Sulfonated poly(ether ether ketone) composite membranes based on amino-modified halloysite nanotubes that effectively immobilize phosphotungstic acid

In this work, we prepared amino-modified halloysite nanotubes (PEI-DHNTs) via the co-deposition of self-polymerized dopamine and polyethylenimine (PEI) on the surface of nanotubes, which was confirmed by X-ray photoelectron spectroscopy (XPS) and Thermogravimetric analysis (TGA). A series of composite proton exchange membranes (PEMs) were prepared by incorporating PEI-DHNTs and phosphotungstic acid (HPW) into sulfonated poly(ether ether ketone) (SPEEK). It was found that both PEI-DHNTs and HPW were well dispersed in the polymer matrix, exhibiting excellent filler-matrix compatibility. The composite membranes demonstrated enhanced proton conductivity, reaching as high as 0.078 S cm⁻¹ with 33.3 wt.% HPW loading, which was ~90% higher than that of SPEEK control membrane. Such improvement was mainly attributed to the strong acid–base pairs formed by PEI-DHNT with both SPEEK and HPW, which shortened proton hopping distance and created more continuous proton conduction pathways. Furthermore, the membrane conductivity remained almost constant after 1 year's immersion in liquid water, indicating the successful immobilization of HPW in the composite membranes.     

Slippery liquid-infused porous surface via thermally induced phase separation for enhanced corrosion protection

Slippery liquid-infused porous surface (SLIPS) is a rising star in corrosion protection owing to its outstanding corrosive medium resistance and self-healing property. The large-area and facile fabrication of SLIPS remains a challenge lying on the way of its practical application. Herein, we develop a novel SLIPS based on a porous polyvinylidene fluoride (PVDF) substrate fabricated by thermally induced phase separation. A sphere-packing structure can be easily obtained by blade-coating followed by cooling. The SLIPS exhibits an extremely low sliding angle of 5.8° so that it can resist the fouling of even the Chinese ink, ascribing to its slippery dynamic surface with low surface energy. We also evaluated the anti-corrosion performance of the SLIPS and superhydrophobic PVDF coating by electrochemical impedance spectroscopy (EIS) and scanning Kelvin probe technique (SKP), both of which exhibited enhanced corrosion resistance in 3.5 wt% NaCl solution due to the physical oil and air barriers against the corrosive medium penetration. Nevertheless, the SLIPS coatings performed outstanding self-healing properties because of the high fluidity of infused oil to recover the surface damages, and the self-healing process was recorded by the SKP.     

Light Hydrocarbon Separations Using Porous Organic Framework Materials

Light hydrocarbons (C₁–C₃) are used as basic energy feedstocks and as commodity organic compounds for the production of many industrially necessary chemicals. Due to the nature of the raw materials and production processes, light hydrocarbons are generated as mixtures, but the high-purity single-component products are of vital importance to the petrochemical industry. Consequently, the separation of these C₁–C₃ products is a crucial industrial procedure that comprises a significant share of the total global energy consumption per year. As a complement to traditional separation methods (distillation, partial hydrogenation, etc.), adsorptive separations using porous solids have received widespread attention due to their lower energy costs and higher efficiency. Extensive research has been devoted to the use of porous materials such as zeolites and metal-organic frameworks (MOFs) as solid adsorbents for these key separations, owing to the high porosity, tunable pore structures, and unsaturated metal sites present in these materials. Recently, porous organic framework (POF) materials composed of organic building blocks linked by covalent bonds have also shown excellent properties in light hydrocarbon adsorption and separation, sparking interest in the use of these materials as adsorbents in separation processes. This Minireview summarizes the recent advances in the use of POFs for light hydrocarbon separations, including the separation of mixtures of methane/ethane, methane/propane, ethylene/ethane, acetylene/ethylene, and propylene/propane, while highlighting the relationships between the structural features of these materials and their separation performances. Finally, the difficulties, challenges, and opportunities associated with leveraging POFs for light hydrocarbon separations are discussed to conclude the review.     

