Synthesis of New RuO2@SiO2 Composite Nanomaterials and their Application as Catalytic Filters for Selective Gas Detection

RuO₂@SiO₂ nanomaterials are prepared using hybrid mesostructured silica (EtO)₂P(O)(CH₂)₃SiO_1.5/x SiO₂ (x = 9, 16) by anchoring the metal precursor [Ru(COD)(COT)] (COD is 1,3‐cyclooctadiene, COT is 1,3,5‐cyclooctatriene) inside the pores of the organized silica matrix through the phosphonate moieties. Following this task, the nanoparticles are fabricated by i) decomposing the metal precursor with hydrogen at room temperature in tetrahydrofuran to achieve ruthenium nanoparticles and ii) thermally treating the ruthenium particles in silica at 450 °C in air to fabricate RuO₂. The materials containing Ru and RuO₂ nanoparticles are characterized by elemental analysis, transmission electron microscopy (TEM), X‐ray diffraction (XRD), nitrogen sorption measurements, and ³¹P and ¹³C NMR. The obtained RuO₂@SiO₂ nanomaterials are evaluated as catalytic filters when deposited onto gas sensors for the preferential detection of propane in the multicomponent gas mixture propane/carbon monoxide/nitrogen dioxide.     

弱碱性抛光液中FA/O 螯合剂和H2O2对Ru CMP的影响研究

Ru作为一种新型阻挡层材料已经应用到了先进的集成电路生产中。但由于金属钌特殊的物理化学性质使其化学机械抛光(CMP)还存在很多问题。为了提高Ru的去除速率,本文研究了FA/O螯合剂和H2O2对Ru的抛光去除速率(RR)和静态腐蚀速率(SER)的影响。实验结果表明,随着H2O2浓度的增加,在抛光过程中,Ru表面形成了致密氧化层,导致Ru的抛光去除速率(RR)和静态腐蚀速率(SER)先增加后减少。通过电化学方法对Ru表面的腐蚀情况进行了分析研究。结果表明,FA/O螯合剂能通过与Ru的氧化物((RuO4)2- 和RuO4 )形成可溶性胺盐([R(NH3)4] (RuO4)2) 提高Ru 的去除速率。同时,为了降低金属Ru CMP后表面粗糙度,在抛光液中加入了非离子表面活性剂AD。     

Dendrimer‐Encapsulated Ruthenium Oxide Nanoparticles as Catalysts in Lithium‐Oxygen Batteries

Dendrimer‐encapsulated ruthenium oxide nanoparticles (DEN‐RuO₂) have been used as catalysts in lithium‐oxygen (Li‐O₂) batteries for the first time. The results obtained from ultraviolet‐visible spectroscopy, electron microscopy and X‐ray photoelectron spectroscopy show that the nanoparticles synthesized by the dendrimer template method are ruthenium oxide, not metallic ruthenium as reported by other groups. The DEN‐RuO₂ significantly improves the cycling stability of Li‐O₂ batteries with carbon electrodes and decreases the charging potential even at ten times less catalyst loading than those reported previously. The monodispersity, porosity, and large number of surface functionalities of the dendrimer template prevent the aggregation of the RuO₂ nanoparticles, making their entire surface area available for catalysis. The potential of using DEN‐RuO₂ as a standalone cathode material for Li‐O₂ batteries is also explored.     

