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Interstitial atoms rather than vacancies mediate the exchange of oxygen between TiO₂and liquid water containing dissolved O₂. 

Injection of interstitial atoms by specially prepared surfaces submerged in liquid water near room temperature offers an attractive approach for post-synthesis defect manipulation and isotopic purification in device structures. However, this approach can be limited by trapping reactions that form small defect clusters. The compositions and dissociation barriers of such clusters remain mostly unknown. This communication seeks to address this gap by measuring the dissociation energies of oxygen interstitial traps in rutile TiO2 and wurtzite ZnO exposed to liquid water. Isotopic self-diffusion measurements using 18O, combined with progressive annealing protocols, suggest the traps are small interstitial clusters with dissociation energies ranging from 1.3 to 1.9 eV. These clusters may comprise a family incorporating various numbers, compositions, and configurations of O and H atoms; however, in TiO2, native interstitial clusters left over from initial synthesis may also play a role. Families of small clusters are probably common in semiconducting oxides and have several consequences for post-synthesis defect manipulation and purification of semiconductors using submerged surfaces. 

Redoxmers are organic molecules that serve as charge carriers in redox flow batteries. While these materials are affordable and easy to source, insufficient stability of their charged states (radical ions) remains a challenge. A common reaction of these species is their disproportionation. This reversible reaction yields unstable multiply charged states, shifting the overall charge transfer equilibrium toward the decomposition products. Here we show how kinetic controls can be engineered into a redoxmer molecule to suppress these unwanted charge transfer reactions. This approach is used to transform Wurster’s blue, which is historically the first example of a stable radical ion in organic chemistry, into an exceptionally durable redoxmer molecule that persists over thousands of electrochemical cycles. 

Due to their almost unlimited scalability, redox flow batteries can make versatile and affordable energy storage systems. Redox active materials (redoxmers) in these batteries largely define their electrochemical performance, including the life span of the battery that depends on the stability of charged redoxmers. In this study, we examine the effects of expanding the π-system in the arene rings on the chemical stability of dialkoxyarene redoxmers that are used to store positive charge in RFBs. When 1,4-dimethoxybenzene is π-extended to 1,4-dimethoxynaphthalene, a lower redox potential, improved kinetic stability, and longer cycling life are observed. However, when an additional ring is fused to make 9,10-dimethoxyanthracene, the radical cation undergoes rapid O-dealkylation possibly due to increased steric strain that drives methoxy out of the arene plane thus breaking the π-conjugation with O 2p orbitals. On the other hand, the planar structure of 1,4-dimethoxynaphthalene may facilitate second-order reactions of radical cations leading to their neutralization in the bulk. Our study suggests that extending the π-system changes reactivity in multiple (sometimes, opposite) ways, so lowering the oxidation potential through π-conjugation to improve redoxmer stability should be pursued with caution. 

Low bond coordination of surface atoms facilitates the injection of oxygen interstitial atoms into the bulk near room temperature from the clean surfaces of semiconducting metal oxides when exposed to liquid water, opening new prospects for postsynthesis defect engineering and isotopic fractionation. The injection rate and penetration depth vary considerably under identical experimental conditions, however, with the adsorption of adventitious carbon suggested as the cause. For water-submerged rutile TiO2(110) and wurtzite ZnO(0001), this work bolsters and refines that hypothesis by combining the isotopic self-diffusion measurements of oxygen with characterization by x-ray photoelectron spectroscopy and atomic force microscopy. Adventitious carbon likely diminishes injection rates by poisoning small concentrations of exceptionally active surface sites that either inject O or dissociate adsorbed OH to injectable O. These effects propagate into the penetration depth via the progressive saturation of Oi traps near the surface, which occurs less extensively as the injected flux decreases. 

Oxygen vacancies (V O ) influence many properties of ZnO in semiconductor devices, yet synthesis methods leave behind variable and unpredictable V O concentrations. Oxygen interstitials (O i ) move far more rapidly, so post-synthesis introduction of O i to control the V O concentration would be desirable. Free surfaces offer such an introduction mechanism if they are free of poisoning foreign adsorbates. Here, isotopic exchange experiments between nonpolar ZnO(101̄0) and O 2 gas, together with mesoscale modeling and first-principles calculations, point to an activation barrier for injection only 0.1–0.2 eV higher than for bulk site hopping. The modest barrier for hopping in turn enables diffusion lengths of tens to hundreds of nanometers only slightly above room temperature, which should facilitate defect engineering under very modest conditions. In addition, low hopping barriers coupled with statistical considerations lead to important qualitative manifestations in diffusion via an interstitialcy mechanism that does not occur for vacancies.