ABSTRACT Alkaline CO 2 electrolysis can reach industrially relevant rates, but it typically incurs substantial carbon losses through carbonate formation, limiting conversion efficiency. In this study, we show that combining a gold‐decorated CuO nanoneedle catalyst (N‑CuAu) with dynamic pulsed electrocatalysis and a synthetic electrolyte with tuned bulk hydroxide concentration ([OH − ]‐Bulk) suppresses carbonation while maintaining high overall performance in an alkaline electrolyzer. The integrated strategy reduces carbon losses to 5.7%, while achieving a single‐pass CO 2 conversion of 51% and an overall Faradaic efficiency (FE) of 92% for selective CO 2 reduction. The resulting carbonate formation ratio is about 182‐fold lower than conventional alkaline CO 2 electrolysis and 27 fold lower than state‐of‐the‐art neutral media CO 2 electrolysis. Using complementary in situ and ex situ characterizations, we identify an operative semi‐quantitative local alkalinity ([OH − ]‐Local) of 0.17 mol/Lit that correlates with suppressed carbonate formation and enhanced selectivity toward alcohol products, while confirming catalyst structural stability under dynamic pulsed operation. Together, these results establish hydroxide microenvironment control as a lever to reconcile high‐performance alkaline CO 2 electrolysis with low carbonation losses.

Polymer electrolytes incorporating Li10GeP2S12 (LGPS) nanoparticles are promising for solid-state lithium batteries due to their potential for enhanced ionic conductivity; yet, the atomistic mechanisms driving this enhancement remain debated. Here, we systematically investigate the relationship between LGPS nanoparticle loading, poly(ethylene oxide) microstructure, and Li-ion transport using a combination of molecular dynamics (MD) simulations, experimental ionic conductivity measurements, and density functional theory (DFT) calculations. MD simulations and experiments reveal good agreement on ionic conductivity as a function of LGPS concentrations of up to 10 wt % (x %), exhibiting a volcano-like curve with ionic conductivity increasing 5-fold from the low concentrations and can be accounted for by a classical transport mechanism governed by polymer segmental dynamics and interface effects. However, at more than 10% LGPS, experiments show further conductivity enhancement that cannot be accounted for by MD simulations, indicating a shift to another transport mechanism. DFT calculations elucidate that, at the polymer| LGPS interface, Li-ion migration proceeds via vacancy-driven hopping, with barriers sensitive to local atomic composition-low-barrier pathways are possible when S atoms dominantly occupy the sites on the interface to facilitate Li-hopping, while pathways involving Ge act as obstacles to Li transport. These results establish that optimized interfacial chemistry and electrolyte structure enable efficient, barrier-lowering migration channels that are distinct from bulk polymer or ceramic behavior. Our approach reconciles experiments with classical simulations at low LGPS concentrations and quantum chemical interface calculations, highlighting design criteria for maximizing the performance of these types of solid composite polymer electrolytes and guiding the development of advanced lithium batteries.

Future lithium batteries are expected to use solid electrolytes to achieve higher energy density and fast charge capabilities. However, most solid electrolytes are thermodynamically unstable against layered oxide cathodes. In this study, the stability of LiCoO2 (LCO) cathode with Li10GeP2S12 (LGPS) solid electrolyte is investigated using ab initio molecular dynamics (AIMD) and machine learning molecular dynamics (MLMD). The propensity of ionic interdiffusion, formation of a passivating interphase layer, and corresponding decay in cell performance is addressed using a continuum model. Large-scale MLMD simulations confirm that the LCO|LGPS interface permits interdiffusion of cobalt (Co) and other ionic species, leading to the formation and growth of a resistive interphase and to dramatic capacity fade even in the first cycle. We examine the literature evidence that incorporating a thin layer of LiNb0.5Ta0.5O3 (LNTO) between LCO and LGPS prevents the interdiffusion of ions. Atomistic simulations suggest that substituting lithium (Li) in LNTO with Co is thermodynamically unfavorable, thereby inhibiting ionic interdiffusion. The stable Nb5+/Ta5+ states form a rigid metal-oxide framework, which consequently also prevents the substitution of niobium (Nb) or tantalum (Ta). However, continuum-level analysis suggests that the higher mechanical stiffness of LNTO can lead to interfacial delamination between the LCO and LNTO. This phenomenon reduces the effectiveness of the protective layer. This paper, therefore, highlights the need to develop novel interlayers that balance low ionic interdiffusion with low mechanical stiffness.

