Molecular-Level Interfacial Chemistry Regulation of MXene Enables Energy Storage beyond Theoretical Limit.

Ti3C2Tx MXene often suffers from poor lithium storage behaviors due to its electrochemically unfavorable OH terminations. Herein, we propose molecular-level interfacial chemistry regulation of Ti3C2Tx MXene with phytic acid (PA) to directly activate its OH terminations. Through constructing hydrogen bonds (H-bonds) between oxygen atoms of PA and OH terminations on Ti3C2Tx surface, interfacial charge distribution of Ti3C2Tx has been effectively regulated, thereby enabling sufficient ion-storage sites and expediting ion transport kinetics for high-performance energy storage. The results show that Li ions preferably bind to H-bond acceptors (oxygen atoms from PA), and the flexibility of H-bonds therefore renders their interactions with adsorbed Li ions chemically "tunable", thus alleviating undesirable localized geometric changes of the OH terminations. Meanwhile the H-bond-induced microscopic dipoles can act as directional Li-ion pumps to expedite ion diffusion kinetics with lower energy barrier. As a result, the as-designed Ti3C2Tx/PA achieves a 2.4-fold capacity enhancement compared with pristine Ti3C2Tx (even beyond theoretical capacity), superior long-term cyclability (220.0 mAh g-1 after 2000 cycles at 2.0 A g-1), and broad temperature adaptability (-20 to 50 °C). This work offers a promising interface engineering strategy to regulate microenvironments of inherent terminations for breaking through the energy storage performance of MXenes.

Microenvironment reconstitution of highly active Ni single atoms on oxygen-incorporated Mo2C for water splitting.

The rational design of efficient bifunctional single-atom electrocatalysts for industrial water splitting and the comprehensive understanding of its complex catalytic mechanisms remain challenging. Here, we report a Ni single atoms supported on oxygen-incorporated Mo2C via Ni-O-Mo bridge bonds, that gives high oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) bifunctional activity. By ex situ synchrotron X-ray absorption spectroscopy and electron microscopy, we found that after HER, the coordination number and bond lengths of Ni-O and Ni-Mo (Ni-O-Mo) were all altered, yet the Ni species still remain atomically dispersed. In contrast, after OER, the atomically dispersed Ni were agglomerated into very small clusters with new Ni-Ni (Ni-O-Ni) bonds appeared. Combining experimental results and DFT calculations, we infer the oxidation degree of Mo2C and the configuration of single-atom Ni are both vital for HER or OER. This study provides both a feasible strategy and model to rational design highly efficient electrocatalysts for water electrolysis.

Guiding the Driving Factors on Plasma Super-Photothermal S-Scheme Core-Shell Nanoreactor to Enhance Photothermal Catalytic H2 Evolution and Selective CO2 Reduction.

Light-induced heat has a non-negligible role in photocatalytic reactions. However, it is still challenging to design highly efficient catalysts that can make use of light and thermal energy synergistically. Herein, the study proposes a plasma super-photothermal S-scheme heterojunction core-shell nanoreactor based on manipulation of the driving factors, which consists of α-Fe2 O3 encapsulated by g-C3 N4 modified with gold quantum dots. α-Fe2 O3 can promote carrier spatial separation while also acting as a thermal core to radiate heat to the shell, while Au quantum dots transfer energetic electrons and heat to g-C3 N4 via surface plasmon resonance. Consequently, the catalytic activity of Au/α-Fe2 O3 @g-C3 N4 is significantly improved by internal and external double hot spots, and it shows an H2 evolution rate of 5762.35 µmol h-1 g-1 , and the selectivity of CO2 conversion to CH4 is 91.2%. This work provides an effective strategy to design new plasma photothermal catalysts for the solar-to-fuel transition.

Under-Coordinated CoFe Layered Double Hydroxide Nanocages Derived from Nanoconfined Hydrolysis of Bimetal Organic Compounds for Efficient Electrocatalytic Water Oxidation.

