Ultrafiltration separation of Am(VI)-polyoxometalate from lanthanides.

Partitioning of americium from lanthanides (Ln) present in used nuclear fuel plays a key role in the sustainable development of nuclear energy1-3. This task is extremely challenging because thermodynamically stable Am(III) and Ln(III) ions have nearly identical ionic radii and coordination chemistry. Oxidization of Am(III) to Am(VI) produces AmO22+ ions distinct with Ln(III) ions, which has the potential to facilitate separations in principle. However, the rapid reduction of Am(VI) back to Am(III) by radiolysis products and organic reagents required for the traditional separation protocols including solvent and solid extractions hampers practical redox-based separations. Herein, we report a nanoscale polyoxometalate (POM) cluster with a vacancy site compatible with the selective coordination of hexavalent actinides (238U, 237Np, 242Pu and 243Am) over trivalent lanthanides in nitric acid media. To our knowledge, this cluster is the most stable Am(VI) species in aqueous media observed so far. Ultrafiltration-based separation of nanoscale Am(VI)-POM clusters from hydrated lanthanide ions by commercially available, fine-pored membranes enables the development of a once-through americium/lanthanide separation strategy that is highly efficient and rapid, does not involve any organic components and requires minimal energy input.

Conversion of chirality to twisting via sequential one-dimensional and two-dimensional growth of graphene spirals.

The properties of two-dimensional (2D) van der Waals materials can be tuned through nanostructuring or controlled layer stacking, where interlayer hybridization induces exotic electronic states and transport phenomena. Here we describe a viable approach and underlying mechanism for the assisted self-assembly of twisted layer graphene. The process, which can be implemented in standard chemical vapour deposition growth, is best described by analogy to origami and kirigami with paper. It involves the controlled induction of wrinkle formation in single-layer graphene with subsequent wrinkle folding, tearing and re-growth. Inherent to the process is the formation of intertwined graphene spirals and conversion of the chiral angle of 1D wrinkles into a 2D twist angle of a 3D superlattice. The approach can be extended to other foldable 2D materials and facilitates the production of miniaturized electronic components, including capacitors, resistors, inductors and superconductors.

Interlayer Charge Transfer Induced Electrical Behavior Transition in 1D AgI@sSWCNT van der Waals Heterostructures.

The emergence of one-dimensional van der Waals heterostructures (1D vdWHs) opens up potential fields with unique properties, but precise synthesis remains a challenge. The utilization of mixed conductive types of carbon nanotubes as templates has imposed restrictions on the investigation of the electrical behavior and interlayer interaction of 1D vdWHs. In this study, we efficiently encapsulated silver iodide in high-purity semiconducting single-walled carbon nanotubes (sSWCNTs), forming 1D AgI@sSWCNT vdWHs. We characterized the semiconductor-metal transition and increased the carrier concentration of individual AgI@sSWCNTs via sensitive dielectric force microscopy and confirmed the results through electrical device tests. The electrical behavior transition was attributed to an interlayer charge transfer, as demonstrated by Kelvin probe force microscopy. Furthermore, we showed that this method of synthesizing 1D heterostructures can be extended to other metal halides. This work opens the door for the further exploration of the electrical properties of 1D vdWHs.

Constructing the Fulde-Ferrell-Larkin-Ovchinnikov State in a CrOCl/NbSe2 van der Waals Heterostructure.

Time reversal symmetry breaking in superconductors, resulting from external magnetic fields or spontaneous magnetization, often leads to unconventional superconducting properties. In this way, an intrinsic phenomenon called the Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) state may be realized by the Zeeman effect. Here, we construct the FFLO state in an artificial CrOCl/NbSe2 van der Waals (vdW) heterostructure by utilizing the superconducting proximity effect of NbSe2 flakes. The proximity-induced superconductivity demonstrates a considerably weak gap of about 0.12 meV, and the in-plane upper critical field reveals the behavior of the FFLO state. First-principles calculations uncover the origin of the proximitized superconductivity, which indicates the importance of Cr vacancies or line defects in CrOCl. Moreover, the FFLO state could be induced by the inherent large spin splitting in CrOCl. Our findings not only provide a practical scheme for constructing the FFLO state but also inspire the discovery of an exotic FFLO state in other two-dimensional vdW heterostructures.