Synthesis of Ruthenium Nanoparticles Stabilized by Heavily Fluorinated Compounds

Ruthenium nanoparticles have been prepared by hydrogenation of the complex Ru(COD)(COT) (COD = 1,5‐cyclooctadiene, COT = 1,3,5‐cyclooctatriene) in the presence of i) heavily fluorinated solid compounds as stabilizers (para‐bis(perfluorooctyl)benzene, 2,4,6‐tris(perfluorooctyl)aniline, and the non‐functionalized 11H,11H,12H,12H,13H,13H,14H,14H,15H,15H,16H, 16H‐perfluorohexacosane (C₁₀F₂₁‐(CH₂)₆‐C₁₀F₂₁)); and ii) the liquid 1H,1H,2H,2H‐perfluorodecylamine. The particles have been characterized by IR spectroscopy, elemental analysis, transmission electron microscopy (TEM), high‐resolution TEM, wide‐ and small‐angle X‐ray scattering (WAXS and SAXS), and scanning electron microscopy with a field‐emission gun (SEM‐FEG). TEM images indicate the presence of aggregated small nanoparticles with a regular mean size of ca. 3 nm. These nanoparticles display the hexagonal close‐packed structure of bulk ruthenium, as shown by WAXS analysis. HRTEM and SEM‐FEG analyses reveal the tendency of the particles to self‐assemble into superstructures (spheres) that can be more or less well defined depending on the fluorinated compound and/or the reaction conditions. This behavior has been confirmed in one case by SAXS measurements attesting the presence of small nanoparticles that are closely packed into clusters.     

Ru–Ru2PΦNPC and NPC@RuO2 Synthesized via Environment‐Friendly and Solid‐Phase Phosphating Process by Saccharomycetes as N/P Sources and Carbon Template for Overall Water Splitting in Acid Electrolyte

Although numerous ruthenium‐based phosphates possess high catalytic activities for hydrogen evolution reaction (HER), most of them rely on dangerous and toxic synthesis routes. Biological slices confirm that Ru ions can penetrate the cell walls of saccharomycete, which facilitates the adsorption of Ru ions. Herein, based on a green synthesis process by saccharomycete cells as the carbon template and nitrogen/phosphorus (N/P) sources, novel Janus‐like ruthenium–ruthenium phosphide nanoparticles embedded into a N/P dual‐doped carbon matrix (Ru–Ru₂PΦNPC) electrocatalyst for HER are synthesized. Electrochemical tests reveal that Ru–Ru₂PΦNPC displays remarkable performance with a low overpotential of 42 mV at 10 mA cm^?2 and demonstrates superior stability at a high current density in 0.5 m H₂SO₄. Furthermore, ruthenium oxide nanoparticles coated N/P dual‐doped carbon (NPC@RuO₂) are also synthesized with a yolk–shell structure using saccharomycete cells as the core template and RuO₂ as a shell to isolate saccharomycete cells from the oxidation reaction during calcination in air. The NPC@RuO₂ as oxygen evolution reaction electrocatalyst possesses a low overpotential of 220 mV at 10 mA cm^?2. Finally, the Ru–Ru₂PΦNPC is integrated as a cathode and NPC@RuO₂ is integrated as an anode to construct a two‐electrode electrolyzer to enable an excellent performance for overall water splitting with a cell voltage of 1.50 V at 10 mA cm^?2 in 0.5 m H₂SO₄.     

Anchoring Hydrous RuO2 on Graphene Sheets for High‐Performance Electrochemical Capacitors

Hydrous ruthenium oxide (RuO₂)/graphene sheet composites (ROGSCs) with different loadings of Ru are prepared by combining sol–gel and low‐temperature annealing processes. The graphene sheets (GSs) are well‐separated by fine RuO₂ particles (5–20 nm) and, simultaneously, the RuO₂ particles are anchored by the richly oxygen‐containing functional groups of reduced, chemically exfoliated GSs onto their surface. Benefits from the combined advantages of GSs and RuO₂ in such a unique structure are that the ROGSC‐based supercapacitors exhibit high specific capacitance (～570 F g^?1 for 38.3 wt% Ru loading), enhanced rate capability, excellent electrochemical stability (～97.9% retention after 1000 cycles), and high energy density (20.1 Wh kg^?1) at low operation rate (100 mA g^?1) or high power density (10000 W kg^?1) at a reasonable energy density (4.3 Wh kg^?1). Interestingly, the total specific capacitance of ROGSCs is higher than the sum of specific capacitances of pure GSs and pure RuO₂ in their relative ratios, which is indicative of a positive synergistic effect of GSs and RuO₂ on the improvement of electrochemical performance. These findings demonstrate the importance and great potential of graphene‐based composites in the development of high‐performance energy‐storage systems.     

