Electron transport via tyrosine-doped oligo-alanine peptide junctions: role of charges and hydrogen bonding.

A way of modulating the solid-state electron transport (ETp) properties of oligopeptide junctions is presented by charges and internal hydrogen bonding, which affect this process markedly. The ETp properties of a series of tyrosine (Tyr)-containing hexa-alanine peptides, self-assembled in monolayers and sandwiched between gold electrodes, are investigated in response to their protonation state. Inserting a Tyr residue into these peptides enhances the ETp carried via their junctions. Deprotonation of the Tyr-containing peptides causes a further increase of ETp efficiency that depends on this residue's position. Combined results of molecular dynamics simulations and spectroscopic experiments suggest that the increased conductance upon deprotonation is mainly a result of enhanced coupling between the charged C-terminus carboxylate group and the adjacent Au electrode. Moreover, intra-peptide hydrogen bonding of the Tyr hydroxyl to the C-terminus carboxylate reduces this coupling. Hence, the extent of such a conductance change depends on the Tyr-carboxylate distance in the peptide's sequence.

Boosting Photocatalytic Activity Using Reduced Graphene Oxide (RGO)/Semiconductor Nanocomposites: Issues and Future Scope.

Semiconductor nanoparticles are promising materials for light-driven processes such as solar-fuel generation, photocatalytic pollutant remediation, and solar-to-electricity conversion. Effective application of these materials alongside light can assist in reducing the dependence on fossil-fuel driven processes and aid in resolving critical environmental issues. However, severe recombination of the photogenerated charge-carriers is a persistent bottleneck in several semiconductors, particularly those that contain multiple cations. This issue typically manifests in the form of reduced lifetime of the photoexcited electrons-holes leading to a decrease in the quantum efficiency of various light-driven applications. On the other hand, semiconducting oxides or sulfides, coupled with reduced graphene oxide (RGO), have drawn a considerable interest recently, partly because of the RGO enhancing charge separation and transportation through its honeycomb sp2 network structure. High electron mobility, conductivity, surface area, and cost-effectiveness are the hallmark of the RGO. This Mini-Review focuses on (1) examining the approach to the integration of RGO with semiconductors to produce binary nanocomposites; (2) insights into the microstructure interface, which plays a critical role in leveraging charge transport; (3) key examples of RGO composites with oxide and sulfide semiconductors with photocatalysis as application; and (4) strategies that have to be pursued to fully leverage the benefit of RGO in RGO/semiconductors to attain high photocatalytic activity for a sustainable future. This Mini-Review focuses on areas requiring additional exploration to fully understand the interfacial science of RGO and semiconductor, for clarity regarding the interfacial stability between RGO and the semiconductor, electronic coupling at the heterojunction, and morphological properties of the nanocomposites. We believe that this Mini-Review will assist with streamlining new directions toward the fabrication of RGO/semiconductor nanocomposites with higher photocatalytic activity for solar-driven multifunctional applications.

Impact of SnF2 Addition on the Chemical and Electronic Surface Structure of CsSnBr3.

We report on the chemical and electronic structure of cesium tin bromide (CsSnBr3) and how it is impacted by the addition of 20 mol % tin fluoride (SnF2) to the precursor solution, using both surface-sensitive lab-based soft X-ray photoelectron spectroscopy (XPS) and near-surface bulk-sensitive synchrotron-based hard XPS (HAXPES). To determine the reproducibility and reliability of conclusions, several (nominally identically prepared) sample sets were investigated. The effects of deposition reproducibility, handling, and transport are found to cause significant changes in the measured properties of the films. Variations in the HAXPES-derived compositions between individual sample sets were observed, but in general, they confirm that the addition of 20 mol % SnF2 improves coverage of the titanium dioxide substrate by CsSnBr3 and decreases the oxidation of SnII to SnIV while also suppressing formation of secondary Br and Cs species. Furthermore, the (surface) composition is found to be Cs-deficient and Sn-rich compared to the nominal stoichiometry. The valence band (VB) shows a SnF2-induced redistribution of Sn 5s-derived density of states, reflecting the changing SnII/SnIV ratio. Notwithstanding some variability in the data, we conclude that SnF2 addition decreases the energy difference between the VB maximum of CsSnBr3 and the Fermi level, which we explain by defect chemistry considerations.

On the influence of multiple cations on the in-gap states and phototransport properties of iodide-based halide perovskites.

In-gap states in solar cell absorbers that are recombination centers determine the cell's photovoltaic performance. Using scanning tunneling spectroscopy (STS), temperature-dependent photoconductivity and steady-state photocarrier-grating measurements we probed, directly and indirectly, the energies of such states, both at the surface and in the bulk of two similar, but different halide perovskites, the single cation MAPbI3 (here MAPI) and the mixed cation halide perovskite, FA0.79MA0.16Cs0.05Pb(I0.83Br0.17)3 (here MCHP). We found a correlation between the energy distribution of the in-gap states, as determined by STS measurements, and their manifestation in the photo-transport parameters of the MCHP absorbers. In particular, our results suggest that the in-gap recombination centers in the MCHP are shallower than those of MAPI. This can be one explanation for the better photovoltaic efficiency of the former.

