Pore-in-Pore Engineering in a Covalent Organic Framework Membrane for Gas Separation.

Covalent organic framework (COF) membranes have emerged as a promising candidate for energy-efficient separations, but the angstrom-precision control of the channel size in the subnanometer region remains a challenge that has so far restricted their potential for gas separation. Herein, we report an ultramicropore-in-nanopore concept of engineering matreshka-like pore-channels inside a COF membrane. In this concept, α-cyclodextrin (α-CD) is in situ encapsulated during the interfacial polymerization which presumably results in a linear assembly (LA) of α-CDs in the 1D nanochannels of COF. The LA-α-CD-in-TpPa-1 membrane shows a high H2 permeance (∼3000 GPU) together with an enhanced selectivity (>30) of H2 over CO2 and CH4 due to the formation of fast and selective H2-transport pathways. The overall performance for H2/CO2 and H2/CH4 separation transcends the Robeson upper bounds and ranks among the most powerful H2-selective membranes. The versatility of this strategy is demonstrated by synthesizing different types of LA-α-CD-in-COF membranes.

Ultra-Fast Preparation of Large-Area Graphdiyne-Based Membranes via Alkynylated Surface-Modification for Nanofiltration.

Graphdiynes (GDYs), two-dimensional graphene-like carbon systems, are considered as potential advanced membrane material due to their unique physicochemical features. Nevertheless, the scale-up of integrated GDY membranes is technologically challenging, and most studies remain at the theoretical stage. Herein, we report a simple and efficient alkynylated surface-mediated strategy to prepare hydrogen-substituted graphdiyne (HsGDY) membranes on commercial alumina tubes. Surface alkynylation initiates an accelerated surface-confined coupling reaction in the presence of a copper catalyst and facilitates the nanoscale epitaxial lateral growth of HsGDY. A continuous and ultra-thin HsGDY membrane (∼100 nm) can be produced within 15 min. The resulting membranes exhibit outstanding molecular sieving together with excellent water permeances (ca. 1100 L m-2 h-1 MPa-1 ), and show a long-term durability in cross-flow nanofiltration, owing to the superhydrophilic surface and hydrophobic pore walls.

Monodisperse Molybdenum Nanoparticles as Highly Efficient Electrocatalysts for Li-S Batteries.

Lithium-sulfur (Li-S) batteries have attracted widespread attention due to their high theoretical energy density. However, their practical application is still hindered by the shuttle effect and the sluggish conversion of lithium polysulfides (LiPSs). Herein, monodisperse molybdenum (Mo) nanoparticles embedded onto nitrogen-doped graphene (Mo@N-G) were developed and used as a highly efficient electrocatalyst to enhance LiPS conversion. The weight ratio of the electrocatalyst in the catalyst/sulfur cathode is only 9%. The unfilled d orbitals of oxidized Mo can attract the electrons of LiPS anions and form Mo-S bonds during the electrochemical process, thus facilitating fast conversion of LiPSs. Li-S batteries based on the Mo@N-G/S cathode can exhibit excellent rate performance, large capacity, and superior cycling stability. Moreover, Mo@N-G also plays an important role in room-temperature quasi-solid-state Li-S batteries. These interesting findings suggest the great potential of Mo nanoparticles in building high-performance Li-S batteries.

A Biomass-Based Integral Approach Enables Li-S Full Pouch Cells with Exceptional Power Density and Energy Density.

Lithium-sulfur (Li-S) batteries, as part of the post-lithium-ion batteries (post-LIBs), are expected to deliver significantly higher energy densities. Their power densities, however, are today considerably worse than that of the LIBs, limiting the Li-S batteries to very few specific applications that need low power and long working time. With the rapid development of single cell components (cathode, anode, or electrolyte) in the last few years, it is expected that an integrated approach can maximize the power density without compromising the energy density in a Li-S full cell. Here, this goal is achieved by using a novel biomass porous carbon matrix (PCM) in the anode, as well as N-Co9 S8 nanoparticles and carbon nanotubes (CNTs) in the cathode. The authors' approach unlocks the potential of the electrodes and enables the Li-S full pouch cells with unprecedented power densities and energy densities (325 Wh kg-1 and 1412 W kg-1 , respectively). This work addresses the problem of low power densities in the current Li-S technology, thus making the Li-S batteries a strong candidate in more application scenarios.

