Double sulfur vacancies by lithium tuning enhance CO2 electroreduction to n-propanol

Electrochemical CO2 reduction can produce valuable products with high energy densities but the process is plagued by poor selectivities and low yields. Propanol represents a challenging product to obtain due to the complicated C3 forming mechanism that requires both stabilization of *C2 intermediates and subsequent C1–C2 coupling. Herein, density function theory calculations revealed that double sulfur vacancies formed on hexagonal copper sulfide can feature as efficient electrocatalytic centers for stabilizing both CO* and OCCO* dimer, and further CO–OCCO coupling to form C3 species, which cannot be realized on CuS with single or no sulfur vacancies. The double sulfur vacancies were then experimentally synthesized by an electrochemical lithium tuning strategy, during which the density of sulfur vacancies was well-tuned by the charge/discharge cycle number. The double sulfur vacancy-rich CuS catalyst exhibited a Faradaic efficiency toward n-propanol of 15.4 ± 1% at −1.05 V versus reversible hydrogen electrode in H-cells, and a high partial current density of 9.9 mA cm−2 at −0.85 V in flow-cells, comparable to the best reported electrochemical CO2 reduction toward n-propanol. Our work suggests an attractive approach to create anion vacancy pairs as catalytic centers for multi-carbon-products.

Investigation of switching uniformity in resistive memory via finite element simulation of conductive-filament formation

Herein, we present simulations of conductive filament formation in resistive random-access memory using a finite element solver. We consider the switching material, which is typically an oxide, as a two-phase material comprising low- and high-resistance phases. The low-resistance phase corresponds to a defective and conducting region with a high anion vacancy concentration, whereas the high-resistance phase corresponds to a non-defective and insulating region with a low anion-vacancy concentration. We adopt a phase variable corresponding to 0 and 1 in the insulating and conducting phases, respectively, and we change the phase variable suitably when new defects are introduced during voltage ramp-up for forming. Initially, some defects are embedded in the switching material. When the applied voltage is ramped up, the phase variable changes from 0 to 1 at locations wherein the electric field exceeds a critical value, which corresponds to the introduction of new defects via vacancy generation. The applied voltage at which the defects percolate to form a filament is considered as the forming voltage. Here, we study the forming-voltage uniformity using simulations, and we find that for typical planar-electrode devices, the forming voltage varies significantly owing to the stochastic location of the initial defects at which the electric field is “crowded.” On the other hand, a protruding electrode can improve the switching uniformity drastically via facilitating the deterministic location of electric-field crowding, which also supported by the reported experimental results.

Constructing anion vacancy-rich MoSSe/G van der Waals heterostructures for high-performance Mg–Li hybrid-ion batteries

Anion vacancies riched MoSSe and graphene van der Waals heterostructures can reduce the ion diffusion barriers and increase the adsorption energy, thereby greatly enhancing the ion diffusion rate and suppressing the rapid voltage drop in discharge.

Strain-induced creation and switching of anion vacancy layers in perovskite oxynitrides

Perovskite oxides can host various anion-vacancy orders, which greatly change their properties, but the order pattern is still difficult to manipulate. Separately, lattice strain between thin film oxides and a substrate induces improved functions and novel states of matter, while little attention has been paid to changes in chemical composition. Here we combine these two aspects to achieve strain-induced creation and switching of anion-vacancy patterns in perovskite films. Epitaxial SrVO3 films are topochemically converted to anion-deficient oxynitrides by ammonia treatment, where the direction or periodicity of defect planes is altered depending on the substrate employed, unlike the known change in crystal orientation. First-principles calculations verified its biaxial strain effect. Like oxide heterostructures, the oxynitride has a superlattice of insulating and metallic blocks. Given the abundance of perovskite families, this study provides new opportunities to design superlattices by chemically modifying simple perovskite oxides with tunable anion-vacancy patterns through epitaxial lattice strain.