Li-Sb Alloy Formation Strategy to Improve Interfacial Stability of All-Solid-State Lithium Batteries.

The solid electrolyte is anticipated to prevent lithium dendrite formation. However, preventing interface reactions and the development of undesirable lithium metal deposition during cycling are difficult and remain unresolved. Here, to comprehend these occurrences better, this study reports an alloy formation strategy for enhanced interface stability by incorporating antimony (Sb) in the lithium argyrodite solid electrolyte Li6PS5Cl (LPSC-P) to form Li-Sb alloy. The Li-Sb alloy emergence at the anodic interface is crucial in facilitating uniform lithium deposition, resulting in excellent long-term stability, and achieving the highest critical current density of 14.5 mA cm-2 (among the reported sulfide solid electrolytes) without lithium dendrite penetration. Furthermore, Li-Sb alloy formation maintain interfacial contact, even, after several plating and stripping. The Li-Sb alloy formation is confirmed by XRD, Raman, and XPS. The work demonstrates the prospect of utilizing alloy-forming electrolytes for advanced solid-state batteries.

Synergistic interfacial electronic modulation of topotactically developed bimetallic CoNiP on NiS nanorods for enhanced alkaline hydrogen evolution reaction.

Designing hybrid transition metal phosphosulfide electrocatalysts is critical for the hydrogen evolution reaction (HER). We propose a novel approach by designing a hierarchical structure of cobalt phosphide (CoP) and nickel phosphide (Ni8P3) nanoparticles topotactically developed on nickel sulfide (Ni3S2) nanorods (CoNiP/NiS) via a sulfuration-phosphorization strategy using conductive 3D nickel foam. Hierarchical heterostructured nanorods were achieved without the need for template removal steps or the assistance of surfactants. This not only simplifies the process but also improves the exposure of active sites for catalytic purposes. Furthermore, the theoretical calculation results revealed that the high H* adsorption-free energy for CoP and Ni8P3 phases significantly decreases upon coupling with Ni3S2, which indicates that the interfacial electronic interaction synergistically modulates both CoP and Ni8P3 (CoNiP) at the coupled interfaces and facilitates the adsorption and desorption of H* intermediates during the HER process. The resulting electrode exhibits excellent performance in the HER catalytic process and shows great performance for further exploration in the urea oxidation reaction (UOR). Our work provides a stepping stone toward rational topotactic transformation of active materials on porous substrates, using electronic structure regulation and heterointerfaces to produce promising electrocatalysts for sustainable, large-scale hydrogen production from water electrolysis.

Nickel-Iron Layered Double Hydroxides/Nickel Sulfide Heterostructured Electrocatalysts on Surface-Modified Ti Foam for the Oxygen Evolution Reaction.

Electrochemical approaches for generating hydrogen from water splitting can be more promising if the challenges in the anodic oxygen evolution reaction (OER) can be harnessed. The interface heterostructure materials offer strong electronic coupling and appropriate charge transport at the interface regions, promoting accessible active sites to prompt kinetics and optimize the adsorption-desorption of active species. Herein, we have designed an efficient multi-interface-engineered Ni3Fe1 LDH/Ni3S2/TW heterostructure on in situ generated titanate web layers from the titanium foam. The synergistic effects of the multi-interface heterostructure caused the exposure of rich interfacial electronic coupling, fast reaction kinetics, and enhanced accessible site activity and site populations. The as-prepared electrocatalyst demonstrates outstanding OER activity, demanding a low overpotential of 220 mV at a high current density of 100 mA cm-2. Similarly, the designed Ni3Fe1 LDH/Ni3S2/TW electrocatalyst exhibits a low Tafel slope of 43.2 mV dec-1 and excellent stability for 100 h of operation, suggesting rapid kinetics and good structural stability. Also, the electrocatalyst shows a low overpotential of 260 mV at 100 mA cm-2 for HER activity. Moreover, the integrated electrocatalyst exhibits an incredible OER activity in simulated seawater with an overpotential of 370 mV at 100 mA cm-2 and stability for 100 h of operation, indicating good OER selectivity. This work might benefit further fabricating effective and stable self-sustained electrocatalysts for water splitting in large-scale applications.

Mechanistic Study on Artificial Stabilization of Lithium Metal Anode via Thermal Pyrolysis of Ammonium Fluoride in Lithium Metal Batteries.

The use of the "Holy Grail" lithium metal anode is pivotal to achieve superior energy density. However, the practice of a lithium metal anode faces practical challenges due to the thermodynamic instability of lithium metal and dendrite growth. Herein, an artificial stabilization of lithium metal was carried out via the thermal pyrolysis of the NH4F salt, which generates HF(g) and NH3(g). An exposure of lithium metal to the generated gas induces a spontaneous reaction that forms multiple solid electrolyte interface (SEI) components, such as LiF, Li3N, Li2NH, LiNH2, and LiH, from a single salt. The artificially multilayered protection on lithium metal (AF-Li) sustains stable lithium stripping/plating. It suppresses the Li dendrite under the Li||Li symmetric cell. The half-cell Li||Cu and Li||MCMB systems depicted the attributions of the protective layer. We demonstrate that the desirable protective layer in AF-Li exhibited remarkable capacity retention (CR) results. LiFePO4 (LFP) showed a CR of 90.6% at 0.5 mA cm-2 after 280 cycles, and LiNi0.5Mn0.3Co0.2O2 (NCM523) showed 58.7% at 3 mA cm-2 after 410 cycles. Formulating the multilayered protection, with the simultaneous formation of multiple SEI components in a facile and cost-effective approach from NH4F as a single salt, made the system competent.