Pressure Tuning and Sn Particle Size Optimization for Enhanced Performance in PbSnF4-Based All-Solid-State Fluoride Ion Batteries.

All-solid-state fluoride ion batteries (ASSFIBs) show remarkable potential as energy storage devices due to their low cost, superior safety, and high energy density. However, the poor ionic conductivity of F- conductor, large volume expansion, and the lack of a suitable anode inhibit their development. In this work, PbSnF4 solid electrolytes in different phases (ß- and γ-PbSnF4) are successfully synthesized and characterized. The ASSFIBs composed of ß-PbSnF4 electrolytes, a BiF3 cathode, and micrometer/nanometer size (µ-/n-) Sn anodes, exhibit substantial capacities. Compared to the µ-Sn anode, the n-Sn anode with nanostructure exhibits superior battery performance in the BiF3/ß-PbSnF4/Sn battery. The optimized battery delivers a high initial discharge capacity of 181.3 mAh g-1 at 8 mA g-1 and can be reversibly cycled at 40 mA g-1 with a high discharge capacity of over 100.0 mAh g-1 after 120 cycles at room temperature. Additionally, it displays high discharge capacities over 90.0 mAh g-1 with excellent cyclability over 100 cycles under -20 °C. Detailed characterization has confirmed that reducing Sn particle size and boosting external pressure are crucial for achieving good defluorination/fluorination behaviors in the Sn anode. These findings pave the way to designing ASSFIBs with high capacities and superior cyclability under different operating temperatures.

Non-Equilibrium Dissipative Assembly with Switchable Biological Functions.

Natural dissipative assembly (DSA) often exhibit energy-driven shifts in natural functions. However, creating man-made DSA that can mimic such biological activities transformation remains relatively rare. Herein, we introduce a cytomembrane-like dissipative assembly system based on chiral supramolecules. This system employs benzoyl cysteine in an out of equilibrium manner, enabling the shifts in biofunctions while minimizing material use. Specifically, aroyl-cystine derivatives primarily assemble into stable M-helix nanofibers under equilibrium conditions. These nanofibers enhance fibroblast adhesion and proliferation through stereospecific interactions with chiral cellular membranes. Upon the addition of chemical fuels, these functional nanofibers temporarily transform into non-equilibrium nanospheres, facilitating efficient drug delivery. Subsequently, these nanospheres revert to their original nanofiber state, effectively recycling the drug. The programmable function-shifting ability of this DSA establishes it as a novel, fuel-driven drug delivery vehicle. And the bioactive DSA not only addresses a gap in synthetic DSAs within biological applications but also sets the stage for innovative designs of 'living' materials.

Two-Dimensional Silver-Isocyanide Frameworks.

Metal-organic frameworks (MOFs) have been widely studied due to their versatile applications and easily tunable structures. However, heteroatom-metal coordination dominates the MOFs community, and the rational synthesis of carbon-metal coordination-based MOFs remains a significant challenge. Herein, two-dimensional (2D) MOFs based on silver-carbon linkages are synthesized through the coordination between silver(I) salt and isocyanide-based monomers at ambient condition. The as-synthesized 2D MOFs possess well-defined crystalline structures and a staggered AB stacking mode. Most interestingly, these 2D MOFs, without π-π stacking between layers, exhibit narrow bandgaps down to 1.42 eV. As electrochemical catalysts for converting CO2 to CO, such 2D MOFs demonstrate Faradaic efficiency over 92%. Surprisingly, the CO2 reduction catalyzed by these MOFs indicates favorable adsorption of CO2 and *COOH on the active carbon sites of the isocyanide groups rather than on silver sites. This is attributed to the critical σ donor role of isocyanides and the corresponding ligand-to-metal charge-transfer effect. This work not only paves the way toward a new family of MOFs based on metal-isocyanide coordination but also offers a rare platform for understanding the electrocatalysis processes on strongly polarized carbon species.