Lithium-carbon dioxide batteries hold great promise for high-energy-density storage applications. However, advancing this technology as a sustainable alternative to Li-ion systems requires a deeper understanding of the underlying reaction mechanisms, which remain elusive. A key challenge stems from the added complexity introduced by the presence of oxygen in CO2 environment. In this study, we employ a stable Cu3(VBi)0.5Se4 mid-entropy catalyst and conduct comprehensive investigation to uncover the underlying reaction mechanisms in Li-CO2 batteries under varying CO2/O2 ratios. Under pure CO2 conditions, the battery shows extended rechargeability, sustaining up to 1200 cycles at a current density of 0.2 mA/cm2 and capacity of 0.1 mAh/cm2. However, at high current densities, the discharge potential drops significantly (below 2.0 V), primarily due to sluggish reaction kinetics caused by solid carbon formation. Interestingly, introducing O2 mitigates this limitation, leading to a 58% increase of the discharge potential (from 1.7 V to 2.7 V) at the current density of 0.8 mA/cm2, signifying a substantial boost in energy output. Our results reveal that the reactions follow distinct pathways, shifting from surface- to solution-based mechanism, and even exhibit coexistence of both mechanisms, depending on the CO2/O2 ratio. These findings offer useful insights for designing sustainable Li-gas batteries utilizing CO2 and O2 mixtures.

Solid-state lithium–metal batteries require electrolytes that combine high ionic conductivity with efficient interfacial transport. In this work, we systematically examine how nanoparticle fillers with distinct chemistries and surface functionalizations govern interfacial Li+ transport in composite polymer electrolytes (CPEs). Inert Al2O3 fillers improve CPE performance through mechanical integrity and interfacial contact with lithium; however, surface modification with γ-methacryloxypropyltrimethoxysilane diminishes these benefits, resulting in reduced electrochemical performance relative to neat Al2O3. In contrast, modifying lithium containing Li6.25Al0.25La3Zr2O12 (LLZO) nanoparticles with the same silane agent substantially impacted cell performance: the interfacial resistance decreased, and the lithium-ion transference number increased, yielding a threefold rise in critical current density to the systems containing modified Al2O3. LLZO functionalized with (3-aminopropyl)triethoxysilane in an aprotic solvent exhibited poorer electrochemical performance. Solid-state NMR showed reduced lithium content in both silane-modified LLZO samples, with more pronounced depletion under protic modification. Complementary T1 measurements revealed a larger fraction of fast-relaxing lithium near the nanoparticle surface, consistent with accelerated local Li-ion dynamics. We attribute performance enhancement with LLZO nanofillers to silane-induced lithium vacancies at or near LLZO surfaces that facilitate interfacial Li+ motion. These results demonstrate that Li-containing fillers are necessary to achieve interfacial transport improvements even when they do not contribute to bulk Li transport, and that performance is governed by changes in local lithium concentration, interfacial chemistry, and ion dynamics. This work establishes a structure–property relationship between silane functionality and ion transport, providing a practical framework for the future interface design toward enabling continuous bulk transport through Li-containing nanofillers in high-performance solid-state electrolytes.

Electrochemical CO2 reduction reaction (eCO2RR) to multi-carbon (C2+) products with copper-based catalysts is often limited by poor selectivity. This challenge arises from the concurrent formation of various intermediates, dictated by the atomic arrangement and electronic properties of surface atoms. In this study, we found that copper (I) oxide (Cu2O) nanocrystals with 50 facets (50F-NC), predominantly featuring (211) facets that offers high density of under-coordinated sites, demonstrate superior ethylene (C2H4) selectivity of 92 % +/- 2 with an overall current density of 212 mA/cm2 at-650 mV vs RHE. Furthermore, after one month of storage in a 1 M KOH electrolyte, this catalyst demonstrated a C2H4 Faradaic efficiency of 87 % highlighting its stabile structure under strong alkaline environments. Operando electrochemical Raman spectroscopy revealed enhanced CO* intermediate coverage on the 50F-NC catalyst, correlating with improved C-C coupling. SEM, TEM, and XPS analyses, along with DFT calculations, suggested that Cu sites on the (211) facet of 50F-NC and those at the Cu/ Cu2O interface formed in-situ due to the surface reconstruction during the reaction, are likely active sites for effective C-C coupling and sustained high-rate C2H4 production.

