Ultralight, Flexible, and Semi-Transparent Metal Oxide Papers for Photoelectrochemical Water Splitting

Thanks to their versatile functionality, metal oxides (MOs) constitute one of the key family materials in a variety of current demands for sensor, catalysis, energy storage and conversion, optical electronics, and piezoelectric mechanics. Much effort has focused on engineering specific nanostructure and macroscopic morphology of MOs that aims to enhance their performances, but the design and controlled synthesis of ultrafine nanostructured MOs in a cost-effective and facile way remains a challenge. In this work, we have exploited the advantages of intrinsic structures of graphene oxide (GO) papers, serving as a sacrificial template, to design and synthesize two-dimensional (2D) layered and free-standing MO papers with ultrafine nanostructures. Physicochemical characterizations showed that these MO materials are nanostructured, porous, flexible, and ultralight. The as-synthesized materials were tested for their potential application in photoelectrochemical (PEC) energy conversion. In terms of PEC water splitting, copper oxide papers were used as an example and exhibited excellent performances with an extremely high photocurrent-to-weight ratio of 3 A cm^–2 g^–1. We have also shown that the synthesis method is generally valid for many earth-abundant transition metals including copper, nickel, iron, cobalt, and manganese

Nanoscale Confinement and Fluorescence Effects of Bacterial Light Harvesting Complex LH2 in Mesoporous Silicas

Many key chemical and biochemical reactions, particularly in living cells, take place in confined space at the mesoscopic scale. Toward understanding of physicochemical nature of biomacromolecules confined in nanoscale space, in this work we have elucidated fluorescence effects of a light harvesting complex LH2 in nanoscale chemical environments. Mesoporous silicas (SBA-15 family) with different shapes and pore sizes were synthesized and used to create nanoscale biomimetic environments for molecular confinement of LH2. A combination of UV–vis absorption, wide-field fluorescence microscopy, and in situ ellipsometry supports that the LH2 complexes are located inside the silica nanopores. Systematic fluorescence effects were observed and depend on degree of space confinement. In particular, the temperature dependence of the steady-state fluorescence spectra was analyzed in detail using condensed matter band shape theories. Systematic electronic-vibrational coupling differences in the LH2 transitions between the free and confined states are found, most likely responsible for the fluorescence effects experimentally observed

Directed Energy Transfer in Films of CdSe Quantum Dots: Beyond the Point Dipole Approximation

Understanding of Förster resonance energy transfer (FRET) in thin films composed of quantum dots (QDs) is of fundamental and technological significance in optimal design of QD based optoelectronic devices. The separation between QDs in the densely packed films is usually smaller than the size of QDs, so that the simple point–dipole approximation, widely used in the conventional approach, can no longer offer quantitative description of the FRET dynamics in such systems. Here, we report the investigations of the FRET dynamics in densely packed films composed of multisized CdSe QDs using ultrafast transient absorption spectroscopy and theoretical modeling. Pairwise interdot transfer time was determined in the range of 1.5 to 2 ns by spectral analyses which enable separation of the FRET contribution from intrinsic exciton decay. A rational model is suggested by taking into account the distribution of the electronic transition densities in the dots and using the film morphology revealed by AFM images. The FRET dynamics predicted by the model are in good quantitative agreement with experimental observations without adjustable parameters. Finally, we use our theoretical model to calculate dynamics of directed energy transfer in ordered multilayer QD films, which we also observe experimentally. The Monte Carlo simulations reveal that three ideal QD monolayers can provide exciton funneling efficiency above 80% from the most distant layer. Thereby, utilization of directed energy transfer can significantly improve light harvesting efficiency of QD devices

Three-Dimensional Graphene Matrix-Supported and Thylakoid Membrane-Based High-Performance Bioelectrochemical Solar Cell

A combination of thylakoid membranes (TMs) as photobiocatalysts with high-surface-area electroactive materials could hold great potential for sustainable “green” solar energy conversion. We have studied the orientated immobilization of TMs on high-surface-area graphene electrodes, which were fabricated by electroreduction of graphene oxide and simultaneous electrodeposition with further aminoaryl functionalization. We have achieved the highest performance to date under direct electron transfer conditions through a biocompatible “wiring” of TMs to graphene sheets. The photobiocurrent density generated by the optimized mediator-free TM-based bioanodes yielded up to 5.24 ± 0.50 μA cm^–2. The photobioelectrochemical cell integrating the photobioanode in combination with an oxygen reducing enzymatic biocathode delivered a maximum power output of 1.79 ± 0.19 μW cm^–2. Our approach ensures a simplified cell design, a greater load of photosynthetic units, a minimized overpotential loss, and an enhanced overall performance

Triazatriangulene as Binding Group for Molecular Electronics

The triazatriangulene (TATA) ring system was investigated as a binding group for tunnel junctions of molecular wires on gold surfaces. Self-assembled monolayers (SAMs) of TATA platforms with three different lengths of phenylene wires were fabricated, and their electrical conductance was recorded by both conducting probe-atomic force microscopy (CP-AFM) and scanning tunneling microscopy (STM). Similar measurements were performed for phenylene SAMs with thiol anchoring groups as references. It was found that, despite the presence of a sp³ hybridized carbon atom in the conduction path, the TATA platform displays a contact resistance only slightly larger than the thiols. This surprising finding has not been reported before and was analyzed by theoretical computations of the transmission functions of the TATA anchored molecular wires. The relatively low contact resistance of the TATA platform along with its high stability and directionality make this binding group very attractive for molecular electronic measurements and devices