Mechanochemically Enabled Metastable Niobium Tungsten Oxides.

Metastable compounds have greatly expanded the synthesizable compositions of solid-state materials and have attracted enormous amounts of attention in recent years. Especially, mechanochemically enabled metastable materials synthesis has been very successful in realizing cation-disordered materials with highly simple crystal structures, such as rock salts. Application of the same strategy for other structural types, especially for non-close-packed structures, is peculiarly underexplored. Niobium tungsten oxides (NbWOs), a class of materials that have been under the spotlight because of their diverse structural varieties and promising electrochemical and thermoelectric properties, are ideally suited to fill such a knowledge gap. In this work, we develop a new series of metastable NbWOs and realize one with a fully cation-disordered structure. Furthermore, we find that metastable NbWOs transform to a cation-disordered cubic structure when applied as a Li-ion battery anode, highlighting an intriguing non-close-packed-close-packed conversion process, as evidenced in various physicochemical characterizations, in terms of diffraction, electronic, and vibrational structures. Finally, by comparing the cation-disordered NbWO with other trending cation-disordered oxides, we raise a few key structural features for cation disorder and suggest a few possible research opportunities for this field.

Self-terminating, heterogeneous solid-electrolyte interphase enables reversible Li-ether cointercalation in graphite anodes.

Ether solvents are suitable for formulating solid-electrolyte interphase (SEI)-less ion-solvent cointercalation electrolytes in graphite for Na-ion and K-ion batteries. However, ether-based electrolytes have been historically perceived to cause exfoliation of graphite and cell failure in Li-ion batteries. In this study, we develop strategies to achieve reversible Li-solvent cointercalation in graphite through combining appropriate Li salts and ether solvents. Specifically, we design 1M LiBF4 1,2-dimethoxyethane (G1), which enables natural graphite to deliver ~91% initial Coulombic efficiency and >88% capacity retention after 400 cycles. We captured the spatial distribution of LiF at various length scales and quantified its heterogeneity. The electrolyte shows self-terminated reactivity on graphite edge planes and results in a grainy, fluorinated pseudo-SEI. The molecular origin of the pseudo-SEI is elucidated by ab initio molecular dynamics (AIMD) simulations. The operando synchrotron analyses further demonstrate the reversible and monotonous phase transformation of cointercalated graphite. Our findings demonstrate the feasibility of Li cointercalation chemistry in graphite for extreme-condition batteries. The work also paves the foundation for understanding and modulating the interphase generated by ether electrolytes in a broad range of electrodes and batteries.

Printed graphene and its composite with copper for electromagnetic interference shielding applications.

Advances in mobile electronics and telecommunication systems along with 5G technologies have been escalating the electromagnetic interference (EMI) problem in recent years. Graphene-based material systems such as pristine graphene, graphene-polymer composites and other graphene-containing candidates have been shown to provide adequate EMI shielding performance. Besides achieving the needed shielding effectiveness (SE), the method of applying the candidate shielding material onto the object in need of protection is of enormous importance due to considerations of ease of application, reduced logistics and infrastructure, rapid prototyping and throughput, versatility to handle both rigid and flexible substrates and cost. Printing readily meets all these criteria and here we demonstrate plasma jet printing of thin films of graphene and its composite with copper to meet the EMI shielding needs. SE over 30 dB is achieved, which represents blocking over 99.9% of the incoming radiation. Graphene and its composite with copper yield higher green index compared to pure copper shields, implying reduced reflection of incoming electromagnetic waves to help reduce secondary pollution.

Unveiling Atomic-Scale Product Selectivity at the Cocatalyst-TiO2 Interface Using X-Ray Techniques: Insights into Interface Reactivity.

The microstructure at the interface between the cocatalyst and semiconductor plays a vital role in concentrating photo-induced carriers and reactants. However, observing the atomic arrangement of this interface directly using an electron microscope is challenging due to the coverings of the semiconductor and cocatalyst. To address this, multiple metal-semiconductor interfaces on three TiO2 crystal facets (M/TiO2 ─N, where M represents Ag, Au, and Pt, and N represents the 001, 010, and 101 single crystal facets). The identical surface atomic configuration of the TiO2 facets allowed us to investigate the evolution of the microstructure within these constructs using spectroscopies and DFT calculations. For the first time, they observed the transformation of saturated Ti6c ─O bonds into unsaturated Ti5c ─O and Ti6c ─O─Pt bonds on the TiO2 ─010 facet after loading Pt. This transformation have a direct impact on the selectivity of the resulting products, leading to the generation of CO and CH4 at the Ti6c ─O─Pt and Pt sites, respectively. These findings pinpoint the pivotal roles played by the atomic arrangement at the M/TiO2 ─N interfaces and provide valuable insights for the development of new methodologies using conventional lab-grade equipment.

