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Journal: Physical chemistry chemical physics : PCCP


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.

Concepts: Carbon dioxide, Nuclear physics, Chemical element, Colloid, Nuclear fission, Activated carbon, Radioactive contamination, Radioactive waste


Plasmonic nanostructures have played a significant role in the field of nanotechnology due to their unprecedented ability to concentrate light at the nanometre scale, which renders them precious for various sensing applications. The adsorption of plasmonic nanoparticles and nanostructures onto solid substrates in a controlled manner is a crucial process for the fabrication of nanoplasmonic devices, in which the nanoparticles amplify the electromagnetic fields for enhanced device performance. In this perspective article we summarize recent developments in the fabrication of flexible nanoplasmonic devices for sensing applications based on surface enhanced Raman scattering (SERS) and localized surface plasmon resonance (LSPR) shifts. We introduce different types of flexible substrates such as filter paper, free-standing nanofibres, elastomers, plastics, carbon nanotubes and graphene, for the fabrication of low-cost flexible nanoplasmonic devices. Various techniques are described that allow impregnation of such flexible substrates with plasmonic nanoparticles, including solution processes, physical vapour deposition and lithographic techniques. From the discussion in this Perspective, it is clear that highly sensitive and reproducible flexible plasmonic devices can currently be fabricated on a large scale at relatively low-cost, toward real-world applications in diagnostics and detection.

Concepts: Electromagnetism, Nanoparticle, Nanotechnology, Surface plasmon resonance, Plasmon, Plasma oscillation, Waves in plasmas


Reactive dynamics simulations with the reactive force field (ReaxFF) were performed in NVE ensembles to study the sintering of two solid calcium oxide (CaO) particles with and without CO(2) chemisorption. The simulated sintering conditions included starting adsorption temperatures at 1000 K and 1500 K and particle separation distances of 0.3 and 0.5 nm. The results revealed that the expansion of sorbent particles during CO(2) chemisorption was attributed to the sintering of two CaO-CaO particles. Increasing the adsorption temperature resulted in more particle expansion and sintering. The shorter the distance between two particles, the faster the rate of sintering during CO(2) adsorption. A detailed analysis on atom spatial variations revealed that the sorbent particles with a larger separation distance had a larger CO(2) uptake because of less sintering incurred. The chemisorptions of CO(2) on CaO particles sintered at high adsorption temperatures were also simulated to mimic the process of sorbent regeneration. It was found that regeneration would be more difficult for sintered particles than for fresh particles. In addition, a possible sintering barrier, magnesium oxide (MgO), was introduced to prevent CaO particles from sintering during CO(2) chemisorption. It was found that the MgO particles could reduce the sintering of CaO particles during CO(2) chemisorption. Simulation results from this study provided some guidelines on synthesizing or selecting sorbents with less sintering effect for multiple CO(2) adsorption-regeneration cycles.

Concepts: Magnesium, Calcium, Oxide, Oxides, Calcium oxide, Magnesium oxide, Beryllium oxide, Strontium oxide


α-Fe(2)O(3) (hematite) photoanodes for the oxygen evolution reaction (OER) were prepared by a cost-efficient sol-gel procedure. Due to low active photoelectrochemical properties observed, it is assumed that the sol-gel procedure leads to hematite films with defects and surface states on which generated charge carriers are recombined or immobilized in trap processes. Electrochemical activation was proven to diminish unfavourable surface groups to some extent. More efficiently, a plasma treatment improves significantly the photoelectrochemical properties of the OER. X-ray photoelectron spectroscopy (XPS) analysis reveals an oxygen enriched surface layer with new oxygen species which may be responsible for the improved electrochemical activity. Due to surface photovoltage an increased fraction of transferred charge carriers from these newly produced surface defects are identified.

Concepts: Photosynthesis, Spectroscopy, Oxygen, X-ray, Iron, Oxide, X-ray photoelectron spectroscopy, Oxygen evolution


The bonding characteristics in cysteine-gold cluster complexes represented by thiolate (Au(n)·Cys(S) (n = 1, 3, 5, 7)) and thiol (Au(n)·Cys(SH) (n = 2, 4, 6, 8)) is investigated by density functional theory with 6-31G(d,p) and Lanl2DZ hybrid basis sets. The complexes exhibit very different bonding characteristic between these two forms. In the Au(n)·Cys(S) complexes, the charge transfers from gold clusters to sulfur atoms. The number of S-Au bonds in the Au(n)·Cys(S) complexes evolves from one to two when n is greater than three. For n equals three, i.e. Au(3)·Cys(S), its ground state only has one S-Au bond. While the only S-Au bond in Au(1)·Cys(S) is mainly covalent, the nature of the S-Au bond in other thiolates is featured with the combination of covalent and donor-acceptor interactions. In particular, one stable isomer of Au(3)·Cys(S) with two S-Au bonds, which is 2 kcal mol(-1) higher in energy than the corresponding ground state, consists of one covalent and one donor-acceptor S-Au bond explicitly. Moreover, the localized three center two electron bonds are formed within the Au clusters, which facilitates the formation of the two S-Au bonds in Au(5)·Cys(S) and Au(7)·Cys(S) complexes. In the Au(n)·Cys(SH) complexes, the donor-acceptor interaction prevails in the Au-SH bond by transferring lone pair electrons from the sulfur atom to the adjacent gold atom. Interestingly, the orbital with much more 6s-component in Au(4)·Cys(SH) enhances the donor-acceptor bonding character, thus yields the strongest bonding among all the Au(n)·Cys(SH) complexes studied in this paper. In general, the bonding strength between gold clusters and cysteine is positively correlated with the S-Au overlap-weighted bond order, but negatively correlated with the S-Au bond length. Lastly, the covalent and donor-acceptor S-Au bond strength is computed to be 48 and 18 kcal mol(-1), respectively.

