Tris(triazolo)triazine-Based Covalent Organic Frameworks for Efficiently Photocatalytic Hydrogen Peroxide Production.

Two-dimensional covalent organic frameworks (2D-COFs) have recently emerged as fascinating scaffolds for solar-to-chemical energy conversion because of their customizable structures and functionalities. Herein, two tris(triazolo)triazine-based COF materials (namely COF-JLU51 and COF-JLU52) featuring large surface area, high crystallinity, excellent stability and photoelectric properties were designed and constructed for the first time. Remarkably, COF-JLU51 gave an outstanding H2O2 production rate of over 4200 µmol g-1 h-1 with excellent reusability in pure water and O2 under one standard sun light, that higher than its isomorphic COF-JLU52 and most of the reported metal-free materials, owing to its superior generation, separation and transport of photogenerated carriers. Experimental and theoretical researches prove that the photocatalytic process undergoes a combination of indirect 2e- O2 reduction reaction (ORR) and 4e- H2O oxidation reaction (WOR). Specifically, an ultrahigh yield of 7624.7 µmol g-1 h-1 with apparent quantum yield of 18.2 % for COF-JLU52 was achieved in a 1 : 1 ratio of benzyl alcohol and water system. This finding contributes novel, nitrogen-rich and high-quality tris(triazolo)triazine-based COF materials, and also designate their bright future in photocatalytic solar transformations.

2-Pyran-4-Ylidene Malononitrile Based Conjugated Microporous Polymers as Metal-Free Heterogeneous Photocatalysts for Organic Synthesis.

Photoactive conjugated microporous polymers (CMPs) as heterogeneous photocatalysts provide a sustainable alternative to classical metal-based semiconductor photosensitizers. However, previously reported CMPs are typically synthesized through metal catalyzed coupling reactions, which bears product separation, but also increases the price of materials. Herein, a new type of sp2 carbon linked DCM-CMPs are successfully designed and synthesized by organic base catalyzed Knoevenagel reaction using 2,6-Dimethyl-4H-pyran-4-ylidene-malononitrile and aromatic polyaldehydes as monomers. The new polymers feature inherent porosity, excellent stability, and fully π-conjugated skeleton with broad visible-light absorption. They effectively induce the synthesis of benzimidazole compounds under light irradiation, and exhibit wide substrate adaptability with outstanding recyclability.

Fully Conjugated Covalent Organic Framework Nanosheets for Visible-Light-Driven Organic Synthesis in Water.

Covalent organic framework (COF) nanosheets have recently garnered great attention as a new class of functional materials. As one of the sustainable processes, however, the photocatalytic organic synthesis in water has not been investigated using COF nanosheets as a photocatalyst to date. Herein, we reported the synthesis of a fully conjugated COF nanosheets with carboxyl functional group through a cooperative strategy of chemical exfoliation and group transformation. The new COF nanosheets was found to be an efficient heterogeneous photocatalyst for a wide range of organic synthesis including selective oxidation of sulfides and oxidative coupling of benzylamines in water under visible-light illumination. This work contributes a new roadmap for the design and synthesis of functional COF-based nanosheets, but also further extends the application boundary of the ultrathin COF nanosheets.

Dual-Parasitic Effect Enables Highly Reversible Zn Metal Anode for Ultralong 25,000 Cycles Aqueous Zinc-Ion Batteries.

The use of electrolyte additives is an efficient approach to mitigating undesirable side reactions and dendrites. However, the existing electrolyte additives do not effectively regulate both the chaotic diffusion of Zn2+ and the decomposition of H2O simultaneously. Herein, a dual-parasitic method is introduced to address the aforementioned issues by incorporating 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIm]OTf) as cosolvent into the Zn(OTf)2 electrolyte. Specifically, the OTf- anion is parasitic in the solvent sheath of Zn2+ to decrease the number of active H2O. Additionally, the EMIm+ cation can construct an electrostatic shield layer and a hybrid organic/inorganic solid electrolyte interface layer to optimize the deposition behavior of Zn2+. This results in a Zn anode with a reversible cycle life of 3000 h, the longest cycle life of full cells (25,000 cycles), and an extremely high initial capacity (4.5 mA h cm-2), providing a promising electrolyte solution for practical applications of rechargeable aqueous zinc-ion batteries.