Heteroatom-Coordinated Palladium Molecular Catalysts for Sustainable Electrochemical Production of Hydrogen Peroxide.

Currently, hydrogen peroxide (H2O2) manufacturing involves an energy-intensive anthraquinone technique that demands expensive solvent extraction and a multistep process with substantial energy consumption. In this work, we synthesized Pd-N4-CO, Pd-S4-NCO, and Pd-N2O2-C single-atom catalysts via an in situ synthesis approach involving heteroatom-rich ligands and activated carbon under mild reaction conditions. It reveals that palladium atoms interact strongly with heteroatom-rich ligands, which provide well-defined and uniform active sites for oxygen (O2) electrochemically reduced to hydrogen peroxide. Interestingly, the Pd-N4-CO electrocatalyst shows excellent performance for the electrocatalytic reduction of O2 to H2O2 via a two-electron transfer process in a base electrolyte, exhibiting a negligible amount of onset overpotential and >95% selectivity within a wide range of applied potentials. The electrocatalysts based on the activity and selectivity toward 2e- ORR follow the order Pd-N4-CO > Pd-N2O2-C > Pd-S4-NCO in agreement with the pull-push mechanism, which is the Pd center strongly coordinated with high electronegativity donor atoms (N and O atoms) and weakly coordinated with the intermediate *OOH to excellent selectivity and sustainable production of H2O2. According to density functional theory, Pd-N4 is the active site for selectivity toward H2O2 generation. This work provides an emerging technique for designing high-performance H2O2 electrosynthesis catalysts and the rational integration of several active sites for green and sustainable chemical synthesis via electrochemical processes.

Generating Multi-Carbon Products by Electrochemical CO2 Reduction via Catalytically Harmonious Ni/Cu Dual Active Sites.

Despite the unique advantages of single-atom catalysts, molecular dual-active sites facilitate the C-C coupling reaction for C2 products toward the CO2 reduction reaction (CO2 RR). The Ni/Cu proximal dual-active site catalyst (Ni/Cu-PASC) is developed, which is a harmonic catalyst with dual-active sites, by simply mixing commercial Ni-phthalocyanine (Ni-Pc) and Cu-phthalocyanine (Cu-Pc) molecules physically. According to scanning transmission electron microscopy (STEM) and transmission electron microscopy (TEM) energy dispersive spectroscopy (EDS) data, Ni and Cu atoms are separated, creating dual-active sites for the CO2 RR. The Ni/Cu-PASC generates ethanol with an FE of 55%. Conversely, Ni-Pc and Cu-Pc have only detected single-carbon products like CO and HCOO- . In situ X-ray absorption spectroscopy (XAS) indicates that CO generation is caused by the stable Ni active site's balanced electronic state. The CO production from Ni-Pc consistently increased the CO concentration over Cu sites attributed to subsequent reduction reaction through a C-C coupling on nearby Cu. The CO bound (HCOO- ) peak, which can be found on Cu-Pc, vanishes on Ni/Cu-PASC, as shown by in situ fourier transformation infrared (FTIR). The characteristic intermediate of *CHO instead of HCOO- proves to be the prerequisite for multi-carbon products by electrochemical CO2 RR. The work demonstrates that the harmonic dual-active sites in Ni/Cu-PASC can be readily available by the cascading proximal active Ni- and Cu-Pc sites.

Tuning Dynamically Formed Active Phases and Catalytic Mechanisms of In Situ Electrochemically Activated Layered Double Hydroxide for Oxygen Evolution Reaction.

The active phase and catalytic mechanisms of Ni-based layered double hydroxide (LDH) materials for oxygen evolution reaction (OER) have no common consensus and remain controversial. Moreover, engineering the site activity and the number of active sites of LDHs is an efficient approach to advance the OER activity, as the thickness and stacking structure of the LDHs layer limit the catalytic activity. This work presents an interesting in situ approach of tuning the site activity and number of active sites of NiMn-LDHs, which exhibit the superior OER performance (onset overpotential of 0.17 V and overpotential of 0.24 V at 10 mA cm-2). The fundamental mechanistic insights and active phases during the OER process are characterized by in operando techniques along with the computational density functional theory calculations, revealing that the Ni site constitutes the OER activity and the dynamically generated NiOOH moiety is the active phase. We also prove that Ni sites undergo a reversible oxidation state under the working conditions to create active NiOOH species which catalyze the water to generate oxygen. These findings suggest that the Ni(III) phase in NiMn-LDHs is the OER active site and Mn promotes the electronic properties of Ni sites. Utilizing in situ/in operando techniques and theoretical calculation, we find that the in situ intercalation of guest anions allows the expansion of the LDH layers and keeps the active NiOOH species under the oxidation state of +3 via electron coupling, which ultimately tunes the site populations and site activity toward the superior OER activity, respectively. This work thus targets to provide insight into strategies to design the next generation of highly active catalysts for water electrolysis and fuel cell technologies.

All that glitters is not gold: A non-destructive probing of Thanjavur painting by Raman spectroscopy.

In this work, we demonstrate the use of Raman spectroscopy in detecting the presence of gold and semi-precious/precious gemstones in one of the classical paintings of India namely the Thanjavur paintings which have been awarded the Geographical Indication. We find through Raman spectroscopy that there are paintings where fake gold is used in the place of original gold foils. This result has been validated by carrying out the energy dispersive X-ray analysis (EDX) which confirms the Raman spectroscopy findings. We propose Raman spectroscopy as a diagnostic tool for detecting the presence of gold and thereby to frame regulations for the Thanjavur painting market which would be of utmost importance to the artisans as well as its connoisseurs.