FeNi Alloy Nanoparticles Encapsulated in Carbon Shells Supported on N-Doped Graphene-Like Carbon as Efficient and Stable Bifunctional Oxygen Electrocatalysts

The development of cost-effective and durable oxygen electrocatalysts remains highly critical but challenging for energy conversion and storage devices. Herein, a novel FeNi alloy nanoparticle core encapsulated in carbon shells supported on a N-enriched graphene-like carbon matrix (denoted as FeNi@C/NG) was constructed by facile pyrolyzing the mixture of metal salts, glucose, and dicyandiamide. The in situ pyrolysis of dicyandiamide in the presence of glucose plays a significant effect on the fabrication of the porous FeNi@C/NG with a high content of doped N and large specific surface area. The optimized FeNi@C/NG catalyst displays not only a superior catalytic performance for the oxygen reduction reaction (ORR, with an onset potential of 1.0 V and half-wave potential of 0.84 V) and oxygen evolution reaction (OER, the potential at 10 mA cm⁻² is 1.66 V) simultaneously in alkaline, but also outstanding long-term cycling durability. The excellent bifunctional ORR/OER electrocatalytic performance is ascribed to the synergism of the carbon shell and FeNi alloy core together with the high-content of nitrogen doped on the large specific surface area graphene-like carbon.     

Stimuli-Responsive Fluorescent Nanoswitches: Solvent-Induced Emission Enhancement of Copper Nanoclusters

Copper nanoclusters (CuNCs) as a new class of fluorescent materials have attracted a great deal of interest due to their outstanding fluorescence properties. In this work, a variety of organic solvents were used to induce self-assembly of glutathione-capped CuNCs (GSH-CuNCs) to form ordered assemblies with enhanced fluorescence properties. Assemblies with multicolor fluorescence emission were constructed on the basis of the aggregation-induced emission (AIE) of GSH-CuNCs and the solvent effect. The fluorescence emission from these GSH-CuNCs assemblies can also be tuned from yellow to purple by changing the organic solvent. A possible mechanism based on the size of the assemblies and electron transfer was explored to explain the solvent effects on GSH-CuNCs. Stimuli-responsive nanoswitches with excellent reversibility can be controlled by changing the type of organic solvent and the ratio of the organic solvent to the aqueous solution of GSH-CuNCs. As the CuNCs assemblies exhibit strong, stable, and color-tunable fluorescence, they were employed as color-conversion materials for recognizing different organic solvents.     

Engineering Bifunctional Host Materials of Sulfur and Lithium-Metal Based on Nitrogen-Enriched Polyacrylonitrile for Li–S Batteries

Lithium–sulfur batteries (LSBs) still suffer from the shuttle effect on the cathode and the lithium dendrite on the anode. Herein, polyacrylonitrile (PAN) is developed into a bifunctional host material to simultaneously address the challenges faced on both the sulfur cathode and lithium anode in LSBs. For the sulfur cathode, PAN is bonded with sulfur to produce sulfurized PAN (SPAN) to avoid the shuttle effect. The SPAN is accommodated into a conductive 3D CNTs-wrapped carbon foam to prepare a self-supporting cathode, which improves the electronic and ionic conductivity, and buffers the volume expansion. Thereby, it delivers reversible capacity, superb rate capability, and outstanding cycling stability. For the Li-metal anode, PAN aerogel is carbonized to give macroporous N-doped cross-linked carbon nanofiber that behaves as a lithiophilic host to regulate Li plating and suppress the growth of Li dendrite. Combining the improvements for both the cathode and anode realizes a remarkable long-term cyclability (765 mAh g⁻¹ after 300 cycles) in a full cell. It provides new opportunity to propel the practical application of advanced LSBs.     

Toward Understanding the Enhanced Pseudocapacitive Storage in 3D SnS/MXene Architectures Enabled by Engineered Surface Reactions

The optimization of three-dimensional (3D) MXene-based electrodes with desired electrochemical performances is highly demanded. Here, a precursor-guided strategy is reported for fabricating the 3D SnS/MXene architecture with tiny SnS nanocrystals (≈5 nm in size) covalently decorated on the wrinkled Ti₃C₂T_x nanosheets through Ti−S bonds (denoted as SnS/Ti₃C₂T_x-O). The formation of Ti−S bonds between SnS and Ti₃C₂T_x was confirmed by extended X-ray absorption fine structure (EXAFS). Rather than bulky SnS plates decorated on Ti₃C₂T_x (SnS/Ti₃C₂T_x-H) by one-step hydrothermal sulfidation followed by post annealing, this SnS/Ti₃C₂T_x-O presents size-dependent structural and dynamic properties. The as-formed 3D hierarchical structure can provide short ion-diffusion pathways and electron transport distances because of the more accessible surface sites. In addition, benefiting from the tiny SnS nanocrystals that can effectively improve Na⁺ diffusion and suppress structural variation upon charge/discharge processes, the as-obtained SnS/Ti₃C₂T_x-O can generate pseudocapacitance-dominated storage behavior enabled by engineered surface reactions. As predicted, this electrode exhibits an enhanced Na storage capacity of 565 mAh g⁻¹ at 0.1 A g⁻¹ after 75 cycles, outperforming SnS/Ti₃C₂T_x-H (336 mAh g⁻¹), SnS (212 mAh g⁻¹), and Ti₃C₂T_x (104 mAh g⁻¹) electrodes.     

