MXene materials in electrochemical energy storage systems.

MXenes, due to their unique geometric structure, rich elemental composition, and intrinsic physicochemical properties, have multi-functional applications. In the field of electrochemical energy storage, MXenes can be used as active components, conductive agents, supports, and catalysts in ion-intercalated batteries, metal-sulfur batteries, and supercapacitors. The electrochemical performance of MXene materials is closely related to their distinctive physical and chemical properties, which depend on their geometry, surface functional groups, and elemental composition. How to regulate MXene materials to optimize electrochemical functions is a key scientific challenge. Herein, we correlated the function of MXene materials with their interlayer structure, surface functional groups, and specific catalytic sites, analyzed the electrochemical function of MXene materials, and showed how to design the electrochemical function of MXene materials based on ion/electron transport. Additionally, this feature article provides an outlook on the opportunities and challenges for MXenes, offering theoretical and technical guidance on using MXene materials in energy storage systems.

Selective Upcycling of Polyethylene over Ru/H-ZSM-5 Bifunctional Catalyst into High-Quality Liquid Fuel at Mild Conditions.

It has been known that plastics with undegradability and long half-times have caused serious environmental and ecological issues. Considering the devastating effects, the development of efficient plastic upcycling technologies with low energy consumption is absolutely imperative. Catalytic hydrogenolysis of single-use polyethylene over Ru-based catalysts to produce high-quality liquid fuel has been one of the current top priority strategies, but it is restricted by some tough challenges, such as the tendency towards methanation resulting from terminal C-C cleavage. Herein, we introduced Ru nanoparticles supported on hollow ZSM-5 zeolite (Ru/H-ZSM-5) for hydrocracking of high-density polyethylene (HDPE) under mild reaction conditions. The implication of experimental results is that the 1Ru/H-ZSM-5 (~1 wt % Ru) acted as an effective and reusable bifunctional catalyst providing higher conversion rate (82.53 %) and liquid fuel (C5-C21) yield (62.87 %). Detailed characterization demonstrated that the optimal performance in hydrocracking of PE could be attributed to the moderate acidity and appropriate positively charged Ru species resulting from the metal-zeolite interaction. This work proposes a promising catalyst for plastic upcycling and reveals its structure-performance relationship, which has guiding significance for catalyst design to improve the yield of high-value liquid fuels.

Sub-millisecond lithiothermal synthesis of graphitic meso-microporous carbon.

Porous carbons with concurrently high specific surface area and electronic conductivity are desirable by virtue of their desirable electron and ion transport ability, but conventional preparing methods suffer from either low yield or inferior quality carbons. Here we developed a lithiothermal approach to bottom-up synthesize highly meso-microporous graphitized carbon (MGC). The preparation can be finished in a few milliseconds by the self-propagating reaction between polytetrafluoroethylene powder and molten lithium (Li) metal, during which instant ultra-high temperature (>3000 K) was produced. This instantaneous carbon vaporization and condensation at ultra-high temperatures and in ultra-short duration enable the MGC to show a highly graphitized and continuously cross-coupled open pore structure. MGC displays superior electrochemical capacitor performance of exceptional power capability and ultralong-term cyclability. The processes used to make this carbon are readily scalable to industrial levels.

Architecture of integrated solid-state zinc-ion battery based on sodium alginate gelation.

How to construct a new electrode/electrolyte interface structure in solid-state batteries (SSBs), enhance interface stability, and improve the cycling performance of SSBs is a great challenge for the development of SSBs. Here, an all-in-one "interface-free" structure was developed. This interfacial structure constructs a full-interface hydrogen bonding network through the abundant hydrogen bond donors and acceptors in the cathode and electrolyte to enhance the interfacial stability and avoid interfacial failure during charging and discharging, and generates cathode-electrolyte interface (CEI) in-situ to effectively regulate zinc ion transport. Square cells assembled in this structure are stabilized for 100 cycles at a current density of 0.1 mA cm-2. This integrated electrode provides a new idea for the long stable cycle of SSBs.

Spatially and Temporally Resolved Dynamic Response of Co-Based Composite Interface during the Oxygen Evolution Reaction.