Solid lithium peroxide (Li2O2) is the major discharge product in Li-air batteries. However, the electronically insulating nature of Li2O2 tends to affect the battery’s performance such as the polarization gap and cyclability. On the other hand, lithium superoxide (LiO2), generated through a one-electron transfer process, offers greater electronic conductivity, lower charge transfer resistance, and thus reduced charge potential. Nevertheless, LiO2 long-term stabilization as a final product remains a significant challenge. In this study, we present the molybdenum (Mo)-based Janus chalcogenide family featuring asymmetric structures as a new generation of cathode catalysts for Li-air batteries. These catalysts demonstrate remarkable efficacy in stabilizing LiO2 discharge products, even under high current densities of 5000mA/g (corresponding to 0.5mA/cm2). Our density functional calculations provide an understanding of why the asymmetric Mo-Janus chalcogenides result in LiO2 formation whereas the symmetric Mo-dichalcogenides produce Li2O2 as the discharge product. These results pave the way to explore a new generation of advanced catalysts for superoxide-based Li-air batteries.

Propylene oxide, a key commodity of the chemical industry for a wide range of consumer products, is synthesized through sequential propane dehydrogenation and epoxidation reactions. However, the lack of a direct catalytic route from propane to propylene oxide reduces efficiency and represents a major challenge for catalysis science. Herein, we report the discovery of a highly active and selective catalyst, made of alumina-supported subnanometer copper clusters, which can directly convert propane to propylene oxide at temperatures as low as 150 °C. Moreover, at higher temperatures, on the same catalysts, the selectivity is switched to propylene. Accompanying theoretical calculations indicate that partially oxidized and/or hydroxylated clusters have low activation energies for both propane dehydrogenation and propylene epoxidation pathways, enabling direct conversion with very high selectivity for propylene oxide. The discovery of a low-temperature catalyst that can convert propane directly to propylene oxide provides an important opportunity for the development of energy-efficient and economic catalysts for this industrially critical process. Similarly, when operating at higher temperatures, these catalysts are posed as potent oxidative dehydrogenation catalysts.

We report atomic-scale gating and visualization of local charge distribution within individual rare-earth-based molecular complexes on a metallic surface. The complexes are formed by a positively charged lanthanum ion coordinated to a (pcam)3 molecule and a negatively charged counterion trapped underneath via electrostatic interactions on a Au(111) surface. Local gating is performed by adding an additional negatively charged counterion to one side of the complex, which results in the redistribution of charges within the complex and a positive shift of the frontier orbitals. This is caused by the internal Stark effect induced by the added counterion. This effect is directly captured using tunneling spectroscopy and spectroscopic mapping at 5 K substrate temperature. The polarizability of the complex is corroborated by density functional theory and analytical calculations based on experimental findings. Furthermore, the influence of charge polarization on nearby complexes is investigated in a cluster purposely assembled using three complexes, which reveals maintaining the charge states as in single complexes. These findings will enable the design of robust charged rare-earth complexes to be tailored for potential solid-state applications.

Through scanning electrochemical microscopy and computational simulation, we show that hydrogen functionalization on graphitic carbon electrodes increases electron transfer kinetics to redox-active species in non-aqueous media.