Antiexfoliating h-BN⊃In2O3 Catalyst for Oxidative Dehydrogenation of Propane in a High-Temperature and Water-Rich Environment.

Hexagonal boron nitride (h-BN) is regarded as one of the most efficient catalysts for oxidative dehydrogenation of propane (ODHP) with high olefin selectivity and productivity. However, the loss of the boron component under a high concentration of water vapor and high temperature seriously hinders its further development. How to make h-BN a stable ODHP catalyst is one of the biggest scientific challenges at present. Herein, we construct h-BN⊃xIn2O3 composite catalysts through the atomic layer deposition (ALD) process. After high-temperature treatment in ODHP reaction conditions, the In2O3 nanoparticles (NPs) are dispersed on the edge of h-BN and observed to be encapsulated by ultrathin boron oxide (BOx) overlayer. A novel strong metal oxide-support interaction (SMOSI) effect between In2O3 NPs and h-BN is observed for the first time. The material characterization reveals that the SMOSI not only improves the interlayer force between h-BN layers with a pinning model but also reduces the affinity of the B-N bond toward O• for inhibiting oxidative cutting of h-BN into fragments at a high temperature and water-rich environment. With the pinning effect of the SMOSI, the catalytic stability of h-BN⊃70In2O3 has been extended nearly five times than that of pristine h-BN, and the intrinsic olefin selectivity/productivity of h-BN is well maintained.

Isomeric Dual-Pore Two-Dimensional Covalent Organic Frameworks.

Two-dimensional (2D) covalent organic frameworks (COFs) with hierarchical porosity have been increasingly recognized as promising materials in various fields. Besides, the 2D COFs with kagome (kgm) topology can exhibit unique optoelectronic features and have extensive applications. However, rational synthesis of the COFs with kgm topology remains challenging because of competition with a square-lattice topology. Herein, we report two isomeric dual-pore 2D COFs with kgm topology using a novel geometric strategy to reduce the symmetry of their building blocks, which are four-armed naphthalene-based and azulene-based isomeric monomers. Owing to the large dipole moment of azulene, as-prepared azulene-based COF (COF-Az) possesses a considerably narrow band gap of down to 1.37 eV, which is much narrower than the naphthalene-based 2D COF (COF-Nap: 2.28 eV) and is the lowest band gap among reported imine-linked dual-pore 2D COFs. Moreover, COF-Az was used as electrode material in a gas sensor and exhibits high selectivity for NO2, including a high response rate (58.7%) to NO2 (10 ppm), fast recovery (72 s), up to 10 weeks of stability, and resistance to 80% relative humidity, which are superior to those of reported COF-based NO2 gas sensors. The calculation and in situ experimental results indicate that the large dipole moment of azulene boosts the sensitivity of the imine linkages. The usage of isomeric building blocks not only enables the synthesis of 2D COFs with isometric kgm topology but also provides an azulene-based 2D platform for studying the structure-property correlations of COFs.

Anisotropic Growth of One-Dimensional Carbides in Single-Walled Carbon Nanotubes with Strong Interaction for Catalysis.