MOF-in-COF molecular sieving membrane for selective hydrogen separation.

Covalent organic frameworks (COFs) are promising materials for advanced molecular-separation membranes, but their wide nanometer-sized pores prevent selective gas separation through molecular sieving. Herein, we propose a MOF-in-COF concept for the confined growth of metal-organic framework (MOFs) inside a supported COF layer to prepare MOF-in-COF membranes. These membranes feature a unique MOF-in-COF micro/nanopore network, presumably due to the formation of MOFs as a pearl string-like chain of unit cells in the 1D channel of 2D COFs. The MOF-in-COF membranes exhibit an excellent hydrogen permeance (>3000 GPU) together with a significant enhancement of separation selectivity of hydrogen over other gases. The superior separation performance for H2/CO2 and H2/CH4 surpasses the Robeson upper bounds, benefiting from the synergy combining precise size sieving and fast molecular transport through the MOF-in-COF channels. The synthesis of different combinations of MOFs and COFs in robust MOF-in-COF membranes demonstrates the versatility of our design strategy.

High-Capacity, Dendrite-Free, and Ultrahigh-Rate Lithium-Metal Anodes Based on Monodisperse N-Doped Hollow Carbon Nanospheres.

To unlock the great potential of lithium metal anodes for high-performance batteries, a number of critical challenges must be addressed. The uncontrolled dendrite growth and volume changes during cycling (especially, at high rates) will lead to short lifespan, low Coulombic efficiency (CE), and security risks of the batteries. Here it is reported that Li metal anodes, employing the monodisperse, lithiophilic, robust, and large-cavity N-doped hollow carbon nanospheres (NHCNSs) as the host, show remarkable performances-high areal capacity (10 mAh cm-2), high CE (up to 99.25% over 500 cycles), complete suppression of dendrite growth, dense packing of Li anode, and an extremely smooth electrode surface during repeated Li plating/stripping. In symmetric cells, a highly stable voltage hysteresis over a long cycling life >1200 h is achieved, and a low and stable voltage hysteresis can be realized even at an ultrahigh current density of 64 mA cm-2. Furthermore, the NHCNSs-based anodes, when paired with a LiFePO4 (LFP) cathode in full cells, give rise to highly improved rate capability (104 mAh g-1 at 10 C) and cycling stability (91.4% capacity retention for 200 cycles), enabling a promising candidate for the next-generation high energy/power density batteries.

High-Flux Vertically Aligned 2D Covalent Organic Framework Membrane with Enhanced Hydrogen Separation.

In this study, we propose a new concept of vertically aligned 2D covalent organic framework (COF) layers forming a membrane for efficient gas separation on the basis of precise size exclusion. Gas transport takes place through the COF interlayer space (typically 0.3-0.4 nm) rather than through the nanometer-sized pore apertures. Construction of such a unique membrane architecture was implemented via in situ oriented growth of 2D COFs inside a skeleton of vertically aligned CoAl-layered double hydroxide (LDH) nanosheets. The resultant vertical COF-LZU1 membrane exhibits a high H2 permeance of ∼3600 GPU together with a desirable separation selectivity for gas mixtures such as H2/CO2 (31.6) and H2/CH4 (29.5), thus surpassing the 2008 Robeson upper bounds. The universality of this approach was demonstrated by successfully producing two types of high-quality vertical COF membranes with superior performance as well as outstanding running stability.

In-tube solid-phase microextraction capillary column packed with mesoporous TiO2 nanoparticles for phosphopeptide analysis.

In this study, an in-tube solid-phase microextraction column packed with mesoporous TiO2 nanoparticles, coupled with MALDI-TOF-MS, was applied to the selective enrichment and detection of phosphopeptides in complex biological samples. The mesoporous TiO2 nanoparticles with high specific surface areas, prepared by a sol-gel and solvothermal method, were injected into the capillary using a slurry packing method with in situ polymerized monolithic segments as frits. Compared with the traditional solid-phase extraction method, the TiO2 -packed column with an effective length of 1 cm exhibited excellent selectivity (α-casein/ß-casein/BSA molar ratio of 1:1:100) and sensitivity (10 fmol of a ß-casein enzymatic hydrolysis sample) for the enrichment of phosphopeptides. These performance characteristics make this system suitable for the detection of phosphorylated peptides in practical biosamples, such as nonfat milk.

