Selective Etching of N‐Doped Graphene Meshes as Metal‐Free Catalyst with Tunable Kinetics,High Activity and the Origin of New Catalytic Behaviors

New N‐doped reduced graphene oxide (N‐RGO) meshes are facile fabricated by selective etching of 3–5 nm nanopores, with controllable doping of N dopants at an ultrahigh N/C ratio up to 15.6 at%, from pristine graphene oxide sheets in one‐pot hydrothermal reaction. The N‐RGO meshes are illustrated to be an efficient metal‐free catalyst toward hydrogenation of 4‐nitrophenol, with new catalytic behaviors emerging in following three aspects: (i) tunable kinetics following pseudofirst order from commonly observed pseudozero order; (ii) strikingly improved activity with 26‐fold increased rate constant (1.0 s⁻¹ g⁻¹ L); (iii) no induction time required prior to reaction due to depressed back conversion, and dramatically decreased apparent activation energy (E_a) (17 kJ mol⁻¹). The origin of these new catalytic properties can be assigned to the synergetic effects between graphitic N doping and structural defects arising from nanopores. Deeper understanding unveils that the concentration of graphitic N is inverse proportion to E_a, while the pyrrolic N has no impact on this reaction, and oxygenate groups hampers it. The porous nature allows the N‐RGO meshes to conduct catalyze reactions in continuous flow fashion.     

Carbon‐Doped Metal Oxide Nanoparticles Prepared from Metal Nitrates in Supercritical CO2‐Enabled Polymer Nanoreactors

Various C‐doped metal oxide nanoparticles (NPs) are prepared from metal nitrates in poly‐(methyl vinyl ether‐co‐maleic anhydride) (PVM/MA) nanoreactors. The loading of metal nitrates in the nanoreactors is realized via a process of solution‐enhanced dispersion by supercritical CO₂. When the temperature exceeds the thermal decomposition temperature of the nitrates, the nitrates‐loaded nanoreactors transform into C‐doped metal oxide NPs. ZnO, NiO, and Co₃O₄ NPs as representative of the doped oxides are successfully fabricated. A precise control over the doping concentration and doping site in the lattice is achieved by changing the mass ratio between PVM/MA and metal nitrate. The controllable carbon doping avoids undesirable aggregation of carbon species and metal oxide NPs, endows the NPs with broad and strong absorption bands in the visible light region, and creates channels for separation of photo‐generated electrons and holes. In this regard, the resultant C‐doped metal oxide NPs exhibit excellent photocatalytic, photo‐induced antibacterial, and photothermal performances.     

Ultrathin‐Carbon‐Layer‐Protected PtCu Nanoparticles Encapsulated in Carbon Capsules: A Structure Engineering of the Anode Electrocatalyst for Direct Formic Acid Fuel Cells

Structure engineering is an effective strategy to enhance the performance of electrocatalysts for the formic acid oxidation reaction. However, it remains a challenge to prepare a highly active electrocatalyst based on a distinct understanding of its structure‐dependent performance. The design and synthesis of ultrathin‐carbon‐layer‐protected PtCu nanoparticles (NPs) encapsulated in a N‐doped carbon capsule (PtCu@NCC) is reported. This system is fabricated by using Zn‐based metal–organic frameworks as the carbon support source and metal‐containing tannic acid as the protecting shell template. It displays 9.8‐ and 9.6‐fold enhancements in mass activity and specific activity compared to commercial Pt/C. Moreover, a constructed direct formic acid fuel cell using PtCu@NCC as the anodic electrocatalyst delivers a maximum power density of 121 mW cm^?2. Significantly, PtCu@NCC exhibits superior structural stability and catalytic durability in both half‐cell and full‐cell tests. A mechanism study reveals that the enhanced activity is partially attributed to facilitated electro‐oxidation kinetics of formic acid in the unique structure of PtCu@NCC, while the excellent durability stems from the “protecting effect” of the in‐situ‐formed ultrathin carbon layer on the surface of the PtCu NPs. This work opens a new avenue for the development of high‐performance electrocatalysts for fuel‐cell applications by offering essential insights into the structure–performance relationship of the materials.     

