Stable and Active Oxidation Catalysis by Cooperative Lattice Oxygen Redox on SmMn2O5 Mullite Surface

The oxygen evolution reaction (OER) activity of pristine NiOOH is enhanced by doping with Fe. However, the precise role of Fe is still being debated. Here, we use the first-principles DFT+U approach to study three different types of active sites: one on pristine and the other two on Fe-doped NiOOH monolayers to account for the direct and indirect roles of Fe. To compare the activity of the active sites, we consider two mechanisms of OER based on the source of O-O bond formation. Our results show that the mechanism involving the coupling of lattice oxygen is generally more favorable than water nucleophilic attack on lattice oxygen. On doping with Fe, the overpotential of NiOOH is reduced by 0.33 V in excellent agreement with experimental findings. Introducing Fe at active sites results in different potential determining steps (PDS) in the two mechanisms, whereas Ni sites in pristine and Fe-doped NiOOH have the same PDS regardless of the mechanism. The Fe sites not only have the lowest overpotential but also decrease the overpotential for Ni sites.

Confined Ir single sites with triggered lattice oxygen redox: Toward boosted and sustained water oxidation catalysis

Joule ◽

10.1016/j.joule.2021.05.018 ◽

2021 ◽

Vol 5 (8) ◽

pp. 2164-2176 ◽

Cited By ~ 2

Author(s):

Zhaoping Shi ◽

Ying Wang ◽

Ji Li ◽

Xian Wang ◽

Yibo Wang ◽

...

Keyword(s):

Water Oxidation ◽

Oxidation Catalysis ◽

Lattice Oxygen ◽

Water Oxidation Catalysis

Active oxidation protection for ABM control surfaces

10.2514/6.1971-391 ◽

1971 ◽

Author(s):

D. CAWTHON ◽

C. JOYNER, JR.

Keyword(s):

Active Oxidation ◽

Oxidation Protection ◽

Control Surfaces

Oxidase Catalysis via an Aerobically Generated Dess-Martin Periodinane Analogue

10.26434/chemrxiv.6149276.v1 ◽

2018 ◽

Author(s):

Asim Maity ◽

Sung-Min Hyun ◽

Alan Wortman ◽

David Powers

Keyword(s):

Chemical Synthesis ◽

Aerobic Oxidation ◽

Substrate Oxidation ◽

Oxidation Catalysis ◽

Hypervalent Iodine ◽

Oxidation Reactions ◽

Broad Array ◽

Oxidation Chemistry ◽

Reactive Oxidants

Hypervalent iodine(V) reagents, such as Dess-Martin periodinane (DMP) and 2-iodoxybenzoic acid (IBX), are broadly useful oxidants in chemical synthesis. Development of strategies to access these reagents from O2 would immediately enable use of O2 as a terminal oxidant in a broad array of substrate oxidation reactions. Recently we disclosed the aerobic synthesis of I(III) reagents by intercepting reactive oxidants generated during aldehyde autoxidation. Here, we couple aerobic oxidation of iodobenzenes with disproportionation of the initially generated I(III) compounds to generate I(V) reagents. The aerobically generated I(V) reagents exhibit substrate oxidation chemistry analogous to that of DMP. Further, the developed aerobic generation of I(V) has enabled the first application of I(V) intermediates in aerobic oxidation catalysis.

Tuning the Activities of Cu2O Nanostructures via the Oxide-Metal Interaction

10.26434/chemrxiv.7938116.v4 ◽

2019 ◽

Author(s):

Wugen Huang ◽

qingfei liu ◽

Zhiwen Zhou ◽

Yangsheng Li ◽

Yong Wang ◽

...

Keyword(s):

Co Oxidation ◽

Oxidation Catalysis ◽

Atomic Scale ◽

Scanning Tunneling ◽

Oxidation Reactions ◽

Tunneling Microscopy ◽

Temperature Oxidation ◽

Metal Interaction ◽

Tremendous Importance ◽

Oxygen Atoms

Despite tremendous importance in catalysis, the design and improvement of the oxide- metal interface has been hampered by the limited understanding on the nature of interfacial sites, as well as the oxide-metal interaction (OMI). Through the construction of well-defined Cu2O-Pt, Cu2O-Ag, Cu2O-Au interfaces, we found that Cu2O Nanostructures (NSs) on Pt exhibit much lower thermal stability than on Ag and Au, although they show the same surface and edge structures, as identified by element-specific scanning tunneling microscopy (ES-STM) images. The activities of the Cu2O-Pt and Cu2O-Au interfaces for CO oxidation were further compared at the atomic scale and showed in general that the interface with Cu2O NSs could annihilate the CO-poisoning problem suffered by Pt group metals and enhance the interaction with O2, which is a limiting step for CO oxidation catalysis on group IB metals. While both interfaces could react with CO at room temperature, the OMI was found to determine the reactivity of supported Cu2O NSs by 1) tuning the activity of interfacial oxygen atoms and 2) stabilizing oxygen vacancies or vice versa, the dissociated oxygen atoms at the interface. Our study provides new insight for OMI and for the development of Cu-based catalysts for low temperature oxidation reactions.