Three-electron reversible redox for a high-energy fluorophosphate cathode: Na3V2O2(PO4)2F.

A three-electron structural reaction for Na3V2O2(PO4)2F (Na3VOPF) in space group I4/mmm shows a priori stabilisation in terms of long-life in the voltage range of 2.0-4.5 V, with embedding of more than one sodium ion to generate Na5VOPF upon discharge to 1.0 V in the first cycle, thereby increasing the specific capacity from ∼170 mA h g-1. The capacity of the crystals was 180 mA h g-1 after 20 cycles. The results provide a probable route to improve fluorophosphate cathode performance.

Microfluidic Synthesis Enables Dense and Uniform Loading of Surfactant-Free PtSn Nanocrystals on Carbon Supports for Enhanced Ethanol Oxidation.

Developing new synthetic methods for carbon supported catalysts with improved performance is of fundamental importance in advancing proton exchange membrane fuel cell (PEMFC) technology. Continuous-flow, microfluidic reactions in capillary tube reactors are described, which are capable of synthesizing surfactant-free, ultrafine PtSn alloyed nanoparticles (NPs) on various carbon supports (for example, commercial carbon black particles, carbon nanotubes, and graphene sheets). The PtSn NPs are highly crystalline with sizes smaller than 2 nm, and they are highly dispersed on the carbon supports with high loadings up to 33 wt%. These characteristics make the as-synthesized carbon-supported PtSn NPs more efficient than state of the art commercial Pt/C catalysts applied to the ethanol oxidation reaction (EOR). Significantly enhanced mass catalytic activity (two-times that of Pt/C) and improved stability are obtained.

One-Step, Facile and Ultrafast Synthesis of Phase- and Size-Controlled Pt-Bi Intermetallic Nanocatalysts through Continuous-Flow Microfluidics.

Ordered intermetallic nanomaterials are of considerable interest for fuel cell applications because of their unique electronic and structural properties. The synthesis of intermetallic compounds generally requires the use of high temperatures and multiple-step processes. The development of techniques for rapid phase- and size-controlled synthesis remains a formidable challenge. The intermetallic compound Pt1Bi2 is a promising candidate catalyst for direct methanol fuel cells because of its high catalytic activity and excellent methanol tolerance. In this work, we explored a one-step, facile and ultrafast phase- and size-controlled process for synthesizing ordered Pt-Bi intermetallic nanoparticles (NPs) within seconds in microfluidic reactors. Single-phase Pt1Bi1 and Pt1Bi2 intermetallic NPs were prepared by tuning the reaction temperature, and size control was achieved by modifying the solvents and the length of the reaction channel. The as-prepared Pt-Bi intermetallic NPs exhibited excellent methanol tolerance capacity and high electrocatalytic activity. Other intermetallic nanomaterials, such as Pt3Fe intermetallic nanowires with a diameter of 8.6 nm and Pt1Sn1 intermetallic nanowires with a diameter of 6.3 nm, were also successfully synthesized using this method, thus demonstrating its feasibility and generality.

Ruthenium-oxide-coated sodium vanadium fluorophosphate nanowires as high-power cathode materials for sodium-ion batteries.

Sodium-ion batteries are a very promising alternative to lithium-ion batteries because of their reliance on an abundant supply of sodium salts, environmental benignity, and low cost. However, the low rate capability and poor long-term stability still hinder their practical application. A cathode material, formed of RuO2 -coated Na3 V2 O2 (PO4 )2 F nanowires, has a 50 nm diameter with the space group of I4/mmm. When used as a cathode material for Na-ion batteries, a reversible capacity of 120 mAh g(-1) at 1 C and 95 mAh g(-1) at 20 C can be achieved after 1000 charge-discharge cycles. The ultrahigh rate capability and enhanced cycling stability are comparable with high performance lithium cathodes. Combining first principles computational investigation with experimental observations, the excellent performance can be attributed to the uniform and highly conductive RuO2 coating and the preferred growth of the (002) plane in the Na3 V2 O2 (PO4 )2 F nanowires.