David Prendergast

Cooperative insertion of CO2 in diamine-appended metal-organic frameworks

The process of carbon capture and sequestration has been proposed as a method of mitigating the build-up of greenhouse gases in the atmosphere. If implemented, the cost of electricity generated by a fossil fuel-burning power plant would rise substantially, owing to the expense of removing CO2 from the effluent stream. There is therefore an urgent need for more efficient gas separation technologies, such as those potentially offered by advanced solid adsorbents. Here we show that diamine-appended metal-organic frameworks can behave as ‘phase-change’ adsorbents, with unusual step-shaped CO2 adsorption isotherms that shift markedly with temperature. Results from spectroscopic, diffraction and computational studies show that the origin of the sharp adsorption step is an unprecedented cooperative process in which, above a metal-dependent threshold pressure, CO2 molecules insert into metal-amine bonds, inducing a reorganization of the amines into well-ordered chains of ammonium carbamate. As a consequence, large CO2 separation capacities can be achieved with small temperature swings, and regeneration energies appreciably lower than achievable with state-of-the-art aqueous amine solutions become feasible. The results provide a mechanistic framework for designing highly efficient adsorbents for removing CO2 from various gas mixtures, and yield insights into the conservation of Mg2+ within the ribulose-1,5-bisphosphate carboxylase/oxygenase family of enzymes.

Attosecond band-gap dynamics in silicon

Electron transfer from valence to conduction band states in semiconductors is the basis of modern electronics. Here, attosecond extreme ultraviolet (XUV) spectroscopy is used to resolve this process in silicon in real time. Electrons injected into the conduction band by few-cycle laser pulses alter the silicon XUV absorption spectrum in sharp steps synchronized with the laser electric field oscillations. The observed ~450-attosecond step rise time provides an upper limit for the carrier-induced band-gap reduction and the electron-electron scattering time in the conduction band. This electronic response is separated from the subsequent band-gap modifications due to lattice motion, which occurs on a time scale of 60 ± 10 femtoseconds, characteristic of the fastest optical phonon. Quantum dynamical simulations interpret the carrier injection step as light-field–induced electron tunneling. Excited electrons in semiconducting silicon are tracked on a time scale faster than the lattice vibrations. [Also see Perspective by Spielmann] Watching electrons dart through silicon The ultimate speed limit in electronic circuitry is set by the motion of the electrons themselves. Schultze et al. applied attosecond spectroscopy to glimpse this motion in a sample of silicon, the semiconducting building block of modern integrated circuits (see the Perspective by Spielmann). The technique distinguished the electron dynamics—which proceed faster than a quadrillionth of a second after laser excitation—from the comparatively slower lattice motion of the silicon atomic nuclei. Science, this issue p. 1348; see also p. 1293

The structure of interfacial water on gold electrodes studied by x-ray absorption spectroscopy

The molecular structure of the electrical double layer determines the chemistry in all electrochemical processes. Using x-ray absorption spectroscopy (XAS), we probed the structure of water near gold electrodes and its bias dependence. Electron yield XAS detected at the gold electrode revealed that the interfacial water molecules have a different structure from those in the bulk. First principles calculations revealed that ~50% of the molecules lie flat on the surface with saturated hydrogen bonds and another substantial fraction with broken hydrogen bonds that do not contribute to the XAS spectrum because their core-excited states are delocalized by coupling with the gold substrate. At negative bias, the population of flat-lying molecules with broken hydrogen bonds increases, producing a spectrum similar to that of bulk water. The water double-layer structure at an electrode changed from ordered to disordered when the applied bias was switched. Dissecting the electrical double layer The structure of water within a nanometer of an electrode surface is known as the electrical double layer. This layer creates a strong electrical field that can affect electrochemical reactions. Velasco-Velez et al. explored the structure of the electrical double layer at a bare gold electrode. With no applied potential and at positive potentials, the layer is highly structured (resembling ice) with few dangling hydrogen bonds. However, at negative potentials, the layer was more like bulk water, and half of the water molecules lie flat on the surface. Science, this issue p. 831

