Showing papers in "Physical Chemistry Chemical Physics in 2013"

Halogen bonding and other σ-hole interactions: a perspective

Abstract: A σ-hole bond is a noncovalent interaction between a covalently-bonded atom of Groups IV–VII and a negative site, e.g. a lone pair of a Lewis base or an anion. It involves a region of positive electrostatic potential, labeled a σ-hole, on the extension of one of the covalent bonds to the atom. The σ-hole is due to the anisotropy of the atom's charge distribution. Halogen bonding is a subset of σ-hole interactions. Their features and properties can be fully explained in terms of electrostatics and polarization plus dispersion. The strengths of the interactions generally correlate well with the magnitudes of the positive and negative electrostatic potentials of the σ-hole and the negative site. In certain instances, however, polarizabilities must be taken into account explicitly, as the polarization of the negative site reaches a level that can be viewed as a degree of dative sharing (coordinate covalence). In the gas phase, σ-hole interactions with neutral bases are often thermodynamically unfavorable due to the relatively large entropy loss upon complex formation.

Enhanced photocatalytic performance of direct Z-scheme g-C3N4–TiO2 photocatalysts for the decomposition of formaldehyde in air

Abstract: Formaldehyde (HCHO) is a major indoor pollutant and long-term exposure to HCHO may cause health problems such as nasal tumors and skin irritation. Photocatalytic oxidation is considered as the most promising strategy for the decomposition of HCHO. Herein, for the first time, a direct g-C3N4–TiO2 Z-scheme photocatalyst without an electron mediator was prepared by a facile calcination route utilizing affordable P25 and urea as the feedstocks. Photocatalytic activities of the as-prepared samples were evaluated by the photocatalytic oxidation decomposition of HCHO in air. It was shown that the photocatalytic activity of the prepared Z-scheme photocatalysts was highly dependent on the g-C3N4 content. At the optimal g-C3N4 content (sample U100 in this study), the apparent reaction rate constant was 7.36 × 10−2 min−1 for HCHO decomposition, which exceeded that of pure P25 (3.53 × 10−2 min−1) by a factor of 2.1. The enhanced photocatalytic activity could be ascribed to the formation of a g-C3N4–TiO2 Z-scheme photocatalyst, which results in the efficient space separation of photo-induced charge carriers. Considering the ease of the preparation method, this work will provide new insights into the design of high-performance Z-scheme photocatalysts for indoor air purification.

Creating, characterizing, and controlling chemistry with SERS hot spots

Abstract: In this perspective we discuss the roles of hot spots in surface-enhanced Raman spectroscopy (SERS). After giving background and defining the hot spot, we evaluate a variety of SERS substrates which often contain hot spots. We compare and discuss the differentiating properties of each substrate. We then provide a thorough analysis of the hot spot contribution to the observed SERS signal both in ensemble-averaged and single-molecule conditions. We also enumerate rules for determining the SERS enhancement factor (EF) to clarify the use of this common metric. Finally, we present a forward-looking overview of applications and uses of hot spots for controlling chemistry on the nanoscale. Although not exhaustive, this perspective is a review of some of the most interesting and promising methodologies for creating, controlling, and using hot spots for electromagnetic amplification.

Fill factor in organic solar cells

Abstract: The fill factor (FF) is an important parameter that determines the power conversion efficiency of an organic solar cell. There are several factors that can significantly influence FF, and these factors interact with each other very intricately. Due to this reason, a deep understanding of FF is quite difficult. Based on the three fundamental elements in the solar cell equivalent circuit, namely series resistance, shunt resistance and diode, we reviews the research progress in understanding on FF in organic solar cells. Physics lying behind the often-observed undesirable S-shaped J–V curves is also summarized. This paper aims to give a brief and comprehensive summary on FF from a fundamental point of view.

What controls the composition and the structure of nanomaterials generated by laser ablation in liquid solution

Abstract: Laser ablation synthesis in liquid solution (LASiS) is a “green” technique that gives access to the preparation of a library of nanomaterials. Bare noble metal spherical particles, multiphase core–shell oxides, metal–semiconductor heterostructures, layered organometallic compounds and other complex nanostructures can be obtained with the same experimental set up, just by varying a few synthetic parameters. How to govern such versatility is one of the current challenges of LASiS and requires a thorough understanding of the physical and chemical processes involved in the synthesis. In this perspective, the fundamental mechanisms of laser ablation in liquids are summarized, organized according to their temporal sequence and correlated with relevant examples taken from the library of nanomaterials disclosed by LASiS, in order to show how synthesis parameters influence the composition and the structure of products. The resulting framework suggests that, to date, much attention has been devoted to the physical aspects of laser–matter interaction and to the characterization of the final products of the synthesis. Conversely, the clarification of chemical processes active during LASiS deserves more research efforts and requires the synergy among multiple investigation techniques.

