More Like this

1. Observation of the fastest chemical processes in the radiolysis of water

   Loh, Z.-H. ; Doumy, G. ; Arnold, C. ; Kjellsson, L. ; Southworth, S. H. ; Al Haddad, A. ; Kumagai, Y. Tu ; Ho, P. J ; March, A. M. ; Schaller, R. D. ; et al ( January 2020 , Science)

   Elementary processes associated with ionization of liquid water provide a framework for understanding radiation-matter interactions in chemistry and biology. Although numerous studies have been conducted on the dynamics of the hydrated electron, its partner arising from ionization of liquid water, H2O+, remains elusive. We used tunable femtosecond soft x-ray pulses from an x-ray free electron laser to reveal the dynamics of the valence hole created by strong-field ionization and to track the primary proton transfer reaction giving rise to the formation of OH. The isolated resonance associated with the valence hole (H2O+/OH) enabled straightforward detection. Molecular dynamics simulations revealed that the x-ray spectra are sensitive to structural dynamics at the ionization site. We found signatures of hydrated-electron dynamics in the x-ray spectrum. 

   more » « less
2. Chromate Incarceration by Nanojars and Its Removal from Water by Liquid–Liquid Extraction

   https://doi.org/10.1021/acs.inorgchem.3c00262  

   Al Isawi, Wisam A. ; Hartman, Christian K. ; Singh, Pooja ; Zeller, Matthias ; Mezei, Gellert ( April 2023 , Inorganic Chemistry)

   The unprecedented liquid–liquid extraction of the dinegative chromate ion (CrO42–) from neutral aqueous solutions into aliphatic hydrocarbon solvents using nanojars as extraction agents is demonstrated. Transferring chromate from water into an organic solvent is extremely challenging due to its large hydration energy (ΔGh° = −950 kJ/mol) and strong oxidizing ability. Owing to their highly hydrophilic anion binding pockets lined by a multitude of hydrogen bond donor OH groups, neutral nanojars of the formula [cis-CuII(μ-OH)(μ-4-Rpz)]n (n = 27–33; pz = pyrazolate anion; R = H or n-octyl) strongly bind the CrO42– ion and efficiently transfer it from water into n-heptane or C11 – C13 isoalkanes (when R = n-octyl). The extracted chromate can easily be recovered from the organic layer by stripping with an aqueous acid solution. Electrospray ionization mass spectrometric, UV–vis and paramagnetic 1H NMR spectroscopic, X-ray crystallographic, and thermal stability studies in solution and chemical stability studies toward NH3, methanol, and Ba2+ ions are employed to explore the binding of the CrO42– ion by nanojars. Titration of carbonate nanojars [CO3 ⊂ {Cu(OH)(pz)}n]2– with H2CrO4 leads to anion exchange and the formation of chromate nanojars [CrO4 ⊂ {Cu(OH)(pz)}n]2–. Details of chromate binding by H-bonding based on single-crystal structures of (Bu4N)2[CrO4 ⊂ {Cu(OH)(pz)}28], four pseudopolymorphs of (Bu4N)2[CrO4 ⊂ {Cu(OH)(pz)}31], and also the methoxy-substituted derivative (Bu4N)2[CrO4 ⊂ {Cu31(OH)30(OCH3)(pz)31}] are presented. 

   more » « less
3. Extreme Ultraviolet Reflection-Absorption (XUV-RA) Spectroscopy: Probing Dynamics at Surfaces from a Molecular Perspective

   https://doi.org/https://doi.org/10.1021/acs.accounts.1c00765  

   Biswas, Somnath ; Baker, L. Robert ( March 2022 , Accounts of chemical research)

   Extreme ultraviolet (XUV) light sources based on high harmonic generation are enabling the development of novel spectroscopic methods to help advance the frontiers of ultrafast science and technology. In this account we discuss the development of XUV-RA spectroscopy at near grazing incident reflection geometry and highlight recent applications of this method to study ultrafast electron dynamics at surfaces. Measuring core-to-valence transitions with broadband, femtosecond pulses of XUV light extends the benefits of x-ray absorption spectroscopy to a laboratory tabletop by providing a chemical fingerprint of materials, including the ability to resolve individual elements with sensitivity to oxidation state, spin state, carrier polarity, and coordination geometry. Combining this chemical state sensitivity with femtosecond time resolution provides new insight into the material properties that govern charge carrier dynamics in complex materials. It is well known that surface dynamics differ significantly from equivalent processes in bulk materials, and that charge separation, trapping, transport, and recombination occurring uniquely at surfaces governs the efficiency of numerous technologically relevant processes spanning photocatalysis, photovoltaics, and information storage and processing. Importantly, XUV-RA spectroscopy at near grazing angle is also surface sensitive with a probe depth of 3 nm, providing a new window into electronic and structural dynamics at surfaces and interfaces. Here we highlight the unique capabilities and recent applications of XUVRA spectroscopy to study photo-induced surface dynamics in metal oxide semiconductors, including photocatalytic oxides (Fe2O3, Co3O4 NiO, and CuFeO2) as well as photoswitchable magnetic oxide (CoFe2O4). We first compare the ultrafast electron self-trapping rates via small polaron formation at the surface and bulk of Fe2O3 where we note that the energetics and kinetics of this process differ significantly at the surface. Additionally, we demonstrate the ability to systematically tune this kinetics by molecular functionalization, thereby, providing a route to control carrier transport at surfaces. We also measure the spectral signatures of charge transfer excitons with site specific localization of both electrons and holes in a series of transition metal oxide semiconductors (Fe2O3, NiO, Co3O4). The presence of valence band holes probed at the oxygen L1-edge confirms a direct relationship between the metal-oxygen bond covalency and water oxidation efficiency. For a mixed metal oxide CuFeO2 in the layered delafossite structure, XUV-RA reveals that the sub-picosecond hole thermalization from O 2p to Cu 3d states of CuFeO2 leads to the spatial separation of electrons and holes, resulting in exceptional photocatalytic performance for H2 evolution and CO2 reduction of this material. Finally, we provide an example to show the ability of XUV-RA to probe spin state specific dynamics in a the photo-switchable ferrimagnet, cobalt ferrite (CoFe2O4). This study provides a detailed understating of ultrafast spin switching in a complex magnetic material with site-specific resolution. In summary, the applications of XUV-RA spectroscopy demonstrated here illustrate the current abilities and future promise of this method to extend molecule-level understanding from well-defined photochemical complexes to complex materials so that charge and spin dynamics at surfaces can be tuned with the precision of molecular photochemistry. 

