Adam H. C. West

Non-syngas direct steam reforming of methanol to hydrogen and carbon dioxide at low temperature.

A non-syngas direct steam reforming route is investigated for the conversion of methanol to hydrogen and carbon dioxide over a CuZnGaO(x) catalyst at 150-200 °C. This route is in marked contrast with the conventional complex route involving steam reformation to syngas (CO/H2) at high temperature, followed by water gas shift and CO cleanup stages for hydrogen production. Here we report that high quality hydrogen and carbon dioxide can be produced in a single-step reaction over the catalyst, with no detectable CO (below detection limit of 1 ppm). This can be used to supply proton exchange membrane fuel cells for mobile applications without invoking any CO shift and cleanup stages. The working catalyst contains, on average, 3-4 nm copper particles, alongside extremely small size of copper clusters stabilized on a defective ZnGa2O4 spinel oxide surface, providing hydrogen productivity of 393.6 ml g(-1)-cat h(-1) at 150 °C.

Barrierless proton transfer across weak CH⋯O hydrogen bonds in dimethyl ether dimer

We present a combined computational and threshold photoelectron photoion coincidence study of two isotopologues of dimethyl ether, (DME - h6)n and (DME - d6)n n = 1 and 2, in the 9-14 eV photon energy range. Multiple isomers of neutral dimethyl ether dimer were considered, all of which may be present, and exhibited varying C-H⋯O interactions. Results from electronic structure calculations predict that all of them undergo barrierless proton transfer upon photoionization to the ground electronic state of the cation. In fact, all neutral isomers were found to relax to the same radical cation structure. The lowest energy dissociative photoionization channel of the dimer leads to CH3OHCH3 (+) by the loss of CH2OCH3 with a 0 K appearance energy of 9.71 ± 0.03 eV and 9.73 ± 0.03 eV for (DME - h6)2 and deuterated (DME - d6)2, respectively. The ground state threshold photoelectron spectrum band of the dimethyl ether dimer is broad and exhibits no vibrational structure. Dimerization results in a 350 meV decrease of the valence band appearance energy, a 140 meV decrease of the band maximum, thus an almost twofold increase in the ground state band width, compared with DME - d6 monomer.

Electron mean free path from angle-dependent photoelectron spectroscopy of aerosol particles

We propose angle-resolved photoelectron spectroscopy of aerosol particles as an alternative way to determine the electron mean free path of low energy electrons in solid and liquid materials. The mean free path is obtained from fits of simulated photoemission images to experimental ones over a broad range of different aerosol particle sizes. The principal advantage of the aerosol approach is twofold. First, aerosol photoemission studies can be performed for many different materials, including liquids. Second, the size-dependent anisotropy of the photoelectrons can be exploited in addition to size-dependent changes in their kinetic energy. These finite size effects depend in different ways on the mean free path and thus provide more information on the mean free path than corresponding liquid jet, thin film, or bulk data. The present contribution is a proof of principle employing a simple model for the photoemission of electrons and preliminary experimental data for potassium chloride aerosol particles.

Direct methanol steam reforming to hydrogen over CuZnGaOx catalysts without CO post-treatment: mechanistic considerations

Utilization of hydrogen gas (and carbon dioxide) from methanol steam reforming reaction directly without CO post-treatment to supply proton exchange membrane fuel cells for mobile applications is an attractive option. CuZnGaOx based mixed oxides prepared by co-precipitation are found to be active as catalysts for the reforming reaction. It is also found that the use of lower temperature and a faster substrate flow rate with a shorter contact time with the catalyst bed can significantly reduce the CO level in the product gas stream. At 150 °C this class of oxides gives a decent methanol conversion but can also totally suppress the CO production at a short contact time, which is in a sharp contrast with conventional CuZnOx based catalysts that give a significant degree of CO formation. Characterization using Diffuse Reflectance Infrared Fourier Transform (DRIFT) analysis presented in this work clearly suggests the importance of the interface between copper metal-defective oxides for the catalysis. Mechanistic aspects of this reaction are therefore discussed in this paper.

