Superionic conducting vacancy-rich β-LiN electrolyte for stable cycling of all-solid-state lithium metal batteries.

The advancement of all-solid-state lithium metal batteries requires breakthroughs in solid-state electrolytes (SSEs) for the suppression of lithium dendrite growth at high current densities and high capacities (>3 mAh cm) and innovation of SSEs in terms of crystal structure, ionic conductivity and rigidness. Here we report a superionic conducting, highly lithium-compatible and air-stable vacancy-rich β-LiN SSE. This vacancy-rich β-LiN SSE shows a high ionic conductivity of 2.

Universal and scalable synthesis of photochromic single-atom catalysts for plastic recycling.

Metal oxide nanostructures with single-atomic heteroatom incorporation are of interest for many applications. However, a universal and scalable synthesis approach with high heteroatom concentrations represents a formidable challenge, primarily due to the pronounced structural disparities between M-O and M-O units. Here, focusing on TiO as the exemplified substrate, we present a diethylene glycol-assisted synthetic platform tailored for the controlled preparation of a library of M-TiO nanostructures, encompassing 15 distinct unary M-TiO nanostructures, along with two types of binary and ternary composites.

CO Dynamics in a Flexible Metal-Organic Framework with Gate-Opening Phenomenon.

As a promising porous material for CO adsorption and storage, elastic layer-structured metal-organic framework-11 (ELM-11) has attracted significant attention owing to its distinct gate-opening phenomenon. There is a sharp increase in CO uptake once reaching the gate-opening threshold pressure. To better understand this gate-opening mechanism, we investigated its transition process from the perspective of CO dynamics and its interaction with the framework via variable-temperature C solid-state nuclear magnetic resonance spectroscopy.

(111) Facet-oriented CuMg Intermetallic Compound with Cu-Mg Sites for CO Electroreduction to Ethanol with Industrial Current Density.

The efficient ethanol electrosynthesis from CO is challenging with low selectivity at high CO electrolysis rates, due to the competition with H and other reduction products. Copper-based bimetallic electrocatalysts are potential candidates for the CO-to-ethanol conversion, but the secondary metal has mainly been focused on active components (such as Ag, Sn) for CO electroreduction, which also promote selectivity of ethylene or other reduction products rather than ethanol. Limited attention has been given to alkali-earth metals due to their inherently active chemical property.

Amorphous Oxyhalide Matters for Achieving Lithium Superionic Conduction.

The recently surged halide-based solid electrolytes (SEs) are great candidates for high-performance all-solid-state batteries (ASSBs), due to their decent ionic conductivity, wide electrochemical stability window, and good compatibility with high-voltage oxide cathodes. In contrast to the crystalline phases in halide SEs, amorphous components are rarely understood but play an important role in Li-ion conduction. Here, we reveal that the presence of amorphous component is common in halide-based SEs that are prepared via mechanochemical method.

Cubic Iodide Li YI Superionic Conductors through Defect Manipulation for All-Solid-State Li Batteries.

Halide solid electrolytes (SEs) have attracted significant attention due to their competitive ionic conductivity and good electrochemical stability. Among typical halide SEs (chlorides, bromides, and iodides), substantial efforts have been dedicated to chlorides or bromides, with iodide SEs receiving less attention. Nevertheless, compared with chlorides or bromides, iodides have both a softer Li sublattice and lower reduction limit, which enable iodides to possess potentially high ionic conductivity and intrinsic anti-reduction stability, respectively.

Design principles for sodium superionic conductors.

Motivated by the high-performance solid-state lithium batteries enabled by lithium superionic conductors, sodium superionic conductor materials have great potential to empower sodium batteries with high energy, low cost, and sustainability. A critical challenge lies in designing and discovering sodium superionic conductors with high ionic conductivities to enable the development of solid-state sodium batteries. Here, by studying the structures and diffusion mechanisms of Li-ion versus Na-ion conducting solids, we reveal the structural feature of face-sharing high-coordination sites for fast sodium-ion conductors.

Precise Tailoring of Lithium-Ion Transport for Ultralong-Cycling Dendrite-Free All-Solid-State Lithium Metal Batteries.

All-solid-state lithium metal batteries can address crucial challenges regarding insufficient battery cycling life and energy density. The demonstration of long-cycling dendrite-free all-solid-state lithium metal batteries requires precise tailoring of lithium-ion transport of solid-state electrolytes (SSEs). In this work, a proof of concept is reported for precise tailoring of lithium-ion transport of a halide SSE, LiInCl, including intragranular (within grains) but also intergranular (between grains) lithium-ion transport.