Pressure-induced bandgap engineering and photoresponse enhancement of wurtzite CuInS2 nanocrystals.

Wurtzite CuInS2 exhibits great potential for optoelectronic applications because of its excellent optical properties and good stability. However, exploring effective strategies to simultaneously optimize its optical and photoelectrical properties remains a challenge. In this study, the bandgap of wurtzite CuInS2 nanocrystals is successfully extended and the photocurrent is enhanced synchronously using external pressure. The bandgap of wurtzite CuInS2 increases with pressure and reaches an optimal value (1.5 eV) for photovoltaic solar energy conversion at about 5.9 GPa. Surprisingly, the photocurrent simultaneously increases nearly 3-fold and reaches the maximum value at this critical pressure. Theoretical calculation indicates that the pressure-induced bandgap extention in wurtzite CuInS2 may be attributed to an increased charge density and ionic polarization between the In-S atoms. The photocurrent preserves a relatively high photoresponse even at 8.8 GPa, but almost disappears above 10.3 GPa. The structural evolution demonstrates that CuInS2 undergoes a phase transformation from the wurtzite phase (P63mc) to the rock salt phase (Fm3̄m) at about 10.3 GPa, which resulted in a direct to indirect bandgap transition and fianlly caused a dramatic reduction in photocurrent. These results not only map a new route toward further increase in the photoelectrical performance of wurtzite CuInS2, but also advance the current research of AI-BIII-CVI2 materials.

Humins with Efficient Electromagnetic Wave Absorption: A By-Product of Furfural Conversion to Isopropyl Levulinate via a Tandem Catalytic Reaction in One-Pot.

Both one-pot catalytic conversion of furfural (FAL) to isopropyl levulinate (PL) and carbonization of by-product (humins) for electromagnetic wave absorption are discussed, which provides inspiration that humins can be applied to electromagnetic wave absorption. In the former, phosphotungstic acid (PW) is employed as a homogeneous catalyst to convert FAL to PL via a tandem reaction in one pot, with the formation of a vast amount of humins. With FAL and various intermediates as substrates, it was found that humins was a polymerization product of FAL, furfuryl alcohol (FOL) and furfuryl ester (FE) with furan rings. In addition, the in situ attenuated total reflection infrared (ATR-IR) spectra also provided a basis for the proposed reaction route. In the latter, with the humins as raw material, P species and WO3 doped nano-porous carbon (Humins-700) platform formed after high-temperature annealing is used for electromagnetic wave absorption and manifests desirable absorption performance. The minimum reflection loss (RLmin ) value is -47.3 dB at 13.0 GHz with a thickness of 2.0 mm and the effective absorption bandwidth reaches 4.5 GHz (11.2-5.7 GHz).

Class of Solid-like Electrolytes for Rechargeable Batteries Based on Metal-Organic Frameworks Infiltrated with Liquid Electrolytes.

A new family of solid-like electrolytes was developed by infiltrating MIL-100(Al), an electrochemically stable metal-organic-framework (MOF) material, with liquid electrolytes that contain cations from the 3rd period (Na+, Mg2+, and Al3+) and the 1st group (Li+, Na+, K+, and Cs+). The anions were immobilized within the MOF scaffolds upon complexing with the open metal sites, allowing effective transport of the cations in the nanoporous channels with high conductivity (up to 1 mS cm-1) and low activation energy (down to 0.2 eV). This general approach enables the fabrication of superior conductive solid-like electrolytes beyond lithium ions.

Pressure-induced isostructural phase transition in Ti3AlC2: experimental and theoretical investigation.