Understanding the effect of surface/bulk defects on the photocatalytic activity of TiO2: anatase versus rutile.

Abstract: The sole effect of surface/bulk defects of TiO2 samples on their photocatalytic activity was investigated. Nano-sized anatase and rutile TiO2 were prepared by hydrothermal method and their surface/bulk defects were adjusted simply by calcination at different temperatures, i.e. 400–700 °C. High temperature calcinations induced the growth of crystalline sizes and a decrease in the surface areas, while the crystalline phase and the exposed facets were kept unchanged during calcination, as indicated by the characterization results from XRD, Raman, nitrogen adsorption–desorption, TEM and UV-Vis spectra. The existence of surface/bulk defects in calcined TiO2 samples was confirmed by photoluminescence and XPS spectra, and the surface/bulk defect ratio was quantitatively analyzed according to positron annihilation results. The photocatalytic activity of calcined TiO2 samples was evaluated in the photocatalytic reforming of methanol and the photocatalytic oxidation of α-phenethyl alcohol. Based on the characterization and catalytic results, a direct correlation between the surface specific photocatalytic activity and the surface/bulk defect density ratio could be drawn for both anatase TiO2 and rutile TiO2. The surface defects of TiO2, i.e. oxygen vacancy clusters, could promote the separation of electron–hole pairs under irradiation, and therefore, enhance the activity during photocatalytic reaction.

Lithium salts as “redox active” p-type dopants for organic semiconductors and their impact in solid-state dye-sensitized solar cells

Abstract: Lithium salts have been shown to dramatically increase the conductivity in a broad range of polymeric and small molecule organic semiconductors (OSs). Here we demonstrate and identify the mechanism by which Li+ p-dopes OSs in the presence of oxygen. After we established the lithium doping mechanism, we re-evaluate the role of lithium bis(trifluoromethylsulfonyl)-imide (Li-TFSI) in 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9′-Spirobifluorene (Spiro-OMeTAD) based solid-state dye-sensitized solar cells (ss-DSSCs). The doping mechanism consumes Li+ during the device operation, which poses a problem, since the lithium salt is required at the dye-sensitized heterojunction to enhance charge generation. This compromise highlights that new additives are required to maximize the performance and the long-term stability of ss-DSSCs.

An advanced cathode for Na-ion batteries with high rate and excellent structural stability

Abstract: Layered P2-Nax[Ni1/3Mn2/3]O2 (0 < x < 2/3) is investigated as a cathode material for Na-ion batteries. A combination of first principles computation, electrochemical and synchrotron characterizations is conducted to elucidate the working mechanism for the improved electrochemical properties. The reversible phase transformation from P2 to O2 is observed. New configurations of Na-ions and vacancy are found at x = 1/3 and 1/2, which correspond to the intermediate phases upon the electrochemical cycling process. The mobility of Na-ions is investigated using the galvanostatic intermittent titration technique (GITT) and the Na diffusion barriers are calculated by the Nudged Elastic Band (NEB) method. Both techniques prove that the mobility of Na-ions is faster than Li-ions in the O3 structure within the 1/3 < x < 2/3 concentration region. Excellent cycling properties and high rate capability can be obtained by limiting the oxygen framework shift during P2–O2 phase transformation, suggesting that this material can be a strong candidate as a sustainable low-cost Na-ion battery cathode.

Redox and electrochemical water splitting catalytic properties of hydrated metal oxide modified electrodes

Abstract: This paper presents a review of the redox and electrocatalytic properties of transition metal oxide electrodes, paying particular attention to the oxygen evolution reaction. Metal oxide materials may be prepared using a variety of methods, resulting in a diverse range of redox and electrocatalytic properties. Here we describe the most common synthetic routes and the important factors relevant to their preparation. The redox and electrocatalytic properties of the resulting oxide layers are ascribed to the presence of extended networks of hydrated surface bound oxymetal complexes termed surfaquo groups. This interpretation presents a possible unifying concept in water oxidation catalysis – bridging the fields of heterogeneous electrocatalysis and homogeneous molecular catalysis.

