Non-Embedded Silver Nanowires/Antimony-Doped Tin Oxide/Polyethylenimine Transparent Electrode for Non-Fullerene Acceptor ITO-Free Inverted Organic Photovoltaics.

Indium tin oxide (ITO)-free solution-processed transparent electrodes are an essential component for the low-cost fabrication of organic optoelectronic devices. High-performance silver nanowires (AgNWs) ITO-free inverted organic photovoltaics (OPVs) usually require a AgNWs-embedded process. A simple cost-effective roll-to-roll production process of inverted ITO-free OPVs with AgNWs as a bottom transparent electrode requires solution-based thick metal oxides as carrier-selective contacts. In this reported study, we show that a solution-processed antimony-doped tin oxide (ATO)/polyethylenimine (PEI) electron-selective contact incorporated on the top of non-embedded AgNWs provides a high-performance ITO-free bottom electrode for non-fullerene acceptor (NFA) inverted OPVs.

Thermal Analysis of Metal-Organic Precursors for Functional Cu:ΝiOx Hole Transporting Layer in Inverted Perovskite Solar Cells: Role of Solution Combustion Chemistry in Cu:ΝiOx Thin Films Processing.

Low temperature solution combustion synthesis emerges as a facile method for the synthesis of functional metal oxides thin films for electronic applications. We study the solution combustion synthesis process of Cu:NiOx using different molar ratios (w/o, 0.1 and 1.5) of fuel acetylacetone (Acac) to oxidizer (Cu, Ni Nitrates) as a function of thermal annealing temperatures 150, 200, and 300 °C. The solution combustion synthesis process, in both thin films and bulk Cu:NiOx, is investigated. Thermal analysis studies using TGA and DTA reveal that the Cu:NiOx thin films show a more gradual mass loss while the bulk Cu:NiOx exhibits a distinct combustion process. The thin films can crystallize to Cu:NiOx at an annealing temperature of 300 °C, irrespective of the Acac/Oxidizer ratio, whereas lower annealing temperatures (150 and 200 °C) produce amorphous materials. A detail characterization study of solution combustion synthesized Cu:NiOx, including XPS, UV-Vis, AFM, and Contact angle measurements, is presented. Finally, 50 nm Cu:NiOx thin films are introduced as HTLs within the inverted perovskite solar cell device architecture. The Cu:NiOx HTL annealed at 150 and 200 °C provided PVSCs with limited functionality, whereas efficient triple-cation Cs0.04(MA0.17FA0.83)0.96 Pb(I0.83Br0.17)3-based PVSCs achieved for Cu:NiOx HTLs for annealing temperature of 300 °C.

All-Inorganic p-n Heterojunction Solar Cells by Solution Combustion Synthesis Using N-type FeMnO3 Perovskite Photoactive Layer.

This study outlines the synthesis and physicochemical characteristics of a solution-processable iron manganite (FeMnO3) nanoparticles via a chemical combustion method using tartaric acid as a fuel whilst demonstrating the performance of this material as a n-type photoactive layer in all-oxide solar cells. It is shown that the solution combustion synthesis (SCS) method enables the formation of pure crystal phase FeMnO3 with controllable particle size. XRD pattern and morphology images from TEM confirm the purity of FeMnO3 phase and the relatively small crystallite size (∼13 nm), firstly reported in the literature. Moreover, to assemble a network of connected FeMnO3 nanoparticles, ß-alanine was used as a capping agent and dimethylformamide (DMF) as a polar aprotic solvent for the colloidal dispersion of FeMnO3 NPs. This procedure yields a ∼500 nm thick FeMnO3 n-type photoactive layer. The proposed method is crucial to obtain functional solution processed NiO/FeMnO3 heterojunction inorganic photovoltaics. Photovoltaic performance and solar cell device limitations of the NiO/FeMnO3-based heterojunction solar cells are presented.

Bottom Contact Metal Oxide Interface Modification Improving the Efficiency of Organic Light Emitting Diodes.