The structural stability of Ti3AlC2 under high pressure is important for understanding its mechanical properties. Here, we conducted a high hydrostatic pressure synchrotron X-ray diffraction experiment and no structural phase transition was observed. Like most other MAX phases, Ti3AlC2 showed an anisotropic compression behavior. Most importantly, an anomaly in c/a ratio was observed at 20.3 GPa, indicating that a pressure-induced isostructural phase transition occurred here. Analysis of the electronic band structure and Fermi surface revealed that three bands crossed the Fermi surface under compression, which suggested that this isostructural phase transition can be considered to be motivated by an electronic topological transition. The subsequent Hall-effect measurements reconfirmed this variation of the electronic band at the Fermi surface, which can be regarded as the electronic origin for the observed isostructural phase transition. These results enrich the basic property data of Ti3AlC2 and would benefit the further understanding of this promising material.

Fabrication of double core-shell Si-based anode materials with nanostructure for lithium-ion battery.

Yolk-shell structure is considered to be a well-designed structure of silicon-based anode. However, there is only one point (point-to-point contact) in the contact region between the silicon core and the shell in this structure, which severely limits the ion transport ability of the electrode. In order to solve this problem, it is important that the core and shell of the core-shell structure are closely linked (face-to-face contact), which ensures good ion diffusion ability. Herein, a double core-shell nanostructure (Si@C@SiO2) was designed for the first time to improve the cycling performance of the electrode by utilising the unique advantages of the SiO2 layer and the closely contacted carbon layer. The improved cycling performance was evidenced by comparing the cycling properties of similar yolk-shell structures (Si@void@SiO2) with equal size of the intermediate shell. Based on the comparison and analysis of the experimental data, Si@C@SiO2 had more stable cycling performance and exceeded that of Si@void@SiO2 after the 276th cycle. More interestingly, the electron/ion transport ability of electrode was further improved by combination of Si@C@SiO2 with reduced graphene oxide (RGO). Clearly, at a current density of 500 mA g-1, the reversible capacity was 753.8 mA h g-1 after 500 cycles, which was 91% of the specific capacity of the first cycle at this current density.

Economical synthesis of composites of FeNi alloy nanoparticles evenly dispersed in two-dimensional reduced graphene oxide as thin and effective electromagnetic wave absorbers.

Developing electromagnetic wave absorbing materials prepared by a facile and economical way is a great challenge. Herein, we report a feasible route to synthesize a series of two-dimensional FeNi/rGO composites by a hydrothermal method followed by a carbonization process. The characterization confirms that nano-sized FeNi alloy nanoparticles are evenly supported onto graphene sheets without aggregation. The homogeneous dispersion of the nanoparticles may result from the introduction of glucose and the oxygen-containing groups on the surface of the graphene oxide. Measurements show that the microwave attenuation capability of the composites can be improved dramatically by adjusting the proportion of dielectric and magnetic components. Consequently, the two-dimensional magnetic material (FeNi/rGO-100) exhibits an excellent microwave absorption performance. In detail, the minimum reflection loss of -42.6 dB and effective bandwidth of 4.0 GHz can be reached with a thinner thickness of 1.5 mm. This study demonstrates that synergistic effects among the magnetic particles, reduced graphene oxide and amorphous carbon layers give rise to the highlighted microwave attenuation ability. Overall, the FeNi/rGO composite is a promising candidate to be used as a microwave absorber, and the feasible and economical method has shown potential application to construct multitudinous two-dimensional materials.

Highly selective and efficient imprinted polymers based on carboxyl-functionalized magnetic nanoparticles for the extraction of gallic acid from pomegranate rind.

With the combined surface imprinting technique and immobilized template strategy, molecularly imprinted magnetic nanoparticles were successfully prepared and coupled with high-performance liquid chromatography to selectively separate and determine gallic acid from the pomegranate rind. On the surface of carboxyl-functionalized magnetic nanospheres, thin imprinting shells were formed using dopamine as monomer and crosslinker. The characteristics, polymerization conditions, and adsorption performances of the resultant nanomaterials were investigated in detail. In addition of good crystallinity, satisfactory magnetism, and uniform morphology of the obtained polymers, they had rapid binding kinetics, high adsorption capacity, and favorable reusability. In the mixed solution of four hydroxybenzoic acids, the prepared nanomaterials have an excellent selectivity to gallic acid with an imprinting factor of as high as 17.5. Therefore, the polymers have great potentials in specific extraction and enrichment of gallic acid from the complex natural resources.