Prospects for hydrogen storage in graphene

Abstract: Hydrogen-based fuel cells are promising solutions for the efficient and clean delivery of electricity. Since hydrogen is an energy carrier, a key step for the development of a reliable hydrogen-based technology requires solving the issue of storage and transport of hydrogen. Several proposals based on the design of advanced materials such as metal hydrides and carbon structures have been made to overcome the limitations of the conventional solution of compressing or liquefying hydrogen in tanks. Nevertheless none of these systems are currently offering the required performances in terms of hydrogen storage capacity and control of adsorption/desorption processes. Therefore the problem of hydrogen storage remains so far unsolved and it continues to represent a significant bottleneck to the advancement and proliferation of fuel cell and hydrogen technologies. Recently, however, several studies on graphene, the one-atom-thick membrane of carbon atoms packed in a honeycomb lattice, have highlighted the potentialities of this material for hydrogen storage and raise new hopes for the development of an efficient solid-state hydrogen storage device. Here we review on-going efforts and studies on functionalized and nanostructured graphene for hydrogen storage and suggest possible developments for efficient storage/release of hydrogen under ambient conditions.

Recent progress in biomedical applications of titanium dioxide

Abstract: As one of the most common chemical materials, titanium dioxide (TiO2) has been prepared and widely used for many years. Among all the applications, the biomedical applications of TiO2 have motivated strong interest and intensive experimental and theoretical studies, owing to its unique photocatalytic properties, excellent biocompatibility, high chemical stability, and low toxicity. Advances in nanoscale science suggest that some of the current problems of life science could be resolved or greatly improved through applying TiO2. This paper presents a critical review of recent advances in the biomedical applications of TiO2, which includes the photodynamic therapy for cancer treatment, drug delivery systems, cell imaging, biosensors for biological assay, and genetic engineering. The characterizations and applications of TiO2 nanoparticles, as well as nanocomposites and nanosystems of TiO2, which have been prepared by different modifications to improve the function of TiO2, are also offered in this review. Additionally, some perspectives on the challenges and new directions for future research in this emerging frontier are discussed.

Systematic exploration of the mechanism of chemical reactions: the global reaction route mapping (GRRM) strategy using the ADDF and AFIR methods

Abstract: Global reaction route mapping (GRRM), a fully-automated search for all important reaction pathways relevant to a given purpose, on the basis of quantum chemical calculations enables systematic elucidation of complex chemical reaction mechanisms However, GRRM had previously been limited to very simple systems This is mainly because such calculations are highly demanding even in small systems when a brute-force sampling is considered Hence, we have developed two independent but complementary methods: anharmonic downward distortion following (ADDF) and artificial force induced reaction (AFIR) methods ADDF can follow reaction pathways starting from local minima on the potential energy surface (PES) toward transition structures (TSs) and dissociation channels AFIR can find pathways starting from two or more reactants toward TSs for their associative reactions In other words, ADDF searches for A → X type isomerization and A → X + Y type dissociation pathways, whereas AFIR finds A + B → X (+ Y) type associative pathways Both follow special paths called the ADDF path and the AFIR path, and these tend to pass through near TSs of corresponding reaction pathways, giving approximate TSs Such approximate TSs can easily be re-optimized to corresponding true TSs by standard geometry optimizations On the basis of these two methods, we have proposed practical strategies of GRRM The GRRM strategies have been applied to a variety of chemical systems ranging from thermal- and photochemical-reactions in small systems to organometallic- and enzyme-catalysis, on the basis of quantum chemical calculations In this perspective, we present an overview of the GRRM strategies and some results of applications Their practical usage for systematic prediction is also discussed

Computing vibrational spectra from ab initio molecular dynamics

Abstract: We review several methods for the calculation of vibrational spectra from ab initio molecular dynamics (AIMD) simulations and we present a new implementation in the trajectory analyzer TRAVIS. In particular, we show mass-weighted power spectra, infrared spectra, and Raman spectra with corresponding depolarization ratios, which are based on time-correlation functions of velocities, dipole moments, and polarizabilities, respectively. Using the four organic molecules methanol, acetone, nitromethane, and pinacol as test systems, we compare the spectra from AIMD simulations of the isolated molecules in gas phase to static calculations relying on the harmonic approximation and to experimental spectra recorded in a nonpolar solvent. The AIMD approach turns out to give superior results when anharmonicity effects are of particular importance. Using the example of methanol, we demonstrate the application to bulk phase systems, which are not directly accessible by static calculations, but for which the AIMD spectra also provide a very good approximation to experimental data. Finally, we investigate the influence of simulation time and temperature in the AIMD on the resulting spectra.