Angle-Resolved Photoemission of Solvated Electrons in Sodium-Doped Clusters.

Angle-resolved photoelectron spectroscopy of the unpaired electron in sodium-doped water, methanol, ammonia, and dimethyl ether clusters is presented. The experimental observations and the complementary calculations are consistent with surface electrons for the cluster size range studied. Evidence against internally solvated electrons is provided by the photoelectron angular distribution. The trends in the ionization energies seem to be mainly determined by the degree of hydrogen bonding in the solvent and the solvation of the ion core. The onset ionization energies of water and methanol clusters do not level off at small cluster sizes but decrease slightly with increasing cluster size.

Angle-resolved valence shell photoelectron spectroscopy of neutral nanosized molecular aggregates

This mini-review provides an overview of the recent developments in the field of angle-resolved photoelectron spectroscopy of neutral weakly-bound molecular aggregates with sizes that range from the gas phase monomer into the lower nanometre regime. A summary of the recent first size-dependent studies of neutral single-component and solute/solvent nano-clusters in the valence-shell region is provided. The challenges in determining independent information on the particle size as well as accurate angular-dependent information are highlighted. Examples of potential artefacts that falsify the true photoelectron angular distribution are discussed.

Solvated Electrons in Clusters: Magic Numbers for the Photoelectron Anisotropy

This paper reports on a curiosity concerning magic numbers in neutral molecular clusters, namely on magic numbers related to the photoelectron anisotropy in angle-resolved photoelectron spectra. With a combination of density functional calculations and experiment, we search for magic numbers in Na(H2O)n, Na(NH3)n, Na(CH3OH)n, and Na(CH3OCH3)n clusters. In clusters of high symmetry, the highest occupied molecular orbital can be delocalized over an extended region, forming a symmetric charge distribution of high s character, which results in a pronounced anisotropy in the photoelectron angular distribution. We find magic numbers at n = 6 and 4 for sodium-doped dimethyl ether and ammonia clusters, respectively, but not for sodium-doped water and methanol clusters, which is likely a consequence of the degree of hydrogen bonding and the number of structural isomers.

Metal Transition in Sodium–Ammonia Nanodroplets

The famous nonmetal-to-metal transition in Na-ammonia solutions is investigated in nanoscale solution droplets by photoelectron spectroscopy. In agreement with the bulk solutions, a strong indication for a transition to the metallic state is found at an average metal concentration of 8.8±2.2 mole%. The smallest entity for the phase transition to be observed consists of approximately 100-200 solvent molecules. The quantification of this critical entity size is a stepping stone toward a deeper understanding of these quantum-classical solutions through direct modeling at the molecular level.

Photoelectron Velocity Map Imaging of Neutral Nanoscale Clusters and Aerosol Particles

A photoelectron imaging spectrometer for the investigation of size-dependent properties of weakly-bound neutral clusters and aerosol particles is presented. The instrument is characterised, calibrated, and tested in our laboratory on a range of model systems. It fulfils two key aspects that are required for quantitative studies on neutral systems. First, accurate size distributions are obtained in situ via the sodium doping method. Second, the experimental setup is optimised to provide accurate and artefact-free photoelectron angular distributions. Pure clusters of (NH3)n and (CH3OCH3)n are studied in the size range from the monomer up to clusters containing a few thousand molecules (<10 nm diameter). From the size evolution of the photoelectron spectra, we track the structural changes in the clusters marking the first steps towards condensation in weakly-bound molecular systems. The ionisation energies are found to decrease with increasing cluster size before reaching a plateau region, indicating possible structural convergence within a given size range. The photoelectron angular distribution, characterised by the β parameter, remains isotropic for (CH3OCH3)n, whilst for (NH3)n β decreases markedly across the studied size range. The main focus of this work is on the photoelectron imaging of sodium in water, methanol, ammonia, and dimethyl ether clusters. Here, the aim is to gain a molecular level understanding of electron solvation in metal-solvent nanosolutions, using our imaging technique to probe the character and location of the unpaired electron as a function of solvent and cluster size. Our experimental studies, supported by ab initio calculations,