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1. Experimental study of the proton-transfer reaction C + H 2 + → CH + + H and its isotopic variant (D 2 + )

   https://doi.org/10.1039/D0CP04810K  

   Hillenbrand, Pierre-Michel ; Bowen, Kyle P. ; Dayou, Fabrice ; Miller, Kenneth A. ; de Ruette, Nathalie ; Urbain, Xavier ; Savin, Daniel W. ( December 2020 , Physical Chemistry Chemical Physics)

   We report absolute integral cross section (ICS) measurements using a dual-source merged-fast-beams apparatus to study the titular reactions over the relative translational energy range of E r ∼ 0.01–10 eV. We used photodetachment of C − to produce a pure beam of atomic C in the ground electronic 3 P term, with statistically populated fine-structure levels. The H 2 + and D 2 + were formed in an electron impact ionization source, with well known vibrational and rotational distributions. The experimental work is complemented by a theoretical study of the CH 2 + electronic system in the reactant and product channels, which helps to clarify the possible reaction mechanisms underlying the ICS measurements. Our measurements provide evidence that the reactions are barrierless and exoergic. They also indicate the apparent absence of an intermolecular isotope effect, to within the total experimental uncertainties. Capture models, taking into account either the charge-induced dipole interaction potential or the combined charge-quadrupole and charge-induced dipole interaction potentials, produce reaction cross sections that lie a factor of ∼4 above the experimental results. Based on our theoretical study, we hypothesize that the reaction is most likely to proceed adiabatically through the 1 4 A′ and 1 4 A′′ states of CH 2 + via the reaction C( 3 P) + H 2 + ( 2 Σ+g) → CH + ( 3 Π) + H( 2 S). We also hypothesize that at low collision energies only H 2 + ( v ≤ 2) and D 2 + ( v ≤ 3) contribute to the titular reactions, due to the onset of dissociative charge transfer for higher vibrational v levels. Incorporating these assumptions into the capture models brings them into better agreement with the experimental results. Still, for energies ≲0.1 eV where capture models are most relevant, the modified charge-induced dipole model yields reaction cross sections with an incorrect energy dependence and lying ∼10% below the experimental results. The capture cross section obtained from the combined charge-quadrupole and charge-induced dipole model better matches the measured energy dependence but lies ∼30–50% above the experimental results. These findings provide important guidance for future quasiclassical trajectory and quantum mechanical treatments of this reaction. 

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2. Controllable Nonclassical Conductance Switching in Nanoscale Phase‐Separated (PbI 2 ) 1− x (BiI 3 ) x Layered Crystals

   https://doi.org/10.1002/adma.202103098  

   Alexander, Grant C. B. ; Krantz, Patrick W. ; Jung, Hee Joon ; Davis, Samuel Kenneth ; Xu, Yaobin ; Dravid, Vinayak P. ; Chandrasekhar, Venkat ; Kanatzidis, Mercouri G. ( October 2021 , Advanced Materials)

   Layered 2D (PbI₂)_1−x(BiI₃)_xmaterials exhibit a nonlinear dependence in structural and charge transport properties unanticipated from the combination of PbI₂and BiI₃. Within (PbI₂)_1−x(BiI₃)_xcrystals, phase integration yields deceptive structural features, while phase boundary separation leads to new conductance switching behavior observed as large peaks in current during current–voltage (I–V) measurements (±100 V). Temperature‐ and time‐dependent electrical measurements demonstrate that the behavior is attributed to ionic transport perpendicular to the layers. High‐resolution transmission electron microscopy reveals that the structure of (PbI₂)_1−x(BiI₃)_xis a “brick wall” consisting of two phases, Pb‐rich and Bi‐rich. These brick‐like features are 10s nm a side and it is posited that iodide ion transport at the interfaces of these regions is responsible for the conductance switching action.

    

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3. Observation of chiral surface excitons in a topological insulator Bi 2 Se 3

   https://doi.org/10.1073/pnas.1813514116  

   Kung, H. -H. ; Goyal, A. P. ; Maslov, D. L. ; Wang, X. ; Lee, A. ; Kemper, A. F. ; Cheong, S. -W. ; Blumberg, G. ( February 2019 , Proceedings of the National Academy of Sciences)