Metal-enhanced fluorescence

Abstract: Preface. Contributors. Mental-Enhanced Fluorescence: Progress Towards a Unified Plasmon-Fluorophore Description (Kadir Aslan and Chris D. Geddes). Spectral Profile Modifications In Metal-Enhanced Fluorescence (E. C. Le Ru, J. Grand, N. Felidj, J. Aubard, G. Levi, A. Hohenau, J. R. Krenn, E. Blackie and P. G. Etchegoin). The Role Of Plasmonic Engineering In Metal-Enhanced Fluorescence (Daniel J. Ross, Nicholas P.W. Pieczonka and R. F. Aroca). Importance of Spectral Overlap: Fluorescence Enhancement by Single Metal Nanoparticles (Keiko Munechika, Yeechi Chen, Jessica M. Smith and.David S. Ginger). Near-IR Metal Enhanced Fluorescence And Controlled Colloidal Aggregation (Jon P. Anderson, Mark Griffiths, John G. Williams, Daniel L. Grone, Dave L. Steffens, and Lyle M. Middendorf). Optimisation Of Plasmonic Enhancement Of Fluorescence For Optical Biosensor Applications (Colette McDonagh, Ondrej Stranik, Robert Nooney and Brian D. MacCraith). Microwave-Accelerated Metal-Enhanced Fluorescence (Kadir Aslan and Chris D. Geddes). Localized Surface Plasmon Coupled Fluorescence Fiber Optic Based Biosensing (Chien Chou, Ja-An Annie Ho, Chii-Chang Chen, Ming-Yaw, Wei-Chih Liu, Ying-Feng Chang, Chen Fu, Si-Han Chen and Ting-Yang Kuo). Surface Plasmon Enhanced Photochemistry (Stephen K. Gray). Metal-Enhanced Generation of Oxygen Rich Species (Yongxia Zhang, Kadir Aslan and Chris D. Geddes). Synthesis Of Anisotropic Noble Metal Nanoparticles (Damian Aherne, Deirdre M. Ledwith and John M. Kelly). Enhanced Fluorescence Detection Enabled By Zinc Oxide Nanomaterials (Jong-in Hahm). ZnO Platforms For Enhanced Directional Fluorescence Applications (H.C. Ong, D.Y. Lei, J. Li and J.B. Xu). E-Beam Lithography And Spontaneous Galvanic Displacement Reactions For Spatially Controlled MEF Applications (Luigi Martiradonna, S. Shiv Shankar and Pier Paolo Pompa). Metal-Enhanced Chemiluminescence (Yongxia Zhang, Kadir Aslan and Chris D. Geddes). Enhanced Fluorescence From Gratings (Chii-Wann Lin, Nan-Fu Chiu, Jiun-Haw Lee and Chih-Kung Lee). Enhancing Fluorescence with Sub-Wavelength Metallic Apertures (Steve Blair and Jerome Wenger). Enhanced Multi-Photon Excitation of Tryptophan-Silver Colloid (Renato E. de Araujo, Diego Rativa and Anderson S. L. Gomes). Plasmon-enhanced radiative rates and applications to organic electronics (Lewis Rothberg and Shanlin Pan). Fluorescent Quenching Gold Nanoparticles: Potential Biomedical Applications (Xiaohua Huang, Ivan H. El-Sayed, and Mostafa A. El-Sayed). Index.

The Kohn–Sham gap, the fundamental gap and the optical gap: the physical meaning of occupied and virtual Kohn–Sham orbital energies

Abstract: A number of consequences of the presence of the exchange–correlation hole potential in the Kohn–Sham potential are elucidated. One consequence is that the HOMO–LUMO orbital energy difference in the KS-DFT model (the KS gap) is not “underestimated” or even “wrong”, but that it is physically expected to be an approximation to the excitation energy if electrons and holes are close, and numerically proves to be so rather accurately. It is physically not an approximation to the difference between ionization energy and electron affinity I − A (fundamental gap or chemical hardness) and also numerically differs considerably from this quantity. The KS virtual orbitals do not possess the notorious diffuseness of the Hartree–Fock virtual orbitals, they often describe excited states much more closely as simple orbital transitions. The Hartree–Fock model does yield an approximation to I − A as the HOMO–LUMO orbital energy difference (in Koopmans' frozen orbital approximation), if the anion is bound, which is often not the case. We stress the spurious nature of HF LUMOs if the orbital energy is positive. One may prefer Hartree–Fock, or mix Hartree–Fock and (approximate) KS operators to obtain a HOMO–LUMO gap as a Koopmans' approximation to I − A (in cases where A exists). That is a different one-electron model, which exists in its own right. But it is not an “improvement” of the KS model, it necessarily deteriorates the (approximate) excitation energy property of the KS gap in molecules, and deteriorates the good shape of the KS virtual orbitals.