Concepts: Electron, Atom, Chemical bond, Disulfide bond, Quantum chemistry, Bond order, Thiol, Bond length


Sponge-like porous Ni(OH)(2)-NiF(2) composite (PNC) film was successfully synthesized by the anodization of nickel in a NH(4)F and H(3)PO(4) containing electrolyte. Thanks to the good conductivity and the highly porous architecture, PNC exhibited not only a high specific capacitance, but also a superior rate capability and a good cyclability (2090 F g(-1) at 10 mV s(-1), capacitance >1200 F g(-1) at 100 A g(-1) after 2000 cycles). Anodization of nickel is proven to be fast and facile and can be easily scaled up. The method described here is promising for the fabrication of supercapacitor electrodes with excellent performance.

Concepts: Electrochemistry, Physical chemistry, Battery, Electrolyte, Electrode, Electrolysis, Anode, Electroplating


Vibronic spectra of 9H-adenine, 9-acetyladenine and several alkyladenines have been recorded by resonant two-photon ionization spectroscopy of the laser-desorbed molecules, entrained in a molecular beam. While adenine and the alkyladenines exhibit similar electronic spectra, 9-acetyladenine behaves considerably different. Theoretical absorption spectra of 9H-adenine and 9-acetyladenine were calculated using the combined density functional theory/multi-reference configuration interaction approach and using second order coupled cluster theory, in order to explain striking differences in the experimental spectra. The major differences between the 9H-adenine and the 9-acetyladenine absorption spectra can be traced back to the different configurations, which contribute to the excitations, both of the lowest ππ* and the nπ* states. While the excitations in 9H-adenine are localized in the chromophore, they show considerable charge transfer character from the chromophore to the acetyl group in the case of 9-acetyladenine.

Concepts: Scientific method, Atom, Difference, Quantum chemistry, Theory, Acetyl, Coupled cluster, Acetoxy group


Mesoporous titanium nitride (TiN) with high surface area and good electrical conductivity was prepared by a novel solid-solid phase separation method from a Zn containing titanium oxide, Zn(2)TiO(4). The PXRD shows single phase rocksalt structure of TiN with a domain size of 25 nm. The conductivity of mesoporous TiN at 35 bar is 395 S cm(-1). The Pt/TiN catalyst exhibits more negative onset potential for methanol electrooxidation (0.15 V) than Pt/C (0.22 V), showing a higher intrinsic electrocatalytic activity, while its peak current density (228 mA mg(-1) Pt) is ∼1.5 times higher than that of Pt/C (148 mA mg(-1) Pt). The Pt/TiN catalyst also demonstrates excellent long-term stability. This work provides an efficient method to prepare mesoporous nitrides as a promising support towards oxidation of small organic molecules in fuel cells.

Concepts: Oxygen, Hydrogen, Electrochemistry, Nitrogen, Aluminium, Electrical conductivity, Nitrides, Titanium nitride


The dynamics of iron tetracarbonyl olefin complexes has been investigated using two-dimensional infrared (2D-IR) spectroscopy. Cross peaks between all CO-stretching bands show that the CO-stretch modes are coupled, and from the cross-peak anisotropies we can confirm previous assignments of the absorption bands. From the pump-probe delay dependence of the diagonal peaks in the 2D-IR spectrum we obtain a correlation time of ∼3 ps for the spectral fluctuations of the CO-stretch modes. We observe a multi-exponential pump-probe delay dependence of the cross-peak intensities, with rate constants ranging from 0.1 ps(-1) to 0.6 ps(-1). To determine whether this delay dependence originates from fluxionality of the complex or from intramolecular vibrational relaxation (IVR), we modulate the free-energy barrier of fluxional rearrangement by varying the pi-backbonding capacities of the olefin ligand in two iron tetracarbonyl olefin complexes: Fe(CO)(4)(cinnamic acid) and Fe(CO)(4)(dimethyl fumarate). Since the pi-backbonding strongly influences the rate of fluxionality, comparing the dynamics in the two complexes allows us to determine to what extent the observed dynamics is caused by fluxionality. We conclude that on the time scale of our experiments (up to 100 ps) the cross-peak dynamics in the iron complexes is determined by intramolecular vibrational energy relaxation. Hence, in contrast to previously investigated irontricarbonyl and ironpentacarbonyl complexes, iron tetracarbonyl olefin complexes exhibit no fluxionality on the picosecond time scale.

Concepts: Time, Spectroscopy, Observation, Complex, Hypothesis, Spectrum, Iron pentacarbonyl, Fluxional molecule


Polyvinylidene fluoride (PVDF) ultrafiltration membranes were investigated for the first time in vanadium redox flow battery (VFB) applications. Surprisingly, PVDF ultrafiltration membranes with hydrophobic pore walls and relatively large pore sizes of several tens of nanometers proved able to separate vanadium ions and protons efficiently, thus being suitable as a VFB separator. The ion selectivity of this new type of VFB membrane could be tuned readily by controlling the membrane morphology via changes in the composition of the membrane casting solution, and the casting thickness. The results showed that the PVDF membranes offered good performances and excellent stability in VFB applications, where it could, performance-wise, truly substitute Nafion in VFB applications, but at a much lower cost.

Concepts: Electron, Hydrogen, Chemistry, Atom, Rechargeable battery, Polyvinylidene fluoride, Vanadium redox battery, Vanadium