Lithium-compatible and air-stable vacancy-rich LiNCl for high-areal capacity, long-cycling all-solid-state lithium metal batteries.

Attaining substantial areal capacity (>3 mAh/cm) and extended cycle longevity in all-solid-state lithium metal batteries necessitates the implementation of solid-state electrolytes (SSEs) capable of withstanding elevated critical current densities and capacities. In this study, we report a high-performing vacancy-rich LiNCl SSE demonstrating excellent lithium compatibility and atmospheric stability and enabling high-areal capacity, long-lasting all-solid-state lithium metal batteries. The LiNCl facilitates efficient lithium-ion transport due to its disordered lattice structure and presence of vacancies.

Halide Heterogeneous Structure Boosting Ionic Diffusion and High-Voltage Stability of Sodium Superionic Conductors.

The development of solid-state sodium-ion batteries (SSSBs) heavily hinges on the development of an superionic Na conductor (SSC) that features high conductivity, (electro)chemical stability, and deformability. The construction of heterogeneous structures offers a promising approach to comprehensively enhancing these properties in a way that differs from traditional structural optimization. Here, this work exploits the structural variance between high- and low-coordination halide frameworks to develop a new class of halide heterogeneous structure electrolytes (HSEs).

Entropy Confinement Promotes Hydrogenolysis Activity for Polyethylene Upcycling.

Chemical upcycling that catalyzes waste plastics back to high-purity chemicals holds great promise in end-of-life plastics valorization. One of the main challenges in this process is the thermodynamic limitations imposed by the high intrinsic entropy of polymer chains, which makes their adsorption on catalysts unfavorable and the transition state unstable. Here, we overcome this challenge by inducing the catalytic reaction inside mesoporous channels, which possess a strong confined ability to polymer chains, allowing for stabilization of the transition state.

Atomically Dispersed Mg-N-C Material Supported Highly Crystalline PtMg Nanoalloys for Efficient Oxygen Reduction Reaction.

Single-atom or atomically dispersed metal materials have emerged as highly efficient catalysts, but their potential as excellent supports has rarely been reported. In this work, we prepared Mg-N-C materials derived from annealing of a Mg-based metal-organic framework (MOF). By introducing Pt, Mg-N-C not only serves as a platform for anchoring Pt nanoparticles but also facilitates the integration of Mg into the Pt face-centered cubic lattice, resulting in the formation of highly crystalline PtMg nanoalloys via the metal-support interfacial interaction.

A family of oxychloride amorphous solid electrolytes for long-cycling all-solid-state lithium batteries.

Solid electrolyte is vital to ensure all-solid-state batteries with improved safety, long cyclability, and feasibility at different temperatures. Herein, we report a new family of amorphous solid electrolytes, xLiO-MCl (M = Ta or Hf, 0.8 ≤ x ≤ 2, y = 5 or 4).

Constrained C adsorbate orientation enables CO-to-acetate electroreduction.

The carbon dioxide and carbon monoxide electroreduction reactions, when powered using low-carbon electricity, offer pathways to the decarbonization of chemical manufacture. Copper (Cu) is relied on today for carbon-carbon coupling, in which it produces mixtures of more than ten C chemicals: a long-standing challenge lies in achieving selectivity to a single principal C product. Acetate is one such C compound on the path to the large but fossil-derived acetic acid market.

Site-Selective Polyolefin Hydrogenolysis on Atomic Ru for Methanation Suppression and Liquid Fuel Production.

Catalytic hydrogenolysis of end-of-life polyolefins can produce value-added liquid fuels and therefore holds great promises in plastic waste reuse and environmental remediation. The major challenge limiting the recycling economic benefit is the severe methanation (usually >20%) induced by terminal C-C cleavage and fragmentation in polyolefin chains. Here, we overcome this challenge by demonstrating that Ru single-atom catalyst can effectively suppress methanation by inhibiting terminal C-C cleavage and preventing chain fragmentation that typically occurs on multi-Ru sites.

Over 2 A cm CO -to-Ethanol Conversion by Alkali-Metal Cation Induced Copper With Dominant (200) Facets.

The high-rate ethanol electrosynthesis from CO is challenging due to the low selectivity and poor activity, which requires the competition with other reduction products and H . Here, the electrochemical reconstruction of Cs Cu Cl perovskite to form surface Cl-bonded, low-coordinated Cs modified Cu(200) nanocubes (CuClCs), is demonstrated. Density functional theory calculations reveal that the CuClCs structure possesses low Bader charges and a large coordination capacity; and thus, can promote the CO -to-ethanol pathway via stabilizing C-O bond in oxygenate intermediates.