Semiconductor-based nanocomposites for photocatalytic H2 production and CO2 conversion.

Abstract: Semiconductor-based photocatalysis has attracted much attention in recent years because of its potential for solving energy and environmental problems that we are now facing. Among many photocatalytic reactions, the splitting of H2O into H2 and O2 and the reduction of CO2 with H2O into organic compounds such as CH4 and CH3OH are two of the most important and challenging reactions. Many studies have been devoted to designing and preparing novel photocatalytic materials for these two reactions. This article highlights recent advances in developing semiconductor-based nanocomposite photocatalysts for the production of H2 and the reduction of CO2. The systems of semiconductor–cocatalyst, semiconductor–carbon (carbon nanotube or graphene) and semiconductor–semiconductor nanocomposites have mainly been described. It has been demonstrated that the design and preparation of nanocomposites with proper structures can facilitate charge separation/migration and decrease the charge recombination probability, thus promoting the photocatalytic activity. Keeping the reduction and oxidation processes in different regions in the nanocomposite may also enhance the photocatalytic efficiency and stability. The location and size of cocatalysts, the interfacial contact between semiconductor and carbon materials, and the heterojunctions between different semiconductors together with the suitable alignment of band edges of semiconductors are key factors determining the photocatalytic behaviours of the nanocomposite catalysts.

Graphene oxide for effective radionuclide removal

Abstract: Here we show the efficacy of graphene oxide (GO) for rapid removal of some of the most toxic and radioactive long-lived human-made radionuclides from contaminated water, even from acidic solutions (pH < 2). The interaction of GO with actinides including Am(III), Th(IV), Pu(IV), Np(V), U(VI) and typical fission products Sr(II), Eu(III) and Tc(VII) were studied, along with their sorption kinetics. Cation/GO coagulation occurs with the formation of nanoparticle aggregates of GO sheets, facilitating their removal. GO is far more effective in removal of transuranium elements from simulated nuclear waste solutions than other routinely used sorbents such as bentonite clays and activated carbon. These results point toward a simple methodology to mollify the severity of nuclear waste contamination, thereby leading to effective measures for environmental remediation.

Electric-double-layer field-effect transistors with ionic liquids.

Abstract: Charge carrier control is a key issue in the development of electronic functions of semiconductive materials. Beyond the simple enhancement of conductivity, high charge carrier accumulation can realize various phenomena, such as chemical reaction, phase transition, magnetic ordering, and superconductivity. Electric double layers (EDLs), formed at solid-electrolyte interfaces, induce extremely large electric fields. This results in a high charge carrier accumulation in the solid, much more effectively than solid dielectric materials. In the present review, we describe recent developments in the field-effect transistors (FETs) with gate dielectrics of ionic liquids, which have attracted much attention due to their wide electrochemical windows, low vapor pressures, and high chemical and physical stability. We explain the capacitance effects of ionic liquids, and describe the various combinations of ionic liquids and organic and inorganic semiconductors that are used to achieve such effects as high transistor performance, insulator-metal transitions, superconductivity, and ferromagnetism, in addition to the applications of the ionic-liquid EDL-FETs in logic devices. We discuss the factors controlling the mobility and threshold voltage in these types of FETs, and show the ionic liquid dependence of the transistor performance.

Eosin Y-sensitized graphitic carbon nitride fabricated by heating urea for visible light photocatalytic hydrogen evolution: the effect of the pyrolysis temperature of urea

Abstract: Graphitic carbon nitride (g-C3N4) was prepared by pyrolysis of urea at different temperatures (450–650 °C), and characterized by thermogravimetric and differential thermal analysis (TG-DTA), elemental analysis (C/H/N), X-ray diffraction (XRD), UV-vis diffuse reflectance spectra (DRS), Brunauer–Emmett–Teller (BET) analysis, Fourier transform-infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectra. The samples prepared at low temperatures (450 and 500 °C) are a mixture of g-C3N4 and impurities, whereas the samples prepared at high temperatures (550, 600 and 650 °C) should be g-C3N4 (polymeric carbon nitride). The polymerization degree of g-C3N4 for the prepared samples increases to a maximum at 600 °C with increasing pyrolysis temperature and then decreases, whereas the defect concentration changes conversely, that is, g-C3N4 prepared at 600 °C has the lowest defect concentration. Using Eosin Y (EY) and the prepared sample as the sensitizer and the matrix, respectively, the photocatalytic activity for hydrogen evolution from aqueous triethanolamine solution was investigated. The g-C3N4 prepared at 600 °C exhibits the highest sensitization activity. Under optimum conditions (1.25 × 10−5 mol L−1 EY and 7.0 wt% Pt), the maximal apparent quantum yield of EY-sensitized g-C3N4 prepared at 600 °C for hydrogen evolution is 18.8%. The highest activity can be attributed to the pure composition, the higher dye adsorption amount and the lowest defect concentration.

