][17] and ORR reactions [18][19][20][21][22][23][24].…”

Section: Introductionmentioning

confidence: 99%

CoTiO3/NrGO nanocomposites for oxygen evolution and oxygen reduction reactions: Synthesis and electrocatalytic performance

Luque-Centeno

Martı́nez-Huerta

Sebastián

et al. 2020

Electrochimica Acta

View full text Add to dashboard Cite

Oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts play an important role in energy conversion and storage devices, but highly active and robust nonprecious metal catalysts are required to address the cost and durability issues. In this work, a modified gel methodology has been used to obtain nanocomposites of perovskite CoTiO 3 and N-doped reduced graphene oxide (NrGO). Moreover, the influence of the annealing extent in the synthesis has been studied. The composites show higher activity in oxygen evolution and reduction reactions in alkaline environment compared to sole ilmenite, which is related to a strong interaction between cobalt titanate and NrGO carbon matrix. The annealing duration appears as a key variable to modulate the physicochemical properties and the electrochemical behavior. The composite prepared at the largest duration (3 hours) exhibit enhanced bifunctional properties for ORR and OER, with onset potentials of 0.93 V and 1.53 V vs. RHE respectively, which is mainly attributed to higher concentration of nitrogen, larger extent of defects and/or the presence of more oxidized Co species in the nanocomposite.

show abstract

Enhancement of Oxygen Evolution Activity of Nickel Oxyhydroxide by Electrolyte Alkali Cations

Cited by 43 publications

References 54 publications

Lattice oxygen activation enabled by high-valence metal sites for enhanced water oxidation

Lattice oxygen activation enabled by high-valence metal sites for enhanced water oxidation

Spectroscopic and Electrokinetic Evidence for a Bifunctional Mechanism of the Oxygen Evolution Reaction

CoTiO3/NrGO nanocomposites for oxygen evolution and oxygen reduction reactions: Synthesis and electrocatalytic performance

Contact Info

Product

Resources

About