The catalytic partial oxidation of methane is achieved at low temperatures (<200 °C) using manganese oxides and manganese salts in mixtures of trifluoroacetic acid and trifluoroacetic anhydride. Dioxygen is used as the in situ terminal oxidant. For Mn oxides (e.g., MnO₂, Mn₂O₃, and Mn₃O₄), we studied stoichiometric methane partial oxidation in HTFA (TFA = trifluoroacetate). Using a Mn trifluoroacetate salt, at 180 °C and under 25 psig of methane, product selectivity for the mono-oxidized product methyl trifluoroacetate (MeTFA) is observed to be >90% at ∼35% methane conversion at approximately 6 turnovers. Under our catalytic methane oxidation reaction conditions, MeTFA is stable against overoxidation, which explains the likely high selectivity at conversions >15%. Using combined experimental studies and DFT calculations, a mechanism involving soluble and molecular Mn species in the catalytic cycle is proposed. The proposed reaction pathway involves initial activation of Mn^II by dioxygen, cleavage of a methane C–H bond by a Mn^III hydroxo intermediate, rebound of the methyl radical to generate MeTFA, and finally regeneration of the starting Mn^II complex. Also, this process is shown to be applicable to the oxidation of ethane, favoring the mono-oxidized product ethyl trifluoroacetate (EtTFA) and reaching ∼46% conversion.

Borepin, a 7-membered boron-containing heterocycle, has become an emerging molecular platform for the development of new materials and optoelectronics. While neutral borepins are well-established, reduced borepin species have remained elusive. Herein we report the first isolable, crystalline borepin radicals ( 2a , 2b ) and anions ( 3a , 3b ), which have been synthesized by potassium graphite (KC₈) reduction of dibenzo[b,d]borepin in the presence of free cyclic(alkyl)(amino) carbene. Borepin radicals and anions have been characterized by EPR or NMR, elemental analysis, X-ray crystallography and cyclic voltammetry. In addition, the bonding features have been investigated computationally using density functional theory.

We report the synthesis, characterization, and electrocatalytic water oxidation activity of two cobalt complexes, (6-FP)Co(NO₃)₂ (1) (6-FP = 8,8′-(1,2-phenylene)diquinoline) and (5-FP)Co(NO₃)₂ (2) (5-FP = 1,2-bis(N-7-azaindolyl)benzene), containing “capping arene” bidentate ligands with nitrogen atom donors. The cobalt complexes 1 and 2 were supported on ordered mesoporous carbon (OMC) by π–π stacking, resulting in heterogenized cobalt materials 6-FP-Co-OMC-1 and 5-FP-Co-OMC-2, respectively, and studied for electrocatalytic water oxidation. We find that 6-FP-Co-OMC-1 exhibits an overpotential of 355 mV for a current density of 10 mA cm^–2 and a turnover frequency (TOF) of ∼0.53 s^–1 at an overpotential of 400 mV at pH 14. 6-FP-Co-OMC-1 exhibits activity that is ∼1.6 times that of 5-FP-Co-OMC-2, which gives a TOF of 0.32 s^–1 at 400 mV overpotential. The structural stability of the single-atom Co site was demonstrated for 6-FP-Co-OMC-1 using X-ray absorption spectroscopy for the molecular complex supported on OMC, but slow degradation in catalyst activity can be attributed to eventual formation of Co oxide clusters. DFT computations of electrocatalytic water oxidation using the molecular complexes as models provide a description of the catalytic mechanism. These studies reveal that the mechanism for O–O bond formation involves an intermediate Co^IV oxo complex that undergoes an intramolecular reductive O–O coupling to form a Co^II–OOH species. Further, the calculations predict that the molecular 6-FP-Co structure is more active for electrocatalytic water oxidation than 5-FP-Co, which is consistent with experimental studies of 6-FP-Co-OMC-1 and 5-FP-Co-OMC-2, highlighting the possibility that the ligand structure influences the catalytic activity of the supported molecular catalysts.

We report a bioinspired non-heme Fe complex with a tripodal [N₃O]⁻ ligand framework (Fe(PMG)(Cl)₂) that is electrocatalytically active toward dioxygen reduction with acetic acid as a proton source in acetonitrile solution. Under electrochemical and chemical conditions, Fe(PMG)(Cl)₂ selectively produces water via a 2+2 mechanism, where H₂O₂ is generated as a discrete intermediate species before further reduction to two equivalents of H₂O. Mechanistic studies support a catalytic cycle for dioxygen reduction where an off-cycle peroxo dimer species is the resting state of the catalyst. Spectroscopic analysis of the reduced complex Fe^II(PMG)Cl shows the stoichiometric formation of an Fe(III)-hydroxide species following exposure to H₂O₂; no catalytic activity for H₂O₂ disproportionation is observed, although the complex is electrochemically active for H₂O₂ reduction to H₂O. Electrochemical studies, spectrochemical experiments, and DFT calculations suggest that the carboxylate moiety of the ligand is sensitive to hydrogen-bonding interactions with the acetic acid proton donor upon reduction from Fe(III)/(II), favoring chloride loss trans to the tris-alkyl amine moiety of the ligand framework. These results offer insight into how mononuclear non-heme Fe active sites in metalloproteins distribute added charge and poise proton donors during reactions with dioxygen.

The mechanisms leading to wake-up and fatigue in ferroelectric hafnium zirconium oxide thin film devices with symmetric RuO₂ electrodes are investigated via polarization, relative permittivity, dielectric nonlinearity, pyroelectric coefficient, and microfocus x-ray diffraction (XRD) measurements. The devices are observed to wake-up for up to 10³ bipolar pulsed field cycles, after which fatigue occurs with polarization approaching zero following 10⁸ cycles. Wake-up is accompanied by a decrease in both high-field permittivity and hysteresis loop pinching and an increase in the pyroelectric coefficient, indicating that the wake-up process involves a combination of transformations from the tetragonal to the orthorhombic phase and domain depinning from defect redistribution. Fatigue is observed to coincide with an increase in irreversible domain wall motion and a decrease in pyroelectric coefficient. Finite pyroelectric coefficients are measured on fully fatigued devices, indicating that domain pinning is a strong contributor to fatigue and that fatigued devices contain domain structures that are unable to switch under the fields applied for measurement. Microfocus XRD patterns measured on each device reveal that the phase constitution is qualitatively unaffected by field cycling and resultant polarization fatigue. These data indicate that the wake-up process has contributions from both phase transformations and domain depinning, whereas the fatigue process is driven primarily by domain pinning, and the near-zero measured switchable polarization is actually a poled device with immobile domains. These observations provide insight into the physical changes occurring during field cycling of HfO₂-based ferroelectrics while examining a possible oxide electrode material for silicon CMOS device implementation.