Fabrication of NiS modified CdS nanorod p–n junction photocatalysts with enhanced visible-light photocatalytic H2-production activity

Abstract: Production of hydrogen from photocatalytic water splitting has become an attractive research area due to the possibility of converting solar energy into green chemical energy. In this study, novel NiS nanoparticle (NP) modified CdS nanorod (NR) p-n junction photocatalysts were prepared by a simple two-step hydrothermal method. Even without the Pt co-catalyst, the as-prepared NiS NP-CdS NR samples exhibited enhanced visible-light photocatalytic activity and good stability for H2-production. The optimal NiS loading content was determined to be 5 mol%, and the corresponding H2-production rate reached 1131 μmol h(-1) g(-1), which is even higher than that of the optimized Pt-CdS NRs. It is believed that the assembly of p-type NiS NPs on the surface of n-type CdS NRs could form a large number of p-n junctions, which could effectively reduce the recombination rates of electrons and holes, thus greatly enhancing the photocatalytic activity. This work not only shows a possibility for the utilization of low cost NiS nanoparticles as a substitute for noble metals (such as Pt) in the photocatalytic H2-production but also provides a new insight into the design and fabrication of other new p-n junction photocatalysts for enhancing H2-production activity.

Conversion reactions for sodium-ion batteries

Abstract: Research on sodium-ion batteries has recently been rediscovered and is currently mainly focused on finding suitable electrode materials that enable cell reactions of high energy densities combined with low cost. Naturally, an assessment of potential electrode materials requires a rational comparison with the analogue reaction in lithium-ion batteries. In this paper, we systematically discuss the broad range of different conversion reactions for sodium-ion batteries based on their basic thermodynamic properties and compare them with their lithium analogues. Capacities, voltages, energy densities and volume expansions are summarized to sketch out the scope for future studies in this research field. We show that for a given conversion electrode material, replacing lithium by sodium leads to a constant shift in cell potential ΔEo(Li–Na) depending on the material class. For chlorides ΔEo(Li–Na) equals nearly zero. The theoretical energy densities of conversion reactions of sodium with fluorides or chlorides as positive electrode materials typically reach values between 700 W h kg−1 and 1000 W h kg−1. Next to the thermodynamic assessment, results on several conversion reactions between copper compounds (CuS, CuO, CuCl, CuCl2) and sodium are being discussed. Reactions with CuS and CuO were chosen because these compounds are frequently studied for conversion reactions with lithium. Chlorides are interesting because of ΔEo(Li–Na) ≈ 0 V. As a result of chloride solubility in the electrolyte, the conversion process proceeds at defined potentials under rather small kinetic limitations.

3D graphene–Fe3O4 nanocomposites with high-performance microwave absorption

Abstract: 3D Fe3O4–graphene nanocomposites were conveniently prepared via a direct hydrothermal grafting method. On the basis of the unique properties of both single-crystalline Fe3O4 and 3D chemically reduced graphene oxide, with characteristics such as ultralow density and high surface area, the as-prepared graphene–Fe3O4 nanocomposites showed high-performance microwave absorption ability and have the potential for application as advanced microwave absorbers.

Plasmonics in the ultraviolet with the poor metals Al, Ga, In, Sn, Tl, Pb, and Bi

Abstract: We discuss how the poor metals Al, Ga, In, Sn, Tl, Pb, and Bi can be used for plasmonics in the near to far ultraviolet (UV) range, similar to the noble metals Ag and Au in the visible (Vis) range. We first discuss the empirical dielectric functions of the poor metals, contrasting them with Ag and Au, and also fitting them to a Drude and multiple Lorentz oscillator form. Using Mie theory, we then compare the optical responses of spherical poor metal nanoparticles to noble metal ones. Finally, nanoparticle dimers are studied using a vectorial finite element method. We show how the poor metals exhibit large electric field enhancements in the UV, comparable to Au in the Vis, which makes them particularly attractive for sensing applications, such as surface enhanced Raman spectroscopy.