Mobility-Lifetime Products in MAPbI3 Films.

Photovoltaic solar cells operate under steady-state conditions that are established during the charge carrier excitation and recombination. However, to date no model of the steady-state recombination scenario in halide perovskites has been proposed. In this Letter we present such a model that is based on a single type of recombination center, which is deduced from our measurements of the illumination intensity dependence of the photoconductivity and the ambipolar diffusion length in those materials. The relation between the present results and those from time-resolved measurements, such as photoluminescence that are commonly reported in the literature, is discussed.

Cesium Enhances Long-Term Stability of Lead Bromide Perovskite-Based Solar Cells.

Direct comparison between perovskite-structured hybrid organic-inorganic methylammonium lead bromide (MAPbBr3) and all-inorganic cesium lead bromide (CsPbBr3), allows identifying possible fundamental differences in their structural, thermal and electronic characteristics. Both materials possess a similar direct optical band gap, but CsPbBr3 demonstrates a higher thermal stability than MAPbBr3. In order to compare device properties, we fabricated solar cells, with similarly synthesized MAPbBr3 or CsPbBr3, over mesoporous titania scaffolds. Both cell types demonstrated comparable photovoltaic performances under AM1.5 illumination, reaching power conversion efficiencies of ∼6% with a poly aryl amine-based derivative as hole transport material. Further analysis shows that Cs-based devices are as efficient as, and more stable than methylammonium-based ones, after aging (storing the cells for 2 weeks in a dry (relative humidity 15-20%) air atmosphere in the dark) for 2 weeks, under constant illumination (at maximum power), and under electron beam irradiation.

Encapsulating Bi2Ti2O7 (BTO) with reduced graphene oxide (RGO): an effective strategy to enhance photocatalytic and photoelectrocatalytic activity of BTO.

Multimetal oxides (AxByOz) offer a higher degree of freedom compared to single metal oxides (AOx) in that these oxides facilitate (i) designing nanomaterials with greater stability, (ii) tuning of the optical bandgap, and (iii) promoting visible light absorption. However, all AxByOz materials such as pyrochlores (A2B2O7)--referred to here as band-gap engineered composite oxide nanomaterials or BECONs--are traditionally prone to severe charge recombination at their surface. To alleviate the charge recombination, an effective strategy is to employ reduced graphene oxide (RGO) as a charge separator. The BECON and the RGO with oppositely charged functional groups attached to them can be integrated at the interface by employing a simple electrostatic self-assembly approach. As a case study, the approach is demonstrated using the Pt-free pyrochlore bismuth titanate (BTO) with RGO, and the application of the composite is investigated for the first time. When tested as a photocatalyst toward hydrogen production, an increase of ∼ 250% using BTO in the presence of RGO was observed. Further, photoelectrochemical measurements indicate an enhancement of ∼ 130% in the photocurrent with RGO inclusion. These two results firmly establish the viability of the electrostatic approach and the inclusion of RGO. The merits of the RGO addition is identified as (i) the RGO-assisted improvement in the separation of the photogenerated charges of BTO, (ii) the enhanced utilization of the charges in a photocatalytic process, and (iii) the maintenance of the BTO/RGO structural integrity after repeated use (established through reusability analysis). The success of the self-assembly strategy presented here lays the foundation for developing other forms of BECONs, belonging to perovskites (ABO3), sillenite (A12BO20), or delafossite (ABO2) groups, hitherto written off due to limited or no photoelectrochemicalactivity.

A unique architecture based on 1 D semiconductor, reduced graphene oxide, and chalcogenide with multifunctional properties.

A unique heterostructured optoelectronic material (HOM), consisting of a reduced graphene oxide (RGO) layer with spatially distributed CdS, suspended by zinc oxide (ZnO) nanorods, is presented. The key features of this HOM are the assembly of the components in a manner so as to realize an effective integration between the constituents and the ability to modify the electronic properties of the RGO. For the first time, the location of RGO (as a suspended layer) along with the tuning of its charge-transport properties (n-/p-type) and its influence on the photo(electro)chemical processes has been examined systematically by using this ZnO/RGO/CdS HOM as a case study. The n-type RGO interlayer facilitates >100 % increase in the photocurrent density and 25 % increase in the photodegradation of a dye, compared to ZnO/CdS, thus demonstrating its multifunctionality. At 3.2 mA cm(-2) , this HOM architecture helps to achieve the highest photocurrent density utilizing ZnO, RGO, and CdS as building blocks in any form. The work is significant for the following reasons: i) other one dimensional (1D) oxides/chalcogenides or 1D oxides/dyes may be designed with similar architectures; ii) HOMs with tunable optical absorbance and charge-transport properties could be realized; iii) related application areas (e.g., sensing or solar fuel generation) should be greatly benefited.

Role of reduced graphene oxide in the critical components of a CdS-sensitized TiO2 -based photoelectrochemical cell.