The performance of solution-processed organic light emitting diodes (OLEDs) is often limited by non-uniform contacts. In this work, we introduce Ni-containing solution-processed metal oxide (MO) interfacial layers inserted between indium tin oxide (ITO) and poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) to improve the bottom electrode contact for OLEDs using the poly(p-phenylene vinylene) (PPV) derivative Super-Yellow (SY) as an emission layer. For ITO/Ni-containing MO/PEDOT:PSS bottom electrode structures we show enhanced wetting properties that result in an improved OLED device efficiency. Best performance is achieved using a Cu-Li co-doped spinel nickel cobaltite [(Cu-Li):NiCo2O4], for which the current efficiency and luminous efficacy of SY OLEDs increased, respectively, by 12% and 11% from the values obtained for standard devices without a Ni-containing MO interface modification between ITO and PEDOT:PSS. The enhanced performance was attributed to the improved morphology of PEDOT:PSS, which consequently increased the hole injection capability of the optimized ITO/(Cu-Li):NiCo2O4/PEDOT:PSS electrode.

Surface Treatment of Cu:NiOx Hole-Transporting Layer Using ß-Alanine for Hysteresis-Free and Thermally Stable Inverted Perovskite Solar Cells.

Inverted perovskite solar cells (PSCs) using a Cu:NiOx hole transporting layer (HTL) often exhibit stability issues and in some cases J/V hysteresis. In this work, we developed a ß-alanine surface treatment process on Cu:NiOx HTL that provides J/V hysteresis-free, highly efficient, and thermally stable inverted PSCs. The improved device performance due to ß-alanine-treated Cu:NiOx HTL is attributed to the formation of an intimate Cu:NiOx/perovskite interface and reduced charge trap density in the bulk perovskite active layer. The ß-alanine surface treatment process on Cu:NiOx HTL eliminates major thermal degradation mechanisms, providing 40 times increased lifetime performance under accelerated heat lifetime conditions. By using the proposed surface treatment, we report optimized devices with high power conversion efficiency (PCE) (up to 15.51%) and up to 1000 h lifetime under accelerated heat lifetime conditions (60 °C, N2).

Interface Engineering of MoS2 -Modified Graphitic Carbon Nitride Nano-photocatalysts for an Efficient Hydrogen Evolution Reaction.

Understanding of photochemical charge transfer processes at nanoscale heterojunctions is essential in developing effective catalysts. Here, we utilize a controllable synthesis method and a combination of optical absorption, photoluminescence, and electrochemical impedance spectroscopic studies to investigate the effect of MoS2 nanosheet lateral dimension and edge length size on the photochemical behavior of MoS2 -modified graphitic carbon nitride (g-C3 N4 ) heterojunctions. These nano-heterostructures, which comprise interlayer junctions with variable area (i. e., MoS2 lateral size ranges from 18 nm to 52 nm), provide a size-tunable interfacial charge transfer through the MoS2 /g-C3 N4 contacts, while exposing a large fraction of surface MoS2 edge sites available for the hydrogen evolution reaction. Importantly, modification of g-C3 N4 with MoS2 layers of 39±5 nm lateral size (20 wt % loading) creates interfacial contacts with relatively large number of MoS2 edge sites and efficient electronic transport phenomena, yielding a high photocatalytic H2 -production activity of 1497 µmol h-1 gcat -1 and an apparent QY of 3.3 % at 410 nm light irradiation. This study thus offers a design strategy to improve light energy conversion efficiency of catalysts by engineering interfaces at the nanoscale in 2D-layered heterojunction materials.

Nanoparticulate Metal Oxide Top Electrode Interface Modification Improves the Thermal Stability of Inverted Perovskite Photovoltaics.

Solution processed γ-Fe2O3 nanoparticles via the solvothermal colloidal synthesis in conjunction with ligand-exchange method are used for interface modification of the top electrode in inverted perovskite solar cells. In comparison to more conventional top electrodes such as PC(70)BM/Al and PC(70)BM/AZO/Al, we show that incorporation of a γ-Fe2O3 provides an alternative solution processed top electrode (PC(70)BM/γ-Fe2O3/Al) that not only results in comparable power conversion efficiencies but also improved thermal stability of inverted perovskite photovoltaics. The origin of improved stability of inverted perovskite solar cells incorporating PC(70)BM/ γ-Fe2O3/Al under accelerated heat lifetime conditions is attributed to the acidic surface nature of γ-Fe2O3 and reduced charge trapped density within PC(70)BM/ γ-Fe2O3/Al top electrode interfaces.

Inverted Perovskite Photovoltaics Using Flame Spray Pyrolysis Solution Based CuAlO2/Cu-O Hole-Selective Contact.

We present the functionalization process of a conductive and transparent CuAlO2/Cu-O hole-transporting layer (HTL). The CuAlO2/Cu-O powders were developed by flame spray pyrolysis and their stabilized dispersions were treated by sonication and centrifugation methods. We show that when the supernatant part of the treated CuAlO2/Cu-O dispersions is used for the development of CuAlO2/Cu-O HTLs the corresponding inverted perovskite-based solar cells show improved functionality and power conversion efficiency of up to 16.3% with negligible hysteresis effect.