Selective photoredox using graphene-based composite photocatalysts

Abstract: Graphene (GR) has proven to be a promising candidate to construct effective GR-based composite photocatalysts with enhanced catalytic activities for solar energy conversion. During the past few years, various GR-based composite photocatalysts have been developed and applied in a myriad of fields. In this perspective review, compared with the traditional applications of GR-based nanocomposites for the "non-selective" degradation of pollutants, photo-deactivation of bacteria and water splitting to H2 and O2, we mainly focus on the recent progress in the applications of GR-based composite photocatalysts for "selective" organic transformations, including reduction of CO2 to renewable fuels, reduction of nitroaromatic compounds to amino compounds, oxidation of alcohols to aldehydes and acids, epoxidation of alkenes, hydroxylation of phenol, and oxidation of tertiary amines. The different roles of GR in these GR-based nanocomposite photocatalysts such as providing a photoelectron reservoir and performing as an organic dye-like macromolecular photosensitizer have been summarized. In addition, graphene oxide (GO) as a co-catalyst in GO-organic species photocatalysts and GO itself as a photocatalyst for selective reduction of CO2 have also been demonstrated. Finally, perspectives on the future research direction of GR-based composite photocatalysts toward selective organic redox transformations are discussed and it is clear that there is a wide scope of opportunities awaiting us in this promising research field.

Temperature dependent absorption cross-sections of O2–O2 collision pairs between 340 and 630 nm and at atmospherically relevant pressure

Abstract: The collisions between two oxygen molecules give rise to O4 absorption in the Earth atmosphere. O4 absorption is relevant to atmospheric transmission and Earth's radiation budget. O4 is further used as a reference gas in Differential Optical Absorption Spectroscopy (DOAS) applications to infer properties of clouds and aerosols. The O4 absorption cross section spectrum of bands centered at 343, 360, 380, 446, 477, 532, 577 and 630 nm is investigated in dry air and oxygen as a function of temperature (203–295 K), and at 820 mbar pressure. We characterize the temperature dependent O4 line shape and provide high precision O4 absorption cross section reference spectra that are suitable for atmospheric O4 measurements. The peak absorption cross-section is found to increase at lower temperatures due to a corresponding narrowing of the spectral band width, while the integrated cross-section remains constant (within <3%, the uncertainty of our measurements). The enthalpy of formation is determined to be ΔH250 = −0.12 ± 0.12 kJ mol−1, which is essentially zero, and supports previous assignments of O4 as collision induced absorption (CIA). At 203 K, van der Waals complexes (O2-dimer) contribute less than 0.14% to the O4 absorption in air. We conclude that O2-dimer is not observable in the Earth atmosphere, and as a consequence the atmospheric O4 distribution is for all practical means and purposes independent of temperature, and can be predicted with an accuracy of better than 10−3 from knowledge of the oxygen concentration profile.

Towards efficient solar hydrogen production by intercalated carbon nitride photocatalyst

Abstract: The development of efficient photocatalytic material for converting solar energy to hydrogen energy as viable alternatives to fossil-fuel technologies is expected to revolutionize energy shortage and environment issues. However, to date, the low quantum yield for solar hydrogen production over photocatalysts has hindered advances in the practical applications of photocatalysis. Here, we show that a carbon nitride intercalation compound (CNIC) synthesized by a simple molten salt route is an efficient polymer photocatalyst with a high quantum yield. We found that coordinating the alkali metals into the C–N plane of carbon nitride will induce the un-uniform spatial charge distribution. The electrons are confined in the intercalated region while the holes are in the far intercalated region, which promoted efficient separation of photogenerated carriers. The donor-type alkali metal ions coordinating into the nitrogen pots of carbon nitrides increase the free carrier concentration and lead to the formation of novel nonradiative paths. This should favor improved transport of the photogenerated electron and hole and decrease the electron–hole recombination rate. As a result, the CNIC exhibits a quantum yield as high as 21.2% under 420 nm light irradiation for solar hydrogen production. Such high quantum yield opens up new opportunities for using cheap semiconducting polymers as energy transducers.