Synthesis of PEOlated Fe3O4@SiO2 Nanoparticles via Bioinspired Silification for Magnetic Resonance Imaging

Inspired by the biosilification process, a highly benign synthesis strategy is successfully developed to synthesize PEOlated Fe₃O₄@SiO₂ nanoparticles (PEOFSN) at room temperature and near‐neutral pH. The success of such a strategy lies in the simultaneous encapsulation of Fe₃O₄ nanocrystals and silica precursors into the core of PEO‐based polymeric micelles. The encapsulation results in the formation of a silica shell being confined to the interface between the core and corona of the Fe₃O₄‐nanocrystal‐loaded polymeric micelles. Consequently, the surface of the Fe₃O₄@SiO₂ nanoparticle is intrinsically covered by a layer of free PEO chains, which enable the PEOFSN to be colloidally stable not only at room temperature, but also upon incubation in the presence of proteins under physiological conditions. In addition, the silica shell formation does not cause any detrimental effects to the encapsulated Fe₃O₄ nanocrystals with respect to their size, morphology, crystallinity, and magnetic properties, as shown by their physicochemical behavior. The PEOFSN are shown to be good candidates for magnetic resonance imaging (MRI) contrast agents as demonstrated by the high r₂/r₁ ratio with long‐term stability under high magnetic field, as well as the lack of cytotoxicity.     

Highly Dispersed Mixed Zirconia and Hafnia Nanoparticles in a Silica Matrix: First Example of a ZrO2–HfO2–SiO2 Ternary Oxide System

ZrO₂ and HfO₂ nanoparticles are homogeneously dispersed in SiO₂ matrices (supported film and bulk powders) by copolymerization of two oxozirconium and oxohafnium clusters (M₄O₂(OMc)₁₂, M = Zr, Hf; OMc = OC(O)–C(CH₃)?CH₂) with (methacryloxypropyl)trimethoxysilane (MAPTMS, (CH2?C(CH₃)C(O)O)–(CH₂)₃Si(OCH₃)₃). After calcination (at a temperature ≥800 °C), a silica matrix with homogeneously distributed MO₂ nanocrystallites is obtained. This route yields a spatially homogeneous dispersion of the metal precursors inside the silica matrix, which is maintained during calcination. The composition of the films and the powders is studied before and after calcination by using Fourier transform infrared (FTIR) analysis, X‐ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), and laser ablation inductively coupled plasma mass spectrometry (LA‐ICPMS). The local environment of the metal atoms in one of the calcined samples is investigated by using X‐ray Absorption Fine Structure (XAFS) spectroscopy. Through X‐ray diffraction (XRD) the crystallization of Hf and Zr oxides is seen at temperatures higher than those expected for the pure oxides, and transmission electron microscopy (TEM) shows the presence of well‐distributed and isolated crystalline oxide nanoparticles (5–10 nm).     

Magnetic Cores with Porous Coatings: Growth of Metal‐Organic Frameworks on Particles Using Liquid Phase Epitaxy

A novel method for the homogeneous coating of magnetic nanoparticles with metal organic frameworks (MOFs) is reported. Using a liquid phase epitaxy process, a well‐defined number of [Cu₃(btc)₂]nH₂O, HKUST‐1, layers are grown on COOH terminated silica magnetic beads. The structure and porosity of the deposited MOF coatings are studied using X‐ray diffraction and BET analysis. In addition, size and shape of the fabricated composites are analyzed by transmission electron microscopy. Potential applications of particle based MOF films include catalytic coatings and chromatographic media.     

