Manganese Oxide as an Inorganic Catalyst for the Oxygen Evolution Reaction Studied by X-Ray Photoelectron and Operando Raman Spectroscopy

Manganese oxide (MnO$_{x}$) is considered a promising material for the oxygen evolution reaction (OER) to replace noble metal catalysts in water splitting. The improvement of MnO$_{x}$ requires mechanistic and kinetic knowledge of the four-electron transfer steps of the OER. X-ray photoelectron spectroscopy, a widely used tool to characterize the electronic structure of thin films, is used in combination with surface-enhanced Raman spectroscopy to gain a deeper knowledge of the different mixed MnO$_{x}$ types and their respective change in chemical composition. Using Raman spectroscopy during electrochemical measurements, all samples were found to reveal Birnessite-type MnO$_{2}$ motifs in alkaline media at an applied potential. Their activity correlates with two shifting Raman active modes, one of them being assigned to the formation of Mn$^{III}$ species, and one to the expansion of layers of MnO$_{6}$ octahedra. A special activation treatment leads independent of the starting material to a highly amorphous mixed-valence oxide, which shows the highest OER activity

Recent Cases

This is a summary of the case law from 1965

Almost-Euclidean subspaces of ℓ1N\ell_1^N via tensor products: a simple approach to randomness reduction

It has been known since 1970's that the N-dimensional $\ell_1$-space contains nearly Euclidean subspaces whose dimension is $\Omega(N)$. However, proofs of existence of such subspaces were probabilistic, hence non-constructive, which made the results not-quite-suitable for subsequently discovered applications to high-dimensional nearest neighbor search, error-correcting codes over the reals, compressive sensing and other computational problems. In this paper we present a "low-tech" scheme which, for any $a > 0$, allows to exhibit nearly Euclidean $\Omega(N)$-dimensional subspaces of $\ell_1^N$ while using only $N^a$ random bits. Our results extend and complement (particularly) recent work by Guruswami-Lee-Wigderson. Characteristic features of our approach include (1) simplicity (we use only tensor products) and (2) yielding "almost Euclidean" subspaces with arbitrarily small distortions.Comment: 11 pages; title change, abstract and references added, other minor change

Thin film growth and band lineup of In2O3 on the layered semiconductor InSe

Thin films of the transparent conducting oxide In2O3 have been prepared in ultrahigh vacuum by reactive evaporation of indium. X-ray diffraction, optical, and electrical measurements were used to characterize properties of films deposited on transparent insulating mica substrates under variation of the oxygen pressure. Photoelectron spectroscopy was used to investigate in situ the interface formation between In2O3 and the layered semiconductor InSe. For thick In2O3 films a work function of φ = 4.3 eV and a surface Fermi level position of EF−EV = 3.0 eV is determined, giving an ionization potential IP = 7.3 eV and an electron affinity χ = 3.7 eV. The interface exhibits a type I band alignment with ΔEV = 2.05 eV, ΔEC = 0.29 eV, and an interface dipole of δ = −0.55 [email protected]

Analytical Study of Solution-Processed Tin Oxide as Electron Transport Layer in Printed Perovskite Solar Cells

Solution‐processed tin oxide (SnO$_{x}$ ) electron transport layers demonstrate excellent performance in various optoelectronic devices and offer the ease of facile and low cost deposition by various printing techniques. The most common precursor solution for the preparation of SnO$_{x}$ thin films is SnCl$_{2}$ dissolved in ethanol. In order to elucidate the mechanism of the precursor conversion at different annealing temperatures and the optoelectronic performance of the SnO$_{x}$ electron transport layer, phonon and vibrational infrared and photoelectron spectroscopies as well as atomic force microscopy are used to probe the chemical, physical, and morphological properties of the SnO$_{x}$ thin films. The influence of two different solvents on the layer morphology of SnO$_{x}$ thin films is investigated. In both cases, an increasing annealing temperature not only improves the structural and chemical properties of solution‐processed SnO$_{x}$, but also reduces the concentration of tin hydroxide species in the bulk and on the surface of these thin films. As a prototypical example for the high potential of printed SnO$_{x}$ layers for solar cells, high performance perovskite solar cells with a stabilized power conversion efficiency of over 15% are presented

Evidence of Band Bending Induced by Hole Trapping at MAPbI3 Perovskite / Metal Interface

International audienceElectron injection by tunneling from a gold electrode and hole transport properties in polycrystalline MAPbI3 has been investigated using variable temperature experiments and numerical simulations. The presence of a large and unexpected band bending at the Au/MAPbI3 interface is revealed and attributed to the trapping of holes, which enhances the injection of electrons via tunneling. These results elucidate the role of volume and interface defects in state-of-the-art hybrid perovskite semiconductors

The Fermi energy in oxides: assessing and understanding the limits using XPS

The Fermi energy in semiconductors can often be freely controlled across the whole energy gap by doping. This is not the case in oxides, where different mechanisms exist, which can limit the range of the Fermi energy. These limits can be caused by i) dopants having deep rather than shallow charge transition levels, ii) self-com­pen­sation where the Fermi energy dependence of the defect formation energy leads to spontaneous formation of compensating defects, iii) the change of the oxidation state of either the cations or the oxygen. The latter is particularly relevant for compounds with transition metal or rare earth cations and has been recently demonstrated to explain the low water splitting efficiency of hematite [1]. Please click Additional Files below to see the full abstract

Optimal Hypercontractivity for Fermi Fields and Related Non-Commutative Integration

Optimal hypercontractivity bounds for the fermion oscillator semigroup are obtained. These are the fermion analogs of the optimal hypercontractivity bounds for the boson oscillator semigroup obtained by Nelson. In the process, several results of independent interest in the theory of non-commutative integration are established. {}.Comment: 18 p., princeton/ecel/7-12-9

Covering convex bodies by cylinders and lattice points by flats

In connection with an unsolved problem of Bang (1951) we give a lower bound for the sum of the base volumes of cylinders covering a d-dimensional convex body in terms of the relevant basic measures of the given convex body. As an application we establish lower bounds on the number of k-dimensional flats (i.e. translates of k-dimensional linear subspaces) needed to cover all the integer points of a given convex body in d-dimensional Euclidean space for 0<k<d