   more » « less
4. ALMA multiline survey of the ISM in two quasar host–companion galaxy pairs at z > 6

   https://doi.org/10.1051/0004-6361/202039696  

   Pensabene, A. ; Decarli, R. ; Bañados, E. ; Venemans, B. ; Walter, F. ; Bertoldi, F. ; Fan, X. ; Farina, E. P. ; Li, J. ; Mazzucchelli, C. ; et al ( August 2021 , Astronomy & Astrophysics)

   null (Ed.)

   We present a multiline survey of the interstellar medium (ISM) in two z  > 6 quasar host galaxies, PJ231−20 ( z  = 6.59) and PJ308−21 ( z  = 6.23), and their two companion galaxies. Observations were carried out using the Atacama Large (sub-)Millimeter Array (ALMA). We targeted 11 transitions including atomic fine-structure lines (FSLs) and molecular lines: [NII] 205 μm , [CI] 369 μm , CO ( J up  = 7, 10, 15, 16), H 2 O 3 12  − 2 21 , 3 21  − 3 12 , 3 03  − 2 12 , and the OH 163 μm doublet. The underlying far-infrared (FIR) continuum samples the Rayleigh-Jeans tail of the respective dust emission. By combining this information with our earlier ALMA [CII] 158 μm observations, we explored the effects of star formation and black hole feedback on the ISM of the galaxies using the CLOUDY radiative transfer models. We estimated dust masses, spectral indexes, IR luminosities, and star-formation rates from the FIR continuum. The analysis of the FSLs indicates that the [CII] 158 μm and [CI] 369 μm emission arises predominantly from the neutral medium in photodissociation regions (PDRs). We find that line deficits agree with those of local luminous IR galaxies. The CO spectral line energy distributions (SLEDs) reveal significant high- J CO excitation in both quasar hosts. Our CO SLED modeling of the quasar PJ231−20 shows that PDRs dominate the molecular mass and CO luminosities for J up  ≤ 7, while the J up  ≥ 10 CO emission is likely driven by X-ray dissociation regions produced by the active galactic nucleus (AGN) at the very center of the quasar host. The J up  > 10 lines are undetected in the other galaxies in our study. The H 2 O 3 21  − 3 12 line detection in the same quasar places this object on the L H 2 O  −  L TIR relation found for low- z sources, thus suggesting that this water vapor transition is predominantly excited by IR pumping. Models of the H 2 O SLED and of the H 2 O-to-OH 163 μm ratio point to PDR contributions with high volume and column density ( n H  ∼ 0.8 × 10 5 cm −3 , N H  = 10 24 cm −2 ) in an intense radiation field. Our analysis suggests a less highly excited medium in the companion galaxies. However, the current data do not allow us to definitively rule out an AGN in these sources, as suggested by previous studies of the same objects. This work demonstrates the power of multiline studies of FIR diagnostics in order to dissect the physical conditions in the first massive galaxies emerging from cosmic dawn. 

   more » « less
5. Low‐temperature synthesis of HfC/HfO 2 nanocomposites from a commercial single‐source precursor

   https://doi.org/10.1002/ces2.10187  

   Mujib, Shakir Bin ; Arunachalam, Saravanan R. ; Singh, Gurpreet ( August 2023 , International Journal of Ceramic Engineering & Science)

   A liquid‐phase polymer‐to‐ceramic approach is reported for the synthesis of hafnium carbide (HfC)/hafnium oxide (HfO₂) composite particles from a commercial precursor. Typically, HfC ceramics have been obtained by sintering of fine powders, which usually results in large particle size and high porosity during densification. In this study a single‐source liquid precursor was first cured at low temperature and then pyrolyzed at varying conditions to achieve HfC ceramics. The chemical structure of the liquid and cured precursors, and the resulting HfC ceramics was studied using various analytical techniques. The nuclear magnetic resonance and Fourier transform infrared spectroscopy indicated the presence of partially hydrated hafnium oxychloride (Hf–O–Cl·nH₂O) in the precursor. Scanning electron microscopy of the resulting HfC crystals showed a size distribution in the range of approx. 600–700 nm. The X‐ray diffraction of the pyrolyzed samples confirmed the formation of crystalline HfC along with monoclinic‐HfO₂and free carbon phase. The formation of HfO₂in the ceramics was significantly reduced by controlling the low‐temperature curing temperature. Pyrolysis at various temperatures showed that HfC formation occurred even at 1000°C. These results show that the reported precursor could be promising for the direct synthesis of ultrahigh temperature HfC ceramics and for precursor infiltration pyrolysis of reinforced ceramic matrix composites.

    

   more » « less