Low-Temperature Combustion Synthesis of a Spinel NiCo2O4 Hole Transport Layer for Perovskite Photovoltaics.

The synthesis and characterization of low-temperature solution-processable monodispersed nickel cobaltite (NiCo2O4) nanoparticles (NPs) via a combustion synthesis is reported using tartaric acid as fuel and the performance as a hole transport layer (HTL) for perovskite solar cells (PVSCs) is demonstrated. NiCo2O4 is a p-type semiconductor consisting of environmentally friendly, abundant elements and higher conductivity compared to NiO. It is shown that the combustion synthesis of spinel NiCo2O4 using tartaric acid as fuel can be used to control the NPs size and provide smooth, compact, and homogeneous functional HTLs processed by blade coating. Study of PVSCs with different NiCo2O4 thickness as HTL reveals a difference on hole extraction efficiency, and for 15 nm, optimized thickness enhanced hole carrier collection is achieved. As a result, p-i-n structure of PVSCs with 15 nm NiCo2O4 HTLs shows reliable performance and power conversion efficiency values in the range of 15.5% with negligible hysteresis.

Controllable Synthesis of Mesoporous Iron Oxide Nanoparticle Assemblies for Chemoselective Catalytic Reduction of Nitroarenes.

Iron(III) oxide is a low-cost material with applications ranging from electronics to magnetism, and catalysis. Recent efforts have targeted new nanostructured forms of Fe2O3 with high surface area-to-volume ratio and large pore volume. Herein, the synthesis of 3D mesoporous networks consisting of 4-5 nm γ-Fe2O3 nanoparticles by a polymer-assisted aggregating self-assembly method is reported. Iron oxide assemblies obtained from the hybrid networks after heat treatment have an open-pore structure with high surface area (up to 167 m(2)g(-1)) and uniform pores (ca. 6.3 nm). The constituent iron oxide nanocrystals can undergo controllable phase transition from γ-Fe2O3 to α-Fe2O3 and to Fe3O4 under different annealing conditions while maintaining the 3D structure and open porosity. These new ensemble structures exhibit high catalytic activity and stability for the selective reduction of aryl and alkyl nitro compounds to the corresponding aryl amines and oximes, even in large-scale synthesis.

Selective capture of hexavalent chromium from an anion-exchange column of metal organic resin-alginic acid composite.

We report an anion exchange composite material based on a protonated amine-functionalized metal-organic framework, denoted Metal Organic Resin-1 (MOR-1), and alginic acid (HA). MOR-1-HA material shows an exceptional capability to rapidly and selectively sorb Cr(vi) under a variety of conditions and in the presence of several competitive ions. The selectivity of MOR-1-HA for Cr(vi) is shown to be the result of strong O3CrVI···NH2 interactions. The composite sorbent can be successfully utilized in an ion-exchange column, in contrast to pristine MOR-1 which forms fine suspensions in water passing through the column. Remarkably, an ion exchange column with only 1% wt MOR-1-HA and 99% wt sand (an inert and inexpensive material) is capable of reducing moderate and trace Cr(vi) concentrations to well below the acceptable safety limits for water. The relatively low cost of MOR-1-HA/sand column and its high regeneration capability and reusability make it particularly attractive for application in the remediation of Cr(vi)-bearing industrial waste.

Correction: Selective capture of hexavalent chromium from an anion-exchange column of metal organic resin-alginic acid composite.

[This corrects the article DOI: 10.1039/C5SC03732H.].

Ordered Mesoporous Polyoxometalate-Organosilica Frameworks as Efficient Photocatalysts of the Hydrogen Evolution Reaction.

Polyoxometalate clusters have been recently established as promising nanomaterials for photocatalytic water splitting. Here, the synthesis is reported of mesoporous polymers composed of a 3D porous network of lacunary [XM11 O39 ]q- (XM11 ; X=P, Si; M=W, Mo) polyoxometalate units connected by ethano-bridged silsesquioxane linkers through a block copolymer-templated crosslinking polymerization of 1,2-bis(triethoxysilyl)ethane in acidic solution. The resulting materials feature an ordered mesostructured ethane-silica (MES) framework that hosts a high density of accessible polyoxometalate clusters, which allows for efficient catalytic reactions. XM11 /MES hybrid polymers have a relatively high activity for the hydrogen evolution reaction with remarkable cycle stability under UV/Vis light irradiation (λ>360 nm), without the need for co-catalysts or additional photosensitizers. It is also shown that the photocatalytic efficiency of these materials arises from the nanoscale pore structure, high surface area and chemical manipulation of the electronic band structure of constituting heteropolyoxo clusters.

