Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments.

Carbon fiber-reinforced polymer (CFRP) materials are widely used in aerospace and recreational equipment, but there is no efficient procedure for their end-of-life recycling. Ongoing work in the chemistry and engineering communities emphasizes recovering carbon fibers from such waste streams by dissolving or destroying the polymer binding. By contrast, our goal is to depolymerize amine-cured epoxy CFRP composites catalytically, thus enabling not only isolation of high-value carbon fibers, but simultaneously opening an approach to recovery of small molecule monomers that can be used to regenerate precursors to new composite resin. To do so will require understanding of the molecular mechanism(s) of such degradation sequences. Prior work has shown the utility of hydrogen peroxide as a reagent to affect epoxy matrix decomposition [1]. Herein we describe the chemical transformations involved in that sequence: the reaction proceeds by oxygen atom transfer to the polymer’s linking aniline group, forming an N-oxide intermediate. The polymer is then cleaved by an elimination and hydrolysis sequence. We find that elimination is the slower step. Scandium trichloride is an efficient catalyst for this step, reducing reaction time in homogeneous model systems and neat cured matrix blocks. The conditions can be applied to composed composite materials, from which pristine carbon fibers can be recovered.

Sodium-ion battery technology has attracted significant attention due to its substantial cost advantage and similar operating mechanism to Li-ion batteries. P2-type sodium manganese oxide cathode is one of the most promising candidates, demonstrating both high capacity and good cycling stability. Here, we explore the lattice oxygen activity in layered sodium transition metal oxides. We synthesize a series of sodium lithium manganese oxides, NaxLi0.25Mn0.75O2 (x = 0.75 – 0.833), to optimize Na content. We further investigate the charge compensation mechanism for the best performing Na0.75Li0.25Mn0.75O2 over an extensive electrochemical cycling window. The large charge and discharge capacity is enabled by reversible lattice oxygen redox in the high voltage region (≥2.5 V), along with Mn redox at the voltages below 2.5 V. Additionally, we reveal a small amount of oxygen gas evolution, 0.04% of the total oxygen in Na0.25Li0.25Mn0.75O2. This initial study will trigger an interest in the lattice oxygen activity in layered sodium metal oxide cathode, therefore, leading to better understanding of its correlation with crystal structure and electrochemical performance.

Pronounced voltage hysteresis in Li-excess cathode materials is commonly thought to be associated with oxygen redox. However, these materials often possess overlapping oxygen and transition-metal redox, whose contributions to hysteresis between charge and discharge are challenging to distinguish. In this work, a two-step aqueous redox titration is developed with the aid of mass spectrometry (MS) to quantify oxidized lattice oxygen and Mn 3+ /4+ redox in a representative Li-excess cation-disordered rock salt-Li 1.2 Mn 0.4 Ti 0.4 O 2 (LMTO). Two MS-countable gas molecules evolve from two separate titrant-analyte reactions, thereby allowing Mn and O redox capacities to be decoupled. The decoupled O and Mn redox coulombic efficiencies are close to 100% for the LMTO cathode, indicating high charge-compensation reversibility. As incremental Mn and O redox capacities are quantitatively decoupled, each redox voltage hysteresis is further evaluated. Overall, LMTO voltage hysteresis arises not only from an intrinsic charge-discharge voltage mismatch related to O redox, but also from asymmetric Mn-redox overvoltages. The results reveal that O and Mn redox both contribute substantially to voltage hysteresis. This work further shows the potential of designing new analytical workflows to experimentally quantify key properties, even in a disordered material having complex local coordination environments.

We previously reported that iridium complex 1a enables the first homogeneous catalytic dehydrogenation of neat formic acid and enjoys unusual stability through millions of turnovers. Binuclear iridium hydride species 5a, which features a provocative C2-symmetric geometry, was isolated from the reaction as a catalyst resting state. By synthesizing and carefully examining the catalytic initiation of a series of analogues to 1a, we establish here a strong correlation between the formation of C2-twisted iridium dimers analogous to 5a and the reactivity of formic acid dehydrogenation: an efficient C2 twist appears unique to 1a and essential to catalytic reactivity.

Nonaqueous sodium- and lithium-oxygen batteries are of interest because of their high theoretical specific energies relative to state-of-the-art Li-ion batteries. However, several challenges limit rechargeability, including instability of the carbon electrode and electrolyte with reactive oxygen species formed during cycling. This work investigates strategies to improve the cycling efficiency of the Na–O2 system and minimize irreversible degradation of electrolyte and electrode materials. We show that charging cells with a constant current/constant voltage (CCCV) protocol is a promising technique made possible by the slight solubility of sodium superoxide in nonaqueous electrolytes. In addition, the type of carbon electrode has a significant impact on cell performance and efficacy of the cycling protocol. Graphitic carbon electrodes coupled with CCCV charging demonstrate higher reversibility, more efficient oxygen evolution, and less outgassing than conventional cells using a porous carbon paper electrode and only a constant current charge. Graphical abstract

A simple post-synthesis heating approach tailors the crystal structure, surface chemistry, and electrochemical properties of sodium titanate anode.

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