Quantum Diamonds at the Beach: Chemical Insights into Silica Growth on Nanoscale Diamond using Multimodal Characterization and Simulation.

Surface chemistry of materials that host quantum bits such as diamond is an important avenue of exploration as quantum computation and quantum sensing platforms mature. Interfacing diamond in general and nanoscale diamond (ND) in particular with silica is a potential route to integrate room temperature quantum bits into photonic devices, fiber optics, cells, or tissues with flexible functionalization chemistry. While silica growth on ND cores has been used successfully for quantum sensing and biolabeling, the surface mechanism to initiate growth was unknown. This report describes the surface chemistry responsible for silica bond formation on diamond and uses X-ray absorption spectroscopy (XAS) to probe the diamond surface chemistry and its electronic structure with increasing silica thickness. A modified Stöber (Cigler) method was used to synthesize 2-35 nm thick shells of SiO2 onto carboxylic acid-rich ND cores. The diamond morphology, surface, and electronic structure were characterized by overlapping techniques including electron microscopy. Importantly, we discovered that SiO2 growth on carboxylated NDs eliminates the presence of carboxylic acids and that basic ethanolic solutions convert the ND surface to an alcohol-rich surface prior to silica growth. The data supports a mechanism that alcohols on the ND surface generate silyl-ether (ND-O-Si-(OH)3) bonds due to rehydroxylation by ammonium hydroxide in ethanol. The suppression of the diamond electronic structure as a function of SiO2 thickness was observed for the first time, and a maximum probing depth of ∼14 nm was calculated. XAS spectra based on the Auger electron escape depth was modeled using the NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to support our experimental results. Additionally, resonant inelastic X-ray scattering (RIXS) maps produced by the transition edge sensor reinforces the chemical analysis provided by XAS. Researchers using diamond or high-pressure high temperature (HPHT) NDs and other exotic materials (e.g., silicon carbide or cubic-boron nitride) for quantum sensing applications may exploit these results to design new layered or core-shell quantum sensors by forming covalent bonds via surface alcohol groups.

Over-Stoichiometric Metastabilization of Cation-Disordered Rock Salts.

Cation-disordered rock salts (DRXs) are well known for their potential to realize the goal of achieving scalable Ni- and Co-free high-energy-density Li-ion batteries. Unlike in most cathode materials, the disordered cation distribution may lead to more factors that control the electrochemistry of DRXs. An important variable that is not emphasized by research community is regarding whether a DRX exists in a more thermodynamically stable form or a more metastable form. Moreover, within the scope of metastable DRXs, over-stoichiometric DRXs, which allow relaxation of the site balance constraint of a rock salt structure, are particularly underexplored. In this work, these findings are reported in locating a generally applicable approach to "metastabilize" thermodynamically stable Mn-based DRXs to metastable ones by introducing Li over-stoichiometry. The over-stoichiometric metastabilization greatly stimulates more redox activities, enables better reversibility of Li deintercalation/intercalation, and changes the energy storage mechanism. The metastabilized DRXs can be transformed back to the thermodynamically stable form, which also reverts the electrochemical properties, further contrasting the two categories of DRXs. This work enriches the structural and compositional space of DRX families and adds new pathways for rationally tuning the properties of DRX cathodes.

X-ray Spectroscopic Study of the Electronic Structure of a Trigonal High-Spin Fe(IV)═O Complex Modeling Non-Heme Enzyme Intermediates and Their Reactivity.

Fe K-edge X-ray absorption spectroscopy (XAS) has long been used for the study of high-valent iron intermediates in biological and artificial catalysts. 4p-mixing into the 3d orbitals complicates the pre-edge analysis but when correctly understood via 1s2p resonant inelastic X-ray scattering and Fe L-edge XAS, it enables deeper insight into the geometric structure and correlates with the electronic structure and reactivity. This study shows that in addition to the 4p-mixing into the 3dz2 orbital due to the short iron-oxo bond, the loss of inversion in the equatorial plane leads to 4p mixing into the 3dx2-y2,xy, providing structural insight and allowing the distinction of 6- vs 5-coordinate active sites as shown through application to the Fe(IV)═O intermediate of taurine dioxygenase. Combined with O K-edge XAS, this study gives an unprecedented experimental insight into the electronic structure of Fe(IV)═O active sites and their selectivity for reactivity enabled by the π-pathway involving the 3dxz/yz orbitals. Finally, the large effect of spin polarization is experimentally assigned in the pre-edge (i.e., the α/ß splitting) and found to be better modeled by multiplet simulations rather than by commonly used time-dependent density functional theory.

