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1. Plasma-droplet interaction study to assess transport limitations and the role of ⋅ OH, O ⋅ ,H ⋅ ,O 2 (a 1 Δ g ),O 3 , He(2 3 S) and Ar(1s 5 ) in formate decomposition

   https://doi.org/10.1088/1361-6595/ac2676  

   Nayak, Gaurav ; Oinuma, Gaku ; Yue, Yuanfu ; Santos Sousa, João ; Bruggeman, Peter J ( November 2021 , Plasma Sources Science and Technology)

   Abstract Plasmas interacting with liquid microdroplets are gaining momentum due to their ability to significantly enhance the reactivity transfer from the gas phase plasma to the liquid. This is, for example, critically important for efficiently decomposing organic pollutants in water. In this contribution, the role of ⋅ OH as well as non- ⋅ OH-driven chemistry initiated by the activation of small water microdroplets in a controlled environment by diffuse RF glow discharge in He with different gas admixtures (Ar, O 2 and humidified He) at atmospheric pressure is quantified. The effect of short-lived radicals such as O ⋅ and H ⋅ atoms, singlet delta oxygen (O 2 ( a 1 Δ g )), O 3 and metastable atoms of He and Ar, besides ⋅ OH radicals, on the decomposition of formate dissolved in droplets was analyzed using detailed plasma diagnostics, droplet characterization and ex situ chemical analysis of the treated droplets. The formate decomposition increased with increasing droplet residence time in the plasma, with ∼70% decomposition occurring within ∼15 ms of the plasma treatment time. The formate oxidation in the droplets is shown to be limited by the gas phase ⋅ OH flux at lower H 2 O concentrations with a significant enhancement in the formate decomposition at the lowest water concentration, attributed to e − /ion-induced reactions. However, the oxidation is diffusion limited in the liquid phase at higher gaseous ⋅ OH concentrations. The formate decomposition in He/O 2 plasma was similar, although with an order of magnitude higher O ⋅ radical density than the ⋅ OH density in the corresponding He/H 2 O plasma. Using a one-dimensional reaction–diffusion model, we showed that O 2 ( a 1 Δ g ) and O 3 did not play a significant role and the decomposition was due to O ⋅ , and possibly ⋅ OH generated in the vapor containing droplet-plasma boundary layer. 

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2. DFT Analysis of Methane C−H Activation and Over‐Oxidation by [Cu 2 O] 2+ and [Cu 2 O 2 ] 2+ Sites in Zeolite Mordenite: Intra‐ versus Inter‐site Over‐Oxidation

   https://doi.org/10.1002/cphc.202100580  

   Panthi, Dipak ; Adeyiga, Olajumoke ; Odoh, Samuel O. ( October 2021 , ChemPhysChem)

   Methane over‐oxidation by copper‐exchanged zeolites prevents realization of high‐yield catalytic conversion. However, there has been little description of the mechanism for methane over‐oxidation at the copper active sites of these zeolites. Using density functional theory (DFT) computations, we reported that tricopper [Cu₃O₃]²⁺active sites can over‐oxidize methane. However, the role of [Cu₃O₃]²⁺sites in methane‐to‐methanol conversion remains under debate. Here, we examine methane over‐oxidation by dicopper [Cu₂O]²⁺and [Cu₂O₂]²⁺sites using DFT in zeolite mordenite (MOR). For [Cu₂O₂]²⁺, we considered the μ‐(η²:η²) peroxo‐, and bis(μ‐oxo) motifs. These sites were considered in the eight‐membered (8MR) ring of MOR. μ‐(η²:η²) peroxo sites are unstable relative to the bis(μ‐oxo) motif with a small interconversion barrier. Unlike [Cu₂O]²⁺which is active for methane C−H activation, [Cu₂O₂]²⁺has a very large methane C−H activation barrier in the 8MR. Stabilization of methanol and methyl at unreacted dicopper sites however leads to over‐oxidation via sequential hydrogen atom abstraction steps. For methanol, these are initiated by abstraction of the CH₃group, followed by OH and can proceed near 200 °C. Thus, for [Cu₂O]²⁺and [Cu₂O₂]²⁺species, over‐oxidation is an inter‐site process. We discuss the implications of these findings for methanol selectivity, especially in comparison to the intra‐site process for [Cu₃O₃]²⁺sites and the role of Brønsted acid sites.