   The protected electron states at the boundaries or on the surfaces of topological insulators (TIs) have been the subject of intense theoretical and experimental investigations. Such states are enforced by very strong spin–orbit interaction in solids composed of heavy elements. Here, we study the composite particles—chiral excitons—formed by the Coulomb attraction between electrons and holes residing on the surface of an archetypical 3D TI,${\mathrm{B}\mathrm{i}}_2{\mathrm{S}\mathrm{e}}_3$. Photoluminescence (PL) emission arising due to recombination of excitons in conventional semiconductors is usually unpolarized because of scattering by phonons and other degrees of freedom during exciton thermalization. On the contrary, we observe almost perfectly polarization-preserving PL emission from chiral excitons. We demonstrate that the chiral excitons can be optically oriented with circularly polarized light in a broad range of excitation energies, even when the latter deviate from the (apparent) optical band gap by hundreds of millielectronvolts, and that the orientation remains preserved even at room temperature. Based on the dependences of the PL spectra on the energy and polarization of incident photons, we propose that chiral excitons are made from massive holes and massless (Dirac) electrons, both with chiral spin textures enforced by strong spin–orbit coupling. A theoretical model based on this proposal describes quantitatively the experimental observations. The optical orientation of composite particles, the chiral excitons, emerges as a general result of strong spin–orbit coupling in a 2D electron system. Our findings can potentially expand applications of TIs in photonics and optoelectronics.

    

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4. Highly porous, low band-gap Ni x Mn 3−x O 4 (0.55 ≤ x ≤ 1.2) spinel nanoparticles with in situ coated carbon as advanced cathode materials for zinc-ion batteries

   https://doi.org/10.1039/c9ta05101e  

   Long, Jun ; Gu, Jinxing ; Yang, Zhanhong ; Mao, Jianfeng ; Hao, Junnan ; Chen, Zhongfang ; Guo, Zaiping ( July 2019 , Journal of Materials Chemistry A)

   Aqueous zinc ion batteries (ZIBs) are emerging as a highly promising alternative technology for grid-scale applications where high safety, environmental-friendliness, and high specific capacities are needed. It remains a significant challenge, however, to develop a cathode with a high rate capability and long-term cycling stability. Here, we demonstrate diffusion-controlled behavior in the intercalation of zinc ions into highly porous, Mn 4+ -rich, and low-band-gap Ni x Mn 3−x O 4 nano-particles with a carbon matrix formed in situ (with the composite denoted as Ni x Mn 3−x O 4 @C, x = 1), which exhibits superior rate capability (139.7 and 98.5 mA h g −1 at 50 and 1200 mA g −1 , respectively) and outstanding cycling stability (128.8 mA h g −1 remaining at 400 mA g −1 after 850 cycles). Based on the obtained experimental results and density functional theory (DFT) calculations, cation-site Ni substitution combined with a sufficient doping concentration can decrease the band gap and effectively improve the electronic conductivity in the crystal. Furthermore, the amorphous carbon shell and highly porous Mn 4+ -rich structure lead to fast electron transport and short Zn 2+ diffusion paths in a mild aqueous electrolyte. This study provides an example of a technique to optimize cathode materials for high-performance rechargeable ZIBs and design advanced intercalation-type materials for other energy storage devices. 

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5. Ni 2 P‐Modified Ta 3 N 5 and TaON for Photocatalytic Nitrate Reduction

   https://doi.org/10.1002/cnma.202000174  

   Wei, Lin ; Adamson, Marquix A. S. ; Vela, Javier ( May 2020 , ChemNanoMat)

   Self‐sustaining photocatalytic NO₃⁻reduction systems could become ideal NO₃⁻removal methods. Developing an efficient, highly active photocatalyst is the key to the photocatalytic reduction of NO₃⁻. In this work, we present the synthesis of Ni₂P‐modified Ta₃N₅(Ni₂P/Ta₃N₅), TaON (Ni₂P/TaON), and TiO₂(Ni₂P/TiO₂). Starting with a 2 mM (28 g/mL NO₃⁻−N) aqueous solution of NO₃⁻, as made Ni₂P/Ta₃N₅and Ni₂P/TaON display as high as 79% and 61% NO₃⁻conversion under 419 nm light within 12 h, which correspond to reaction rates per gram of 196 μmol g⁻¹ h⁻¹and 153 μmol g⁻¹ h⁻¹, respectively, and apparent quantum yields of 3–4%. Compared to 24% NO₃⁻conversion in Ni₂P/TiO₂, Ni₂P/Ta₃N₅and Ni₂P/TaON exhibit higher activities due to the visible light active semiconductor (SC) substrates Ta₃N₅and TaON. We also discuss two possible electron migration pathways in Ni₂P/semiconductor heterostructures. Our experimental results suggest one dominant electron migration pathway in these materials, namely: Photo‐generated electrons migrate from the semiconductor to co‐catalyst Ni₂P, and upshift its Fermi level. The higher Fermi level provides greater driving force and allows NO₃⁻reduction to occur on the Ni₂P surface.

    

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