Scrutinizing formally NiIV centers through the lenses of core spectroscopy, molecular orbital theory, and valence bond theory.

Nickel K- and L2,3-edge X-ray absorption spectra (XAS) are discussed for 16 complexes and complex ions with nickel centers spanning a range of formal oxidation states from II to IV. K-edge XAS alone is shown to be an ambiguous metric of physical oxidation state for these Ni complexes. Meanwhile, L2,3-edge XAS reveals that the physical d-counts of the formally NiIV compounds measured lie well above the d6 count implied by the oxidation state formalism. The generality of this phenomenon is explored computationally by scrutinizing 8 additional complexes. The extreme case of NiF62- is considered using high-level molecular orbital approaches as well as advanced valence bond methods. The emergent electronic structure picture reveals that even highly electronegative F-donors are incapable of supporting a physical d6 NiIV center. The reactivity of NiIV complexes is then discussed, highlighting the dominant role of the ligands in this chemistry over that of the metal centers.

Operando characterization and regulation of metal dissolution and redeposition dynamics near battery electrode surface.

Mn dissolution has been a long-standing, ubiquitous issue that negatively impacts the performance of Mn-based battery materials. Mn dissolution involves complex chemical and structural transformations at the electrode-electrolyte interface. The continuously evolving electrode-electrolyte interface has posed great challenges for characterizing the dynamic interfacial process and quantitatively establishing the correlation with battery performance. In this study, we visualize and quantify the temporally and spatially resolved Mn dissolution/redeposition (D/R) dynamics of electrochemically operating Mn-containing cathodes. The particle-level and electrode-level analyses reveal that the D/R dynamics is associated with distinct interfacial degradation mechanisms at different states of charge. Our results statistically differentiate the contributions of surface reconstruction and Jahn-Teller distortion to the Mn dissolution at different operating voltages. Introducing sulfonated polymers (Nafion) into composite electrodes can modulate the D/R dynamics by trapping the dissolved Mn species and rapidly establishing local Mn D/R equilibrium. This work represents an inaugural effort to pinpoint the chemical and structural transformations responsible for Mn dissolution via an operando synchrotron study and develops an effective method to regulate Mn interfacial dynamics for improving battery performance.

Lewis acid-assisted reduction of nitrite to nitric and nitrous oxides via the elusive nitrite radical dianion.

Reduction of nitrite anions (NO2-) to nitric oxide (NO), nitrous oxide (N2O) and ultimately dinitrogen (N2) takes place in a variety of environments, including in the soil as part of the biogeochemical nitrogen cycle and in acidified nuclear waste. Nitrite reduction typically takes place within the coordination sphere of a redox-active transition metal. Here we show that Lewis acid coordination can substantially modify the reduction potential of this polyoxoanion to allow for its reduction under non-aqueous conditions (-0.74 V versus NHE). Detailed characterization confirms the formation of the borane-capped radical nitrite dianion (NO22-), which features a N(II) oxidation state. Protonation of the nitrite dianion results in the facile loss of nitric oxide (NO), whereas its reaction with NO results in disproportionation to nitrous oxide (N2O) and nitrite (NO2-). This system connects three redox levels in the global nitrogen cycle and provides fundamental insights into the conversion of NO2- to NO.

Local Structure of Sulfur Vacancies on the Basal Plane of Monolayer MoS2.

The nature of the S-vacancy is central to controlling the electronic properties of monolayer MoS2. Understanding the geometric and electronic structures of the S-vacancy on the basal plane of monolayer MoS2 remains elusive. Here, operando S K-edge X-ray absorption spectroscopy shows the formation of clustered S-vacancies on the basal plane of monolayer MoS2 under reaction conditions (H2 atmosphere, 100-600 °C). First-principles calculations predict spectral fingerprints consistent with the experimental results. The Mo K-edge extended X-ray absorption fine structure shows the local structure as coordinatively unsaturated Mo with 4.1 ± 0.4 S atoms as nearest neighbors (above 400 °C in an H2 atmosphere). Conversely, the 6-fold Mo-Mo coordination in the crystal remains unchanged. Electrochemistry confirms similar active sites for hydrogen evolution. The identity of the S-vacancy defect on the basal plane of monolayer MoS2 is herein elucidated for applications in optoelectronics and catalysis.

