Self‐Assembling Synthesis of Free‐standing Nanoporous Graphene–Transition‐Metal Oxide Flexible Electrodes for High‐Performance Lithium‐Ion Batteries and Supercapacitors

The synthesis of nanoporous graphene by a convenient carbon nanofiber assisted self‐assembly approach is reported. Porous structures with large pore volumes, high surface areas, and well‐controlled pore sizes were achieved by employing spherical silica as hard templates with different diameters. Through a general wet‐immersion method, transition‐metal oxide (Fe₃O₄, Co₃O₄, NiO) nanocrystals can be easily loaded into nanoporous graphene papers to form three‐dimensional flexible nanoarchitectures. When directly applied as electrodes in lithium‐ion batteries and supercapacitors, the materials exhibited superior electrochemical performances, including an ultra‐high specific capacity, an extended long cycle life, and a high rate capability. In particular, nanoporous Fe₃O₄–graphene composites can deliver a reversible specific capacity of 1427.5 mAh g^?1 at a high current density of 1000 mA g^?1 as anode materials in lithium‐ion batteries. Furthermore, nanoporous Co₃O₄–graphene composites achieved a high supercapacitance of 424.2 F g^?1. This work demonstrated that the as‐developed freestanding nanoporous graphene papers could have significant potential for energy storage and conversion applications.     

A Dewetted‐Dealloyed Nanoporous Pt Co‐Catalyst Formed on TiO2 Nanotube Arrays Leads to Strongly Enhanced Photocatalytic H2 Production

Pt nanoparticles are typically decorated as co‐catalyst on semiconductors to enhance the photocatalytic performance. Due to the low abundance and high cost of Pt, reaching a high activity with minimized co‐catalyst loadings is a key challenge in the field. We explore a dewetting‐dealloying strategy to fabricate on TiO₂ nanotubes nanoporous Pt nanoparticles, aiming at improving the co‐catalyst mass activity for H₂ generation. For this, we sputter first Pt‐Ni bi‐layers of controllable thickness (nm range) on highly ordered TiO₂ nanotube arrays, and then induce dewetting‐alloying of the Pt‐Ni bi‐layers by a suitable annealing step in a reducing atmosphere: the thermal treatment causes the Pt and Ni films to agglomerate and at the same time mix with each other, forming on the TiO₂ nanotube surface metal islands of a mixed PtNi composition. In a subsequent step we perform chemical dealloying of Ni that is selectively etched out from the bimetallic dewetted islands, leaving behind nanoporous Pt decorations. Under optimized conditions, the nanoporous Pt‐decorated TiO₂ structures show a>6 times higher photocatalytic H₂ generation activity compared to structures modified with a comparable loading of dewetted, non‐porous Pt. We ascribe this beneficial effect to the nanoporous nature of the dealloyed Pt co‐catalyst, which provides an increased surface‐to‐volume ratio and thus a more efficient electron transfer and a higher density of active sites at the co‐catalyst surface for H₂ evolution.     

A Nonenzymatic Glucose Sensor Using Nanoporous Platinum Electrodes Prepared by Electrochemical Alloying/Dealloying in a Water‐Insensitive Zinc Chloride‐1‐Ethyl‐3‐Methylimidazolium Chloride Ionic Liquid

We report here a nonenzymatic sensor by using a nanoporous platinum electrode to detect glucose directly. The electrode was fabricated by electrochemical deposition and dissolution of PtZn alloy in zinc chloride‐1‐ethyl‐3‐methylimidazolium chloride (ZnCl₂‐EMIC) ionic liquid. Both SEM and electrochemical studies showed the evidences for the nanoporous characteristics of the as‐prepared Pt electrodes. Amperometric measurements allow observation of the electrochemical oxidation of glucose at 0.4 V (vs. Ag/AgCl) in pH 7.4 phosphate buffer solution. The sensor also demonstrates significant reproducibility in glucose detection; the higher the roughness factor of the Pt electrode, the lower the detection limit of glucose. The interfering species such as ascorbic acid and p‐acetamidophenol can be avoided by using a Pt electrode with a high roughness factor of 151. Overall, the nanoporous Pt electrode is promising for enzymeless detection of glucose at physiological condition.     