Ru Species Supported on MOF‐Derived N‐Doped TiO2/C Hybrids as Efficient Electrocatalytic/Photocatalytic Hydrogen Evolution Reaction Catalysts

The development of efficient catalysts is of great importance for hydrogen evolution reaction (HER) of water splitting via electrocatalytic/photocatalytic processes to remediate the current severe environmental and energy problems. By aid of the stabilization effects of uncoordinated groups and inherent pore‐confinement of amine‐functionalized metal–organic frameworks (NH₂‐MIL‐125), two forms of Ru species including nanoparticles (NPs) and/or single atoms (SAs) can be firmly embedded in NH₂‐MIL‐125 derived N‐doped TiO₂/C support (N‐TC), and thus obtain two kinds of samples named Ru‐NPs/SAs@N‐TC and Ru‐SAs@N‐TC, respectively. In the synthetic process, the initial feeding amount of Ru³⁺ ions not only strongly determines the final size and dispersion states of Ru species but also the morphology and defective structures of N‐TC support. Impressively, Ru‐NPs/SAs@N‐TC exhibit superior catalytic activities to Ru‐SAs@N‐TC for either electrocatalytic or photocatalytic HER. This should be attributed to its larger specific surface area and benefiting from synergistic coupling of Ru NPs and Ru SAs. It is envisioned that the present work can provide a new avenue for development of high‐efficiency and multifunctional hybrid catalysts in sustainable energy conversion.     

Laser Assisted Solution Synthesis of High Performance Graphene Supported Electrocatalysts

Simple, yet versatile, methods to functionalize graphene flakes with metal (oxide) nanoparticles are in demand, particularly for the development of advanced catalysts. Herein, based on light‐induced electrochemistry, a laser‐assisted, continuous, solution route for the simultaneous reduction and modification of graphene oxide with catalytic nanoparticles is reported. Electrochemical graphene oxide (EGO) is used as starting material and electron–hole pair source due to its low degree of oxidation, which imparts structural integrity and an ability to withstand photodegradation. Simply illuminating a solution stream containing EGO and metal salt (e.g., H₂PtCl₆ or RuCl₃) with a 248 nm wavelength laser produces reduced EGO (rEGO, oxygen content 4.0 at%) flakes, decorated with Pt (≈2.0 nm) or RuO₂ (≈2.8 nm) nanoparticles. The RuO₂–rEGO flakes exhibit superior catalytic activity for the oxygen evolution reaction, requiring a small overpotential of 225 mV to reach a current density of 10 mA cm^?2. The Pt–rEGO flakes (10.2 wt% of Pt) show enhanced mass activity for the hydrogen evolution reaction, and similar performance for oxygen reduction reaction compared to a commercial 20 wt% Pt/C catalyst. This simple production method is also used to deposit PtPd alloy and MnO_x nanoparticles on rEGO, demonstrating its versatility in synthesizing functional nanoparticle‐modified graphene materials.     

A Versatile Solid Photosensitizer: Periodic Mesoporous Organosilicas with Ruthenium Tris(bipyridine) Complexes Embedded in the Pore Walls

Here, the synthesis of periodic mesoporous organosilicas (PMOs) containing large amounts of ruthenium(II) (Ru) tris(bipyridine) complexes within the pore walls as a solid photosensitizer is reported. The PMOs containing Ru complexes (Ru‐PMOs) are synthesized from highly purified Ru complex precursors with three attached alkylsilatrane groups in the presence of a nonionic surfactant (triblock copolymer) using polyacrylic acid as a promoter. The Ru‐PMOs show strong absorption in the visible light region up to 600 nm due to a metal–ligand charge transfer band, and redox behaviour at ≈0.8 V versus Ag/AgNO₃ due to one‐electron oxidation, that are very similar to those of homogeneous Ru(dmb)₃(PF₆)₂ (dmb = 4,4′‐dimethyl‐2,2′‐bipyridine) solution, despite the fact that the Ru complexes are embedded in the pore walls at high density. Ru‐PMOs loaded with platinum metal or iridium oxide provide efficient photocatalysis for hydrogen evolution or water oxidation, respectively, under irradiation with visible light up to 600 nm in the presence of sacrificial agents. These results indicate that Ru‐PMO is a versatile solid photosensitizer for the construction of various heterogeneous photocatalytic systems simply by placing catalytic materials in the stable mesochannels.     