Resolving Charge Distribution for Compositionally Heterogeneous Battery Cathode Materials.

The isostructural nature of Li-layered cathodes allows for accommodating multiple transition metals (TMs). However, little is known about how the local TM stoichiometry influences the charging behavior of battery particles thus impacting battery performance. Here, we develop heterogeneous compositional distributions in polycrystalline LiNi1-x-yMnxCoyO2 (NMC) particles to investigate the interplay between local stoichiometry and charge distribution. These NMC particles exhibit a broad, continuous distribution of local Ni/Mn/Co stoichiometry, which does not compromise the global layeredness. The local Mn and Ni concentrations in individual NMC particles are positively and negatively correlated with the electrochemically induced Ni oxidation, respectively, whereas the Co concentration does not impose a clear effect on the Ni oxidation. The resulting material delivers excellent reversible capacity, rate capability, and cycle life at high operating voltages. Engineering Ni/Mn/Co distribution in NMC particles may provide a path toward controlling the charge distribution and thus chemomechanical properties of polycrystalline battery particles.

Quantifying the Steric Effect on Metal-Ligand Bonding in Fe Carbene Photosensitizers with Fe 2p3d Resonant Inelastic X-ray Scattering.

Understanding the electronic structure and chemical bonding of transition metal complexes is important for improving the function of molecular photosensitizers and catalysts. We have utilized X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) at the Fe L3 edge to investigate the electronic structure of two Fe N-heterocyclic carbene complexes with similar chemical structures but different steric effects and contrasting excited-state dynamics: [Fe(bmip)2]2+ and [Fe(btbip)2]2+, bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)pyridine and btbip = 2,6-bis(3-tert-butyl-imidazole-1-ylidene)pyridine. In combination with charge transfer multiplet and ab initio calculations, we quantified how changes in Fe-carbene bond length due to steric effects modify the metal-ligand bonding, including σ/π donation and π back-donation. We find that σ donation is significantly stronger in [Fe(bmip)2]2+, whereas the π back-donation is similar in both complexes. The resulting stronger ligand field and nephelauxetic effect in [Fe(bmip)2]2+ lead to approximately 1 eV destabilization of the quintet metal-centered 5T2g excited state compared to [Fe(btbip)2]2+, providing an explanation for the absence of a photoinduced 5T2g population and a longer metal-to-ligand charge-transfer excited-state lifetime in [Fe(bmip)2]2+. This work demonstrates how combined modeling of XAS and RIXS spectra can be utilized to understand the electronic structure of transition metal complexes governed by correlated electrons and donation/back-donation interactions.

Metastable Brominated Nanodiamond Surface Enables Room Temperature and Catalysis-Free Amine Chemistry.

Bromination of high-pressure, high-temperature (HPHT) nanodiamond (ND) surfaces has not been explored and can open new avenues for increased chemical reactivity and diamond lattice covalent bond formation. The large bond dissociation energy of the diamond lattice-oxygen bond is a challenge that prevents new bonds from forming, and most researchers simply use oxygen-terminated NDs (alcohols and acids) as reactive species. In this work, we transformed a tertiary-alcohol-rich ND surface to an amine surface with ∼50% surface coverage and was limited by the initial rate of bromination. We observed that alkyl bromide moieties are highly labile on HPHT NDs and are metastable as previously found using density functional theory. The strong leaving group properties of the alkyl bromide intermediate were found to form diamond-nitrogen bonds at room temperature and without catalysts. This robust pathway to activate a chemically inert ND surface broadens the modalities for surface termination, and the unique surface properties of brominated and aminated NDs are impactful to researchers for chemically tuning diamond for quantum sensing or biolabeling applications.

Revealing the Dynamics and Roles of Iron Incorporation in Nickel Hydroxide Water Oxidation Catalysts.

The surface of an electrocatalyst undergoes dynamic chemical and structural transformations under electrochemical operating conditions. There is a dynamic exchange of metal cations between the electrocatalyst and electrolyte. Understanding how iron in the electrolyte gets incorporated in the nickel hydroxide electrocatalyst is critical for pinpointing the roles of Fe during water oxidation. Here, we report that iron incorporation and oxygen evolution reaction (OER) are highly coupled, especially at high working potentials. The iron incorporation rate is much higher at OER potentials than that at the OER dormant state (low potentials). At OER potentials, iron incorporation favors electrochemically more reactive edge sites, as visualized by synchrotron X-ray fluorescence microscopy. Using X-ray absorption spectroscopy and density functional theory calculations, we show that Fe incorporation can suppress the oxidation of Ni and enhance the Ni reducibility, leading to improved OER catalytic activity. Our findings provide a holistic approach to understanding and tailoring Fe incorporation dynamics across the electrocatalyst-electrolyte interface, thus controlling catalytic processes.