Hierarchically structured bimetal hydroxides are promising for electrocatalytic oxygen evolution reaction (OER), yet synthetically challenging. Here, the nanoconfined hydrolysis of a hitherto unknown CoFe-bimetal-organic compound (b-MOC) is reported for the controllable synthesis of highly OER active nanostructures of CoFe layered double hydroxide (LDH). The nanoporous structures trigger the nanoconfined hydrolysis in the sacrificial b-MOC template, producing CoFe LDH core-shell octahedrons, nanoporous octahedrons, and hollow nanocages with abundant under-coordinated metal sites. The hollow nanocages of CoFe LDH demonstrate a remarkable turnover frequency (TOF) of 0.0505 s-1 for OER catalysis at an overpotential of 300 mV. It is durable in up to 50 h of electrolysis at step current densities of 10-100 mA cm-2 . Ex situ and in situ X-ray absorption spectroscopic analysis combined with theoretical calculations suggests that under-coordinated Co cations can bind with deprotonated Fe-OH motifs to form OER active Fe-O-Co dimmers in the electrochemical oxidation process, thereby contributing to the good catalytic activity. This work presents an efficient strategy for the synthesis of highly under-coordinated bimetal hydroxide nanostructures. The mechanistic understanding underscores the power of maximizing the amount of bimetal-dimer sites for efficient OER catalysis.

Conductive Ti3C2Tx networks to optimize Na3V2O2(PO4)2F cathodes for improved rate capability and low-temperature operation.

Na3V2O2(PO4)2F (NVOPF) is gaining attention as a high-energy cathode candidate for sodium-ion batteries owing to its wide operating voltage, high energy density and excellent thermal stability. However, its intrinsic poor electrical conductivity results in its current sodium-storage performance being far below expectations. Herein, two-dimensional Ti3C2Tx MXene nanosheets with excellent electrical conductivity are introduced to construct an interconnected conductive framework to tightly encapsulate NVOPF nanoparticles. The Ti3C2Tx nanosheets ensure superior electronic contacts, along with inhibiting the agglomeration of NVOPF nanoparticles, thus accelerating electron and ion transfer during sodium-ion de/intercalation and maximizing the storage capacity. As a result, the optimized NVOPF/Ti3C2Tx cathode exhibits high rate capabilities (111 mA h g-1 at 0.2 C and 78 mA h g-1 at 20 C), with an impressively high capacity retention of 74.8% over a wide temperature range (from -20 to 20 °C). Additionally, the assembled sodium-ion full cell provides a highly reversible capacity of 116 mA h g-1 at 1 C, with a capacity retention of 67.2% after 100 cycles. These inspiring results provide new insights for improving the charge-transfer kinetics of the NVOPF cathode and this methodology may be extended to other cathode materials.

Super-Photothermal Effect-Mediated Fast Reaction Kinetic in S-Scheme Organic/Inorganic Heterojunction Hollow Spheres Toward Optimized Photocatalytic Performance.

Using full solar spectrum for energy conversion and environmental remediation is a major challenge, and solar-driven photothermal chemistry is a promising route to achieve this goal. Herein, this work reports a photothermal nano-constrained reactor based on hollow structured g-C3 N4 @ZnIn2 S4 core-shell S-scheme heterojunction, where the synergistic effect of super-photothermal effect and S-scheme heterostructure significantly improve the photocatalytic performance of g-C3 N4 . The formation mechanism of g-C3 N4 @ZnIn2 S4 is predicted in advance by theoretical calculations and advanced techniques, and the super-photothermal effect of g-C3 N4 @ZnIn2 S4 and its contribution to the near-field chemical reaction is confirmed by numerical simulations and infrared thermography. Consequently, the photocatalytic degradation rate of g-C3 N4 @ZnIn2 S4 for tetracycline hydrochloride is 99.3%, and the photocatalytic hydrogen production is up to 4075.65 µmol h-1 g-1 , which are 6.94 and 30.87 times those of pure g-C3 N4 , respectively. The combination of S-scheme heterojunction and thermal synergism provides a promising insight for the design of an efficient photocatalytic reaction platform.

Sc-HOPO: A Potential Construct for Use in Radioscandium-Based Radiopharmaceuticals.

