Role of Pyridine as a Biomimetic Organo-Hydride for Homogeneous Reduction of CO2 to Methanol

We use quantum chemical calculations to elucidate a viable homogeneous mechanism for pyridine-catalyzed reduction of CO2 to methanol. In the first component of the catalytic cycle, pyridine (Py) undergoes a H+ transfer (PT) to form pyridinium (PyH+) followed by an e- transfer (ET) to produce pyridinium radical (PyH0). Examples of systems to effect this ET to populate the LUMO of PyH+(E0calc ~ -1.3V vs. SCE) to form the solution phase PyH0 via highly reducing electrons include the photo-electrochemical p-GaP system (ECBM ~ -1.5V vs. SCE at pH= 5) and the photochemical [Ru(phen)3]2+/ascorbate system. We predict that PyH0 undergoes further PT-ET steps to form the key closed-shell, dearomatized 1,2-dihydropyridine (PyH2) species. Our proposed sequential PT-ET-PT-ET mechanism transforming Py into PyH2 is consistent with the mechanism described in the formation of related dihydropyridines. Because it is driven by its proclivity to regain aromaticity, PyH2 is a potent recyclable organo-hydride donor that mimics the role of NADPH in the formation of C-H bonds in the photosynthetic CO2 reduction process. In particular, in the second component of the catalytic cycle, we predict that the PyH2/Py redox couple is kinetically and thermodynamically competent in catalytically effecting hydride and proton transfers (the latter often mediated by a proton relay chain) to CO2 and its two succeeding intermediates, namely formic acid and formaldehyde, to ultimately form CH3OH. The hydride and proton transfers for the first reduction step, i.e. reduction of CO2, are sequential in nature; by contrast, they are coupled in each of the two subsequent hydride and proton transfers to reduce formic acid and formaldehyde.

Charge Storage in Cation Incorporated {alpha}-MnO2

Electrochemical supercapacitors utilizing {alpha}-MnO2 offer the possibility of both high power density and high energy density. Unfortunately, the mechanism of electrochemical charge storage in {alpha}-MnO2 and the effect of operating conditions on the charge storage mechanism are generally not well understood. Here, we present the first detailed charge storage mechanism of {alpha}-MnO2 and explain the capacity differences between {alpha}- and {beta}-MnO2 using a combined theoretical electrochemical and band structure analysis. We identify the importance of the band gap, work function, the point of zero charge, and the tunnel sizes of the electrode material, as well as the pH and stability window of the electrolyte in determining the viability of a given electrode material. The high capacity of {alpha}-MnO2 results from cation induced charge-switching states in the band gap that overlap with the scanned potential allowed by the electrolyte. The charge-switching states originate from interstitial and substitutional cations (H+, Li+, Na+, and K+) incorporated into the material. Interstitial cations are found to induce charge-switching states by stabilizing Mn-O antibonding orbitals from the conduction band. Substitutional cations interact with O[2p] dangling bonds that are destabilized from the valence band by Mn vacancies to induce charge-switching states. We calculate the equilibrium electrochemical potentials at which these states are reduced and predict the effect of the electrochemical operating conditions on their contribution to charge storage. The mechanism and theoretical approach we report is general and can be used to computationally screen new materials for improved charge storage via ion incorporation.

Bulk and Surface Tunneling Hydrogen Defects in Alumina

We perform ab initio calculations of hydrogen-based tunneling defects in alumina to identify deleterious two-level systems (TLS) in superconducting qubits. The defects analyzed include bulk hydrogenated Al vacancies, bulk hydrogen interstitial defects, and a surface OH rotor. The formation energies of the defects are first computed for an Al- and O-rich environment to give the likelihood of defect occurrence during growth. The potential energy surfaces are then computed and the corresponding dipole moments are evaluated to determine the coupling of the defects to an electric field. Finally, the tunneling energy is computed for the hydrogen defect and the analogous deuterium defect, providing an estimate of the TLS energy and the corresponding frequency for photon absorption. We predict that hydrogenated cation vacancy defects will form a significant density of GHz-frequency TLSs in alumina.

Dispersion of a single $4f$ impurity state in photoemission spectra of Yb/W(110)

Angle-resolved photoemission spectra of a monolayer of Yb on W(110) reveal energy splittings and dispersion of the Yb 4f states that are obviously due to their hybridization with W-derived valence bands. These effects occur at well defined points of the surface Brillouin zone although a smearing over reciprocal space is expected from the structural incoherence of the Yb and W lattices. We conclude therefore that dispersion is not related to the periodic arrangement of the $4f$ states but reflects the k-dependent interaction of a single Yb 4f impurity with W bands.