ChemInform Abstract: Revisiting the Polyoxometalate‐Based Late‐Transition‐Metal‐Oxo Complexes: The “Oxo Wall” Stands.

New XRD data of the previously published K₁₄[P₂W₁₉O₆₉(H₂O)] (I), the ¹⁷O NMR spectrum of (Bu₄N)₇[PW₁₁O₃₉], a careful titration of “K₇H₂ [Au(O)(OH₂)P₂W₂₀O₇₀ (OH₂)₂]” followed by ³¹P NMR spectroscopy, and a new X‐ray crystal structure of the compound reformulated as K₁₂ [PdWO(H₂O)(PW₉O₃₄)₂] (II) are reported.     

An unexpected tetragonal unit cell for N‐(L‐2‐aminobutyryl)‐L‐serine

The title dipeptide {systematic name: (S)‐2‐[(S)‐2‐azaniumylbutanamido]‐3‐hydroxypropanoate}, C₇H₁₄N₂O₄, was synthesized in the anticipation that it would form nanoporous crystals with hexagonal symmetry. Single‐crystal X‐ray diffraction analysis showed that it had instead adopted a unit cell in the space group I4, similar to L‐alanyl‐L‐alanine [Fletterick, Tsai & Hughes (1970). J. Phys. Chem. 75 , 918–922]. The resulting packing arrangement has a high density for a peptide (1.462 Mg m⁻³), which is rendered possible by extensive disorder over two positions for the ethyl side chain of the 2‐aminobutyric acid fragment and over three positions for the serine side chain.<!?tpb=17.5pt>     

Highly Magnetic Nanoporous Carbon/Iron‐Oxide Hybrid Materials

The preparation of size‐controllable Fe₂O₃ nanoparticles grown in nanoporous carbon with tuneable pore diameters is reported. These hybrid materials exhibit strong non‐linear magnetic properties and a magnetic moment of approximately 229 emu g^?1, which is the highest value ever reported for nanoporous hybrids, and can be attributed to the nanosieve effect and the strong interaction between the nanoparticles and the carbon walls.     

A Titanium‐Doped SiOx Passivation Layer for Greatly Enhanced Performance of a Hematite‐Based Photoelectrochemical System

This study introduces an in situ fabrication of nanoporous hematite with a Ti‐doped SiO_x passivation layer for a high‐performance water‐splitting system. The nanoporous hematite with a Ti‐doped SiO_x layer (Ti‐(SiO_x/np‐Fe₂O₃)) has a photocurrent density of 2.44 mA cm^?2 at 1.23 V_RHE and 3.70 mA cm^?2 at 1.50 V_RHE. When a cobalt phosphate co‐catalyst was applied to Ti‐(SiO_x/np‐Fe₂O₃), the photocurrent density reached 3.19 mA cm^?2 at 1.23 V_RHE with stability, which shows great potential of the use of the Ti‐doped SiO_x layer with a synergistic effect of decreased charge recombination, the increased number of active sites, and the reduced hole‐diffusion pathway from the hematite to the electrolyte.     

Octadecanuclear Gear Wheels by Self‐Assembly of Self‐Assembled “Double Saddle”‐Type Coordination Entities: Molecular “Rangoli”

A series of self‐assembled “double saddle”‐type trinuclear complexes of [Pd₃L′₃ L ₂] formulation have been synthesized by complexation of a series of cis‐protected palladium(II) components with a slightly divergent “E‐shaped” non‐chelating tridentate ligand, 1,1′‐(pyridine‐3,5‐diyl)bis(3‐(pyridin‐3‐yl)urea ( L ). The cis‐protecting agents L′ employed in the study are ethylenediamine (en), tetramethylethylenediamine (tmeda), 2,2′‐bipyridine (bpy), and 1,10‐phenanthroline (phen), for 1 , 2 , 3 , and 4 , respectively. The crystal structures of [Pd₃(tmeda)₃( L )₂](NO₃)₆ ( 2 ), [Pd₃(bpy)₃( L )₂](NO₃)₆ ( 3 ), and [Pd₃(phen)₃( L )₂](NO₃)₆ ( 4 ) unequivocally support the new architecture. Two of the “double saddle”‐type complexes ( 3 and 4 ) are suitably crafted with π surfaces at the strategically located cis‐protecting sites to facilitate intermolecular π–π interactions in the solid state. As a consequence, six units of the 3 (or 4 ) are assembled, by means of six‐pairs of π–π stacking interactions, in a circular geometry to form an octadecanuclear molecular ring of [(Pd₃L′₃ L ₂)₆] composition. The overall arrangement of the rings in the crystal packing is equated with the traditional Indian art form rangoli.     