Nano-particle assembled porous core-shell ZnMn2O4 microspheres with superb performance for lithium batteries.

Porous ZnMn2O4 microspheres were prepared via a facile co-precipitation method followed by calcination at various temperatures and evaluated as anode materials for lithium ion batteries. The sample prepared at 600 °C outperformed the other samples in terms of electrochemical performance with high reversible capacity, high-rate capability, and excellent cycling performance. The capacity of the sample remained as high as 999 mAh g-1 at a current rate of 100 mA g-1 after 50 cycles-one of the best ever reported for ZnMn2O4-based materials. A high reversible capacity of 400 mAh g-1 was retainable at a current density of 2000 mA g-1 after 2500 cycles. A novel electrochemical reaction mechanism of ZnMn2O4 anodes was established and investigated at length. The Mn3O4 observed during the charge process was largely responsible for the enhanced performance, as confirmed by x-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. The relatively large surface area, abundant porosity, large ion exchange space, and strong mechanical stability of the porous connected 3D framework were responsible for the unique oxidation/reduction Mn2+ â†” Mn3+ process we observed.

Novel cigarlike TiO2 nanofibers: fabrication, improved mechanical, and electrochemical performances.

By coupling the self-assembly of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) containing titanium precursors with the electrospinning technique, novel cigarlike nanofibers with an outer-shell and inner-continuous-pore structure and resultant fabrics were fabricated. Different from typical porous metal oxides, the prepared high-surface-area nonwoven fabrics show excellent mechanical properties. Not only are these fabrics self-supporting over a large area, but they can also be cut using scissors, which is important for large-scale applications. Furthermore, as electrode materials in Li-ion batteries, these fabrics exhibit much higher charge/discharge capacity and cycle stability compared with the commercially available nanosized TiO2 (P25). The improved mechanical and electrochemical performances are attributed to the presence of an outer-shell, inner-bicontinuous structures (including continuous TiO2 frame and continuous nanopores) and hierarchical pores from the cigarlike nanofibers.

Complex open-framework germanate built by 8-coordinated Ge(10) clusters.

A novel open-framework germanate |(C5H14N2)2(C5H12N2)0.5(H2O)2.5|[Ge12.5O26(OH)2] with three-dimensional 10- and 11-ring channels, denoted as SU-67, has been synthesized under hydrothermal conditions using 2-methylpiperazine (MPP) as the structure-directing agent (SDA). The synthesis is intimately related to that of JLG-5, a tubular germanate built from Ge7 clusters. The influences of synthesis parameters are discussed. A strong influence of the hydrofluoric acid quantity on the resulting cluster building units can be concluded. The framework of SU-67 is based on an elaborate topological pattern of connected Ge10 clusters forming intersecting 10- and 11-ring channels and has a low framework density (12.4 Ge atoms per 1000 Å(3)). We have discovered that the topology of SU-67 is a new 8-connected nce-8-I41/acd net. Strong hydrogen bonding among the organic SDAs, water molecules, and Ge10 clusters resulted in helical networks in SU-67.

A zeolite family with chiral and achiral structures built from the same building layer.

Porosity and chirality are two of the most important properties for materials in the chemical and pharmaceutical industry. Inorganic microporous materials such as zeolites have been widely used in ion-exchange, selective sorption/separation and catalytic processes. The pore size and shape in zeolites play important roles for specific applications. Chiral inorganic microporous materials are particularly desirable with respect to their possible use in enantioselective sorption, separation and catalysis. At present, among the 179 zeolite framework types reported, only three exhibit chiral frameworks. Synthesizing enantiopure, porous tetrahedral framework structures represents a great challenge for chemists. Here, we report the silicogermanates SU-32 (polymorph A), SU-15 (polymorph B) (SU, Stockholm University) and a hypothetical polymorph C, all built by different stacking of a novel building layer. Whereas polymorphs B and C are achiral, each crystal of polymorph A exhibits only one hand and has an intrinsically chiral zeolite structure. SU-15 and SU-32 are thermally stable on calcination.