Phase Transformation and Lithiation Effect on Electronic Structure of LixFePO4: An In-Depth Study by Soft X-ray and Simulations

Through soft X-ray absorption spectroscopy, hard X-ray Raman scattering, and theoretical simulations, we provide the most in-depth and systematic study of the phase transformation and (de)lithiation effect on electronic structure in Li(x)FePO(4) nanoparticles and single crystals. Soft X-ray reveals directly the valence states of Fe 3d electrons in the vicinity of Fermi level, which is sensitive to the local lattice distortion, but more importantly offers detailed information on the evolution of electronic states at different electrochemical stages. The soft X-ray spectra of Li(x)FePO(4) nanoparticles evolve vividly with the (de)lithiation level. The spectra fingerprint the (de)lithiation process with rich information on Li distribution, valency, spin states, and crystal field. The high-resolution spectra reveal a subtle but critical deviation from two-phase transformation in our electrochemically prepared samples. In addition, we performed both first-principles calculations and multiplet simulations of the spectra and quantitatively determined the 3d valence states that are completely redistributed through (de)lithiation. This electronic reconfiguration was further verified by the polarization-dependent spectra collected on LiFePO(4) single crystals, especially along the lithium diffusion direction. The evolution of the 3d states is overall consistent with the local lattice distortion and provides a fundamental picture of the (de)lithiation effects on electronic structure in the Li(x)FePO(4) system.

Imaging local electronic corrugations and doped regions in graphene

Electronic structure heterogeneities are ubiquitous in two-dimensional graphene and profoundly impact the transport properties of this material. Here we show the mapping of discrete electronic domains within a single graphene sheet using scanning transmission X-ray microscopy in conjunction with ab initio density functional theory calculations. Scanning transmission X-ray microscopy imaging provides a wealth of detail regarding the extent to which the unoccupied levels of graphene are modified by corrugation, doping and adventitious impurities, as a result of synthesis and processing. Local electronic corrugations, visualized as distortions of the π*cloud, have been imaged alongside inhomogeneously doped regions characterized by distinctive spectral signatures of altered unoccupied density of states. The combination of density functional theory calculations, scanning transmission X-ray microscopy imaging, and in situ near-edge X-ray absorption fine structure spectroscopy experiments also provide resolution of a longstanding debate in the literature regarding the spectral assignments of pre-edge and interlayer states.

Strain-Induced Band Gap Modification in Coherent Core/Shell Nanostructures

Using first-principles calculations within density functional theory, we study the relative impacts of quantum confinement and strain on the electronic structure of two II-VI semiconductor compounds with a large lattice-mismatch, CdSe and CdTe, in core/shell nanowire geometries with different core radii and shell thicknesses. For fixed CdSe core radius, we find that the electronic band gap in the core is significantly reduced with increasing CdTe shell thickness, by an amount comparable to that expected from quantum confinement, due to the development of a large and highly anisotropic strain throughout the heterostructure. A straightforward analysis allows us to separate quantitatively changes in band gap due to quantum confinement and strain. Our studies elucidate and quantify the importance of strain in determining the electronic and optical properties of core/shell nanostructures.

X-ray Absorption Spectra of Dissolved Polysulfides in Lithium-Sulfur Batteries from First-Principles.

The X-ray absorption spectra (XAS) of lithium polysulfides (Li2Sx) of various chain lengths (x) dissolved in a model solvent are obtained from first-principles calculations. The spectra exhibit two main absorption features near the sulfur K-edge, which are unambiguously interpreted as a pre-edge near 2471 eV due to the terminal sulfur atoms at either end of the linear polysulfide dianions and a main-edge near 2473 eV due to the (x - 2) internal atoms in the chain, except in the case of Li2S2, which only has a low-energy feature. We find an almost linear dependence between the ratio of the peaks and chain length, although the linear dependence is modified by the delocalized, molecular nature of the core-excited states that can span up to six neighboring sulfur atoms. Thus, our results indicate that the ratio of the peak area, and not the peak intensities, should be used when attempting to differentiate the polysulfides from XAS.