Stoichiometrically Controlled Revocable Self‐Assembled “Spiro” versus Quadruple‐Stranded “Double‐Decker” Type Coordination Cages

The simple combination of Pd^II with the tris‐monodentate ligand bis(pyridin‐3‐ylmethyl) pyridine‐3,5‐dicarboxylate, L , at ratios of 1:2 and 3:4 demonstrated the stoichiometrically controlled exclusive formation of the “spiro‐type” Pd₁L₂ macrocycle, 1 , and the quadruple‐stranded Pd₃L₄ cage, 2 , respectively. The architecture of 2 is elaborated with two compartments that can accommodate two units of fluoride, chloride, or bromide ions, one in each of the enclosures. However, the entry of iodide is altogether restricted. Complexes 1 and 2 are interconvertible under suitable conditions.     

Nanoporous Carbon Tubes from Fullerene Crystals as the π‐Electron Carbon Source

Here we report the thermal conversion of one‐dimensional (1D) fullerene (C₆₀) single‐crystal nanorods and nanotubes to nanoporous carbon materials with retention of the initial 1D morphology. The 1D C₆₀ crystals are heated directly at very high temperature (up to 2000 °C) in vacuum, yielding a new family of nanoporous carbons having π‐electron conjugation within the sp²‐carbon robust frameworks. These new nanoporous carbon materials show excellent electrochemical capacitance and superior sensing properties for aromatic compounds compared to commercial activated carbons.     

Accelerating Membrane‐based CO2 Separation by Soluble Nanoporous Polymer Networks Produced by Mechanochemical Oxidative Coupling

Achieving homogeneous dispersion of nanoporous fillers within membrane architectures remains a great challenge for mixed‐matrix membrane (MMMs) technology. Imparting solution processability of nanoporous materials would help advance the development of MMMs for membrane‐based gas separations. A mechanochemically assisted oxidative coupling polymerization strategy was used to create a new family of soluble nanoporous polymer networks. The solid‐state ball‐milling method affords inherent molecular weight control over polymer growth and therefore provides unexpected solubility for the resulting nanoporous frameworks. MMM‐based CO₂/CH₄ separation performance was significantly accelerated by these new soluble fillers. We anticipate this facile method will facilitate new possibilities for the rational design and synthesis of soluble nanoporous polymer networks and promote their applications in membrane‐based gas separations.     

Application of Sulfonic Acid Functionalized SBA‐15 as a New Nanoporous Acid Catalyst in the Green One‐Pot Synthesis of Spirooxindole‐4H‐pyrans

Sulfonic acid functionalized SBA‐15 (SBA‐Pr‐SO₃H) as a new nanoporous solid acid catalyst was applied in the green one‐pot synthesis of spirooxindole‐4H‐pyrans via condensation of isatins, malononitrile or methyl cyanoacetate or ethyl cyanoacetate, and 4‐hydroxycoumarin in water solvent. SBA‐Pr‐SO₃H was proved to be an efficient heterogeneous nanoporous solid acid catalyst with a pore size of 6 nm that could be easily handled and removed from the reaction mixture by simple filtration and can be recovered and reused for several times without any loss of activity. The significant merits of present methodology are its simplicity, short reaction time, good yields, and environmentally benign mild reaction condition as water was used as a green solvent.     