Layer‐by‐layer AuCl3 doping of stacked graphene films

We investigated the effect of layer‐by‐layer AuCl₃ doping on the electrical and optical properties of stacked graphene films. Graphene grown by the chemical‐vapor deposition method on a Cu‐foil was chemically doped by AuCl₃ solution with a concentration of 20 mM. Eight different configurations were prepared and analyzed by using four‐point probe measurements, optical transmittance measurements, scanning electron microscopy, and micro‐Raman spectroscopy to compare the optical and electrical characteristics of the different graphene samples. In our study, the top‐layer doping method was very effective because better performances considering both sheet resistance and optical transmittance were observed from the configurations with the top‐layer doped. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microwave‐Assisted One‐Pot Synthesis of Metal‐Free Nitrogen and Phosphorus Dual‐Doped Nanocarbon for Electrocatalysis and Cell Imaging

Metal‐free nitrogen and phosphorus dual‐doped, electrocatlytically active, functionalized nanocarbon (FNC) and photoluminescent carbon nanodots (PCNDs) are simultaneously synthesized using a facile one‐pot microwave‐assisted process. The successful incorporation of phosphorus and nitrogen to oxygen rich PCNDs and FNC are confirmed using surface morphological and spectral studies. The characterization studies of FNC further reveals the presence of edge‐plane‐like sites/defects and remarkable electrocatalytical activity. In addition to the electroctalytical activity, FNC shows attractive properties as a metal‐free oxygen reduction catalyst and is resistant to methanol crossover effects in alkaline media. The 5–10 nm PCNDs, which exhibit blue fluorescence under UV exposure, are successfully used for bioimaging applications.     

Highly Water‐Dispersible,Highly Conductive,and Biocompatible Polypyrrole‐Coated Silica Particles Stabilized and Doped by Chondroitin Sulfate

Currently available methods to prepare conducting polymers‐coated colloidal substrates for biomedical applications need to be improved because they involve the use of toxic reagents and tend to result in aggregated products with diminished conductivity. The work herein describes for the first time a facile strategy for preparing highly water‐dispersible, highly conductive, and biocompatible polypyrrole‐coated silica core–shell (SiO₂@PPy) particles using only chondroitin sulfate (CS), a biologically derived polymer, as the stabilizer and dopant. The CS preadsorbed onto silica surface serves as a template to control the confined growth of the PPy shell and doping of in situ polymerized PPy shell. The thickness of the PPy shell can be tuned from 8 to 17 nm by varying the CS preadsorbed amount. Increasing the thickness of the adsorbed CS layer can control the deposition of thinner PPy shells on an SiO₂ core surface to provide highly water‐dispersible SiO₂@PPy particles. Moreover, CS‐doped SiO₂@PPy particles exhibit conductivities as high as 5.3 S cm^?1. The conductivity of the particles depends on the PPy mass loading and the doping level of the PPy shell. Furthermore, the SiO₂@PPy particles exhibit good biocompatibility and therefore have potential applications in biomedicine.     

Formation of three‐dimensional GaAs microstructures by combination of wet and metal‐assisted chemical etching

Previously, plasma‐enhanced dry etching has been used to generate three‐dimensional GaAs semiconductor structures, however, dry etching induces surface damages that degrade optical properties. Here, we demonstrate the fabrication method forming various types of GaAs microstructures through the combination etching process using the wet‐chemical solution. In this method, a gold (Au)‐pattern is employed as an etching mask to facilitate not only the typical wet etching but also the metal‐assisted chemical etching (MacEtch). High‐aspect‐ratio, tapered GaAs micropillars are produced by using [HF]:[H₂O₂]:[EtOH] as an etching solution, and their taper angle can be tuned by changing the molar ratio of the etching solution. In addition, GaAs microholes are formed when UV light is illuminated during the etching process. Since the wet etching process is free of the surface damage compared to the dry etching process, the GaAs microstructures demonstrated to be well formed here are promising for the applications of III–V optoelectronic devices such as solar cells, laser diodes, and photonic crystal devices. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Yolk–Shell‐Structured Cu/Fe@γ‐Fe2O3 Nanoparticles Loaded Graphitic Porous Carbon for the Oxygen Reduction Reaction