Tungsten and molybdenum carbides have shown great potential in catalysis and superconductivity. However, the synthesis of ultrathin W/Mo carbides with a controlled dimension and unique structure is still difficult. Here, inspired by the host-guest assembly strategy with single-walled carbon nanotubes (SWCNTs) as a transparent template, we reported the synthesis of ultrathin (0.8-2.0 nm) W2C and Mo2C nanowires confined in SWCNTs deriving from the encapsulated W/Mo polyoxometalate clusters. The atom-resolved electron microscope combined with spectroscopy and theoretical calculations revealed that the strong interaction between the highly carbophilic W/Mo and SWCNT resulted in the anisotropic growth of carbide nanowires along a specific crystal direction, accompanied by lattice strain and electron donation to the SWCNTs. The SWCNT template endowed carbides with resistance to H2O corrosion. Different from normal modification on the outer surface of SWCNTs, such M2C@SWCNTs (M = W, Mo) provided a delocalized and electron-enriched SWCNT surface to uniformly construct the negatively charged Pd catalyst, which was demonstrated to inhibit the formation of active PdHx hydride and thus achieve highly selective semihydrogenation of a series of alkynes. This work could provide a nondestructive way to design the electron-delocalized SWCNT surface and expand the methodology in synthesizing unusual 1D ultrathin carbophilic-metal nanowires (e.g., TaC, NbC, ß-W) with precise control of the anisotropy in SWCNT arrays.

Metal-Organic Framework@Metal Oxide Heterostructures Induced by Electron-Beam Radiation.

Metal organic frameworks (MOFs) are a distinct family of crystalline porous materials finding extensive applications. Their synthesis often requires elevated temperature and relatively long reaction time. We report here the first case of MOF synthesis activated by high-energy (1.5 MeV) electron beam radiation from a commercially available electron-accelerator. Using ZIF-8 as a representative for demonstration, this type of synthesis can be accomplished under ambient conditions within minutes, leading to energy consumption about two orders of magnitude lower than that of the solvothermal condition. Interestingly, by controlling the absorbed dose in the synthesis, the electron beam not only activates the formation reaction of ZIF-8, but also partially etches the material during the synthesis affording a hierarchical pore architecture and highly crystalline ZnO nanoparticles on the surface of ZIF-8. This gives rise to a new strategy to obtain MOF@metal oxide heterostructures, finding utilities in photocatalytic degradation of organic dyes.

Isotopic Labelling of Confined Carbyne.

Carbyne is a one-dimensional allotrope of carbon consisting of a linear chain of carbon atoms bonded to each other with exceptional strength. Its outstanding mechanical, optical, and electronic properties have been theoretically predicted, but its stability has only been achieved when grown encapsulated in the hollow core of carbon nanotubes. One of the advantages of this confinement is that its properties can be controlled by the chain's length and surrounding environment. We investigated an alternative way of gaining control of its properties is using isotope labelling as tuning mechanism. The optimized liquid precursor was first chosen among several options, which can greatly enhance the yield of the confined carbyne. Then isotopic labelled liquid precursor was encapsulated for further synthesis of isotopic labelled confined carbyne. This allowed us to obtain pioneering results on isotope engineered carbyne with around 11.9 % of 13 C-labelling using 13 C-methanol as precursor.

Direct Imaging of Atomic Permeation Through a Vacancy Defect in the Carbon Lattice.

Porous graphene has shown promise as a new generation of selective membrane for sieving atoms, ions and molecules. However, the atomistic mechanisms of permeation through defects in the graphenic lattice are still unclear and remain unobserved in action, at the atomic level. Here, the direct observation of palladium atoms from a nanoparticle passing through a defect in a single-walled carbon nanotube one-by-one has been achieved with atomic resolution in real time, revealing key stages of the atomic permeation. Bonding between the moving atom and dangling bonds around the orifice, immediately before and after passing through the subnano-pore, plays an important role in the process. Curvature of the graphenic lattice crucially defines the direction of permeation from concave to convex side due to a difference in metal-carbon bonding at the curved surfaces as confirmed by density functional theory calculations, demonstrating the potential of porous carbon nanotubes for atom sieving.

Colyliform Crystalline 2D Covalent Organic Frameworks (COFs) with Quasi-3D Topologies for Rapid I2 Adsorption.