Synthesis of Ordered Mesoporous CuO/CeO2 Composite Frameworks as Anode Catalysts for Water Oxidation.

Cerium-rich metal oxide materials have recently emerged as promising candidates for the photocatalytic oxygen evolution reaction (OER). In this article, we report the synthesis of ordered mesoporous CuO/CeO2 composite frameworks with different contents of copper(II) oxide and demonstrate their activity for photocatalytic O2 production via UV-Vis light-driven oxidation of water. Mesoporous CuO/CeO2 materials have been successfully prepared by a nanocasting route, using mesoporous silica as a rigid template. X-ray diffraction, electron transmission microscopy and N2 porosimetry characterization of the as-prepared products reveal a mesoporous structure composed of parallel arranged nanorods, with a large surface area and a narrow pore size distribution. The molecular structure and optical properties of the composite materials were investigated with Raman and UV-Vis/NIR diffuse reflectance spectroscopy. Catalytic results indicated that incorporation of CuO clusters in the CeO2 lattice improved the photochemical properties. As a result, the CuO/CeO2 composite catalyst containing ~38 wt % CuO reaches a high O2 evolution rate of ~19.6 µmol·h-1 (or 392 µmol·h-1·g-1) with an apparent quantum efficiency of 17.6% at λ = 365 ± 10 nm. This OER activity compares favorably with that obtained from the non-porous CuO/CeO2 counterpart (~1.3 µmol·h-1) and pure mesoporous CeO2 (~1 µmol·h-1).

Ternary [Al(2)O(3)-electrolyte-Cu(2+)] species: EPR spectroscopy and surface complexation modeling.

Cu(2+) binding on gamma-Al(2)O(3) is modulated by common electrolyte ions such as Mg(2+), SO(4)(2-), and PO(4)(3-) in a complex manner: (a) At high concentrations of electrolyte ions, Cu(2+) uptake by gamma-Al(2)O(3) is inhibited. This is partially due to bulk ionic strength effects and, mostly, due to direct competition between Mg(2+) and Cu(2+) ions for the SO(-) surface sites of gamma-Al(2)O(3). (b) At low concentrations of electrolyte ions, Cu(2+) uptake by gamma-Al(2)O(3) can be enhanced. This is due to synergistic coadsorption of Cu(2+) and electrolyte anions, SO(4)(2-) and PO(4)(3-)(.) This results in the formation of ternary surface species (SOH(2)SO(4)Cu)(+), (SOH(2)PO(4)Cu), and (SOH(2)HPO(4)Cu)(+) which enhance Cu(2+) uptake at pH<6. The effect of phosphate ions may be particularly strong resulting in a 100% Cu uptake by the oxide surface. (c) EPR spectroscopy shows that at pH<>pH(PZC) Cu(2+) may coordinate to two SO(-) groups. At pH<

A theoretical and experimental physicochemical study of sulfur species in the anoxic lagoon of Aitoliko-Greece.

The spatiotemporal changes of metals, inorganic ions and physiochemical parameters of Aitoliko lagoon, an anoxic wetland in Western Greece, were studied with special emphasis in sulfur species. Theoretical physicochemical modeling was performed for the sulfur speciation, based on experimental pH and redox potential data. Accordingly, the speciation of sulfur in the lagoon can be operationally divided in two domains: (a) for depths d = 0-10 m below the surface, the sulfur speciation can be described by equilibrium reactions between the aqueous species. (b) At depths d > 10 m a progressive decline for SO4(2-) concentration is observed between theory and experiment. At the lagoon-bottom an elevated concentration of 19+/-2 mM SO4(2-) was measured, which cannot be described by physicochemical equilibrium based on the pH, E(h), O2 concentrations measured in situ. Accordingly, we suggest that additional biogeochemical processes, such as sulfur bacteria activity, have to be invoked. Of particular importance is that the experimental pH-pe values cross the critical region where the interplay of SO4(2-)/S2(-)/H2S occurs. This explains why a relatively small fluctuation of pH, pe values may result in a shift of the equilibrium over one sulfur species. This explains the, otherwise accidental, previously reported releases of H2S in the air over the lagoon.