Core–shell Cu/γ‐Fe₂O₃@C and yolk–shell‐structured Cu/Fe@γ‐Fe₂O₃@C particles are prepared by a facile synthesis method using copper oxide as template particles, resorcinol‐formaldehyde as the carbon precursor, and iron nitrate solution as the iron source via pyrolysis. With increasing carbonization temperature and time, solid γ‐Fe₂O₃ cores are formed and then transformed into Fe@γ‐Fe₂O₃ yolk–shell‐structured particles via Ostwald ripening under nitrogen gas flow. The composition variations are studied, and the formation mechanism is proposed for the generation of the hollow and yolk–shell‐structured metal and metal oxides. Moreover, highly graphitic carbons can be obtained by etching the metal and metal oxide nanoparticles through an acid treatment. The electrocatalytic activity for oxygen reduction reaction is investigated on Cu/γ‐Fe₂O₃@C, Cu/Fe@γ‐Fe₂O₃@C, and graphitic carbons, indicating comparable or even superior performance to other Fe‐based nanocatalysts.     

The interaction of iron and metal‐free meso‐tetra (4‐sulfonatophenyl) porphines with CVD graphene: a comparative Raman spectroscopy study

In this work, a non‐covalent interaction of iron and metal‐free meso‐tetra (4‐sulfonatophenyl) porphines (FeTPPS and TPPS, respectively) with high‐quality single‐layer graphene is studied by Raman spectroscopy. Such a kind of graphene functionalization is promising for a development of novel optoelectronic devices and sensors. Our results show that the central metal atom of porphyrin macrocycle, iron particularly, plays an important role in the integrity of FeTPPS on graphene surface; however, the predicted Raman enhancement is not significant. The interaction of metal‐free TPPS with graphene leads to the deprotonation of TPPS molecules and higher Raman enhancement values. Moreover, initially deprotonated TPPS solutions after the adsorption onto the graphene surface demonstrate the appearance of new Raman bands and significantly enhanced Raman signals. We propose that a strong interaction between deprotonated TPPS and graphene is realized through pyrrole and desulfonated phenyl rings of closely located planar TPPS molecules on the graphene surface. The results show that both the protonation of porphyrin macrocycle and the existence of central metal atom are crucial for a formation of nanocomposites with defined electronic properties. Copyright © 2014 John Wiley & Sons, Ltd.     

Amorphous BeN as a new solid host for rare‐earth‐related luminescent materials

Beryllium‐nitride (BeN) thin films were prepared by sputtering a Be target in an atmosphere of pure nitrogen. The films were doped with samarium simply by placing a piece of Sm metal on the surface of the Be target. Under these deposition conditions the films present an amorphous structure and an optical bandgap of approx. 4 eV. They also exhibit visible light emission due to Sm³⁺ ions as a result of either photon or electron excitation. The present experimental results show that amorphous BeN films are suitable, and efficient, III‐nitride hosts for rare‐earth doping purposes. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Modelling the effects of nitrogen doping on the carbon nanofiber growth via catalytic plasma‐enhanced chemical vapour deposition process

An analytical model is developed to describe the effects of nitrogen doping on the growth of the carbon nanofibers (CNFs) and to elucidate the growth mechanism of nitrogen‐contained carbon nanofibers (N‐CNFs) on the catalyst substrate surface through the plasma‐enhanced chemical vapour deposition (PECVD) process. The analytical model accounts for the charging of CNFs, kinetics of all plasma species (electrons, ions, and neutrals) in the reactive plasma, generation of carbon species on the catalyst nanoparticle surface due to dissociation of hydrocarbons, CNF growth due to diffusion and precipitation of carbon species, and various other processes. First‐order differential equations have been solved for glow discharge plasma parameters for undoped CNFs (CNF growth in C₂H₂/H₂ plasma) and nitrogen‐doped CNFs (N‐CNF growth in C₂H₂/NH₃ plasma). Our investigation found that nitrogen‐doped CNFs exhibit lower tip diameters and smaller heights compared to the undoped CNFs. In addition, we have estimated that nitrogen‐doped CNFs have more enhanced field emission characteristics than the undoped CNFs. Moreover, we have also observed that N‐CNFs' growth rate increases and tip diameter decreases as the C₂H₂/NH₃ gas ratio decreases. The theoretical results of the present investigation are consistent with the existing experimental observations.     