Constructing three-dimensional (3D) structural characteristics on two-dimensional (2D) covalent organic frameworks (COFs) is a good approach to effectively improve the permeability and mass transfer rate of the materials and realize the rapid adsorption for guest molecules, while avoiding the high cost and monomer scarcity in preparing 3D COFs. Herein, we report for the first time a series of colyliform crystalline 2D COFs with quasi-three-dimensional (Q-3D) topologies, consisting of unique "stereoscopic" triangular pores, large interlayer spacings and flexible constitutional units which makes the pores elastic and self-adaptable for the guest transmission. The as-prepared QTD-COFs have a faster adsorption rate (2.51 g h-1 ) for iodine than traditional 2D COFs, with an unprecedented maximum adsorption capacity of 6.29 g g-1 . The excellent adsorption performance, as well as the prominent irradiation stability allow the QTD-COFs to be applied for the rapid removal of radioactive iodine.

Dynamic Covalent Formation of Concave Disulfide Macrocycles Mechanically Interlocked with Single-Walled Carbon Nanotubes.

The formation of discrete macrocycles wrapped around single-walled carbon nanotubes (SWCNTs) has recently emerged as an appealing strategy to functionalize these carbon nanomaterials and modify their properties. Here, we demonstrate that the reversible disulfide exchange reaction, which proceeds under mild conditions, can install relatively large amounts of mechanically interlocked disulfide macrocycles on the one-dimensional nanotubes. Size-selective functionalization of a mixture of SWCNTs of different diameters were observed, presumably arising from error correction and the presence of relatively rigid, curved π-systems in the key building blocks. A combination of UV/Vis/NIR, Raman, photoluminescence excitation, and transient absorption spectroscopy indicated that the small (6,4)-SWCNTs were predominantly functionalized by the small macrocycles 12 , whereas the larger (6,5)-SWCNTs were an ideal match for the larger macrocycles 22 . This size selectivity, which was rationalized computationally, could prove useful for the purification of nanotube mixtures, since the disulfide macrocycles can be removed quantitatively under mild reductive conditions.

Transition-Metal Oxides/Carbides@Carbon Nanotube Composites as Multifunctional Electrocatalysts for Challenging Oxidations and Reductions.

The rapid development of renewable-energy technologies such as water splitting, rechargeable metal-air batteries, and fuel cells requires highly efficient electrocatalysts capable of the oxygen-reduction reaction (ORR) and the oxygen-evolution reaction (OER). Herein, we report a facile sonication-driven synthesis to deposit the molecular manganese vanadium oxide precursor [Mn4 V4 O17 (OAc)3 ]3- on multiwalled carbon nanotubes (MWCNTs). Thermal conversion of this composite at 900 °C gives nanostructured manganese vanadium oxides/carbides, which are stably linked to the MWCNTs. The resulting composites show excellent electrochemical reactivity for ORR and OER, and significant reactivity enhancements compared with the precursors and a Pt/C reference are reported. Notably, even under harsh acidic conditions, long-term OER activity at low overpotential is reported. In addition, we report exceptional activity of the composites for the industrially important Cl2 evolution from an aqueous HCl electrolyte. The new composite material shows how molecular deposition routes leading to highly active and stable multifunctional electrocatalysts can be developed. The facile design could in principle be extended to multiple catalyst classes by tuning of the molecular metal oxide precursor employed.

Surface-enhanced infrared attenuated total reflection spectroscopy via carbon nanodots for small molecules in aqueous solution.