NiCo Alloy Nanoparticles Decorated on N‐Doped Carbon Nanofibers as Highly Active and Durable Oxygen Electrocatalyst

The exploring of catalysts with high‐efficiency and low‐cost for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the key issues for many renewable energy systems including fuel cells, metal–air batteries, and water splitting. Despite several decades pursuing, bifunctional oxygen catalysts with high catalytic performance at low‐cost, especially the one that could be easily scaled up for mass production are still missing and highly desired. Herein, a hybrid catalyst with NiCo alloy nanoparticles decorated on N‐doped carbon nanofibers is synthesized by a facile electrospinning method and postcalcination treatment. The hybrid catalyst NiCo@N‐C 2 exhibits outstanding ORR and OER catalytic performances, which is even surprisingly superior to the commercial Pt/C and RuO₂ catalysts, respectively. The synergetic effects between alloy nanoparticles and the N‐doped carbon fiber are considered as the main contributions for the excellent catalytic activities, which include decreasing the intrinsic and charge transfer resistances, increasing C?C, graphitic‐N/pyridinic‐N contents in the hybrid catalyst. This work opens up a new way to fabricate high‐efficient, low‐cost oxygen catalysts with high production.     

Orange and Red Organic Light‐Emitting Devices Employing Neutral Ru(II) Emitters: Rational Design and Prospects for Color Tuning

A new series of charge‐neutral Ru(II ) pyridyl and isoquinoline pyrazolate complexes, [Ru(bppz)₂(PPh₂Me)₂] (bbpz: 3‐tert‐butyl‐5‐pyridyl pyrazolate) ( 1 ), [Ru(fppz)₂(PPh₂Me)₂] (fppz: 3‐trifluoromethyl‐5‐pyridyl pyrazolate) ( 2 ), [Ru(ibpz)₂(PPhMe₂)₂] (ibpz: 3‐tert‐butyl‐5‐(1‐isoquinolyl) pyrazolate) ( 3 ), [Ru(ibpz)₂(PPh₂Me)₂] ( 4 ), [Ru(ifpz)₂(PPh₂Me)₂] (ifpz: 3‐trifluoromethyl‐5‐(1‐isoquinolyl) pyrazolate) ( 5 ), [Ru(ibpz)₂(dpp?)] (dpp? represents cis‐1,2‐bis‐(diphenylphosphino)ethene) ( 6 ), and [Ru(ifpz)₂(dpp?)] ( 7 ), have been synthesized, and their structural, electrochemical, and photophysical properties have been characterized. A comprehensive time‐dependant density functional theory (TDDFT) approach has been used to assign the observed electronic transitions to specific frontier orbital configurations. A multilayer organic light‐emitting device (OLED) using 24 wt % of 5 as the dopant emitter in a 4,4′‐N,N′‐dicarbazolyl‐1,1′‐biphenyl (CBP) host with 4,4′‐bis[N‐(1‐naphthyl)‐N‐phenylamino]biphenyl (NPB) as the hole‐transport layer exhibits saturated red emission with an external quantum efficiency (EQE) of 5.10 %, luminous efficiency of 5.74 cd A^–1, and power efficiency of 2.62 lm W^–1. The incorporation of a thin layer of poly(styrene sulfonate)‐doped poly(3,4‐ethylenedioxythiophene) (PEDOT) between indium tin oxide (ITO) and NPB gave anoptimized device with an EQE of 7.03 %, luminous efficiency of 8.02 cd A^–1, and power efficiency of 2.74 lm W^–1 at 20 mA cm^–2. These values represent a breakthrough in the field of OLEDs using less expensive Ru(II ) metal complexes. The nonionic nature of the complexes as well as their high emission quantum efficiencies and short radiative lifetimes are believed to be the key factors enabling this unprecedented achievement. The prospects for color tuning based on Ru(II ) complexes are also discussed in light of some theoretical calculations.     