Three isotopes of scandium─43Sc, 44Sc, and 47Sc─have attracted increasing attention as potential candidates for use in imaging and therapy, respectively, as well as for possible theranostic use as an elementally matched pair. Here, we present the octadentate chelator 3,4,3-(LI-1,2-HOPO) (or HOPO), an effective chelator for hard cations, as a potential ligand for use in radioscandium constructs with simple radiolabeling under mild conditions. HOPO forms a 1:1 Sc-HOPO complex that was fully characterized, both experimentally and theoretically. [47Sc]Sc-HOPO exhibited good stability in chemical and biological challenges over 7 days. In healthy mice, [43,47Sc]Sc-HOPO cleared the body rapidly with no signs of demetalation. HOPO is a strong candidate for use in radioscandium-based radiopharmaceuticals.

Double-atom dealloying-derived Frank partial dislocations in cobalt nanocatalysts boost metal-air batteries and fuel cells.

Oxygen reduction reaction (ORR), an essential reaction in metal-air batteries and fuel cells, still faces many challenges, such as exploiting cost-effective nonprecious metal electrocatalysts and identifying their surface catalytic sites. Here we introduce bulk defects, Frank partial dislocations (FPDs), into metallic cobalt to construct a highly active and stable catalyst and demonstrate an atomic-level insight into its surface terminal catalysis. Through thermally dealloying bimetallic carbide (Co3ZnC), FPDs were in situ generated in the final dealloyed metallic cobalt. Both theoretical calculations and atomic characterizations uncovered that FPD-driven surface terminations create a distinctive type of surface catalytic site that combines concave geometry and compressive strain, and this two-in-one site intensively weakens oxygen binding. When being evaluated for the ORR, the catalyst exhibits onset and half-wave potentials of 1.02 and 0.90 V (versus the reversible hydrogen electrode), respectively, and negligible activity decay after 30,000 cycles. Furthermore, zinc-air batteries and H2-O2/air fuel cells built with this catalyst also achieve remarkable performance, making it a promising alternative to state-of-the-art Pt-based catalysts. Our findings pave the way for the use of bulk defects to upgrade the catalytic properties of nonprecious electrocatalysts.

Strain-regulated Gibbs free energy enables reversible redox chemistry of chalcogenides for sodium ion batteries.

Manipulating the reversible redox chemistry of transition metal dichalcogenides for energy storage often faces great challenges as it is difficult to regulate the discharged products directly. Herein we report that tensile-strained MoSe2 (TS-MoSe2) can act as a host to transfer its strain to corresponding discharged product Mo, thus contributing to the regulation of Gibbs free energy change (ΔG) and enabling a reversible sodium storage mechanism. The inherited strain results in lattice distortion of Mo, which adjusts the d-band center upshifted closer to the Fermi level to enhance the adsorbability of Na2Se, thereby leading to a decreased ΔG of the redox chemistry between Mo/Na2Se and MoSe2. Ex situ and in situ experiments revealed that, unlike the unstrained MoSe2, TS-MoSe2 shows a highly reversible sodium storage, along with an evidently improved reaction kinetics. This work sheds light on the study on electrochemical energy storage mechanism of other electrode materials.

Advances and challenges in metal selenides enabled by nanostructures for electrochemical energy storage applications.

The development of nanomaterials and their related electrochemical energy storage (EES) devices can provide solutions for improving the performance and development of existing EES systems owing to their high electronic conductivity and ion transport and abundant embeddable sites. Recent progress has demonstrated that metal selenides are attracting increasing attention in the field of EES because of their unique structures, high theoretical capacities, rich element resources, and high conductivity. However, there are still many challenges in their application in EES, and thus the use of nanoscale metal selenide materials in commercial devices is limited. In this review, we summarize recent advances in the nanostructured design of metal selenides (e.g., zero-, one-, two-, and three-dimensional, and self-supported structures) and present their advantages in terms of EES performance. Moreover, some remarks on the potential challenges and research prospects of nanostructured metal selenides in the field of EES are presented.

MXene Enhanced the Electromechanical Performance of a Nafion-Based Actuator.

Ionic electroactive polymer-based actuators have attracted much attention due to their low potential stimuli. In this work, MXene-Nafion composite actuators were fabricated, and the actuation performances were tested. The morphology of the as-made MXene-Nafion composite showed that the composite membrane was homogeneous, with an MXene doping level up to 5 wt%. In addition, the results of blocked force, response speed, and durability demonstrated that the actuation behavior of the composite-based actuator was enhanced due to the efficient dispersion of the two-dimensional nanofiller MXene. In addition, the blocking force of the composite actuator with a doping level of 0.5 wt% was about 6 times that of the pure Nafion without back-relaxation and durability degradation during the testing period.