Li-CO2 batteries are promising energy storage systems due to their high theoretical energy density and CO2 fixation capability, relying on reversible Li2CO3 /C formation during discharge/charge cycles. We present a multiscale modeling framework integrating Density Functional Theory (DFT), Ab-Initio Molecular Dynamics (AIMD), classical Molecular Dynamics (MD), and Finite Element Analysis (FEA) to investigate atomic and cell-level properties. The considered Li-CO2 battery consists of a lithium metal anode, an ionic liquid electrolyte, and a carbon cloth cathode with Sb0.67Bi1.33Te3 catalyst. DFT and AIMD determined the electrical conductivities of Sb0.67Bi1.33Te3 and Li2CO3 using the Kubo-Greenwood formalism and studied the CO2 reduction mechanism on the cathode catalyst. MD simulations calculated the CO2 diffusion coefficient, Li + transference number, ionic conductivity, and Li + solvation structure. The FEA model, parameterized with atomistic simulation data, reproduced the available experimental voltage-capacity profile at 1 mA/cm and revealed spatio-temporal variations in Li2 2 CO3 /C deposition, porosity, and CO2 concentration dependence on discharge rates in the cathode. Accordingly, Li2CO3 can form large and thin film deposits, leading to dispersed and local porosity changes at 0.1 mA/cm and 1 mA/cm2 2 , respectively. The capacity decreases exponentially from 81,570 mAh/g at 0.1 mA/cm to 6200 mAh/g at 1 mA/cm , 2 2 due to pore clogging from excessive discharge product deposition that limits CO2 transport to the cathode interior. Therefore, the performance of Li-CO2 batteries can be improved by enhancing CO2 transport, regulating Li2CO3 deposition, and optimizing cathode architecture.

Sodium-oxygen (Na-O2) batteries are considered a promising energy storage alternative to current state-of-the-art technologies owing to their high theoretical energy density, along with the natural abundance and low price of Na metal. The chemistry of these batteries depends on sodium superoxide (NaO2) or peroxide (Na2O2) being formed/decomposed. Most Na-O2 batteries form NaO2, but reversibility is usually quite limited due to side reactions at interfaces. By using new materials, including a highly active catalyst based on vanadium phosphide (VP) nanoparticles, an ether/ionic liquid-based electrolyte, and an effective sodium bromide (NaBr) anode protection layer, the sources of interface reactivity can be reduced to achieve a Na-O2 battery cell that is rechargeable for 1070 cycles with a high energy efficiency of more than 83%. Density functional theory calculations, along with experimental characterization confirm the three factors leading to the long cycle life, including the effectiveness of the NaBr protective layer on the anode, a tetraglyme/EMIM-BF4 based electrolyte that prevents oxidation of the VP cathode catalyst surface, and the EMIM-BF4 ionic liquid aiding in avoiding electrolyte decomposition on NaO2.

Next-generation lithium-ion batteries are expected to use solid electrolytes (SEs) to enable higher energy density and extreme fast-charge capabilities. One major mode of degradation at the cathode|SE interface is delamination between the cathode active materials and SEs, which leads to performance decay. Experimental observations indicate that implementation of interphase layers can minimize the cathode|SE delamination induced capacity fade. A multiscale computational methodology is developed here to investigate the applicability of boron substituted lithium carbonate (Li2+x B x C1-x O3, x = 0.5, or LBCO) to minimize the delamination at the cathode|SE interface. Atomistic simulations indicate that the fracture energies at both the cathode|LBCO and LBCO|SE interfaces are higher than those at the cathode|SE interface, which reduces the extent of delamination. Mesoscale simulations indicate that, apart from increasing the fracture energy, decreasing the evolution of strain energy by lowering the elastic modulus of the interphase layer can also minimize the extent of delamination at the cathode|SE interface. However, the adoption of an interphase layer with high ionic conductivity is necessary to minimize the ohmic losses during operation at higher current densities. This study provides guidance on selecting interphase layers with specific properties and thicknesses to minimize both interfacial delamination and impedance growth.

This contribution presents a comprehensive extension of the QM9 dataset (originally at 133 K molecules) with the calculation of G4MP2 enthalpies for 9,841 molecules, featuring up to nine heavy atoms. We present QM9-LOHC, a (de)hydrogenation dataset of 10,373 reactions, including a minimum of 5.5% weight hydrogen storage capacity in line with the Department of Energy standards for Liquid Organic Hydrogen Carriers (LOHC). By utilizing the accurate quantum chemical method G4MP2 we expand the QM9 database and explore new avenues for the exploration of hydrogen storage technologies (electrochemical LOHCs, alkali metal-LOHCs, and mixtures of LOHCs). The QM9-LOHC dataset, with its focus on reactions that vary only by hydrogen saturation levels, provides a needed data resource for advancing the design and optimization of both conventional and innovative LOHC systems, and high-fidelity data for molecular discovery.

