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1.
Adv Mater ; 34(30): e2202072, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35580350

RESUMO

Surface oxygen vacancies have been widely discussed to be crucial for tailoring the activity of various chemical reactions from CO, NO, to water oxidation by using oxide-supported catalysts. However, the real role and potential function of surface oxygen vacancies in the reaction remains unclear because of their very short lifetime. Here, it is reported that surface oxygen vacancies can be well confined electrostatically for a polarization screening near the perimeter interface between Pt {111} nanocrystals and the negative polar surface (001) of ferroelectric PbTiO3. Strikingly, such a catalyst demonstrates a tunable catalytic CO oxidation kinetics from 200 °C to near room temperature by increasing the O2 gas pressure, accompanied by the conversion curve from a hysteresis-free loop to one with hysteresis. The combination of reaction kinetics, electronic energy loss spectroscopy (EELS) analysis, and density functional theory (DFT) calculations, indicates that the oxygen vacancies stabilized by the negative polar surface are the active sites for O2 adsorption as a rate-determining step, and then dissociated O moves to the surface of the Pt nanocrystals for oxidizing adsorbed CO. The results open a new pathway for tunable catalytic activity of CO oxidation.

2.
Nat Mater ; 21(6): 673-680, 2022 06.
Artigo em Inglês | MEDLINE | ID: mdl-35210585

RESUMO

The oxygen evolution reaction is central to making chemicals and energy carriers using electrons. Combining the great tunability of enzymatic systems with known oxide-based catalysts can create breakthrough opportunities to achieve both high activity and stability. Here we report a series of metal hydroxide-organic frameworks (MHOFs) synthesized by transforming layered hydroxides into two-dimensional sheets crosslinked using aromatic carboxylate linkers. MHOFs act as a tunable catalytic platform for the oxygen evolution reaction, where the π-π interactions between adjacent stacked linkers dictate stability, while the nature of transition metals in the hydroxides modulates catalytic activity. Substituting Ni-based MHOFs with acidic cations or electron-withdrawing linkers enhances oxygen evolution reaction activity by over three orders of magnitude per metal site, with Fe substitution achieving a mass activity of 80 A [Formula: see text] at 0.3 V overpotential for 20 h. Density functional theory calculations correlate the enhanced oxygen evolution reaction activity with the MHOF-based modulation of Ni redox and the optimized binding of oxygenated intermediates.


Assuntos
Estruturas Metalorgânicas , Oxigênio , Catálise , Hidróxidos
3.
Acc Chem Res ; 55(3): 298-308, 2022 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-35050573

RESUMO

ConspectusThe transition from fossil fuels to renewable energy requires the development of efficient and cost-effective energy storage technologies. A promising way forward is to harness the energy of intermittent renewable sources, such as solar and wind, to perform (electro)catalytic reactions to generate fuels, thus storing energy in the form of chemical bonds. However, current catalysts rely on the use of expensive, rare, or geographically localized elements, such as platinum. Widespread adoption of new (electro)catalytic technologies hinges on the discovery and development of materials containing earth-abundant elements, which can efficiently catalyze an array of (electro)chemical reactions.In the context of catalysis, descriptors provide correlations between fundamental physical properties, such as the electronic structure, and the resulting catalytic activity. The use of easily accessible descriptors has proven to be a powerful method to advance and accelerate discovery and design of new catalyst materials. The position of the oxygen electronic 2p band center has been proposed to capture the basic physical properties of oxides, including oxygen vacancy formation energy, diffusion barrier of oxygen ions, and work function. Moreover, the adsorption strength of relevant reaction intermediates at the surface of oxides can be strongly correlated with the energy of the oxygen 2p states, which affects the catalytic activity of reactions, such as oxygen electrocatalysis, and oxidative dehydrogenation of organic molecules. Such descriptors for catalytic activity can be used to predict the activity of new catalysts and understand trends and behavior among different catalysts.In this Account, we discuss how the energy of the oxygen 2p states can be used as a descriptor for oxide bulk and surface chemical properties. We show how the oxide redox properties vary linearly with the position of the oxygen 2p band center with respect to the Fermi level, and we discuss how this descriptor can be expanded across different materials and structural families, including possible generalizations to compounds outside oxides. We highlight the power of the oxygen 2p band center to predict the catalytic activity of oxides. We conclude with an outlook examining under which conditions this descriptor can be applied to predict oxide properties and possible opportunities for further refining and accelerating property predictions of oxides by leveraging material databases and machine learning.

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