Facile Fabrication of Bicomponent CoO/CoFe2O4‐N‐Doped Graphene Hybrids with Ultrahigh Lithium Storage Capacity

A facile strategy is developed to fabricate bicomponent CoO/CoFe₂O₄‐N‐doped graphene hybrids (CoO/CoFe₂O₄‐NG). These hybrids are demonstrated to be potential high‐performance anodes for lithium‐ion batteries (LIBs). The CoO/CoFe₂O₄ nanoplatelets are finely dispersed on the surface of N‐doped graphene nanosheets (CoO/CoFe₂O₄‐NG). The CoO/CoFe₂O₄‐NG electrode exhibits ultrahigh specific capacity with 1172 mA h g^?1 at 500 mA g^?1 and 970 mA h g^?1 at 1000 mA g^?1 as well as excellent cycle stability due to the synergetic effects of N‐doped graphene and CoO/CoFe₂O₄ nanoplatelets. The well‐dispersed bicomponent CoO/CoFe₂O₄ is responsible for the high specific capacity. The N‐doped graphene with high specific surface area has dual roles: to provide active sites for dispersing the CoO/CoFe₂O₄ species and to function as an electrical conducting matrix for fast charge transfer. This method provides a simple and efficient way to configure the hybridized electrode materials with high lithium storage capacity.     

Reduced pore diameter fluctuations of macroporous silicon fabricated from neutron‐transmutation‐doped material

The precision of photo‐electrochemical etching of perfectly‐ordered macropores in single‐crystalline silicon is limited by pore diameter fluctuations due to doping variations of the starting wafer (striations). The doping variation originates from the rotation during crystal growth in the float‐zone or Czochralski process, respectively. Experimentally, variations of the pore diameter up to 7% can occur. These so‐called striations limit performance of possible applications of macroporous silicon. As doping inhomogeneities are the reason for the striations, uniformly doped silicon wafers by neutron transmutation doping were used for the first time. Photoelectrochemical etching of neutron transmutated silicon has been carried out and the pore diameter fluctuation has been reduced by about 40% compared to standard doped float‐zone wafers. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nitrogen‐Doped Carbon with Mesopore Confinement Efficiently Enhances the Tolerance,Sensitivity, and Stability of a Pt Catalyst for the Oxygen Reduction Reaction

Electrocatalysts for the oxygen reduction reaction (ORR) present some of the most challenging vulnerability issues reducing ORR performance and shortening their practical lifetime. Fuel crossover resistance, selective activity, and catalytic stability of ORR catalysts are still to be addressed. Here, a facile and in situ template‐free synthesis of Pt‐containing mesoporous nitrogen‐doped carbon composites (Pt‐m‐N‐C) is designed and specifically developed to overcome its drawback as an electrocatalyst for ORR, while its high activity is sustained. The as‐prepared Pt‐m‐N‐C catalyst exhibits high electrocatalytic activity, dominant four‐electron oxygen reduction pathway, superior stability, fuel crossover resistance, and selective activity to a commercial Pt/C catalyst in 0.1 m KOH aqueous solution. Such excellent performance benefits from in situ covalent incorporation of Pt nanoparticles with optimal size into N‐doped carbon support, dense active catalytic sites on surface, excellent electrical contacts between the catalytic sites and the electron‐conducting host, and a favorable mesoporous structure for the stabilization of the Pt nanoparticles by pore confinement and diffusion of oxygen molecules.     