Amphiphile nanoarchitectonics: from basic physical chemistry to advanced applications

Abstract: Amphiphiles, either synthetic or natural, are structurally simple molecules with the unprecedented capacity to self-assemble into complex, hierarchical geometries in nanospace. Effective self-assembly processes of amphiphiles are often used to mimic biological systems, such as assembly of lipids and proteins, which has paved a way for bottom-up nanotechnology with bio-like advanced functions. Recent developments in nanostructure formation combine simple processes of assembly with the more advanced concept of nanoarchitectonics. In this perspective, we summarize research on self-assembly of amphiphilic molecules such as lipids, surfactants or block copolymers that are a focus of interest for many colloid, polymer, and materials scientists and which have become increasingly important in emerging nanotechnology and practical applications, latter of which are often accomplished by amphiphile-like polymers. Because the fundamental science of amphiphiles was initially developed for their solution assembly then transferred to assemblies on surfaces as a development of nanotechnological techniques, this perspective attempts to mirror this development by introducing solution systems and progressing to interfacial systems, which are roughly categorized as (i) basic properties of amphiphiles, (ii) self-assembly of amphiphiles in bulk phases, (iii) assembly on static surfaces, (iv) assembly at dynamic interfaces, and (v) advanced topics from simulation to application. This progression also represents the evolution of amphiphile science and technology from simple assemblies to advanced assemblies to nanoarchitectonics.

Three-dimensional B,N-doped graphene foam as a metal-free catalyst for oxygen reduction reaction

Abstract: Using a modified chemical vapor deposition (CVD) method, we have prepared a class of new graphene foams (GFs) doped with nitrogen, boron or both. Nitrogen-doped graphene foams (N-GFs) with a nitrogen doping level of 3.1 atom% were prepared by CVD of CH4 in the presence of NH3 while boron-doped graphene foams (B-GFs) with a boron doping level of 2.1 atom% were produced by using toluene and triethyl borate as a carbon and a boron source. On the other hand, graphene foams co-doped with nitrogen (4.5 atom%) and boron (3 atom%) (BN-GFs) were prepared by CVD using melamine diborate as the precursor. In all cases, scanning electron microscope (SEM) images revealed well-defined foam-like microstructures, while electrochemical measurements showed much higher electrocatalytic activities toward oxygen reduction reaction for the doped graphene foams than their undoped counterparts.

Catalytic activity of Co–Nx/C electrocatalysts for oxygen reduction reaction: a density functional theory study

Abstract: First-principles DFT computations are performed to explain the origin and the mechanism of oxygen reduction reaction (ORR) on Co–Nx (x = 2, 4) based self-assembled carbon supported electrocatalysts in alkaline and acidic media. The results show that the formation of graphitic Co–N4 defect is energetically more favorable than the formation of graphitic Co–N2 defect. Furthermore graphitic Co–N4 defects are predicted to be stable at all potentials (U = 0–1.23 V) in the present study while Co–N2 defects are predicted to be unstable at high potentials. Therefore the Co–N4 defect is predicted to be the dominant in-plane graphitic defect in Co–Nx/C electrocatalysts. O2 chemisorbs to Co–N4 and Co–N2 defects indicating that both defect motifs are active for the reduction of O2 to peroxide. However, the weak interaction between peroxide and Co–N4 defect shows that this defect does not promote complete ORR and a second site for the reduction of peroxide is required, supporting a 2 × 2e− dual site ORR mechanism independent of pH of the electrolyte. In contrast, the much stronger interaction between peroxide and Co–N2 defect supports a 2 × 2e− single site ORR mechanism in alkaline and acidic media.

Inhibition of ice nucleation by slippery liquid-infused porous surfaces (SLIPS)

Abstract: Ice repellent coatings have been studied and keenly sought after for many years, where any advances in the durability of such coatings will result in huge energy savings across many fields. Progress in creating anti-ice and anti-frost surfaces has been particularly rapid since the discovery and development of slippery, liquid infused porous surfaces (SLIPS). Here we use SLIPS-coated differential scanning calorimeter (DSC) pans to investigate the effects of the surface modification on the nucleation of supercooled water. This investigation is inherently different from previous studies which looked at the adhesion of ice to SLIPS surfaces, or the formation of ice under high humidity conditions. Given the stochastic nature of nucleation of ice from supercooled water, multiple runs on the same sample are needed to determine if a given surface coating has a real and statistically significant effect on the nucleation temperature. We have cycled supercooling to freezing and then thawing of deionized water in hydrophilic (untreated aluminum), hydrophobic, superhydrophobic, and SLIPS-treated DSC pans multiple times to determine the effects of surface treatment on the nucleation and subsequent growth of ice. We find that SLIPS coatings lower the nucleation temperature of supercooled water in contact with statistical significance and show no deterioration or change in the coating performance even after 150 freeze–thaw cycles.