Interfacial interaction dictates the overall catalytic performance and catalytic behavior rules of the composite catalyst. However, understanding of interfacial active sites at the microscopic scale is still limited. Importantly, identifying the dynamic action mechanism of the "real" active site at the interface necessitates nanoscale, high spatial-time-resolved complementary-operando techniques. In this work, a Co3O4 homojunction with a well-defined interface effect is developed as a model system to explore the spatial-correlation dynamic response of the interface toward oxygen evolution reaction. Quasi in situ scanning transmission electron microscopy-electron energy-loss spectroscopy with high spatial resolution visually confirms the size characteristics of the interface effect in the spatial dimension, showing that the activation of active sites originates from strong interfacial electron interactions at a scale of 3 nm. Multiple time-resolved operando spectroscopy techniques explicitly capture dynamic changes in the adsorption behavior for key reaction intermediates. Combined with density functional theory calculations, we reveal that the dynamic adjustment of multiple adsorption configurations of intermediates by highly activated active sites at the interface facilitates the O-O coupling and *OOH deprotonation processes. The dual dynamic regulation mechanism accelerates the kinetics of oxygen evolution and serves as a pivotal factor in promoting the oxygen evolution activity of the composite structure. The resulting composite catalyst (Co-B@Co3O4/Co3O4 NSs) exhibits an approximately 70-fold turnover frequency and 20-fold mass activity than the monomer structure (Co3O4 NSs) and leads to significant activity (η10 ∼257 mV). The visual complementary analysis of multimodal operando/in situ techniques provides us with a powerful platform to advance our fundamental understanding of interfacial structure-activity relationships in composite structured catalysts.

Acylspermidines are conserved mitochondrial sirtuin-dependent metabolites.

Sirtuins are nicotinamide adenine dinucleotide (NAD+)-dependent protein lysine deacylases regulating metabolism and stress responses; however, characterization of the removed acyl groups and their downstream metabolic fates remains incomplete. Here we employed untargeted comparative metabolomics to reinvestigate mitochondrial sirtuin biochemistry. First, we identified N-glutarylspermidines as metabolites downstream of the mitochondrial sirtuin SIR-2.3 in Caenorhabditis elegans and demonstrated that SIR-2.3 functions as a lysine deglutarylase and that N-glutarylspermidines can be derived from O-glutaryl-ADP-ribose. Subsequent targeted analysis of C. elegans, mouse and human metabolomes revealed a chemically diverse range of N-acylspermidines, and formation of N-succinylspermidines and/or N-glutarylspermidines was observed downstream of mammalian mitochondrial sirtuin SIRT5 in two cell lines, consistent with annotated functions of SIRT5. Finally, N-glutarylspermidines were found to adversely affect C. elegans lifespan and mammalian cell proliferation. Our results indicate that N-acylspermidines are conserved metabolites downstream of mitochondrial sirtuins that facilitate annotation of sirtuin enzymatic activities in vivo and may contribute to sirtuin-dependent phenotypes.

Amino acid and protein specificity of protein fatty acylation in C. elegans.

Protein lipidation plays critical roles in regulating protein function and localization. However, the chemical diversity and specificity of fatty acyl group utilization have not been investigated using untargeted approaches, and it is unclear to what extent structures and biosynthetic origins of S-acyl moieties differ from N- and O-fatty acylation. Here, we show that fatty acylation patterns in Caenorhabditis elegans differ markedly between different amino acid residues. Hydroxylamine capture revealed predominant cysteine S-acylation with 15-methylhexadecanoic acid (isoC17:0), a monomethyl branched-chain fatty acid (mmBCFA) derived from endogenous leucine catabolism. In contrast, enzymatic protein hydrolysis showed that N-terminal glycine was acylated almost exclusively with straight-chain myristic acid, whereas lysine was acylated preferentially with two different mmBCFAs and serine was acylated promiscuously with a broad range of fatty acids, including eicosapentaenoic acid. Global profiling of fatty acylated proteins using a set of click chemistry-capable alkyne probes for branched- and straight-chain fatty acids uncovered 1,013 S-acylated proteins and 510 hydroxylamine-resistant N- or O-acylated proteins. Subsets of S-acylated proteins were labeled almost exclusively by either a branched-chain or a straight-chain probe, demonstrating acylation specificity at the protein level. Acylation specificity was confirmed for selected examples, including the S-acyltransferase DHHC-10. Last, homology searches for the identified acylated proteins revealed a high degree of conservation of acylation site patterns across metazoa. Our results show that protein fatty acylation patterns integrate distinct branches of lipid metabolism in a residue- and protein-specific manner, providing a basis for mechanistic studies at both the amino acid and protein levels.