Tracking Uptake and Metabolism of Xenometallomycins Using a Multi-Isotope Tagging Strategy.

Synthetic and naturally occurring siderophores and their conjugates provide access to the bacterial cytoplasm via active membrane transport. Previously, we displaced iron with the radioactive isotope 67Ga to quantify and track in vitro and in vivo uptake and distribution of siderophore Trojan Horse antibiotic conjugates. Here, we introduce a multi-isotope tagging strategy to individually elucidate the fate of metal cargo and the ligand construct with radioisotopes 67Ga and 124I. We synthesized gallium(III) model complexes of a ciprofloxacin-functionalized linear desferrichrome (Ga-D6) and deferoxamine (Ga-D7) incorporating an iodo-tyrosine linker to enable radiolabeling using the metal-binding (67Ga) and the cargo-conjugation site (124I). Radiochemical experiments with Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa wt strains show that 67Ga-D6/D7 and Ga-D6-124I/D7-124I have comparable uptake, indicating intact complex import and siderophore-mediated uptake. In naive mice, 67Ga-D6/D7 and Ga-D6-124I/D7-124I demonstrate predominantly renal clearance; urine metabolite analysis indicates in vivo dissociation of Ga(III) is a likely mechanism of degradation for 67Ga-D6/D7 when compared to ligand radiolabeled compounds, Ga-D6-124I/D7-124I, which remain >60% intact in urine. Cumulatively, this work demonstrates that a multi-isotope tagging strategy effectively elucidates the in vitro uptake, pharmacokinetics, and in vivo stability of xenometallomycins with modular chemical structures.

Highly graphited carbon-coated FeTiO3 nanosheets in situ derived from MXene: an efficient bifunctional catalyst for Zn-air batteries.

Developing high-efficiency and low-cost catalysts for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is of great significance for the commercialization of rechargeable metal-air batteries. Herein, we demonstrated the construction of graphited carbon-coated FeTiO3 (FeTiO3@C) via in situ annealing Ti3C2Tx nanosheets in a rusted-reactor and its efficient bifunctional activity for rechargeable Zn-air batteries (RZABs). The electron-transport dynamics of FeTiO3@C can be improved by using highly conductive graphited carbon derived from Ti3C2Tx. The FeTiO3@C catalyst annealed at 500 °C exhibits excellent OER and ORR activities. Specifically, FeTiO3@C shows a low overpotential of 323 mV at 10 mA cm-2 and a small Tafel slope of 53 mV dec-1 towards the alkaline OER. During the OER process, FeTiO3@C can be partially converted into highly active iron oxyhydroxide via in situ electrochemical reconstruction, which serves as the active species. After being assembled to RZABs, it shows an open-circuit potential of 1.33 V, a high trip efficiency of 63.4% and long-time cycling stability. This work can provide a new avenue for developing bifunctional electrocatalysts for RZABs used in portable devices.

The Underlying Molecular Mechanism of Fence Engineering to Break the Activity-Stability Trade-Off in Catalysts for the Hydrogen Evolution Reaction.

Non-precious-metal (NPM) catalysts often face the formidable challenge of a trade-off between long-term stability and high activity, which has not yet been widely addressed. Herein we propose a distinct molecule-selective fence as a promising concept to solve this activity-stability trade-off. The fence encloses the catalyst and prevents species poisonous to the catalyst from reaching it, but allows catalytic reaction-related species to diffuse freely. We constructed a CoS2 fence layer on the external surface of highly active cobalt-doped MoS2 , achieving a remarkable catalytic stability towards the alkaline hydrogen evolution reaction and improved activity. In situ spectroscopy uncovered the underlying molecular mechanism of the CoS2 fence for breaking the activity-stability trade-off of the MoS2 catalyst. This work offers valuable guidance for rationally designing efficient and stable NPM catalysts.

