Recent Advances on Pt-Free Electro-Catalysts for Dye-Sensitized Solar Cells

Since Prof. Grätzel and co-workers achieved breakthrough progress on dye-sensitized solar cells (DSSCs) in 1991, DSSCs have been extensively investigated and wildly developed as a potential renewable power source in the last two decades due to their low cost, low energy-intensive processing, and high roll-to-roll compatibility. During this period, the highest efficiency recorded for DSSC under ideal solar light (AM 1.5G, 100 mW cm⁻²) has increased from ~7% to ~14.3%. For the practical use of solar cells, the performance of photovoltaic devices in several conditions with weak light irradiation (e.g., indoor) or various light incident angles are also an important item. Accordingly, DSSCs exhibit high competitiveness in solar cell markets because their performances are less affected by the light intensity and are less sensitive to the light incident angle. However, the most used catalyst in the counter electrode (CE) of a typical DSSC is platinum (Pt), which is an expensive noble metal and is rare on earth. To further reduce the cost of the fabrication of DSSCs on the industrial scale, it is better to develop Pt-free electro-catalysts for the CEs of DSSCs, such as transition metallic compounds, conducting polymers, carbonaceous materials, and their composites. In this article, we will provide a short review on the Pt-free electro-catalyst CEs of DSSCs with superior cell compared to Pt CEs; additionally, those selected reports were published within the past 5 years.     

The simplest non-minimal matter–geometry coupling in the <Emphasis Type="Italic">f</Emphasis>(<Emphasis Type="Italic">R</Emphasis>, <Emphasis Type="Italic">T</Emphasis>) cosmology

f(R, T) gravity is an extended theory of gravity in which the gravitational action contains general terms of both the Ricci scalar R and the trace of the energy-momentum tensor T. In this way, f(R, T) models are capable of describing a non-minimal coupling between geometry (through terms in R) and matter (through terms in T). In this article we construct a cosmological model from the simplest non-minimal matter–geometry coupling within the f(R, T) gravity formalism, by means of an effective energy-momentum tensor, given by the sum of the usual matter energy-momentum tensor with a dark energy contribution, with the latter coming from the matter–geometry coupling terms. We apply the energy conditions to our solutions in order to obtain a range of values for the free parameters of the model which yield a healthy and well-behaved scenario. For some values of the free parameters which are submissive to the energy conditions application, it is possible to predict a transition from a decelerated period of the expansion of the universe to a period of acceleration (dark energy era). We also propose further applications of this particular case of the f(R, T) formalism in order to check its reliability in other fields, rather than cosmology.     

Photo-Controlled Gating of Selective Bacterial Membrane Interaction and Enhanced Antibacterial Activity for Wound Healing

Reversible biointerfaces are essential for on-demand molecular recognition to regulate stimuli-responsive bioactivity such as specific interactions with cell membranes. The reversibility on a single platform allows the smart material to kill pathogens or attach/detach cells. Herein, we introduce a 2D-MoS₂ functionalized with cationic azobenzene that interacts selectively with either Gram-positive or Gram-negative bacteria in a light-gated fashion. The trans conformation ( trans -Azo-MoS₂ ) selectively kills Gram-negative bacteria, whereas the cis form ( cis -Azo-MoS₂ ), under UV light, exhibits antibacterial activity against Gram-positive strains. The mechanistic investigation indicates that the cis -Azo-MoS₂ exhibits higher affinity towards the membrane of Gram-positive bacteria compared to trans -Azo-MoS₂ . In case of Gram-negative bacteria, trans -Azo-MoS₂ internalizes more efficiently than cis -Azo-MoS₂ and generates intracellular ROS to kill the bacteria. While the trans -Azo-MoS₂ exhibits strong electrostatic interactions and internalizes faster into Gram-negative bacterial cells, cis -Azo-MoS₂ primarily interacts with Gram-positive bacteria through hydrophobic and H-bonding interactions. The difference in molecular mechanism leads to photo-controlled Gram-selectivity and enhanced antibacterial activity. We found strain-specific and high bactericidal activity (minimal bactericidal concentration, 0.65 μg/ml) with low cytotoxicity, which we extended to wound healing applications. This methodology provides a single platform for efficiently switching between conformers to reversibly control the strain-selective bactericidal activity regulated by light.     

Synthesis of epoxy-terminated polymers by radical polymerization using α-(t-butylperoxymethyl)styrene as chain transfer agent

Epoxy-terminated polystyrene has been synthesized by radical polymerization using α-(t-butylperoxymethyl) styrene (TPMS) as the chain transfer agent. The chain transfer constants were found to be 0.66 and 0.80 at 60 and 70°C, respectively. The presence of epoxy end groups was confirmed by functional group modification of epoxide to aldehyde by treatment with BF₃.Et₂O. Thermal stability of TPMS was followed by differential scanning calorimetry and iodimetry. Thermal decomposition of TPMS in toluene follows first order kinetics with an activation energy of 23 kcal/mol. © 1996 John Wiley & Sons, Inc.     