Angstrom-Resolved Interfacial Structure in Buried Organic-Inorganic Junctions.

Charge transport processes at interfaces play a crucial role in many processes. Here, the first soft x-ray second harmonic generation (SXR SHG) interfacial spectrum of a buried interface (boron-Parylene N) is reported. SXR SHG shows distinct spectral features that are not observed in x-ray absorption spectra, demonstrating its extraordinary interfacial sensitivity. Comparison to electronic structure calculations indicates a boron-organic separation distance of 1.9 Å, with changes of less than 1 Å resulting in easily detectable SXR SHG spectral shifts (ca. hundreds of milli-electron volts).

Operando Study of Thermal Oxidation of Monolayer MoS2.

Monolayer MoS2 is a promising semiconductor to overcome the physical dimension limits of microelectronic devices. Understanding the thermochemical stability of MoS2 is essential since these devices generate heat and are susceptible to oxidative environments. Herein, the promoting effect of molybdenum oxides (MoO x ) particles on the thermal oxidation of MoS2 monolayers is shown by employing operando X-ray absorption spectroscopy, ex situ scanning electron microscopy and X-ray photoelectron spectroscopy. The study demonstrates that chemical vapor deposition-grown MoS2 monolayers contain intrinsic MoO x and are quickly oxidized at 100 °C (3 vol% O2/He), in contrast to previously reported oxidation thresholds (e.g., 250 °C, t ≤ 1 h in the air). Otherwise, removing MoO x increases the thermal oxidation onset temperature of monolayer MoS2 to 300 °C. These results indicate that MoO x promote oxidation. An oxide-free lattice is critical to the long-term stability of monolayer MoS2 in state-of-the-art 2D electronic, optical, and catalytic applications.

Carrier-specific dynamics in 2H-MoTe2 observed by femtosecond soft x-ray absorption spectroscopy using an x-ray free-electron laser.

Femtosecond carrier dynamics in layered 2H-MoTe2 semiconductor crystals have been investigated using soft x-ray transient absorption spectroscopy at the x-ray free-electron laser (XFEL) of the Pohang Accelerator Laboratory. Following above-bandgap optical excitation of 2H-MoTe2, the photoexcited hole distribution is directly probed via short-lived transitions from the Te 3d 5/2 core level (M5-edge, 572-577 eV) to transiently unoccupied states in the valence band. The optically excited electrons are separately probed via the reduced absorption probability at the Te M5-edge involving partially occupied states of the conduction band. A 400 ± 110 fs delay is observed between this transient electron signal near the conduction band minimum compared to higher-lying states within the conduction band, which we assign to hot electron relaxation. Additionally, the transient absorption signals below and above the Te M5 edge, assigned to photoexcited holes and electrons, respectively, are observed to decay concomitantly on a 1-2 ps timescale, which is interpreted as electron-hole recombination. The present work provides a benchmark for applications of XFELs for soft x-ray absorption studies of carrier-specific dynamics in semiconductors, and future opportunities enabled by this method are discussed.

Operando Tailoring of Defects and Strains in Corrugated ß-Ni(OH)2 Nanosheets for Stable and High-Rate Energy Storage.

Nickel hydroxide represents a technologically important material for energy storage, such as hybrid supercapacitors. It has two different crystallographic polymorphs, α- and ß-Ni(OH)2 , showing advantages in either theoretical capacity or cycling/rate performance, manifesting a trade-off trend that needs to be optimized for practical applications. Here, the synergistic superiorities in both activity and stability of corrugated ß-Ni(OH)2 nanosheets are demonstrated through an electrochemical abuse approach. With ≈91% capacity retention after 10 000 cycles, the corrugated ß-Ni(OH)2 nanosheets can deliver a gravimetric capacity of 457 C g-1 at a high current density of 30 A g-1 , which is nearly two and four times that of the regular α- and ß-Ni(OH)2 , respectively. Operando spectroscopy and finite element analysis reveal that greatly enhanced chemical activity and structural robustness can be attributed to the in situ tailored lattice defects and the strain-induced highly curved micromorphology. This work demonstrates a multi-scale defect-and-strain co-design strategy, which is helpful for rational design and tuned fabrication of next-generation electrode materials for stable and high-rate energy storage.