Lithium superoxide (LiO 2 ) is generally regarded as an intermediate formed during the Li-O 2 battery discharge and transformed into lithium peroxide (Li 2 O 2 ). Indeed, its chemical/electrochemical stability is low, making it recognized as a temporary discharge product in Li-O 2 battery chemistry. However, in 2016, utilizing an iridium (Ir)-based electrocatalyst, Curtiss and Amine et al. found that LiO 2 can be epitaxially grown on the surface of Ir catalyst and can be stable under cycling conditions. 1 In the study, a templating mechanism was suggested, where a good lattice matching of LiIr 3 surfaces (formed on the Ir catalyst) with that of LiO 2 facilitates LiO 2 formation as a singular discharge product. Following studies showed some superior electrochemical properties of LiO 2 in comparison to Li 2 O 2 , including lower charge overpotentials. Meanwhile, some other transition metal compounds have recently exhibited LiO 2 formation, where the formation mechanism suggested may not be a templating method. In this case, there could be strong adsorption of LiO 2 in specific structures, resulting in suppressed Li 2 O 2 generation. Herein, we will present experimental and computational results on some new catalysts for LiO 2 formation and discuss possible underlying mechanisms. Acnowledgement This work was primarily supported by the US Department of Energy under contract DE-AC02-06CH11357 from the Vehicle Technologies Office, Department of Energy, Office of Energy Efficiency and Renewable Energy. Reference 1 Curtiss. L. and Amine. K. et al. A lithium–oxygen battery based on lithium superoxide. Nature 2016, 529 , 377-382

Li-CO2 batteries with a high theoretical energy density (1876 Wh kg(-1)) have unique benefits for reversible carbon fixation for energy storage systems. However, due to lack of stable and highly active catalysts, the long-term operation of Li-CO2 batteries is limited to low current densities (mainly <0.2 mA cm(-2)) that are far from practical conditions. In this work, it is discovered that, with an ionic liquid-based electrolyte, highly active and stable transition metal trichalcogenide alloy catalysts of Sb(0.6)7Bi(1.33)X(3) (X = S, Te) enable operation of the Li-CO2 battery at a very high current rate of 1 mA cm(-2) for up to 220 cycles. It is revealed that: i) the type of chalcogenide (Te vs S) significantly affects the electronic and catalytic properties of the catalysts, ii) a coupled cation-electron charge transfer process facilitates the carbon dioxide reduction reaction (CO2RR) occurring during discharge, and iii) the concentration of ionic liquid in the electrolyte controls the number of participating CO2 molecules in reactions. A combination of these key factors is found to be crucial for a successful operation of the Li-CO2 chemistry at high current rates. This work introduces a new class of catalysts with potential to fundamentally solve challenges of this type of batteries.

Rare-earth complexes are vital for separation chemistry and useful in many advanced applications including emission and energy upconversion. Here, 2D rare-earth clusters having net charges are formed on a metal surface, enabling investigations of their structural and electronic properties on a one-cluster-at-a-time basis using scanning tunneling microscopy. While these ionic complexes are highly mobile on the surface at ≈100 K, their mobility is greatly reduced at 5 K and reveals stable and self-limiting clusters. In each cluster, a pair of charged rare-earth complexes formed by electrostatic and dispersive interactions act as a basic unit, and the clusters are chiral. Unlike other non-ionic molecular clusters formed on the surfaces, these rare-earth clusters show mechanical stability. Moreover, their high mobility on the surface suggests that they are in a 2D liquid-like state.

Kohei Uosaki opened discussion of the paper by Zhangquan Peng: I am wondering how pure your electrolyte solutions were. Often a non-aqueous solution used for battery research is not as clean as aqueous solutions. While the procedure to obtain water-based electrolyte solutions is well establishe