Ultrathin Two-dimensional Layered Composite Carbosilicates from in situ Unzipped Carbon Nanotubes and Exfoliated Bulk Silica.

A key task in today's inorganic synthetic chemistry is to develop effective reactions, routes, and associated techniques aiming to create new functional materials with specifically desired multilevel structures and properties. Herein, we report an ultrathin two-dimensional layered composite of graphene ribbon and silicate via a simple and scalable one-pot reaction, which leads to the creation of a novel carbon-metal-silicate hybrid family: carbosilicate. The graphene ribbon is in situ formed by unzipping carbon nanotubes, while the ultrathin silicate is in situ obtained from bulk silica or commercial glass; transition metals (Fe or Ni) oxidized by water act as bridging agent, covalently bonding the two structures. The unprecedented structure combines the superior properties of the silicate and the nanocarbon, which triggers some specific novel properties. All processes during synthesis are complementary to each other. The associated synergistic chemistry could stimulate the discovery of a large class of more interesting, functionalized structures and materials.

In Situ Visualization and Mechanistic Understandings on Facet-Dependent Atomic Redispersion of Platinum on CeO2.

Redispersion is an effective method for regeneration of sintered metal-supported catalysts. However, the ambiguous mechanistic understanding hinders the delicate controlling of active metals at the atomic level. Herein, the redispersion mechanism of atomically dispersed Pt on CeO2 is revealed and manipulated by in situ techniques combining well-designed model catalysts. Pt nanoparticles (NPs) sintered on CeO2 nano-octahedra under reduction and oxidation conditions, while redispersed on CeO2 nanocubes above ∼500 °C in an oxidizing atmosphere. The dynamic shrinkage and disappearance of Pt NPs on CeO2 (100) facets was directly visualized by in situ TEM. The generated atomically dispersed Pt with the square-planar [PtO4]2+ structure on CeO2 (100) facets was also confirmed by combining Cs-corrected STEM and spectroscopy techniques. The redispersion and atomic control were ascribed to the high mobility of PtO2 at high temperatures and its strong binding with square-planar O4 sites over CeO2 (100). These understandings are important for the regulation of atomically dispersed platinum catalysts.

Controlling Metal-Oxide Reducibility for Efficient C-H Bond Activation in Hydrocarbons.

Knowing the structure of catalytically active species/phases and providing methods for their purposeful generation are two prerequisites for the design of catalysts with desired performance. Herein, we introduce a simple method for precise preparation of supported/bulk catalysts. It utilizes the ability of metal oxides to dissolve and to simultaneously precipitate during their treatment in an aqueous ammonia solution. Applying this method for a conventional VOx -Al2 O3 catalyst, the concentration of coordinatively unsaturated Al sites was tuned simply by changing the pH value of the solution. These sites affect the strength of V-O-Al bonds of isolated VOx species and thus the reducibility of the latter. This method is also applicable for controlling the reducibility of bulk catalysts as demonstrated for a CeO2 -ZrO2 -Al2 O3 system. The application potential of the developed catalysts was confirmed in the oxidative dehydrogenation of ethylbenzene to styrene with CO2 and in the non-oxidative propane dehydrogenation to propene. Our approach is extendable to the preparation of any metal oxide catalysts dissolvable in an ammonia solution.

Quantitative Analysis of the Interface between Titanium Dioxide Support and Noble Metal by Electron Energy Loss Spectroscopy.