Constructing a Stable Si-N-Enriched Interface Boosts Lithium Storage Kinetics in a Silicon-Based Anode.

The stable operation of a SiOx anode largely depends on the intrinsic chemistry of the electrode/electrolyte interface; however, an unstable interface structure and undesirable parasitic reactions with the electrolyte of the SiOx anode often result in the formation of a fragile solid-electrolyte interphase (SEI) and serious capacity decay during the lithiation/delithiation process. Herein, a Si-N-enriched N-doped carbon coating is constructed on the surface of SiOx yolk-shell nanospheres (abbreviated as SiOx@NC) to optimize the SEI film. The two-dimensional covalently bound Si-N interface, on one hand, can suppress the interfacial reactivity of the SiOx anode to enable the formation of a thin SEI film with accelerated diffusion kinetics of ions and, on the other hand, acts as a Li+ conductor during the delithiation process, allowing Li+ to diffuse rapidly in the SiOx matrix, thereby improving the long-term cycling stability and rapid charge/discharge capability of the SiOx anode. A series of characterizations show that the interface charge-transfer barrier and the Li+ diffusion energy barrier through the SEI film are the main factors that determine the interfacial electrochemical behavior and lithium storage performance. This work clarifies the relationship between the SEI characteristics and the interfacial transfer dynamics and aims to offer a more basic basis for the screening of other electrode materials.

In Situ Coupling of MnO and Co@N-Doped Graphite Carbon Derived from Prussian Blue Analogous Achieves High-Performance Reversible Oxygen Electrocatalysis for Zn-Air Batteries.

Coupling dual active components into one integrated catalyst as well as understanding their electronic interaction behavior on reversible oxygen electrocatalysis is central to achieving high energy-conversion efficiency for Zn-air batteries (ZABs). Herein, we demonstrate an effective couple of MnO and Co nanocrystals embedded in N-doped graphite carbon to integrate a highly efficient bifunctional catalyst (denoted as MnO/Co@NGC) toward oxygen reduction and evolution reaction (ORR/OER). MnO/Co@NGC was first successfully prepared by the one-step pyrolysis of Mn3[Co(CN)6]2·9H2O@PVP (poly(vinyl pyrrolidone)), and X-ray absorption near-edge structure analysis revealed that the charges were transferred from MnO to Co@NGC, which makes MnO more electrophilic to facilitate the initial electrochemical adsorption of OH- for improving the OER activity. As expected, the as-designed MnO/Co@NGC displays excellent bifunctional ORR/OER activity with a small overpotential gap of only 0.736 V, providing the ZABs with a high trip efficiency of 57.2% as well as excellent cycling stability. This work not only offers a bifunctional ORR/OER electrocatalyst but also further highlights the interfacial charge distribution in oxygen electrocatalysis, affording a promising approach for developing advanced energy-related materials.

Oxygen Vacancies Boosting Lithium-Ion Diffusion Kinetics of Lithium Germanate for High-Performance Lithium Storage.

Oxygen vacancies play a positive role in optimizing the physical and chemical properties of metal oxides. In this work, we demonstrated oxygen vacancy-promoted enhancement of Li-ion diffusion kinetics in Li2GeO3 nanoparticle-encapsulated carbon nanofibers (denoted as Li2GeO3-x/C) and accordingly boosted lithium storage. The introduction of the oxygen vacancies in Li2GeO3-x/C can enhance electronic conductivity and evidently decrease activation energy of Li-ion transport, thus resulting in evidently accelerated Li-ion diffusion kinetics during the lithiation/delithiation process. Thus, the Li2GeO3-x/C nanofibers exhibit an exceptionally large discharge capacity of 1460.5 mA h g-1 at 0.1 A g-1, high initial Coulombic efficiency of 81.3%, and excellent rate capability. This facile and efficient strategy could provide a reference for injecting the oxygen vacancies into other metal oxides for high-performance anode materials.

Uptake and Removal of Uranium by and from Human Teeth.

