Strain vs. charge mediated magnetoelectric coupling across the magnetic oxide/ferroelectric interfaces.

We utilize polarized neutron reflectometry (PNR) in consort with ab initio based density functional theory (DFT) calculations to study magnetoelectric coupling at the interface of a ferroelectric PbZr0.2Ti0.8O3 (PZT) and magnetic La0.67Sr0.33MnO3 (LSMO) heterostructure grown on a Nb-doped SrTiO3 (001) substrate. Functional device working conditions are mimicked by gating the heterostructure with a Pt top electrode to apply an external electric field, which alters the magnitude and switches the direction of the ferroelectric (FE) polarization, across the PZT layer. PNR results show that the gated PZT/LSMO exhibits interfacial magnetic phase modulation attributed to ferromagnetic (FM) to A-antiferromagnetic (A-AF) phase transitions resulting from hole accumulation. When the net FE polarization points towards the interface (positive), the interface doesn't undergo a magnetic phase transition and retains its global FM ordered state. In addition to changes in the interfacial magnetic ordering, the global magnetization of LSMO increases while switching the polarization from positive to negative and decreases vice versa. DFT calculations indicate that this enhanced magnetization also correlates with an out of plane tensile strain, whereas the suppressed magnetization for positive polarization is attributed to out of plane compressive strain. These calculations also show the coexistence of FM and A-AF phases at zero out of plane strain. Charge modulations throughout the LSMO layer appear to be unaffected by strain, suggesting that these charge mediated effects do not significantly change the global magnetization. Our PNR results and DFT calculations are in consort to verify that the interfacial magnetic modulations are due to co-action of strain and charge mediated effects with the strain and charge effects dominant at different length scale.

Ab initio study of magnetoelectric coupling in La0.66Sr0.33MnO3 / PbZr0.2Ti0.8O3 multiferroic heterostructures.

Multiferroic heterostructures composed of thin layers of ferromagnetic and ferroelectric perovskites have attracted considerable attention in recent years. We apply ab initio computational methods based on density functional theory to study the magnetoelectric coupling at the (0 0 1) interface between [Formula: see text] (LSMO) and [Formula: see text] (PZT). Our study demonstrates that the ferroelectric polarization of PZT has a strong influence on the distribution of magnetization in LSMO. The presence of polarized PZT changes the balance between the ferromagnetic and antiferromagnetic states of LSMO. The observed interfacial magnetoelectric effect can be explained by the variation of the charge density across the LSMO/PZT interface and by the change of the magnetic order in the LSMO layer adjacent to PZT.

Tetracyanoethylene oxide- functionalized graphene and graphite characterized by Raman and Auger spectroscopy.

The tetracyanoethylene oxide (TCNEO) functionalization of chemical vapor deposition grown large area graphene and graphite was performed using reaction of TCNEO with carbon surface in chlorobenzene. The successful functionalization has been confirmed by Raman and Auger spectroscopy, and by numerical modeling of the structure and vibrational modes of TCNEO-functionalized graphene. Raman spectra of TCNEO-functionalized graphene and graphite show several groups of lines corresponding to vibrations of attached carbonyl ylide. One of key signatures of TCNEO attachment is the high intensity Raman band at ~1450 cm-1, which represents the C-C=C in plane vibrations in functionalization-distorted graphene. Raman spectra indicate the existence of central (pristine) attachment of TCNEO to graphene surface.

Adsorption of ethane, ethylene, propane, and propylene on a magnesium-based metal-organic framework.

Separation of olefin/paraffin is an energy-intensive and difficult separation process in petrochemical industry. Energy-efficient adsorption process is considered as a promising alternative to the traditional cryogenic distillation for separating olefin/paraffin mixtures. In this work, we explored the feasibility of adsorptive separation of olefin/paraffin mixtures using a magnesium-based metal-organic framework, Mg-MOF-74. Adsorption equilibria and kinetics of ethane, ethylene, propane, and propylene on a Mg-MOF-74 adsorbent were determined at 278, 298, and 318 K and pressures up to 100 kPa. A dual-site Sips model was used to correlate the adsorption equilibrium data, and a micropore diffusion model was applied to extract the diffusivities from the adsorption kinetics data. A grand canonical Monte Carlo simulation was conducted to calculate the adsorption isotherms and to elucidate the adsorption mechanisms. The simulation results showed that all four adsorbate molecules are preferentially adsorbed on the open metal sites where each metal site binds one adsorbate molecule. Propylene and propane have a stronger affinity to the Mg-MOF-74 adsorbent than ethane and ethylene because of their significant dipole moments. Adsorption equilibrium selectivity, combined equilibrium and kinetic selectivity, and adsorbent selection parameter for pressure swing adsorption processes were estimated. The relatively high values of adsorption selectivity suggest that it is feasible to separate ethylene/ethane, propylene/propane, and propylene/ethylene pairs in a vacuum swing adsorption process using Mg-MOF-74 as an adsorbent.

Kinetic separation of carbon dioxide and methane on a copper metal-organic framework.

Separation of carbon dioxide and methane is an important issue in upgrading low-quality natural gas. Adsorption equilibria and kinetics of CO(2) and CH(4) on a copper metal-organic framework (MOF), Cu(hfipbb)(H(2)hfipbb)(0.5) [H(2)hfipbb=4,4'-(hexafluoroisopropylidene) bis(benzoic acid)], were investigated to evaluate the feasibility of removing CO(2) from CH(4) in a pressure swing adsorption process using this new MOF adsorbent. The heat of adsorption of CO(2) on the Cu-MOF at zero-coverage (29.7 kJ/mol) is much lower than those on a carbon molecular sieve and a zeolite 5A adsorbent; and the heat of adsorption of CH(4) on the Cu-MOF (21.4 kJ/mol) is similar to that on the zeolite 5A adsorbent and smaller than that on a carbon molecular sieve. The Cu-MOF being investigated has apertures of (~3.5 × 3.5 Å), which favors the kinetically controlled separation of CO(2) and CH(4). The kinetic selectivity is found to be 26 at 298 K, and the overall selectivity (combining the equilibrium and kinetic effects) is about 25 for an adsorption separation process. These results suggest that the Cu-MOF adsorbent is an attractive alternative adsorbent for the CO(2)/CH(4) separation.