Polysulfide-Blocking Microporous Polymer Membrane Tailored for Hybrid Li-Sulfur Flow Batteries

Redox flow batteries (RFBs) present unique opportunities for multi-hour electrochemical energy storage (EES) at low cost. Too often, the barrier for implementing them in large-scale EES is the unfettered migration of redox active species across the membrane, which shortens battery life and reduces Coulombic efficiency. To advance RFBs for reliable EES, a new paradigm for controlling membrane transport selectivity is needed. We show here that size- and ion-selective transport can be achieved using membranes fabricated from polymers of intrinsic microporosity (PIMs). As a proof-of-concept demonstration, a first-generation PIM membrane dramatically reduced polysulfide crossover (and shuttling at the anode) in lithium-sulfur batteries, even when sulfur cathodes were prepared as flowable energy-dense fluids. The design of our membrane platform was informed by molecular dynamics simulations of the solvated structures of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) vs lithiated polysulfides (Li2Sx, where x = 8, 6, and 4) in glyme-based electrolytes of different oligomer length. These simulations suggested polymer films with pore dimensions less than 1.2-1.7 nm might incur the desired ion-selectivity. Indeed, the polysulfide blocking ability of the PIM-1 membrane (∼0.8 nm pores) was improved 500-fold over mesoporous Celgard separators (∼17 nm pores). As a result, significantly improved battery performance was demonstrated, even in the absence of LiNO3 anode-protecting additives.

The electronic structure of liquid water within density-functional theory

In the last decade, computational studies of liquid water have mostly concentrated on ground-state properties. However, recent spectroscopic measurements have been used to infer the structure of water, and the interpretation of optical and x-ray spectra requires accurate theoretical models of excited electronic states, not only of the ground state. To this end, we investigate the electronic properties of water at ambient conditions using ab initio density-functional theory within the generalized gradient approximation (DFT/GGA), focusing on the unoccupied subspace of Kohn-Sham eigenstates. We generate long (250 ps) classical trajectories for large supercells, up to 256 molecules, from which uncorrelated configurations of water molecules are extracted for use in DFT/GGA calculations of the electronic structure. We find that the density of occupied states of this molecular liquid is well described with 32-molecule supercells using a single k point (k=0) to approximate integration over the first Brillouin zone. However, the description of the unoccupied electronic density of states (u-EDOS) is sensitive to finite size effects. Small, 32-molecule supercell calculations, using the Gamma-point approximation, yield a spuriously isolated state above the Fermi level. Nevertheless, the more accurate u-EDOS of large, 256-molecule supercells may be reproduced using smaller supercells and increased k-point sampling. This indicates that the electronic structure of molecular liquids such as water is relatively insensitive to the long-range disorder in the molecular structure. These results have important implications for efficiently increasing the accuracy of spectral calculations for water and other molecular liquids.

Tuning Semiconductor Band Edge Energies for Solar Photocatalysis via Surface Ligand Passivation

Semiconductor photocatalysts capable of broadband solar photon absorption may be nonetheless precluded from use in driving water splitting and other solar-to-fuel related reactions due to unfavorable band edge energy alignment. Using first-principles density functional theory and beyond, we calculate the electronic structure of passivated CdSe surfaces and explore the opportunity to tune band edge energies of this and related semiconductors via electrostatic dipoles associated with chemisorbed ligands. We predict substantial shifts in band edge energies originating from both the induced dipole at the ligand/CdSe interface and the intrinsic dipole of the ligand. Building on important induced dipole contributions, we further show that, by changing the size and orientation of the ligands intrinsic dipole moment via functionalization, we can control the direction and magnitude of the shifts of CdSe electronic levels. Our calculations suggest a general strategy for enabling new active semiconductor photocatalysts with both optimal opto-electronic, and photo- and electrochemical properties.