Strong Metal–Support Interaction and Reactivity of Ultrathin Oxide Films

Shaikhutdinov, Shamil K.

doi:10.1007/s10562-018-2499-9

Cited by 24 publications

(29 citation statements)

References 59 publications

(66 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[ 22,23 ] A special type of surface reconstructions that can happen in an oxygen‐rich environment is the formation of ultrathin oxide overlayers. [ 24–26 ] Beyond transition metal‐based catalysis, such oxidized overlayers have also shown their importance in carbon‐based catalysts. [ 27,28 ] Here, we report that a kinetically stable reconstructed oxide overlayer on Mo 3 P boosts its electrocatalytic performance toward exceptional ORR and OER activities, that is, current densities of 7.21 mA cm −2 at 2.0 V versus Li/Li + (ORR) and 6.85 mA cm −2 at 4.2 V versus Li/Li + (OER) in a non‐aqueous electrolyte, exceeding the performance of existing catalysts reported to date.…”

Section: Figurementioning

confidence: 99%

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

et al. 2020

View full text Add to dashboard Cite

OER) or only remain active for one of the reactions (different ORR/OER rates). [1-5] This can result in high overpotentials-excess energy above its thermodynamic value (2.96 V)-required to form and decompose lithium peroxide (Li 2 O 2) at the cathode during discharge (ORR) and charge (OER) processes, respectively. Numerous metal catalysts such as platinum (Pt), gold (Au), and ruthenium (Ru), as well as non-metallic catalysts such as transition-metal oxides, transition-metal dichalcogenides, and carbon-based catalysts, have been employed to resolve this issue, however, no major breakthrough has been reported to date. [4,6-11] Therefore, designing a highly active catalyst that can minimize the energy barriers-excess input energy-to form and decompose Li 2 O 2 nanoparticles at the cathode is a key challenge for the development of this technology. Electrocatalytic properties of transition metal phosphides have received great attention and been subject of theoretical and experimental studies. [12-16] Wang et al. demonstrated a convenient and straightforward approach to the synthesis of a 3D selfsupported Ni 5 P 4-Ni 2 P nanosheet cathode, very stable in acidic medium with an outstanding hydrogen evolution reaction (HER) activity. [17] Some other studies include development of The main drawbacks of today's state-of-the-art lithium-air (Li-air) batteries are their low energy efficiency and limited cycle life due to the lack of earth-abundant cathode catalysts that can drive both oxygen reduction and evolution reactions (ORR and OER) at high rates at thermodynamic potentials. Here, inexpensive trimolybdenum phosphide (Mo 3 P) nanoparticles with an exceptional activity-ORR and OER current densities of 7.21 and 6.85 mA cm −2 at 2.0 and 4.2 V versus Li/Li + , respectively-in an oxygen-saturated non-aqueous electrolyte are reported. The Tafel plots indicate remarkably low charge transfer resistance-Tafel slopes of 35 and 38 mV dec −1 for ORR and OER, respectively-resulting in the lowest ORR overpotential of 4.0 mV and OER overpotential of 5.1 mV reported to date. Using this catalyst, a Li-air battery cell with low discharge and charge overpotentials of 80 and 270 mV, respectively, and high energy efficiency of 90.2% in the first cycle is demonstrated. A long cycle life of 1200 is also achieved for this cell. Density functional theory calculations of ORR and OER on Mo 3 P (110) reveal that an oxide overlayer formed on the surface gives rise to the observed high ORR and OER electrocatalytic activity and small discharge/charge overpotentials. The advancement of lithium-air (Li-air) batteries, proposed as a potential alternative for existing energy storage systems, is mainly hampered by low energy efficiency and limited cycle life. One of the major drawbacks for today's Li-air batteries is that developed catalysts exhibit sluggish activity for both oxygen reduction and evolution reactions (ORR and

show abstract

Section: Figurementioning

confidence: 99%

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

et al. 2020

View full text Add to dashboard Cite

show abstract

“…For a more exhaustive panorama of this topic the reader is referred to many existing excellent reviews and perspectives such as Refs. 124,[131][132][133][134][135] , to cite some among the most recent ones.…”

Section: Reviewmentioning

confidence: 99%

“…When the encapsulation of metal particles by the FeO bilayer is complete, a way to enhance the catalytic activity is to work under oxygen rich atmosphere and at lower temperatures, when an oxidized FeO 2-x overlayer can be formed which can be catalytically active towards reactions like water dissociation 141 . The debate on the transformations and properties of Pt(111)/FeO x is still open and very active 142 , and a recent review 135 discusses the most recent results on this system in an exhaustive way. Further results on this system comes from Zhang et al 142 , who suggested that both FeO and FeO 2-x overlayers play a role in CO oxidation, and that the reaction takes place at the interface between the reduced and the oxidized phase.…”

Section: Reviewmentioning

confidence: 99%

2D oxides on metal materials: concepts, status, and perspectives

Barcaro

Fortunelli

2019

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…Transmission electron microscopy unambiguously showed the encapsulation of supported PGM catalysts by their metal oxide support [42][43][44][45]. Besides partial wetting or complete encapsulation of metallic nanoparticles by the oxidic support, also the formation of intermetallic compounds or alloys has been observed, especially at very high temperature under reducing conditions [46,47].…”

Section: Introductionmentioning

confidence: 92%

Reactivity and Stability of Ultrathin VOx Films on Pt(111) in Catalytic Methanol Oxidation

2020

View full text Add to dashboard Cite

The growth of ultrathin layers of VOx (< 12 monolayers) on Pt(111) and the activity of these layers in catalytic methanol oxidation at 10−4 mbar have been studied with low-energy electron diffraction, Auger electron spectroscopy, rate measurements, and with photoemission electron microscopy. Reactive deposition of V in O2 at 670 K obeys a Stranski–Krastanov growth mode with a (√3 × √3)R30° structure representing the limiting case for epitaxial growth of 3D-VOx. The activity of VOx/Pt(111) in catalytic methanol oxidation is very low and no redistribution dynamics is observed lifting the initial spatial homogeneity of the VOx layer. Under reaction conditions, part of the surface vanadium diffuses into the Pt subsurface region. Exposure to O2 causes part of the V to diffuse back to the surface, but only up to one monolayer of VOx can be stabilized in this way at 10−4 mbar.

show abstract

Strong Metal–Support Interaction and Reactivity of Ultrathin Oxide Films

Cited by 24 publications

References 59 publications

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

2D oxides on metal materials: concepts, status, and perspectives

Reactivity and Stability of Ultrathin VOx Films on Pt(111) in Catalytic Methanol Oxidation

Contact Info

Product

Resources

About

Strong Metal–Support Interaction and Reactivity of Ultrathin Oxide Films

Cited by 24 publications

References 59 publications

Kinetically Stable Oxide Overlayers on Mo3P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Kinetically Stable Oxide Overlayers on Mo3P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

2D oxides on metal materials: concepts, status, and perspectives

Reactivity and Stability of Ultrathin VOx Films on Pt(111) in Catalytic Methanol Oxidation

Contact Info

Product

Resources

About

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life