Multipolar Porphyrin-Triazatruxene Arrays for Two-Photon Fluorescence Cell Imaging

Two-photon excited fluorescent (TPEF) materials are highly desirable for bioimaging applications owing to their unique characteristics of deep-tissue penetration and high spatiotemporal resolution. Herein, by connecting one, two, or three electron-deficient zinc porphyrin units to an electron-rich triazatruxene core via ethynyl π-bridges, conjugated multipolar molecules TAT-(ZnP) _n (n=1–3) were developed as TPEF materials for cell imaging. The three new dyes present high fluorescence quantum yields (0.40–0.47) and rationally improved two-photon absorption (TPA) properties. In particular, the peak TPA cross section of TAT-ZnP (436 GM) is significantly larger than that of the ZnP reference (59 GM). The δ_TPA values of TAT-(ZnP)₂ and TAT-(ZnP)₃ further increase to 1031 and up to 1496 GM, respectively, indicating the effect of incorporated ZnP units on the TPA properties. The substantial improvement of the TPEF properties is attributed to the formation of π-conjugated quadrapole/octupole molecules and the extension of D -π-A-D systems, which has been rationalized by density function theory (DFT) calculations. Moreover, all of the three new dyes display good biocompatibility and preferential targeting ability toward cytomembrane, thus can be superior candidates for TPEF imaging of living cells. Overall, this work demonstrated a promising strategy for the development of porphyrin-based TPEF materials by the construction and extension of D -π-A-D multipolar array.     

Stabilizing DNAzymes through Encapsulation in a Metal–Organic Framework

DNAzymes are a promising class of bioinspired catalyst; however, their structural instability limits their potential. Herein, a method to stabilize DNAzymes by encapsulating them in a metal–organic framework (MOF) host is reported. This biomimetic mineralization process makes DNAzymes active under a wider range of conditions. The concept is demonstrated by encapsulating hemin-G-quadruplex (Hemin-G4) into zeolitic imidazolate framework-90 (ZIF-90), which indeed increases the DNAzyme's structural stability. The stabilized DNAzymes show activities in the presence of Exonuclease I, organic solvents, or high temperature. Owing to its elevated stability and heterogeneous nature, it is possible to perform catalysis under continuous-flow conditions, and the DNAzyme can be reactivated in situ by introducing K⁺. Moreover, it is found that the encapsulated DNAzyme maintains its high enantiomer selectivity, demonstrated by the sulfoxidation of thioanisole to (S)-methyl phenyl sulfoxide. This concept of stabilizing DNAzymes expands their potential application in chemical industry.     

Ultrathin Mn Doped Ni-MOF Nanosheet Array for Highly Capacitive and Stable Asymmetric Supercapacitor

In this study, we demonstrate that an Mn-doped ultrathin Ni-MOF nanosheet array on nickel foam (Mn_0.1-Ni-MOF/NF) serves as a highly capacitive and stable supercapacitor positive electrode. The Mn_0.1-Ni-MOF/NF shows an areal capacity of 6.48 C cm⁻² (specific capacity C: 1178 C g⁻¹) at 2 mA cm⁻² in 6.0 m KOH, outperforming most reported MOF-based materials. More importantly, it possesses excellent cycle stability to maintain 80.6 % capacity after 5000 cycles. An asymmetric supercapacitor device utilizing Mn_0.1-Ni-MOF/NF as the positive electrode and activated carbon as the negative electrode attains a high energy density of 39.6 Wh kg⁻¹ at 143.8 Wkg⁻¹ power density with a capacitance retention of 83.6 % after 5000 cycles.