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Vanadium oxides exist in a multitude of phases with varying structure and stoichiometry. This abundance of phases can be extended through the use of other oxides as supports, and through redox treatments. However, the combined effects of different supports and redox treatments can be difficult to identify, particularly when present as different terminating facets on nanoparticles. Here, we examine structural dynamics of 2D vanadium oxides supported on anatase TiO2 nanoparticles, correlated with changes in oxidation state, using in situ transmission electron microscopy imaging and electron energy loss spectroscopy. As the average oxidation state is reduced below V(IV), an ordered cubic V(II) phase is observed exclusively at the high-index {10l} facets of the support. This local accommodation of highly reduced states is necessary for explaining the observed range of average oxidation states. In turn, the findings show that oxidation states extending from V(V)-V(IV) to V(II) can be simultaneously stabilized by different supporting oxide surfaces during exposure to atmospheres with controlled redox potential.
RESUMO
Redox processes of oxide materials are fundamental in catalysis. These processes depend on the surface structure and stoichiometry of the oxide and are therefore expected to vary between surface facets. However, there is a lack of direct measurements of redox properties on the nanoscale for analysing the importance of such faceting effects in technical materials. Here, we address the facet-dependent redox properties of vanadium-oxide-covered anatase nanoparticles of relevance to, e.g., selective catalytic reduction of nitrogen oxides. The vanadium oxidation states at individual nanoscale facets are resolved in situ under catalytically relevant conditions by combining transmission electron microscopy imaging and electron energy loss spectroscopy. The measurements reveal that vanadium on {001} facets consistently retain higher oxidation states than on {10l} facets. Insight into such structure-sensitivity of surface redox processes opens prospects of tailoring oxide nanoparticles with enhanced catalytic functionalities.
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Electrochemical reactions depend on the electrochemical interface between the electrode surfaces and the electrolytes. To control and advance electrochemical reactions there is a need to develop realistic simulation models of the electrochemical interface to understand the interface from an atomistic point-of-view. Here we present a method for obtaining thermodynamic realistic interface structures, a procedure we use to derive specific coverages and to obtain ab initio simulated cyclic voltammograms. As a case study, the method and procedure is applied in a matrix study of three Cu facets in three different electrolytes. The results have been validated by direct comparison to experimental cyclic voltammograms. The alkaline (NaOH) cyclic voltammograms are described by H* and OH*, while in neutral medium (KHCO3 ) the CO 3* species are dominating and in acidic (KCl) the Cl* species prevail. An almost one-to-one mapping is observed from simulation to experiments giving an atomistic understanding of the interface structure of the Cu facets. Atomistic understanding of the interface at relevant eletrolyte conditions will further allow realistic modelling of electrochemical reactions of importance for future eletrocatalytic studies.
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Nitrogen-doped carbon materials featuring atomically dispersed metal cations (M-N-C) are an emerging family of materials with potential applications for electrocatalysis. The electrocatalytic activity of M-N-C materials toward four-electron oxygen reduction reaction (ORR) to H2O is a mainstream line of research for replacing platinum-group-metal-based catalysts at the cathode of fuel cells. However, fundamental and practical aspects of their electrocatalytic activity toward two-electron ORR to H2O2, a future green "dream" process for chemical industry, remain poorly understood. Here we combined computational and experimental efforts to uncover the trends in electrochemical H2O2 production over a series of M-N-C materials (M = Mn, Fe, Co, Ni, and Cu) exclusively comprising atomically dispersed M-Nx sites from molecular first-principles to bench-scale electrolyzers operating at industrial current density. We investigated the effect of the nature of a 3d metal within a series of M-N-C catalysts on the electrocatalytic activity/selectivity for ORR (H2O2 and H2O products) and H2O2 reduction reaction (H2O2RR). Co-N-C catalyst was uncovered with outstanding H2O2 productivity considering its high ORR activity, highest H2O2 selectivity, and lowest H2O2RR activity. The activity-selectivity trend over M-N-C materials was further analyzed by density functional theory, providing molecular-scale understandings of experimental volcano trends for four- and two-electron ORR. The predicted binding energy of HO* intermediate over Co-N-C catalyst is located near the top of the volcano accounting for favorable two-electron ORR. The industrial H2O2 productivity over Co-N-C catalyst was demonstrated in a microflow cell, exhibiting an unprecedented production rate of more than 4 mol peroxide gcatalyst-1 h-1 at a current density of 50 mA cm-2.