Synthesis and Characterization of Discrete Nickel Phosphide Nanoparticles: Effect of Surface Ligation Chemistry on Catalytic Hydrodesulfurization of Thiophene

Discrete, unsupported nanoparticles of Ni₂P have been prepared by using a solution‐phase method with bis(1,5‐cyclooctadiene)nickel(0) [Ni(COD)₂] as the nickel source and trioctylphosphine (TOP) as the phosphorus source in the presence of the coordinating solvent trioctylphosphine oxide (TOPO). Ni₂P nanoparticles prepared at 345 °C have an average crystallite size of 10.2 ± 0.7 nm and are capped with TOP and/or TOPO coordinating agents. The surface of the Ni₂P nanoparticles can be modified by washing with CHCl₃ or by exchanging TOP/TOPO groups with mercaptoundecanoic acid (MUA). The surface areas of these nanoparticles are on the order of 30–70 m² g^–1. As‐prepared and MUA‐capped nanoparticles undergo a phase transformation at 370 °C under reducing conditions, but CHCl₃‐washed Ni₂P nanoparticles retain the Ni₂P structure. CHCl₃‐washed and MUA‐capped nanoparticles exhibit higher HDS catalytic activity than as‐prepared nanoparticles or unsupported Ni₂P prepared by temperature‐programmed reduction of a phosphate precursor. The surface modifications have a clear effect on the catalytic activity as well as the thermal stability of Ni₂P nanoparticles under reducing conditions.     

Fully Reversible Homogeneous and Heterogeneous Li Storage in RuO2 with High Capacity

In this paper, we report that Li can be stored in RuO₂ with an unusually high coulombic efficiency. The process involves three electrochemical steps: i) formation of a Ru/Li₂O nanocomposite, ii) formation of a Li‐containing surface film, and iii) interfacial deposition of Li within the Ru/Li₂O matrix. Corresponding to the storage of 5.6 mole of Li ions per mole of RuO₂, a high capacity of 1130 mAh g^–1 is achieved. Furthermore, virtually all inserted Li ions can be extracted, corresponding to a nearly 100 % coulombic efficiency at the first cycle. Achieving a complete reversibility for such a Li storage system through complex heterogeneous solid‐state electrochemical reactions is possible because of the formation of nanoscale Ru/Li₂O during Li insertion and nano‐RuO₂ during Li extraction, in addition to the favorable transport properties of RuO₂ itself.     

Ultrathin Luminescent Films of Rigid Dinuclear Ruthenium(II) Trisbipyridine Complexes

Two asymmetric, luminescent, bimetallic ruthenium trisbipyridine complexes with the general formula [Ru(bpy)₃‐ph₄‐Ru(bpy) L₂](PF₆)₄ (bpy = 2,2′‐bipyridine, ph = phenyl, L = 4,4′‐di‐n‐undecyl‐2,2′‐bipyridine ( 1 ); 4,4′‐di‐non‐1‐enyl‐2,2′‐bipyridine ( 2 )) have been synthesized and characterized. The introduction of two 4,4′‐dialkyl‐2,2′‐bipyridine ligands on one of the ruthenium centers does not influence the electronic structure of the overall complexes to a large extent. Owing to the hydrophobic and hydrophilic nature of the two terminal metal complexes, the compounds 1 and 2 are expected to form Langmuir monolayers at the air/water interface. The film‐forming properties of the amphiphilic complexes have been investigated by measuring surface‐pressure–molecular‐area (π–A) isotherms and recording Brewster‐angle microscopy images. Complexes 1 and 2 were shown to form monolayer films at the air/water interface, which have subsequently been transferred to solid substrates using the Langmuir–Blodgett (LB) technique. The homogeneity of the resulting LB films has been investigated using atomic force microscopy and has been compared with that of LB films of the reference compound [Ru(bpy)₃‐ph₄‐Ru(bpy)₃](PF₆)₄ ( 3 ), which lacks the alkyl chains. The presence of the hydrocarbon chains on one side of the rigid bimetallic complexes was shown to be a prerequisite for the formation of homogeneous monolayers, as with 3 only multilayer formation was obtained. Confocal laser scanning microscopy measurements proved that the LB films of complexes 1 and 2 display a homogeneous red emission upon photoexcitation. Such important results represent the first step towards the fabrication of mono‐ or few‐molecular‐layer electroluminescent devices.     