Oxygen Electroreduction by Single PtPd Nanocubes Encaged in Hollow Carbon Nanospheres: Improved Durability and Strong Effect of Carbon‐Shell Thickness

As a cathode reaction in fuel cells, oxygen reduction reaction (ORR) plays a critical role in determining the overall performance of a fuel cell. It is still a big challenge to find effective ways to improve the catalytic activity, efficiency, and especially stability of ORR electrocatalysts. In the present study, single nanoparticle electrocatalysis for ORR is realized for the first time by encaging PtPd nanocube in hollow and porous carbon nanosphere (PtPd@HCS). Through tuning the carbon‐shell thickness by carbonization temperature, the effects of carbon‐shell thickness on ORR catalytic performance of PtPd@HCS are systematically investigated. The PtPd@HCS calcinated at 800 °C (PtPd@HCS‐800) with the thinnest carbon shell (3.52 nm) and rich pore structure exhibits enhanced ORR catalytic activity and stability. The strategy mentioned here is expected to provide a new method to design single nanoparticle electrocatalysts for fuel cells with high catalytic performance and reduced loading of precious metals.     

Co9S8 Nanoparticles Incorporated in Hierarchically Porous 3D Few‐Layer Graphene‐Like Carbon with S,N‐Doping as Superior Electrocatalyst for Oxygen Reduction Reaction

Electrochemical oxygen reduction reaction (ORR), using nonprecious metal catalysts, has attracted great attention due to the importance in renewable energy technologies, such as fuel cells and metal–air batteries. A simple and scalable synthetic route is demonstrated for the preparation of a novel 3D hybrid nanocatalyst consisting of Co₉S₈ nanoparticles which are incorporated in N,S‐doped carbon (N, S–C) with rational structure design. In particular, the hybrid catalyst is prepared by direct pyrolysis and calcination of a gel mixture of Mg,Co nitrate‐thiourea‐glycine under Ar atmosphere, with subsequent HCl washing. The properties of obtained hybrid catalyst are quite dependent on calcination temperature and added glycine amount. Under a molar ratio of Co5‐Mg15‐tu10‐gl45 and a calcination temperature of 900 °C, Co₉S₈ nanoparticles are embedded in a well‐developed carbon matrix which shows a porous 3D few‐layer graphene‐like N, S–C with open and hierarchical micro–meso–macro pore structure. Because of the synergistic effect between Co₉S₈ nanoparticles and well‐developed carbon support, the composite exhibits high ORR activity close to that of commercial Pt/C catalyst. More importantly, the composite displays superior long‐term stability and good tolerance against methanol. The strategy developed here provides a novel and efficient approach to prepare a cost‐effective and highly active ORR electrocatalyst.     

Surface‐enhanced Raman scattering of molecules adsorbed on Co‐doped ZnO nanoparticles

Transition‐metal‐doped semiconductor nanoparticles (NPs) have been well studied for their optical and catalytic properties but seldom studied by surface‐enhanced Raman scattering (SERS). In this paper, transition‐metal‐doped semiconductor NPs are investigated for their SERS property. Four groups of Co‐doped (0.5, 1, 3, and 5%) ZnO (Co ZnO) NPs and pure ZnO NPs were synthesized and studied. When 4‐mercaptobenzoic acid was used as probing molecule, significant SERS signals were obtained on all the five samples. Moreover, it is very interesting to observe a relationship between the Co‐doping concentration and enhancement of the SERS signals. SERS intensities first increase with doping concentration (up to 1%), and then decrease with further increase in doping concentration (up to 5%). Charge transfer (CT) is considered to be the main contribution to this phenomenon. Different CT ratios from substrates to molecules seem to induce different intensities of the SERS signals. In our experiments, the crystalline defects of Co ZnO NPs caused by the Co dopant affect the CT ratios. A possible mechanism of CT from the valance band of Co ZnO NPs to the lower unoccupied molecular orbital of the molecules via energy of the surface states is suggested. X‐ray photoelectron spectra, UV vis spectra, and Raman spectra were used to characterize the structure and defects in Co ZnO NPs. Copyright © 2011 John Wiley & Sons, Ltd.     