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Electrochemical CO reduction holds the promise to be a cornerstone for sustainable production of fuels and chemicals. However, the underlying understanding of the carbon-carbon coupling toward multiple-carbon products is not complete. Here we present thermodynamically realistic structures of the electrochemical interfaces, determined by explicit ab initio simulations. We investigate how key CO reduction reaction intermediates are stabilized in different electrolytes and at different pH values. We find that the catalytic trends previously observed experimentally can be explained by the interplay between the metal surface and the electrolyte. For the Cu(100) facet with a phosphate buffer electrolyte, the energy efficiency is found to be limited by blocking of a phosphate anion, while in alkali hydroxide solutions (MOH, M = Na, K, Cs), OH* intermediates may be present, and at high overpotential the H* coverage limits the reaction. The results provide insight into the electrochemical interface structure, revealing the limitations for multiple-carbon products, and offer a direct comparison to experiments.
RESUMO
The electrochemical oxidation of methane to methanol at remote oil fields where methane is flared is the ultimate solution to harness this valuable energy resource. In this study we identify a fundamental surface catalytic limitation of this process in terms of a compromise between selectivity and activity, as oxygen evolution is a competing reaction. By investigating two classes of materials, rutile oxides and two-dimensional transition metal nitrides and carbides (MXenes), we find a linear relationship between the energy needed to activate methane, i.e. to break the first C-H bond, and oxygen binding energies on the surface. Based on a simple kinetic model we can conclude that in order to obtain sufficient activity oxygen has to bind weakly to the surface but there is an upper limit to retain selectivity. Few potentially interesting candidates are found but this relatively simple description enables future large scale screening studies for more optimal candidates.
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Surface redox processes involving oxygen atom exchange are fundamental in catalytic reactions mediated by metal oxides. These processes are often difficult to uncover due to changes in the surface stoichiometry and atomic arrangement. Here we employ high-resolution transmission electron microscopy to study vanadium oxide supported on titanium dioxide, which is of relevance as a catalyst in, e.g., nitrogen oxide emission abatement for environmental protection. The observations reveal a reversible transformation of the vanadium oxide surface between an ordered and disordered state, concomitant with a reversible change in the vanadium oxidation state, when alternating between oxidizing and reducing conditions. The transformation depends on the anatase titanium dioxide surface termination and the vanadium oxide layer thickness, suggesting that the properties of vanadium oxide are sensitive to the supporting oxide. These atomic-resolution observations offer a basis for rationalizing previous reports on shape-sensitive catalytic properties.Redox processes in metal oxide surfaces can exhibit structure sensitivities which are difficult to uncover. Here, the authors use atomic-resolution imaging to demonstrate facet dependent alterations in the surfaces of supported vanadium oxide upon reduction and oxidation.
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To understand the structure-reactivity relationships for mixed-metal oxide catalysts, well-defined systems are required. Mixtures of vanadia and titania (TiO2) are of particular interest for application in heterogeneous catalysis, with TiO2 often acting as the support. By utilizing high-resolution scanning tunneling microscopy, we studied the interaction of vanadium (V) with the anatase TiO2(101) surface in the sub-monolayer regime. At 80 K, metallic V nucleates into homogeneously distributed clusters onto the terraces with no preference for nucleation at the step edges. However, embedding of single V atoms into TiO2 occurs following annealing at room temperature. In conjunction with X-ray photoelectron spectroscopy data and density functional theory calculations, we propose that monomeric V atoms occupy positions of regular surface Ti sites, i.e., Ti atoms are substituted by V atoms.
RESUMO
The energetics, structures and activity of a monomeric VO3H/TiO2(001) catalyst are investigated for the selective catalytic reduction (SCR) reaction by the use of density functional theory (DFT). Furthermore we study the influences of a dopant substitute in the TiO2 support and its effects on the known properties of the SCR system such as Brønsted acidity and reducibility of vanadium. We find for the reduction part of the SCR mechanism that it involves two Ti-O-V oxygen sites. One is a hydroxyl possessing Brønsted acidity which contributes to the formation of NH4(+), while the other accepts a proton which charge stabilizes the reduced active site. In the reduction the proton is donated to the latter due to a reaction between NH3 and NO that forms a H2NNO molecule which decomposes into N2(g) and H2O(g). A dopant substitution of 10 different dopants: Si, Ge, Se, Zr, Sn, Te, Hf, V, Mo and W at each of the sites, which participate in the reaction, modifies the energetics and therefore the SCR activity. We find that Brønsted acidity is a descriptor for the SCR activity at low temperatures. Based on this descriptor we find that Zr, Hf and Sn have a positive effect as they decrease the activation energy for the SCR reaction.