Hasnain Hafiz

Experimental Observation of Redox-Induced Fe–N Switching Behavior as a Determinant Role for Oxygen Reduction Activity

The commercialization of electrochemical energy conversion and storage devices relies largely upon the development of highly active catalysts based on abundant and inexpensive materials. Despite recent achievements in this respect, further progress is hindered by the poor understanding of the nature of active sites and reaction mechanisms. Herein, by characterizing representative iron-based catalysts under reactive conditions, we identify three Fe-N4-like catalytic centers with distinctly different Fe-N switching behaviors (Fe moving toward or away from the N4-plane) during the oxygen reduction reaction (ORR), and show that their ORR activities are essentially governed by the dynamic structure associated with the Fe(2+/3+) redox transition, rather than the static structure of the bare sites. Our findings reveal the structural origin of the enhanced catalytic activity of pyrolyzed Fe-based catalysts compared to nonpyrolyzed Fe-macrocycle compounds. More generally, the fundamental insights into the dynamic nature of transition-metal compounds during electron-transfer reactions will potentially guide rational design of these materials for broad applications.

Spectroscopic evidence for negative electronic compressibility in a quasi-three-dimensional spin–orbit correlated metal

Negative compressibility is a sign of thermodynamic instability of open or non-equilibrium systems. In quantum materials consisting of multiple mutually coupled subsystems, the compressibility of one subsystem can be negative if it is countered by positive compressibility of the others. Manifestations of this effect have so far been limited to low-dimensional dilute electron systems. Here, we present evidence from angle-resolved photoemission spectroscopy (ARPES) for negative electronic compressibility (NEC) in the quasi-three-dimensional (3D) spin-orbit correlated metal (Sr1-xLax)3Ir2O7. Increased electron filling accompanies an anomalous decrease of the chemical potential, as indicated by the overall movement of the deep valence bands. Such anomaly, suggestive of NEC, is shown to be primarily driven by the lowering in energy of the conduction band as the correlated bandgap reduces. Our finding points to a distinct pathway towards an uncharted territory of NEC featuring bulk correlated metals with unique potential for applications in low-power nanoelectronics and novel metamaterials.

Non-destructive measurement of in-operando lithium concentration in batteries via x-ray Compton scattering

Non-destructive determination of lithium distribution in a working battery is key for addressing both efficiency and safety issues. Although various techniques have been developed to map the lithium distribution in electrodes, these methods are mostly applicable to test cells. Here we propose the use of high-energy x-ray Compton scattering spectroscopy to measure the local lithium concentration in closed electrochemical cells. A combination of experimental measurements and parallel first-principles computations is used to show that the shape parameter S of the Compton profile is linearly proportional to lithium concentration and thus provides a viable descriptor for this important quantity. The merits and applicability of our method are demonstrated with illustrative examples of LixMn2O4 cathodes and a working commercial lithium coin battery CR2032.

Fermi Arcs vs. Fermi Pockets in Electron-doped Perovskite Iridates

We report on an angle resolved photoemission (ARPES) study of bulk electron-doped perovskite iridate, (Sr1−xLax)3Ir2O7. Fermi surface pockets are observed with a total electron count in keeping with that expected from La substitution. Depending on the energy and polarization of the incident photons, these pockets show up in the form of disconnected “Fermi arcs”, reminiscent of those reported recently in surface electron-doped Sr2IrO4. Our observed spectral variation is consistent with the coexistence of an electronic supermodulation with structural distortion in the system.

Identifying a descriptor for d-orbital delocalization in cathodes of Li batteries based on x-ray Compton scattering

We discuss how x-ray Compton scattering spectra can be used for investigating the evolution of electronic states in cathode materials of Li batteries under the lithiation/delithiation process. In particular, our analysis of the Compton spectra taken from polycrystalline LixCoO2 samples shows that the spectra are dominated by the contribution of the O-2p redox orbital. We identify a distinct signature of d-orbital delocalization, which is tied directly to the conductivity of the material, providing a descriptor based on Compton spectra for monitoring the lithiation range with improved conductivity and kinetics for electrochemical operation. Our study demonstrates that Compton scattering spectroscopy can provide a window for probing complex electronic mechanisms underlying the charging and discharging processes in Li-battery materials.

