Ahmed A. Elzatahry

Sol–Gel Design Strategy for Ultradispersed TiO2 Nanoparticles on Graphene for High-Performance Lithium Ion Batteries

The rational design and controllable synthesis of strongly coupled inorganic/graphene hybrids represents a long-standing challenge for developing advanced catalysts and energy-storage materials. Here, we report a simple sol-gel method toward creating ultradispersed TiO2 nanoparticles on graphene with an unprecedented degree of control based on the precise separation and manipulation of nanoparticles nucleated, grown, anchored, and crystallized and the reduction of graphene oxide (GO). The hybrid materials show ultradispersed anatase nanoparticles (~5 nm), ultrathin thickness (≤3 layers), and a high surface area of ~229 m(2)/g and exhibit a high specific capacity of ~94 mA h g(-1) at ~59 C, which is twice as that of mechanically mixed composites (~41 mA h g(-1)), demonstrating the potential of strongly synergistic coupling effects for advanced functional systems.

General strategy to synthesize uniform mesoporous TiO2/Graphene/Mesoporous TiO2 sandwich-like nanosheets for highly reversible lithium storage

Uniform oxide deposition on graphene to form a sandwich-like configuration is a well-known challenge mainly due to their large lattice mismatches and poor affinities. Herein, we report a general strategy to synthesize uniform mesoporous TiO2/graphene/mesoporous TiO2 sandwich-like nanosheets (denoted as G@mTiO2), which cannot be achieved by conventional one-pot synthetic methods. We show that by rational control of hydrolysis and condensation of Ti precursors in a slow way, GO sheets can be conformably coated by amorphous TiO2 shells, which then can be facilely transformed into the well-defined G@mTiO2 nanosheets by annealing. This amorphous-to-crystalline strategy conveniently allows bypassing strain fields that would inevitably arise if direct growth of mesoporous anatase shells on graphene. As distinct from the most common structures of graphene-based composites (mixed, wrapped, or anchored models), the resultant materials display a uniform sandwich-like configuration: few-layer graphene conformably encapsulated by mesoporous TiO2 shells. This new G@mTiO2 nanosheet exhibits ultrathin nature (∼34 nm), small size and high crystalline nanocrystals (∼6 nm), high surface areas (∼252 m(2)/g) and uniform mesopores (∼3.4 nm). We further show that the thickness of mesoporous TiO2 shells can be facilely adjusted as desired by controlling the ammonia content, and this facile strategy can be easily extended to design other oxide/graphene/oxide sandwich-like materials. More importantly, we showcase the benefits of the resultant G@mTiO2 nanosheets as anodes in lithium ion batteries: they deliver an extra high capacity, an excellent high-rate capability, and long cycle life.

Highly Reversible and Large Lithium Storage in Mesoporous Si/C Nanocomposite Anodes with Silicon Nanoparticles Embedded in a Carbon Framework

A magnesiothermic reduction approach is designed to synthesize mesoporous Si/C nanocomposites with ultrasmall, uniform silicon nanoparticles (ca. 3 nm) embedded in a rigid mesoporous carbon framework. The resultant mesoporous Si/C nanocomposites present excellent performance with high reversible capacity, good Coulombic efficiency and rate capability, and outstanding cycling stability in lithium-ion battery applications.

Highly Ordered Mesoporous Tungsten Oxides with a Large Pore Size and Crystalline Framework for H2S Sensing

An ordered mesoporous WO3 material with a highly crystalline framework was synthesized by using amphiphilic poly(ethylene oxide)-b-polystyrene (PEO-b-PS) diblock copolymers as a structure-directing agent through a solvent-evaporation-induced self-assembly method combined with a simple template-carbonization strategy. The obtained mesoporous WO3 materials have a large uniform mesopore size (ca. 10.9 nm) and a high surface area (ca. 121 m(2)  g(-1)). The mesoporous WO3-based H2S gas sensor shows an excellent performance for H2S sensing at low concentration (0.25 ppm) with fast response (2 s) and recovery (38 s). The high mesoporosity and continuous crystalline framework are responsible for the excellent performance in H2S sensing.

An Interface Coassembly in Biliquid Phase: Toward Core-Shell Magnetic Mesoporous Silica Microspheres with Tunable Pore Size.

Core-shell magnetic mesoporous silica microspheres (Magn-MSMs) with tunable large mesopores in the shell are highly desired in biocatalysis, magnetic bioseparation, and enrichment. In this study, a shearing assisted interface coassembly in n-hexane/water biliquid systems is developed to synthesize uniform Magn-MSMs with magnetic core and mesoporous silica shell for an efficient size-selective biocatalysis. The synthesis features the rational control over the electrostatic interaction among cationic surfactant molecules, silicate oligomers, and Fe3O4@RF microspheres (RF: resorcinol formaldehyde) in the presence of shearing-regulated solubilization of n-hexane in surfactant micelles. Through this multicomponent interface coassembly, surfactant-silica mesostructured composite has been uniformly deposited on the Fe3O4@RF microspheres, and core-shell Magn-MSMs are obtained after removing the surfactant and n-hexane. The obtained Magn-MSMs possess excellent water dispersibility, uniform diameter (600 nm), large and tunable perpendicular mesopores (5.0-9.0 nm), high surface area (498-623 m(2)/g), large pore volume (0.91-0.98 cm(3)/g), and high magnetization (34.5-37.1 emu/g). By utilization of their large and open mesopores, Magn-MSMs with a pore size of about 9.0 nm have been demonstrated to be able to immobilize a large bioenzyme (trypsin with size of 4.0 nm) with a high loading capacity of ∼97 μg/mg via chemically binding. Magn-MSMs with immobilized trypsin exhibit an excellent convenient and size selective enzymolysis of low molecular proteins in the mixture of proteins of different sizes and a good recycling performance by using the magnetic separability of the microspheres.