Random‐Graft Polymer‐Directed Synthesis of Inorganic Mesostructures with Ultrathin Frameworks

A widely employed route for synthesizing mesostructured materials is the use of surfactant micelles or amphiphilic block copolymers as structure‐directing agents. A versatile synthesis method is described for mesostructured materials composed of ultrathin inorganic frameworks using amorphous linear‐chain polymers functionalized with a random distribution of side groups that can participate in inorganic crystallization. Tight binding of the side groups with inorganic species enforces strain in the polymer backbones, limiting the crystallization to the ultrathin micellar scale. This method is demonstrated for a variety of materials, such as hierarchically nanoporous zeolites, their aluminophosphate analogue, TiO₂ nanosheets of sub‐nanometer thickness, and mesoporous TiO₂, SnO₂, and ZrO₂. This polymer‐directed synthesis is expected to widen our accessibility to unexplored mesostructured materials in a simple and mass‐producible manner.     

“Click”‐Triggered Self‐Healing Graphene Nanocomposites

Strategies to compensate material fatigue are among the most challenging issues, being most prominently addressed by the use of nano‐ and microscaled fillers, or via new chemical concepts such as self‐healing materials. A capsule‐based self‐healing material is reported, where the adverse effect of reduced tensile strength due to the embedded capsules is counterbalanced by a graphene‐based filler, the latter additionally acting as a catalyst for the self‐healing reaction. The concept is based on “click”‐based chemistry, a universal methodology to efficiently link components at ambient reaction conditions, thus generating a “reactive glue” at the cracked site. A capsule‐based healing system via a graphene‐based Cu₂O (TRGO‐Cu₂O‐filler) is used, acting as both the catalytic species for crosslinking and the required reinforcement agent within the material, in turn compensating the reduction in tensile strength exerted by the embedded capsules. Room‐temperature self‐healing within 48 h is achieved, with the investigated specimen containing TRGO‐Cu₂O demonstrating significantly faster self‐healing compared to homogeneous (Cu(PPh₃)₃F, Cu(PPh₃)₃Br), and heterogeneous (Cu/C) copper(I) catalysts.

     

A Promising MgII‐Ion‐Selective Luminescent Probe: Structures and Properties of Dy–Mn Polymers with High Symmetry

Two Dy–Mn polymers, {[Dy(L¹)₃Mn_1.5(H₂O)₃]?3.125 H₂O}_n ( 1 , L¹=pyridine‐2,6‐dicarboxylic acid) and {[Dy(L²)₃Mn_1.5(H₂O)₆]?8.25 H₂O}_n ( 2 , L² = 4‐hydroxylpyridine‐2,6‐dicarboxylic acid), with high symmetry (S₆) have been prepared. Polymer 1 has a nanoporous 3D framework with channel of about 17.6 Å diameter, while 2 has a honeycomb‐type 2D structure with the cavity of approximately 14.4 Å diameter. In the construction of multidimensional porous polymers with 3d–4f mixed metals, it is the first observation that a ligand substituent effect leads to dramatic differences in the structures formed. Luminescent studies reveal that the emission intensities of 1 and 2 increase significantly upon the addition of Mg²⁺, whereas the introduction of other metal ions leaves the intensity unchanged or even weakens it; hence, both of them may serve as good candidates of Mg²⁺ luminescent probes. To our knowledge, complex 1 is also the first example of a 3d–4f metal‐based nanoporous polymer to exhibit luminescent selectivity for Mg²⁺. Magnetic susceptibility measurements reveal a rather rare ferromagnetic interaction in 2 . Thermal gravimetric analyses and powder X‐ray diffraction investigations have also been performed, suggestive of high thermal stability of 1 .     

Nanoporous membranes by cooperative self‐assembly of functionalized SEBS and titania

Sol–gel chemistry was adeptly exploited to fabricate nanoporous membranes by cooperative self‐assembly of modified triblock copolymer (SEBS‐NH₂) and titania network. Reinforcement of the matrix was achieved by hydrolytic condensation of tetraisopropoxytitanate without/with compatiblizing agent (3‐glycidyloxypropyl triethoxysilane), yielding two hybrid systems. Incorporation of different proportions of TiO₂ provoked well‐built variations in morphology of compatiblized SEBS‐NH₂/TiO₂ nanocomposites. At low titania loading, spherical nanoparticles were found well‐dispersed in regimented triblock domains while addition of higher amounts of TiO₂ generated nanoporous membranes by mutual self‐assembling of matrix and the reinforcement. Relative improvement of tensile and thermal properties over uncompatiblized nanocomposites was observed owing to enhanced interfacial interactions. Eventually, a combination of the two phases (17.5 wt. % titania in SEBS‐NH₂) demonstrated ample mechanical reinforcement, thermal and morphological profiles, ensuing robust self‐assembled nanostructures. Forthcoming prospects are envisioned as well. Copyright © 2013 John Wiley & Sons, Ltd.     