    

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3. Formation of Nanoscale [Ge 4 O 16 Al 48 (OH) 108 (H 2 O) 24 ] 20+ from Condensation of ϵ‐GeAl 12 8+ Keggin Polycations**

   https://doi.org/10.1002/ange.202017321  

   Shohel, Mohammad ; Bjorklund, Jennifer L. ; Smith, Jack A. ; Kravchuk, Dmytro V. ; Mason, Sara E. ; Forbes, Tori Z. ( March 2021 , Angewandte Chemie)

   Keggin‐type polyaluminum cations belong to a unique class of compounds with their large positive charge, hydroxo bridges, and divergent isomerization/oligomerization. Previous reports indicated that oligomerization of this species can only occur through one isomer (δ), but herein we report the isolation of largest Keggin‐type cluster that occurs through self‐condensation of four ϵ‐isomers ϵ‐GeAl₁₂⁸⁺to form [Ge₄O₁₆Al₄₈(OH)₁₀₈(H₂O)₂₄]²⁰⁺cluster (Ge₄Al₄₈). The cluster was crystallized and structurally characterized by single‐crystal X‐ray diffraction (SCXRD) and the elemental composition was confirmed by ICP‐MS and SEM‐EDS. Additional dynamic light scattering experiments confirms the presence of theGe₄Al₄₈in thermally aged solutions. DFT calculations reveal that a single atom Ge substitution in tetrahedral site of ϵ‐isomer is the key for the formation ofGe₄Al₄₈because it activates deprotonation at key surface sites that control the self‐condensation process.

    

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4. Formation of Nanoscale [Ge 4 O 16 Al 48 (OH) 108 (H 2 O) 24 ] 20+ from Condensation of ϵ‐GeAl 12 8+ Keggin Polycations**

   https://doi.org/10.1002/anie.202017321  

   Shohel, Mohammad ; Bjorklund, Jennifer L. ; Smith, Jack A. ; Kravchuk, Dmytro V. ; Mason, Sara E. ; Forbes, Tori Z. ( March 2021 , Angewandte Chemie International Edition)

   Keggin‐type polyaluminum cations belong to a unique class of compounds with their large positive charge, hydroxo bridges, and divergent isomerization/oligomerization. Previous reports indicated that oligomerization of this species can only occur through one isomer (δ), but herein we report the isolation of largest Keggin‐type cluster that occurs through self‐condensation of four ϵ‐isomers ϵ‐GeAl₁₂⁸⁺to form [Ge₄O₁₆Al₄₈(OH)₁₀₈(H₂O)₂₄]²⁰⁺cluster (Ge₄Al₄₈). The cluster was crystallized and structurally characterized by single‐crystal X‐ray diffraction (SCXRD) and the elemental composition was confirmed by ICP‐MS and SEM‐EDS. Additional dynamic light scattering experiments confirms the presence of theGe₄Al₄₈in thermally aged solutions. DFT calculations reveal that a single atom Ge substitution in tetrahedral site of ϵ‐isomer is the key for the formation ofGe₄Al₄₈because it activates deprotonation at key surface sites that control the self‐condensation process.

    

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5. Selective Wet and Dry Etching of NiO over β-Ga 2 O 3

   https://doi.org/10.1149/2162-8777/ac94a0  

   Chiang, Chao-Ching ; Xia, Xinyi ; Li, Jian-Sian ; Ren, Fan ; Pearton, S. J. ( October 2022 , ECS Journal of Solid State Science and Technology)

   Patterning of NiO/Ga 2 O 3 heterojunctions requires development of selective wet and dry etch processes. Solutions of 1:4 HNO 3 :H 2 O exhibited measurable etch rates for NiO above 40 °C and activation energy for wet etching of 172.9 kJ.mol −1 (41.3 kCal.mol −1 , 1.8 eV atom −1 ), which is firmly in the reaction-limited regime. The selectivity over β -Ga 2 O 3 was infinite for temperatures up to 55 °C. The strong negative enthalpy for producing the etch product Ga(OH) 4 suggests HNO 3 -based wet etching of NiO occurs via formation and dissolution of hydroxides. For dry etching, Cl 2 /Ar Inductively Coupled Plasmas produced etch rates for NiO up to 800 Å.min −1 , with maximum selectivities of <1 over β -Ga 2 O 3 . The ion energy threshold for initiation of etching of NiO was ∼55 eV and the etch mechanism was ion-driven, as determined the linear dependence of etch rate on the square root of ion energy incident on the surface. 

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