In Situ Conversion Reaction Triggered Alloy@Antiperovskite Hybrid Layers for Lithiophilic and Robust Lithium/Garnet Interfaces

Garnet-type electrolytes demonstrate promising prospects in the field of solid-state lithium batteries owing to their superior ionic conductivity and high (electro)chemical stability toward Li metal, whereas the critical issue of Li dendrite growth and even infiltration throughout garnets limits their practical applications. Herein, a hybrid interlayer consisting of Li₃Bi alloy embedded in antiperovskite-type Li₃OCl matrix is in situ constructed at Li/Li_6.75La₃Zr_1.75Ta_0.25O₁₂ interface by taking the conversion reaction of BiOCl with Li metal. The lithiophilic nature of such interlayer enables an intimate contact of garnet against Li metal, guaranteeing a dramatically reduced interfacial resistance of 27 Ω cm². In addition, the inside electron-conducting Li₃Bi nanoparticles homogenize the interfacial potential distribution, while the outside ion-conducting Li₃OCl matrix with a bandgap of 5.06 eV blocks electron tunneling from Li bulk. Profiting from such synergistic effect, the resultant Li symmetric cell displays a high critical current density of 1.1 mA cm⁻², along with an ultralong cycling life of 1000 h at 0.5 mA cm⁻². Furthermore, the corresponding solid LiNi_0.6Co_0.2Mn_0.2O₂/Li cell delivers a high cycling stability for 150 times accompanied by a capacity retention of 82%. This study puts forward a potential solution for construction of functional layers at Li/garnet interfaces by making use of in situ conversion reaction.     

Constructing N?Cu?S Interface Chemical Bonds over SnS2 for Efficient Solar-Driven Photoelectrochemical Water Splitting

The restricted charge transfer and slow oxygen evolution reaction (OER) dynamics tremendously hamper the realistic implementation of SnS₂ photoanodes for photoelectrochemical (PEC) water splitting. Here, a novel strategy is developed to construct interfacial N Cu S bonds between N C skeletons and SnS₂ (Cu N C@SnS₂) for efficient PEC water splitting. Compared with SnS₂, the PEC activity of Cu N C@SnS₂ photoelectrode is tremendously heightened, obtaining a current density of 3.40 mA cm² at 1.23 V_RHE with a negatively shifted onset potential of 0.04 V_RHE, which is 6.54 times higher than that of SnS₂. The detailed experimental characterizations and theoretical calculation demonstrate that the interfacial N Cu S bonds enhance the OER kinetic, reduce the surface overpotential, facilitate the separation of photon-generated carriers, and provide a fast transmission channel for electrons. This work presents a new approach for modulating charge transfer by interfacial bond design in heterojunction photoelectrodes toward promoting PEC performance and solar energy application.     

Embedding Ru Clusters and Single Atoms into Perovskite Oxide Boosts Nitrogen Fixation and Affords Ultrahigh Ammonia Yield Rate

Ammonia is a key chemical feedstock worldwide. Compared with the well-known Haber–Bosch method, electrocatalytic nitrogen reduction reaction (ENRR) can eventually consume less energy and have less CO₂ emission. In this study, a plasma-enhanced chemical vapor deposition method is used to anchor transition metal element onto 2D conductive material. Among all attempts, Ru single-atom and Ru-cluster-embedded perovskite oxide are discovered with promising electrocatalysis performance for ENRR (NH₃ yield rate of up to 137.5 ± 5.8 µg h⁻¹ mg_cat⁻¹ and Faradaic efficiency of unexpected 56.9 ± 4.1%), reaching the top record of Ru-based catalysts reported so far. In situ experiments and density functional theory calculations confirm that the existence of Ru clusters can regulate the electronic structure of Ru single atoms and decrease the energy barrier of the first hydrogenation step (*NN to *NNH). Anchoring Ru onto various 2D perovskite oxides (LaMO-Ru, MCr, Mn, Co, or Ni) also show boosted ENRR performance. Not only this study provides an unique strategy toward transition-metal-anchored new 2D conductive materials, but also paves the way for fundamental understanding the correlation between cluster-involved single-atom sites and catalytic performance.