An optimized ion trap geometry to measure quadrupole shifts of ~(171)Yb~+ clocks

We propose a new ion-trap geometry to carry out accurate measurements of the quadrupole shifts in the ~(171)Yb ion.This trap will minimize the quadrupole shift due to the harmonic component of the confining potential by an order of magnitude.This will be useful to reduce the uncertainties in the clock frequency measurements of the 6s ~2S_(1/2)→4f~(13)6s~2 ~2F_(7/2)and 6s ~2S_(1/2)→5d~2D_(3/2) transitions,from which we can deduce the precise values of the quadrupole moments(0s) of the 4f~(13)6s~2 ~2F_(7/2) and 5d~2D_(3/2) states.Moreover,it may be able to affirm the validity of the measured 0 value of the4f~(13)6s~2~2F_(7/2) state,for which three independent theoretical studies defer almost by one order of magnitude from the measurement.We also calculate 0s using the relativistic coupled-cluster(RCC) method.We use these 0 values to estimate the quadrupole shift that can be measured in our proposed ion trap experiment.     

Polymeric Nanocomposites of Polyurethane Block Copolymers and Functionalized Multi‐Walled Carbon Nanotubes as Crosslinkers

Summary: We report on a new route to synthesize polymeric carbon nanotube‐polyurethane (PU) nanocomposites. Multi‐walled carbon nanotubes (MWNTs) functionalized by chemical modification were incorporated as a crosslinker in prepolymer, which was prepared from a reaction of 4,4′‐methylene bis(phenylisocyanate) and poly(ε‐caprolactone)diol. The reinforcing effect of carbon nanotubes in crosslinked MWNT‐PU nanocomposites was more pronounced as compared to that in conventional MWNT‐PU nanocomposites. The optimum content of chemically modified MWNTs for crosslinking with polyurethane was determined to be approximately 4 wt.‐% in our samples, based on observation of a NCO peak in FT‐IR spectroscopy. MWNT‐crosslinked polyurethane containing 4 wt.‐% modified MWNTs showed the highest modulus and tensile strength among the composites and pure PU. The presence of functionalized MWNTs in the polymeric nanocomposite yielded enhancement in the thermal stability due to crosslinking of the MWNTs with PU.

Possible configuration for MWNT‐PU nanocomposite molecules and FT‐IR spectra of samples obtained during reaction of prepolymer with functionalized MWNTs (second step).     

First report on a semicrystalline vinyl polyperoxide

Vinyl polyperoxides constitute a narrow but important class of polymers because they show several novel physicochemical properties. Having a highly flexible backbone, they are also highly viscous amorphous materials. Interestingly, we found that poly(α-phenyl styrene peroxide) (PAPSP) forms a crystalline structure that is perhaps the first crystalline structure known in the family of polyperoxides. From detailed powder X-ray diffraction analysis and simulation studies, PAPSP was found to have a helical conformation. Another interesting feature of PAPSP is that it is highly thermally stable and photostable compared to other known polyperoxides. This makes PAPSP the most eligible candidate for exploring novel application potentials. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4033–4036, 1999     

Synthesis of zirconocene-acetylene and zirconocene-diacetylene polymer

A new class of organometallic polymer having a backbone of conjugated Poly-yne and Zr-metal atoms has been prepared. Trichloroethylene (TCE) and Hexachlorobutadiene (HCB) are quantitatively converted by n-butyllithium to dilithioacetylene (LiCCLi) and dilithiodiacetylene (Li CC CC Li) respectively. Quenching with Cp₂*ZrCl₂ affords high yields of the polymers Zr(Cp₂*)CC_n and Zr(Cp₂*)CC CC_n where Cp* = C₅(CH₃)₅ = pentamethyl cyclopentadienyl. The Cp₂*ZrCl₂ and the polymers were characterized by viscosity, molecular weight, elemental analysis, FTIR, NMR spectra, and TGA. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3899–3902, 1999     

Reaction of polyperoxides with triphenylphosphine

The triphenylphosphine deoxygenation of the polyperoxides, poly(styrene peroxide), poly(methyl methacrylate peroxide), and poly(α-methylstyrene peroxide) proceed via the phosphorane intermediates, which in the presence of moisture hydrolyze to give the respective diols. At higher temperatures and under dry conditions the phosphorane decomposes into epoxide and triphenylphosphine oxide. The reaction has been studied by ¹H-, ¹³C-, and ³¹P-NMR spectroscopy. The results obtained are consistent with a concerted insertion of the biphile, triphenylphosphine, into the peroxy bond and this reaction pathway seems to be new as far as the chemistry of polyperoxides is concerned. Though the aim of this investigation was to test the selective deoxygenation of polyperoxide by triphenylphosphine as a method of preparing polyethers, it turned out to be a fruitful method of synthesis of stereospecific diols. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1167–1172, 1997     

Manipulating Nonclassicality via Quantum State Engineering Processes: Vacuum Filtration and Single Photon Addition

The effect of two quantum state engineering processes that can be used to burn a hole at vacuum in the photon number distribution of quantum states of radiation field is compared using various witnesses of lower- and higher-order nonclassicality as well as a measure of nonclassicality. Specifically, the modification in nonclassical properties due to vacuum state filtration and a single photon addition on an even coherent state, binomial state, and Kerr state are investigated using the criteria of lower- and higher-order antibunching, squeezing, and sub-Poissonian photon statistics. Further, the amount of nonclassicality present in these engineered quantum states having enormous applications in continuous variable quantum communication is quantified and analyzed by using an linear entropy-based entanglement potential. It is observed that all the quantum states studied here are highly nonclassical, and the hole-burning processes can introduce/enhance nonclassical features. However, it is not true in general. A hole at vacuum implies a maximally nonclassical state (as far as Lee's nonclassical depth is concerned), but a particular process of hole burning at vacuum does not ensure the existence of any particular nonclassical feature. Specifically, lower- and higher-order squeezing are not observed for photon-added and vacuum filtered even coherent states.