In this study, carbon nanodots (CNDs) with excellent aqueous dispersibility, narrow size distribution, and oxygen-rich functional groups have been prepared via a green electrochemical method. Graphite electrodes were directly electrolyzed at ambient temperatures to form uniform CNDs in deionized water, which is free from additional oxidant/reductant. As-synthesized CNDs have been applied to coat an attenuated total reflection (ATR) waveguide enabling surface-enhanced infrared absorption (SEIRA) spectroscopic studies for detecting a variety of analytes in aqueous phase with remarkably enhanced IR band intensities. Finally, the proposed ATR-SEIRA strategy enabled quantitatively analyzing adenine in aqueous solution after optimizing the amount of CNDs, the solution pH, and potential CND aggregation. Graphical abstract.

Direct Correlation of Carbon Nanotube Nucleation and Growth with the Atomic Structure of Rhenium Nanocatalysts Stimulated and Imaged by the Electron Beam.

Subnanometer Re clusters confined in a single-walled carbon nanotube are activated by the 80 keV electron beam to promote the catalytic growth of a new carbon nanotube. Transmission electron microscopy images the entire process step-by-step, with atomic resolution in real time, revealing details of the initial nucleation followed by a two-stage growth. The atomic dynamics of the Re cluster correlate strongly with the nanotube formation process, with the growth accelerating when the catalyst becomes more ordered. In addition to the nanotube growth catalyzed by Re nanoclusters, individual atoms of Re released from the nanocluster play a role in the nanotube formation.

Ligand-exchange mechanism: new insight into solid-phase extraction of uranium based on a combined experimental and theoretical study.

In numerous reports on selective solid-phase extraction (SPE) of uranium, the extraction of uranium is generally accepted as a direct coordination of the ligands on the solid matrix with the uranyl, in which the critical effect of the hydration shell on the uranyl is neglected. The related mechanism in the extraction process remains unclear. Herein, the detailed calculation of activation energy and the geometry of the identified transition states reveal that the uranium extraction by a newly-synthesized urea-functionalized graphite oxide (Urea-GO) is in essence an exchange process between the ligands on Urea-GO and the coordinated water molecules in the first hydration shell of the uranyl. Moreover, we demonstrate that it is the ketone oxygen in the urea ligand to displace the coordinated water molecule of uranyl due to its stronger bonding ability and lower steric-hindrance, whereas the nitrogen atom in the same ligand is proved to be an electron donor that enables the oxygen atom to have stronger affinity for uranium through electron delocalization effects evaluated on the basis of calculations of the second-order interaction energy between donor and acceptor orbitals. We therefore propose a new ligand-exchange mechanism for the SPE process. This study advances the fundamental understanding of uranium extraction, and provides theoretical and practical guidance on ligand design for selective complexation of uranium(VI) and other metal ions in aqueous solution. Finally, the effect of nitrate ions on the extraction of uranyl was successfully explained based on the experimental and theoretical study.

Atomically Engineered Defect-Rich Palladium Metallene for High-Performance Alkaline Oxygen Reduction Electrocatalysis.

Defect engineering is a key chemical tool to modulate the electronic structure and reactivity of nanostructured catalysts. Here, it is reported how targeted introduction of defect sites in a 2D palladium metallene nanostructure results in a highly active catalyst for the alkaline oxygen reduction reaction (ORR). A defect-rich WOx and MoOx modified Pd metallene (denoted: D-Pd M) is synthesized by a facile and scalable approach. Detailed structural analyses reveal the presence of three distinct atomic-level defects, that are pores, concave surfaces, and surface-anchored individual WOx and MoOx sites. Mechanistic studies reveal that these defects result in excellent catalytic ORR activity (half-wave potential 0.93 V vs. RHE, mass activity 1.3 A mgPd-1 at 0.9 V vs. RHE), outperforming the commercial references Pt/C and Pd/C by factors of ≈7 and ≈4, respectively. The practical usage of the compound is demonstrated by integration into a custom-built Zn-air battery. At low D-Pd M loading (26 µgPd cm-2), the system achieves high specific capacity (809 mAh gZn -1) and shows excellent discharge potential stability. This study therefore provides a blueprint for the molecular design of defect sites in 2D metallene nanostructures for advanced energy technology applications.