A gradient oxy-thiophosphate-coated Ni-rich layered oxide cathode for stable all-solid-state Li-ion batteries.

High-energy Ni-rich layered oxide cathode materials such as LiNiMnCoO (NMC811) suffer from detrimental side reactions and interfacial structural instability when coupled with sulfide solid-state electrolytes in all-solid-state lithium-based batteries. To circumvent this issue, here we propose a gradient coating of the NMC811 particles with lithium oxy-thiophosphate (LiPOS). Via atomic layer deposition of LiPO and subsequent in situ formation of a gradient LiPOS coating, a precise and conformal covering for NMC811 particles is obtained.

The Role of Bismuth in Suppressing the CO Poisoning in Alkaline Methanol Electrooxidation: Switching the Reaction from the CO to Formate Pathway.

While tuning the electronic structure of Pt can thermodynamically alleviate CO poisoning in direct methanol fuel cells, the impact of interactions between intermediates on the reaction pathway is seldom studied. Herein, we contrive a PtBi model catalyst and realize a complete inhibition of the CO pathway and concurrent enhancement of the formate pathway in the alkaline methanol electrooxidation. The key role of Bi is enriching OH adsorbates (OH) on the catalyst surface.

MoTiC MXene-Supported Ru Clusters for Efficient Photothermal Reverse Water-Gas Shift.

Driving metal-cluster-catalyzed high-temperature chemical reactions by sunlight holds promise for the development of negative-carbon-footprint industrial catalysis, which has yet often been hindered by the poor ability of metal clusters to harvest and utilize the full spectrum of solar energy. Here, we report the preparation of MoTiC MXene-supported Ru clusters (Ru/MoTiC) with pronounced broadband sunlight absorption ability and high sintering resistance. Under illumination of focused sunlight, Ru/MoTiC can catalyze the reverse water-gas shift (RWGS) reaction to produce carbon monoxide from the greenhouse gas carbon dioxide and renewable hydrogen with enhanced activity, selectivity, and stability compared to their nanoparticle counterparts.

Superionic Conducting Halide Frameworks Enabled by Interface-Bonded Halides.

The revival of ternary halides Li-M-X (M = Y, In, Zr, etc.; X = F, Cl, Br) as solid-state electrolytes (SSEs) shows promise in realizing practical solid-state batteries due to their direct compatibility toward high-voltage cathodes and favorable room-temperature ionic conductivities. Most of the reported superionic halide SSEs have a structural pattern of [MCl] octahedra and generate a tetrahedron-assisted Li ion diffusion pathway.

Unveiling the Local Structure and Electronic Properties of PdBi Surface Alloy for Selective Hydrogenation of Propyne.

Building a reliable relationship between the electronic structure of alloyed metallic catalysts and catalytic performance is important but remains challenging due to the interference from many entangled factors. Herein, a PdBi surface alloy structural model, by tuning the deposition rate of Bi atoms relative to the atomic interdiffusion rate at the interface, realizes a continuous modulation of the electronic structure of Pd. Using advanced X-ray characterization techniques, we provide a precise depiction of the electronic structure of the PdBi surface alloy.

Surface Co-Modification of Halide Anions and Potassium Cations Promotes High-Rate CO -to-Ethanol Electrosynthesis.

The high-rate electrochemical CO conversion to ethanol with high partial current density is attractive but challenging, which requires competing with other reduction products as well as hydrogen evolution. This work demonstrates the in situ reconstruction of KCuF perovskite under CO electroreduction conditions to fabricate a surface fluorine-bonded, single-potassium-atom-modified Cu(111) nanocrystal (K-F-Cu-CO ). Density functional theory calculations reveal that the co-modification of both F and K atoms on the Cu(111) surface can promote the ethanol pathway via stabilization of the CO bond and selective hydrogenation of the CC bond in the CH CHO* intermediate, while the single modification of either F or K is less effective.

Favorable Bonding and Band Structures of CuZnSnS and CdS Films and Their Photovoltaic Interfaces.

Thin-film photovoltaic cells using CuZnSnS (CZTS, p-type) have many advantages, such as high photoconversion, low cost, and great tunability with earth-abundant, nontoxic elements, all of which are necessary to be long-term contributors to next-generation solar energy harvesting. Accurate measurements of bonding and band structures of both the thin-film materials and their interfaces are paramount to designing the solar devices layer-by-layer. Here, finely tuned 1 μm thick CZTS films, 50 nm thick CdS layers (n-type), and their 1 μm/2 nm p-n junction were fabricated inexpensively using our previously studied methods and investigated extensively for maximizing the key interface in the CZTS solar devices.