Tuning the Activities of Cu2O Nanostructures via the Oxide-Metal Interaction

10.26434/chemrxiv.7938116.v3 ◽

2019 ◽

Author(s):

Wugen Huang ◽

Yangsheng Li ◽

Yong Wang ◽

Yunchuan Tu ◽

Dehui Deng ◽

...

Keyword(s):

Co Oxidation ◽

Oxidation Catalysis ◽

Atomic Scale ◽

Scanning Tunneling ◽

Oxidation Reactions ◽

Tunneling Microscopy ◽

Temperature Oxidation ◽

Metal Interaction ◽

Tremendous Importance ◽

Oxygen Atoms

Despite tremendous importance in catalysis, the design and improvement of the oxide- metal interface has been hampered by the limited understanding on the nature of interfacial sites, as well as the oxide-metal interaction (OMI). Through the construction of well-defined Cu2O-Pt, Cu2O-Ag, Cu2O-Au interfaces, we found that Cu2O Nanostructures (NSs) on Pt exhibit much lower thermal stability than on Ag and Au, although they show the same surface and edge structures, as identified by element-specific scanning tunneling microscopy (ES-STM) images. The activities of the Cu2O-Pt and Cu2O-Au interfaces for CO oxidation were further compared at the atomic scale and showed in general that the interface with Cu2O NSs could annihilate the CO-poisoning problem suffered by Pt group metals and enhance the interaction with O2, which is a limiting step for CO oxidation catalysis on group IB metals. While both interfaces could react with CO at room temperature, the OMI was found to determine the reactivity of supported Cu2O NSs by 1) tuning the activity of interfacial oxygen atoms and 2) stabilizing oxygen vacancies or vice versa, the dissociated oxygen atoms at the interface. Our study provides new insight for OMI and for the development of Cu-based catalysts for low temperature oxidation reactions.

The search for intermediates formed during water-oxidation catalysis

Chem Catalysis ◽

10.1016/j.checat.2021.06.004 ◽

2021 ◽

Vol 1 (2) ◽

pp. 248-250

Author(s):

Rosalie K. Hocking

Keyword(s):

Water Oxidation ◽

Oxidation Catalysis ◽

Water Oxidation Catalysis

Surface Lattice Oxygen Activation by Nitrogen-Doped Manganese Dioxide as an Effective and Longevous Catalyst for Indoor HCHO Decomposition

ACS Applied Materials & Interfaces ◽

10.1021/acsami.1c04369 ◽

2021 ◽

Author(s):

Jinwei Chen ◽

Haiyan Tang ◽

Meng Huang ◽

Yong Yan ◽

Jin Zhang ◽

...

Keyword(s):

Manganese Dioxide ◽

Oxygen Activation ◽

Lattice Oxygen ◽

Nitrogen Doped ◽

Surface Lattice

Molecular Water Oxidation Catalysis: Characterization of Subnanosecond Processes and Ruthenium “Green Dimer” Formation

ACS Applied Energy Materials ◽

10.1021/acsaem.0c02959 ◽

2021 ◽

Author(s):

Iwona Grądzka-Kurzaj ◽

Mateusz Gierszewski ◽

Brian J. J. Timmer ◽

Marcin Ziółek

Keyword(s):

Water Oxidation ◽

Oxidation Catalysis ◽

Molecular Water ◽

Dimer Formation ◽

Water Oxidation Catalysis

Metal-Organic Frameworks in Oxidation Catalysis with Hydrogen Peroxide

Catalysts ◽

10.3390/catal11020283 ◽

2021 ◽

Vol 11 (2) ◽

pp. 283

Author(s):

Oxana Kholdeeva ◽

Nataliya Maksimchuk

Keyword(s):

Hydrogen Peroxide ◽

Liquid Phase ◽

Selective Oxidation ◽

Metal Organic Frameworks ◽

Short Review ◽

Catalytic Performance ◽

Oxidation Catalysis ◽

Catalyst Stability ◽

Aqueous Hydrogen Peroxide ◽

Metal Organic

In recent years, metal–organic frameworks (MOFs) have received increasing attention as selective oxidation catalysts and supports for their construction. In this short review paper, we survey recent findings concerning use of MOFs in heterogeneous liquid-phase selective oxidation catalysis with the green oxidant–aqueous hydrogen peroxide. MOFs having outstanding thermal and chemical stability, such as Cr(III)-based MIL-101, Ti(IV)-based MIL-125, Zr(IV)-based UiO-66(67), Zn(II)-based ZIF-8, and some others, will be in the main focus of this work. The effects of the metal nature and MOF structure on catalytic activity and oxidation selectivity are analyzed and the mechanisms of hydrogen peroxide activation are discussed. In some cases, we also make an attempt to analyze relationships between liquid-phase adsorption properties of MOFs and peculiarities of their catalytic performance. Attempts of using MOFs as supports for construction of single-site catalysts through their modification with heterometals will be also addressed in relation to the use of such catalysts for activation of H2O2. Special attention is given to the critical issues of catalyst stability and reusability. The scope and limitations of MOF catalysts in H2O2-based selective oxidation are discussed.