Visualizing redox orbitals and their potentials in advanced lithium-ion battery materials using high-resolution x-ray Compton scattering

A spectroscopic descriptor of the link between lattice distortion and voltage in Li battery materials. Reduction-oxidation (redox) reactions are the key processes that underlie the batteries powering smartphones, laptops, and electric cars. A redox process involves transfer of electrons between two species. For example, in a lithium-ion battery, current is generated when conduction electrons from the lithium anode are transferred to the redox orbitals of the cathode material. The ability to visualize or image the redox orbitals and how these orbitals evolve under lithiation and delithiation processes is thus of great fundamental and practical interest for understanding the workings of battery materials. We show that inelastic scattering spectroscopy using high-energy x-ray photons (Compton scattering) can yield faithful momentum space images of the redox orbitals by considering lithium iron phosphate (LiFePO4 or LFP) as an exemplar cathode battery material. Our analysis reveals a new link between voltage and the localization of transition metal 3d orbitals and provides insight into the puzzling mechanism of potential shift and how it is connected to the modification of the bond between the transition metal and oxygen atoms. Our study thus opens a novel spectroscopic pathway for improving the performance of battery materials.

A Minimal tight-binding model for ferromagnetic canted bilayer manganites

Half-metallicity in materials has been a subject of extensive research due to its potential for applications in spintronics. Ferromagnetic manganites have been seen as a good candidate, and aside from a small minority-spin pocket observed in La2−2xSr1+2xMn2O7 (x = 0.38), transport measurements show that ferromagnetic manganites essentially behave like half metals. Here we develop robust tight-binding models to describe the electronic band structure of the majority as well as minority spin states of ferromagnetic, spin-canted antiferromagnetic, and fully antiferromagnetic bilayer manganites. Both the bilayer coupling between the MnO2 planes and the mixing of the |x2 − y2 > and |3z2 − r2 > Mn 3d orbitals play an important role in the subtle behavior of the bilayer splitting. Effects of kz dispersion are included.

Resolving unoccupied electronic states with laser ARPES in bismuth-based cuprate superconductors

Angle-resolved photoemission spectroscopy (ARPES) is typically used to study only the occupied electronic band structure of a material. Here we use laser-based ARPES to observe a feature in bismuth-based superconductors that, in contrast, is related to the unoccupied states. Specifically, we observe a dispersive suppression of intensity cutting across the valence band, which, when compared with relativistic one-step calculations, can be traced to two final-state gaps in the bands 6 eV above the Fermi level. This finding opens up possibilities to bring the ultra-high momentum resolution of existing laser-ARPES instruments to the unoccupied electron states. For cases where the final-state gap is not the object of study, we find that its effects can be made to vanish under certain experimental conditions.

Electronic structure of oxide electrode materials studied by Compton profiles

Kosuke Suzuki1, Bernardo Barbiellini2, Yuki Orikasa3, Stanislaw Kaprzyk4, Masayoshi Itou5, Hasnain Hafiz2, Yoshiharu Uchimoto6, Arun Bansil2, Yoshiharu Sakurai5, Hiroshi Sakurai1 1Faculty Of Science And Technology, Gunma University, Kiryu, Japan, 2Department of Physics, Northeastern University, Boston, United States, 3Department of Applied Chemistry, Ritsumeikan University, Kusatsu, Japan, 4Faculty of Physics and Applied Computer Science, AGH University of Science and Technology, Krakow, Poland, 5Japan Synchrotron Radiation Research Institute (JASRI), SPring-8, Sayo, Japan, 6Graduate School of Human and Environmental Studies, Kyoto University, Sakyo-ku, Japan E-mail: kosuzuki@gunma-u.ac.jp

Fermi-surface-free superconductivity in underdoped (Bi,Pb)(Sr,La)2CuO6+δ (Bi2201)

Fermi-surface-free superconductivity arises when the superconducting order pulls down spectral weight from a band that is completely above the Fermi energy in the normal state. We show that this can arise in hole-doped cuprates when a competing order causes a reconstruction of the Fermi surface. The change in Fermi surface topology is accompanied by a characteristic rise in the spectral weight. Our results support the presence of a trisected superconducting dome, and suggest that superconductivity is responsible for stabilizing the (π,π) magnetic order at higher doping.