Corrosion Engineering on Iron Foam toward Efficiently Electrocatalytic Overall Water Splitting Powered by Sustainable Energy

Exploiting highly effective and low-cost electrocatalysts for the hydrogen evolution reaction (HER) is a pressing challenge for the development of sustainable hydrogen energy. In this work, a facile and industrially compatible one-pot corrosion strategy for the rapid synthesis of amorphous RuO₂-decorated FeOOH nanosheets on iron foam (FF Na Ru) within 1 h is reported. Corrosion is a common and inevitable phenomenon that occurs on metal surfaces without electricity input, high temperature, and tedious synthetic procedures. The FF Na Ru electrode is superhydrophilic and aerophobic, which guarantees intimate contact with the electrolyte and accelerates the instantaneous escape of produced gas bubbles during the electrocatalytic process. Moreover, the strong electronic interactions between RuO₂ and FeOOH promote the electrocatalytic process via dramatically improving the electrochemical interfacial properties. Thus, the FF Na Ru electrocatalyst presents excellent catalytic activity towards the HER (30 mV at 10 mA cm^–2) and overall water-splitting (230 mV at 10 mA cm^–2) in 1 M KOH. The overall water-splitting could be simply powered by sustainable and intermittent sunlight, wind, and thermal energies motivated Stirling engine. Density functional theory calculations confirm that coupling effects between RuO₂ and FeOOH are also responsible for promoting the electrocatalytic HER performance.     

Carbon Electrodes Modified with TiO2/Metal Nanoparticles and Their Application for the Detection of Trinitrotoluene

The preparation of modified, catalytically active, functional carbon electrodes and their application to the electrochemical reduction of trinitrotoluene (TNT) is reported. Modification of the electrodes is performed with composites of nanometer‐sized, mesoporous titanium dioxide, which acts as a support containing inserted/deposited nanoparticles of ruthenium, platinum, or gold. These composites are prepared by a novel sonochemical synthesis using simple and low‐cost precursors. Cyclic voltammetry shows that 2,4,6‐trinitrotoluene can be reduced on thus‐modified carbon‐paper electrodes at potentials of around –0.5 V (vs. Ag/AgCl/Cl^–) in aqueous solutions. Unexpectedly, carbon‐paper electrodes modified with the TiO₂/nano‐Pt composites demonstrate a remarkable electrochemical activity toward the reduction of trinitrotoluene. A significant finding is that the two electrode processes—the reduction of TNT and of oxygen—are quite well separated in potential on the modified carbon‐paper electrodes because of selective electrochemical activity of the TiO₂/nano‐Pt and TiO₂/nano‐Au composites. TiO₂/nano‐Ru composites are found to be much less electrochemically active for the detection of TNT compared to the previous two. It was also established that the titanium dioxide support of TiO₂/nano‐Pt composites plays a specific role for facilitating the TNT‐ and oxygen‐reduction processes.     

Self‐Assembly and Characterization of Mesostructured Silica Films with a 3D Arrangement of Isolated Spherical Mesopores

We report the self‐assembly and characterization of mesoporous silica thin films with a 3D ordered arrangement of isolated spherical pores. The preparation method was based on solvent‐evaporation induced self‐assembly (EISA), with MTES (CH₃–Si(OCH₂CH₃)₃) as the silica precursor and a polystyrene‐block‐poly(ethylene oxide) (PS‐b‐PEO) diblock copolymer as the structure‐directing agent. The synthetic approach was designed to suppress the siloxane condensation rate of the siloxane network, allowing co‐self‐assembly of the silica and the amphiphile, followed by retraction of the PEO chains from the silica matrix and matrix consolidation, to occur unimpeded. The calcined films retained the methyl ligands and exhibited no measurable microporosity, thereby indicating that the 3D‐ordered spherical mesopores are not interconnected. A solvent‐mediated formation mechanism is proposed for the absence of microporosity. Due to their closed porosity and hydrophobicity, the MTES‐based films and MTES‐TEOS (Si(OCH₂CH₃)₄)‐based hybrid films we describe should be promising for applications such as low‐k dielectrics.