Uranium-238 (238U), a long-lived radiometal, is widespread in the environment because of both naturally occurring processes and anthropogenic processes. The ingestion or inhalation of large amounts of U is a major threat to humans, and its toxicity is considered mostly chemical rather than radiological. Therefore, a way to remove uranium ingested by humans from uranium-contaminated water or from the air is critically needed. This study investigated the uranium uptake by hydroxyapatite (HAP), a compound found in human bone and teeth. The uptake of U by teeth is a result of U transport as dissolved uranyl (UO22+) in contaminated water, and U adsorption has been linked to delays in both tooth eruption and development. In this present work, the influence of pH, contact time, initial U concentration, and buffer solution on the uptake and removal of U in synthetic HAP was investigated and modeled. The influence of pH (pH of human saliva, 6.7-7.4) on the uptake of uranyl was negligible. Furthermore, the kinetics were extremely fast; in one second of exposure, 98% of uranyl was uptaken by HAP. The uptake followed pseudo-second-order kinetics and a Freundlich isotherm model. A 0.2 M sodium carbonate solution removed all the uranyl from HAP after 1 h. Another series of in vitro tests were performed with real teeth as targets. We found that, for a 50 mg/L U in PBS solution adjusted to physiological pH, ∼35% of the uranyl was uptaken by the tooth after 1 h, following pseudo-first-order kinetics. Among several washing solutions tested, a commercially available carbonate, as well as a commercially available fluoride solution, enabled removal of all the uranyl taken up by the teeth.

Surface Charge Engineering for Covalently Assembling Three-Dimensional MXene Network for All-Climate Sodium Ion Batteries.

MXenes, as excellent candidate anode materials for sodium ion batteries (SIBs), suffer from sluggish ion-diffusion kinetics resulting from the anchoring effect of the negatively charged functional groups on their surface on sodium ions. Herein, we introduce positively charged conductive polyaniline (PANI) to induce self-assembly of Ti3C2Tx MXenes into a three-dimensional PANI/Ti3C2Tx network. In this PANI/Ti3C2Tx network, PANI not only intercalates into Ti3C2Tx nanosheets to enlarge the interlayer spacing, but also promotes negative-to-positive transition of the surface charges of the Ti3C2Tx nanosheets, significantly improving ion-diffusion kinetics. Electrochemical test results further confirm the superb ion-diffusion kinetics of the PANI/Ti3C2Tx network. Meanwhile, a covalent interaction (Ti-N) between PANI and Ti3C2Tx, proved by X-ray photoelectron spectra (XPS) and X-ray absorption near-edge structure (XANES) tests, plays a key role in stabilizing this network structure. Therefore, PANI/Ti3C2Tx exhibits excellent sodium storage performances with a high specific capacity, superior rate performance and ultralong lifespan at high current density. More importantly, when operated at rigorous temperatures from +50 to -30 °C, PANI/Ti3C2Tx also exhibits good electrochemical performances. The present work presents a simple strategy for designing 3D porous MXene-based materials to realize high rate performance and all-climate energy storage device.

Boosting the lithium-ion and sodium-ion storage performances of pyrite by regulating the energy barrier of ion transport.

Pyrite (FeS2) is a functional material of great importance for lithium/sodium ion batteries (LIBs/SIBs), but its sluggish dynamics greatly hinder its high performance. Here, we demonstrate an effective strategy of regulating the energy barrier of ion transport to significantly enhance the sluggish dynamics of FeS2 by Co doping. Compared to pristine FeS2, a series of Co-doped FeS2 shows enhanced alkali metal ion storage performance and most typically, the optimized Fe0.7Co0.3S2 sample displays high reversible capacities, of 1170 mA h g-1 for LIBs and 650 mA h g-1 for SIBs at a current density of 0.1 A g-1 as well as super long-life cycling stability for SIBs (1200 cycles at 5 A g-1). The evidently enhanced performances of Fe0.7Co0.3S2 for LIBs/SIBs can be attributed to its significantly decreased activation energy of ion transport, thus leading to greatly accelerated ion transport dynamics. Furthermore, galvanostatic intermittent titration technique (GITT) experiments also support this important regulation effect of Co doping on the ion transport dynamics of FeS2. The excellent ion transport dynamics induce a strong pseudo-capacitance behavior in both SIBs and LIBs, and their pseudo-capacitance contributions are more than 90% at 1.0 mV s-1. This work provides a new perspective to improve the alkali metal ion storage performance by optimizing the ion transport dynamics.