The interface structure of supported catalysts plays a significant role in the strong metal-support interactions (SMSI). However, it remains limited on interpreting interface structures, thus affecting the understanding of SMSI origin and impact on catalytic performance. Herein, electronic energy loss spectroscopy was adopted to characterize the interface microstructures of Pt/TiO2 materials. After high-temperature reduction processing, it was observed that the coating on the surface of the Pt metal particles was TiOx. Then, based on Gaussian function fitting, an effective and valid method was established for quantitative analysis on Ti L edge loss spectrum. This method allowed us to accurately determine the stoichiometric number of TiOx phases. In order to probe the classical phenomenon of strong metal-support interactions in more detail, we also discussed and analyzed the origin of TiOx and its effect on the electronic structure of the material using density functional theory calculations. The structure of surfaces and interfaces as well as the chemical evolution of supported catalysts on a microscale have been revealed, thereby providing a new analysis method and research perspectives for the future study of metal-support interactions.

A strong bimetal-support interaction in ethanol steam reforming.

The metal-support interaction (MSI) in heterogeneous catalysts plays a crucial role in reforming reaction to produce renewable hydrogen, but conventional objects are limited to single metal and support. Herein, we report a type of RhNi/TiO2 catalysts with tunable RhNi-TiO2 strong bimetal-support interaction (SBMSI) derived from structure topological transformation of RhNiTi-layered double hydroxides (RhNiTi-LDHs) precursors. The resulting 0.5RhNi/TiO2 catalyst (with 0.5 wt.% Rh) exhibits extraordinary catalytic performance toward ethanol steam reforming (ESR) reaction with a H2 yield of 61.7%, a H2 production rate of 12.2 L h-1 gcat-1 and a high operational stability (300 h), which is preponderant to the state-of-the-art catalysts. By virtue of synergistic catalysis of multifunctional interface structure (Rh-Niδ--Ov-Ti3+; Ov denotes oxygen vacancy), the generation of formate intermediate (the rate-determining step in ESR reaction) from steam reforming of CO and CHx is significantly promoted on 0.5RhNi/TiO2 catalyst, accounting for its ultra-high H2 production.

Chemical Electron Microscopy (CEM) for Heterogeneous Catalysis at Nano: Recent Progress and Challenges.

Chemical electron microscopy (CEM), a toolbox that comprises imaging and spectroscopy techniques, provides dynamic morphological, structural, chemical, and electronic information about an object in chemical environment under conditions of observable performance. CEM has experienced a revolutionary improvement in the past years and is becoming an effective characterization method for revealing the mechanism of chemical reactions, such as catalysis. Here, we mainly address the concept of CEM for heterogeneous catalysis in the gas phase and what CEM could uniquely contribute to catalysis, and illustrate what we can know better with CEM and the challenges and future development of CEM.

CoOx nanoparticles loaded on carbon spheres with synergistic effects for effective inhibition of shuttle effect in Li-S batteries.

Lithium-sulfur (Li-S) batteries, as one of the new energy storage batteries, show immense potential due to their high theoretical specific capacity and theoretical energy density. However, there are still some problems to be solved, among which the shuttle effect of lithium polysulfides is one extremely serious issue with respect to the industrial application of Li-S batteries. Rational design of electrode materials with effective catalytic conversion ability is an effective route to accelerate the conversion of lithium polysulfides (LiPSs). Herein, considering the adsorption and catalysis of LiPSs, CoOx nanoparticles (NPs) loaded on carbon sphere composites (CoOx/CS) were designed and constructed as cathode materials. The CoOx NPs obtained, with ultralow weight ratio and uniform distribution, consist of CoO, Co3O4, and metallic Co. The polar CoO and Co3O4 enable chemical adsorption towards LiPSs through Co-S coordination, and the conductive metallic Co can improve electronic conductivity and reduce impedance, which is beneficial for ion diffusion at the cathode. Based on these synergistic effects, the CoOx/CS electrode exhibits accelerated redox kinetics and enhanced catalytic activity for conversion of LiPSs. Consequently, the CoOx/CS cathode delivers improved cycling performance, with an initial capacity of 980.8 mA h g-1 at 0.1C and a reversible specific capacity of 408.4 mA h g-1 after 200 cycles, along with enhanced rate performance. This work provides a facile route to construct cobalt-based catalytic electrodes for Li-S batteries, and promotes understanding of the LiPSs conversion mechanism.

Parallel pathways for serotonin biosynthesis and metabolism in C. elegans.