Solar-Driven Photoelectrochemical Probing of Nanodot/Nanowire/Cell Interface

We report a nitrogen-doped carbon nanodot (N-Cdot)/TiO2 nanowire photoanode for solar-driven, real-time, and sensitive photoelectrochemical probing of the cellular generation of H2S, an important endogenous gasotransmitter based on a tunable interfacial charge carrier transfer mechanism. Synthesized by a microwave-assisted solvothermal method and subsequent surface chemical conjugation, the obtained N-Cdot/TiO2 nanowire photoanode shows much enhanced photoelectrochemical photocurrent compared with pristine TiO2 nanowires. This photocurrent increase is attributed to the injection of photogenerated electrons from N-Cdots to TiO2 nanowires, confirmed by density functional theory simulation. In addition, the charge transfer efficiency is quenched by Cu(2+), whereas the introduction of H2S or S(2-) ions resets the charge transfer and subsequently the photocurrent, thus leading to sensitive photoelectrochemical recording of the H2S level in buffer and cellular environments. Moreover, this N-Cdot-TiO2 nanowire photoanode has been demonstrated for direct growth and interfacing of H9c2 cardiac myoblasts, with the capability of interrogating H2S cellular generation pathways by vascular endothelial growth factor stimulation as well as inhibition.

Synthesis of 2D-Mesoporous-Carbon/MoS2 Heterostructures with Well-Defined Interfaces for High-Performance Lithium-Ion Batteries

A sandwich-like 2D-mesoporous-carbon/MoS2 -nanosheet heterostructure is fabricated for the first time. The hybrid structure is composed of three well-stacked monolayers: an ordered-mesoporous-carbon monolayer, a MoS2 monolayer, and a further ordered-mesoporous-carbon monolayer. This unique heterostructure exhibits excellent electrochemical performance as an anode material for lithium-ion batteries.

Radially oriented mesoporous TiO2 microspheres with single-crystal–like anatase walls for high-efficiency optoelectronic devices

Uniform mesoporous single-crystal TiO2 spheres with radial channels from driving orientation assembly can be used for energy storage. Highly crystalline mesoporous materials with oriented configurations are in demand for high-performance energy conversion devices. We report a simple evaporation-driven oriented assembly method to synthesize three-dimensional open mesoporous TiO2 microspheres with a diameter of ~800 nm, well-controlled radially oriented hexagonal mesochannels, and crystalline anatase walls. The mesoporous TiO2 spheres have a large accessible surface area (112 m2/g), a large pore volume (0.164 cm3/g), and highly single-crystal–like anatase walls with dominant (101) exposed facets, making them ideal for conducting mesoscopic photoanode films. Dye-sensitized solar cells (DSSCs) based on the mesoporous TiO2 microspheres and commercial dye N719 have a photoelectric conversion efficiency of up to 12.1%. This evaporation-driven approach can create opportunities for tailoring the orientation of inorganic building blocks in the assembly of various mesoporous materials.

Myriophyllum-like hierarchical TiN@Ni3N nanowire arrays for bifunctional water splitting catalysts

Inspired by Myriophyllum, a natural plant, we report an efficient electrochemical water splitting device based on hierarchical TiN@Ni3N nanowire arrays. The bifunctional TiN@Ni3N nanowire arrays serve as both hydrogen evolution reaction (HER) and oxygen reaction evolution (OER) catalysts in this device. As a hydrogen evolution catalyst, the TiN@Ni3N nanowire arrays possess an onset overpotential of 15 mV vs. the reversible hydrogen electrode (RHE), a Tafel slope of 42.1 mV dec−1, and an excellent stability of <13% degradation after being operated for 10 h, much better than Pt disks and Ni3N nanosheets in alkaline electrolytes. For oxygen evolution performance, the Myriophyllum-like TiN@Ni3N nanowire arrays exhibit an onset potential of 1.52 V vs. RHE, and a high stability of 72.1% current retention after being measured for 16 h in the potentiostatic mode. Furthermore, a symmetric electrochemical water splitting device was assembled by using the Myriophyllum-like TiN@Ni3N nanowire arrays as two electrodes, possessing a water splitting onset of ∼1.57 V with a current retention of 63.8% after 16 h of operation.

Ultradispersed Palladium Nanoparticles in Three-Dimensional Dendritic Mesoporous Silica Nanospheres: Toward Active and Stable Heterogeneous Catalysts

Immobilization of highly monodispersed palladium nanoparticles in colloidal mesoporous silica supports has been successfully achieved. The Pd nanoparticles with a uniform small size of ∼1.2 nm can be homogeneously distributed in individual mesopore channels of amino group-functionalized three-dimensional dendritic mesoporous silica nanospheres (3D-dendritic MSNSs) with a Pd content of ∼2.8%. The 3D-dendritic MSNSs-based nanoreactors show high activity in Suzuki-Miyaura cross-coupling reactions of bromobenzene with phenylboronic acid, obtaining a yield over 99% with 0.075 mol % Pd catalyst at room temperature in the dark within 12 h. More importantly, the excellent catalytic performance can be maintained with a negligible decrease lasting at least six cycles. It further reveals that the mesoporous frameworks of the colloidal silica supports can be well-preserved after four catalytic runs; meanwhile, the Pd nanoparticles in the mesopore channels also can remain the sizes of 1.5±0.3 nm without significant transfer and aggregation. The unique mesostructure of the 3D-dendritic MSNSs with mesopore channels of short length and large diameter is supposed to be the key role in immobilization of active and robust heterogeneous catalysts, and it would have more hopeful prospects in catalytic applications.