Nitrogen (N)-doped reduced graphene oxide (nRGO) is systematically incorporated into a TiO(2) -CdS photoelectrochemical (PEC) cell and its role is examined in the three main components of the cell: 1) the CdS-sensitized TiO(2) photoanode, 2) the cathode, and 3) the S(2-)/S(.-) aqueous redox electrolyte. The nRGO layer is sandwiched between TiO(2) nanorods (deposited by using a solvothermal method) and CdS (deposited by using the successive ionic-layer-adsorption and -reaction method). Scanning electron microscopy with energy dispersive X-ray analysis (EDS) reveals the spatial distribution of CdS and nRGO, whereas nRGO formation is evident from Mott Schottky analysis. Chronoamperometry and PEC analysis indicate that upon incorporation of nRGO, a photocurrent density that is at least 27 times higher than that of pristine TiO(2) is achieved; this increase is attributable to the ability of the nRGO to efficiently separate and transport charges. Stability analysis performed by continuous photoillumination over ∼3 h indicates a 26% and 42 % reduction in the photocurrent in the presence and absence of the nRGO respectively. Formation of SO(4)(2-) is identified as the cause for this photocurrent reduction by using X-ray photoelectron spectroscopy. It is also shown that nRGO-coated glass is as effective as a Pt counter electrode in the PEC cell. Unlike the benefits offered by nRGO at the anode and cathode, introducing it in the redox electrolyte is detrimental. Systematic and complementary electrolyte and film-based studies on this aspect reveal evidence of the capacitive behavior of nRGO. Competition between the nRGO and the oxidized electrolyte is identified, based on linear-sweep voltammetry analysis, as the limiting step to efficient charge transport in the electrolyte.

Mn-modified Bi2Ti2O7 photocatalysts: bandgap engineered multifunctional photocatalysts for hydrogen generation.

In this study, a hydrogen generation photocatalyst based on bismuth titanate (Bi2Ti2O7 - BTO) modified with manganese (Mn) has been developed. Mn of varying weight percent was added to construct a modified BTO catalyst (Mn_BTO), in order to enhance the opto-electronic and photocatalytic hydrogen generation capabilities of the pristine BTO. The structural, morphological, and optical properties of the photocatalysts were evaluated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV-visible spectrophotometry. The XRD, SEM, and TEM analyses indicate the formation of the pyrochlore BTO phase with particles of dimensions 30 ± 10 nm. The UV-visible study revealed a reduction in the bandgap of Mn_BTO and enhanced absorption in the visible range, compared to the pristine BTO. The catalyst was optimized for maximum hydrogen generation from a water-methanol (sacrificial electron donor) system in a slurry reactor. The photocatalytic hydrogen evolution studies indicate that the Mn_BTO with up to 1 wt% Mn facilitates an optimal 140% increase in the hydrogen yield. The role of formic acid and formaldehyde as additives in photocatalytic hydrogen evolution has also been examined. The effect of Mn content, mechanistic overview, and reusability of the catalyst are discussed.

Highly biocompatible and water-dispersible, amine functionalized magnetite nanoparticles, prepared by a low temperature, air-assisted polyol process: a new platform for bio-separation and diagnostics.

A low temperature polyol process, based on glycolaldehyde mediated partial reduction of FeCl(3).6H(2)O at 120 degrees C in the presence of sodium acetate as an alkali source and 2, 2(')-(ethylenedioxy)-bis-(ethylamine) as an electrostatic stabilizer has been used for the gram-scale preparation of biocompatible, water-dispersible, amine functionalized magnetite nanoparticles (MNPs) with an average diameter of 6 +/- 0.75 nm. With a reasonably high magnetization (37.8 e.m.u.) and amine groups on the outer surface of the nanoparticles, we demonstrated the magnetic separation and concentration implications of these ultrasmall particles in immunoassay. MRI studies indicated that these nanoparticles had the desired relaxivity for T(2) contrast enhancement in vivo. In vitro biocompatibility, cell uptake and MR imaging studies established that these nanoparticles were safe in clinical dosages and by virtue of their ultrasmall sizes and positively charged surfaces could be easily internalized by cancer cells. All these positive attributes make these functional nanoparticles a promising platform for further in vitro and in vivo evaluations.

Biofunctionalized, phosphonate-grafted, ultrasmall iron oxide nanoparticles for combined targeted cancer therapy and multimodal imaging.

A novel, inexpensive biofunctionalization approach is adopted to develop a multimodal and theranostic nanoagent, which combines cancer-targeted magnetic resonance/optical imaging and pH-sensitive drug release into one system. This multifunctional nanosystem, based on an ultrasmall superparamagnetic iron oxide (USPIO) nanocore, is modified with a hydrophilic, biocompatible, and biodegradable coating of N-phosphonomethyl iminodiacetic acid (PMIDA). Using appropriate spacers, functional molecules, such as rhodamine B isothiocyanate, folic acid, and methotrexate, are coupled to the amine-derivatized USPIO-PMIDA support with the aim of endowing simultaneous targeting, imaging, and intracellular drug-delivering capability. For the first time, phosphonic acid chemistry is successfully exploited to develop a stealth, multifunctional nanoprobe that can selectively target, detect, and kill cancer cells overexpressing the folate receptor, while allowing real-time monitoring of tumor response to drug treatment through dual-modal fluorescence and magnetic resonance imaging.