The neurotransmitter serotonin plays a central role in animal behavior and physiology, and many of its functions are regulated via evolutionarily conserved biosynthesis and degradation pathways. Here we show that in Caenorhabditis elegans, serotonin is abundantly produced in nonneuronal tissues via phenylalanine hydroxylase, in addition to canonical biosynthesis via tryptophan hydroxylase in neurons. Combining CRISPR-Cas9 genome editing, comparative metabolomics and synthesis, we demonstrate that most serotonin in C. elegans is incorporated into N-acetylserotonin-derived glucosides, which are retained in the worm body and further modified via the carboxylesterase CEST-4. Expression patterns of CEST-4 suggest that serotonin or serotonin derivatives are transported between different tissues. Last, we show that bacterial indole production interacts with serotonin metabolism via CEST-4. Our results reveal a parallel pathway for serotonin biosynthesis in nonneuronal cell types and further indicate that serotonin-derived metabolites may serve distinct signaling functions and contribute to previously described serotonin-dependent phenotypes.

Patterning the consecutive Pd3 to Pd1 on Pd2Ga surface via temperature-promoted reactive metal-support interaction.

Atom-by-atom control of a catalyst surface is a central yet challenging topic in heterogeneous catalysis, which enables precisely confined adsorption and oriented approach of reactant molecules. Here, exposed surfaces with either consecutive Pd trimers (Pd3) or isolated Pd atoms (Pd1) are architected for Pd2Ga intermetallic nanoparticles (NPs) using reactive metal-support interaction (RMSI). At elevated temperatures under hydrogen, in situ atomic-scale transmission electron microscopy directly visualizes the refacetting of Pd2Ga NPs from energetically favorable (013)/(020) facets to (011)/(002). Infrared spectroscopy and acetylene hydrogenation reaction complementarily confirm the evolution from consecutive Pd3 to Pd1 sites of Pd2Ga catalysts with the concurrent fingerprinting CO adsorption and featured reactivities. Through theoretical calculations and modeling, we reveal that the restructured Pd2Ga surface results from the preferential arrangement of additionally reduced Ga atoms on the surface. Our work provides previously unidentified mechanistic insight into temperature-promoted RMSI and possible solutions to control and rearrange the surface atoms of supported intermetallic catalyst.

Nucleation of Single-Wall Carbon Nanotubes from Faceted Pt Catalyst Particles Revealed by in Situ Transmission Electron Microscopy.

Revealing the nucleation and growth mechanism of single-wall carbon nanotubes (SWCNTs) from faceted solid catalysts is crucial to the control of their structure and properties. However, due to the small size and complex growth environment, the early stages and dynamic process of SWCNT nucleation have rarely been directly revealed, especially under atmospheric conditions. Here, we report the atomic-resolved nucleation of SWCNTs from the faces of truncated octahedral Pt catalysts under atmospheric pressure using a transmission electron microscope equipped with a gas-cell. It was found that the graphene layers were initially formed preferentially on (111) surfaces, which then joined together to form an annular belt and a hemispherical cap, followed by the elongation of the SWCNT. Based on the observations, an annular belt assembly nucleation model and a possible chirality control mechanism are proposed for SWCNTs grown from well-faceted Pt catalysts, which provides useful guidance for the controlled synthesis of SWCNTs by catalyst design.

Cobalt Nanoparticles Loaded on MXene for Li-S Batteries: Anchoring Polysulfides and Accelerating Redox Reactions.

Catalysis is regarded as an effective strategy to fundamentally increase sulfur utilization, accelerating the kinetics of the transformation between lithium polysulfides (LiPSs) and lithium sulfide (Li2 S) on a substrate. However, the intermodulation of catalysts and sulfur species is elusive, which is limited to the comprehensive analysis of electrochemical performance in the dynamic reaction process. Herein, cobalt nanoparticles loaded on MXene nanosheets (Co/Ti2 C) are selected as sulfur hosts and the representative catalyst. By combining ex situ electrochemical results and interfacial structural chemical monitoring, the catalysis process of Co/Ti2 C toward LiPSs conversion is revealed, and the outstanding performance originates from the optimization of chemical adsorption, catalytic activity, and lithium-ion transfer behaviors, which is based on electronic/ion modulation and sufficient interfaces among catalysts and electrolyte. This work can guide the construction of electronic modulation at triple-phase interface catalysis to overcome the shuttle effect and facilitate sulfur redox kinetics in Li-S batteries.