Nanoporous Ag–GaN thin films prepared by metal‐assisted electroless etching and deposition as three‐dimensional substrates for surface‐enhanced Raman scattering

Three‐dimensional (3D) nanoporous gallium nitride (PGaN) scaffolds are fabricated by Pt‐assisted electroless hydrofluoric acid (HF) etching of crystalline GaN followed by in situ electroless deposition of Ag nanostructures onto the interior surfaces of the nanopores, yielding a large surface area substrate for surface‐enhanced Raman scattering (SERS). The resulting 3D SERS‐active substrates have been optimized by varying reaction parameters and starting material concentration, exhibiting enhanced Raman signals 10–100× more intense than either (1) sputtered Ag‐coated porous GaN or (2) Ag‐coated planar GaN. The increase in SERS signal is attributed to a combination of the large surface area and the inherent transparency of PGaN in the visible spectral region. Overall, Ag‐decorated PGaN is a promising platform for high sensitivity SERS detection and chemical analysis, particularly for reaction and metabolic products that can be trapped inside the highly anisotropic nanoscale pores of PGaN. The potential of this sampling mode is illustrated by the ability to acquire Raman spectra of adenine down to 5 fmol. Additionally, correlated SERS and laser desorption/ionization mass spectrometry spectra can be acquired from same sample spot without further preparation, opening new possibilities for the investigation of surface‐bound molecules with substantially enhanced information content. Copyright © 2012 John Wiley & Sons, Ltd.     

Full Protection for Graphene‐Incorporated Micro‐/Nanocomposites Containing Ultra‐small Active Nanoparticles: the Best Li‐Storage Properties

In recent years, graphene‐incorporated micro‐/nanocomposites represent one of the hottest developing directions for the composite materials. However, a large number of active nanoparticles (NPs) are still in the unprotected state in most constructed graphene‐containing designs, which will seriously impair the effects of the graphene additives. Here, a fully protected Fe₃O₄‐based micro‐/nanocomposite (G/Fe₃O₄@C) is rationally developed by carbon‐boxing the common graphene/Fe₃O₄ microparticulates (G/Fe₃O₄). The processes and results of full protection are tracked in detail and characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy, and nitrogen absorption–desorption isotherms, as well as scanning and transition electron microscopy. When used as the anode for lithium‐ion batteries, the fully protected G/Fe₃O₄@C exhibits the best lithium‐storage properties in terms of the highest rate capabilities and the longest cycle life compared to the common G/Fe₃O₄ composites and commercial Fe₃O₄ products. These much improved properties are mainly attributed to its novel structural features including complete protection of active Fe₃O₄ nanoparticles by the surface carbon box, a robust conductive network composed of nitrogen‐doped graphene nanosheets, ultra‐small Fe₃O₄ NPs of 4–5 nm, abundant mesopores to accommodate the volume variation during cycling, and micrometer‐sized secondary particles.     

Oxygen Vacancies Enhancing Electrocatalysis Performance of Porous Copper Oxide

Porous CuO particles with oxygen vacancies are first synthetized by a simple calcination of Cu₂C₂O₄ particles. Oxygen vacancies are confirmed by high resolution transmission electron microscopy, electron paramagnetic resonance measurements, and X‐ray photoelectron spectroscopy. When porous CuO particles with oxygen vacancies are as‐assembled as nonenzymatic glucose sensors, they reveal high sensitivity and good anti‐interference ability. The existing oxygen vacancies can help to increase the rate that electron reaches to the surface and accelerate the kinetics of the surface redox reactions to enhance the electrochemical performances of materials. In this work, the response time of porous CuO particles with oxygen vacancies' modified electrode for the electrocatalysis reaction is less than 3 s. Meanwhile, the calibration plot is linear over the wide concentration range of 0.5 × 10^?6‐6.32 × 10^?3m and a detection limit of 50 × 10^?9m . The developed sensor displays high sensitivity of 10 490.45 µA mm ^?1 cm^?2 and good anti‐interference ability, which is prior than many previous noble metal‐based and Cu‐based electrocatalysts.