2‐Aminobenzenethiol‐Functionalized Silver‐Decorated Nanoporous Silicon Photoelectrodes for Selective CO2 Reduction

A molecularly thin layer of 2‐aminobenzenethiol (2‐ABT) was adsorbed onto nanoporous p‐type silicon (b‐Si) photocathodes decorated with Ag nanoparticles (Ag NPs). The addition of 2‐ABT alters the balance of the CO₂ reduction and hydrogen evolution reactions, resulting in more selective and efficient reduction of CO₂ to CO. The 2‐ABT adsorbate layer was characterized by Fourier transform infrared (FTIR) spectroscopy and modeled by density functional theory calculations. Ex situ X‐ray photoelectron spectroscopy (XPS) of the 2‐ABT modified electrodes suggests that surface Ag atoms are in the +1 oxidation state and coordinated to 2‐ABT via Ag?S bonds. Under visible light illumination, the onset potential for CO₂ reduction was ?50 mV vs. RHE, an anodic shift of about 150 mV relative to a sample without 2‐ABT. The adsorption of 2‐ABT lowers the overpotentials for both CO₂ reduction and hydrogen evolution. A comparison of electrodes functionalized with different aromatic thiols and amines suggests that the primary role of the thiol group in 2‐ABT is to anchor the NH₂ group near the Ag surface, where it serves to bind CO₂ and also to assist in proton transfer.     

Advanced High‐Voltage Aqueous Lithium‐Ion Battery Enabled by “Water‐in‐Bisalt” Electrolyte

A new super‐concentrated aqueous electrolyte is proposed by introducing a second lithium salt. The resultant ultra‐high concentration of 28 m led to more effective formation of a protective interphase on the anode along with further suppression of water activities at both anode and cathode surfaces. The improved electrochemical stability allows the use of TiO₂ as the anode material, and a 2.5 V aqueous Li‐ion cell based on LiMn₂O₄ and carbon‐coated TiO₂ delivered the unprecedented energy density of 100 Wh kg^?1 for rechargeable aqueous Li‐ion cells, along with excellent cycling stability and high coulombic efficiency. It has been demonstrated that the introduction of a second salts into the “water‐in‐salt” electrolyte further pushed the energy densities of aqueous Li‐ion cells closer to those of the state‐of‐the‐art Li‐ion batteries.     

Cost‐efficient magnetic nanoporous carbon derived from citrus peel for the selective adsorption of seven insecticides

A magnetic solid‐phase extraction adsorbent that consisted of citrus peel‐derived nanoporous carbon and silica‐coated Fe₃O₄ microspheres (C/SiO₂@Fe₃O₄) was successfully fabricated by co‐precipitation. As a modifier for magnetic microspheres, citrus peel‐derived nanoporous carbon was not only economical and renewable for its raw material, but exerted enormous nanosized pore structure, which could directly influence the type of adsorbed analytes. The C/SiO₂@Fe₃O₄ also possessed the advantages of Fe₃O₄ microspheres like superparamagnetism, which could be easily separated magnetically after adsorption. Integrating the superior of biomass‐derived nanoporous carbon and Fe₃O₄ microspheres, the as‐prepared C/SiO₂@Fe₃O₄ showed high extraction efficiency for target analytes. The obtained material was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and the Brunauer–Emmett–Teller method, which demonstrated that C/SiO₂@Fe₃O₄ was successfully synthesized. Under the optimal conditions, the adsorbent was selected for the selective adsorption of seven insecticides before gas chromatography with mass spectrometry detection, and good linearity was obtained in the concentration range of 2–200 μg/kg with the correlation coefficient ranging from 0.9952 to 0.9997. The limits of detection were in the range of 0.03–0.39 μg/kg. The proposed method has been successfully applied to the enrichment and detection of seven insecticides in real vegetable samples.