Metal Cocatalyst Engineering in Metal-Semiconductor Hybrid Photocatalysts Achieves a Fivefold Enhancement of Hydrogen Evolution.

This study explores the optimal morphology of photochemical hydrogen evolution catalysts in a one-dimensional system. Systematic engineering of metal tips on precisely defined CdSe@CdS dot-in-rods is conducted to exert control over morphology, composition, and both factors. The outcome yields an optimized configuration, a Au-Pt core-shell structure with a rough Pt surface (Au@r-Pt), which exhibits a remarkable fivefold increase in quantum efficiency, reaching 86 % at 455 nm and superior hydrogen evolution rates under visible and AM1.5 G irradiation conditions with prolonged stability. Kinetic investigations using photoelectrochemical and time-resolved measurements demonstrate a greater extent and extended lifetime of the charge-separated state on the tips as well as rapid water reduction kinetics on high-energy surfaces. This approach sheds light on the critical role of cocatalysts in hybrid photocatalytic systems for achieving high performance.

Nanoscale Cathodoluminescence Thermometry with a Lanthanide-Doped Heavy-Metal Oxide in Transmission Electron Microscopy.

When navigated by the available energy of a system, often provided in the form of heat, physical processes or chemical reactions fleet on a free-energy landscape, thus changing the structure. In in situ transmission electron microscopy (TEM), where material structures are measured and manipulated inside the microscope while being subjected to external stimuli such as electrical fields, laser irradiation, or mechanical stress, it is necessary to precisely determine the local temperature of the specimen to provide a comprehensive understanding of material behavior and to establish the relationship among energy, structure, and properties at the nanoscale. Here, we propose using cathodoluminescence (CL) spectroscopy in TEM for in situ measurement of the local temperature. Gadolinium oxide particles doped with emissive europium ions present an opportunity to utilize them as a temperature probe in CL measurements via a ratiometric approach. We show the thermometric performance of the probe and demonstrate a precision of ±5 K in the temperature range from 113 to 323 K with the spatial resolution limited by the size of the particles, which surpasses other methods for temperature determination. With the CL-based thermometry, we further demonstrate measuring local temperature under laser irradiation.

Pt cocatalyst morphology on semiconductor nanorod photocatalysts enhances charge trapping and water reduction.

In photocatalysis, metal-semiconductor hybrid structures have been proposed for ideal photocatalytic systems. In this study, we investigate the effect of morphology and surface nature of Pt cocatalysts on photocatalytic hydrogen evolution activity in Pt-tipped CdSe nanorods. Three distinct morphologies of Pt cocatalysts were synthesized and employed as visible light photocatalysts. The rough tips exhibit the highest activity, followed by the round and cubic tips. Kinetic investigations using transient absorption spectroscopy reveal that the cubic tips exhibit lower charge-separated states feasible for reacting with water and water reduction rates due to their defectless surface facets. In contrast, the rough tips show a similar charge-separation value but a two-fold higher surface reaction rate than the round tips, resulting in a significant enhancement of hydrogen evolution. These findings highlight the importance of rational design on metal cocatalysts in addition to the main semiconductor bodies for maximizing photocatalytic activities.

Tailoring Two-Dimensional Matter Using Strong Light-Matter Interactions.

The shaping of matter into desired nanometric structures with on-demand functionalities can enhance the miniaturization of devices in nanotechnology. Herein, strong light-matter interaction was used as an optical lithographic tool to tailor two-dimensional (2D) matter into nanoscale architectures. We transformed 2D black phosphorus (BP) into ultrafine, well-defined, beyond-diffraction-limit nanostructures of ten times smaller size and a hundred times smaller spacing than the incident, femtosecond-pulsed light wavelength. Consequently, nanoribbons and nanocubes/cuboids scaling tens of nanometers were formed by the structured ablation along the extremely confined periodic light fields originating from modulation instability, the tailoring process of which was visualized in real time via light-coupled in situ transmission electron microscopy. The current findings on the controllable nanoscale shaping of BP will enable exotic physical phenomena and further advance the optical lithographic techniques for 2D materials.

Simplified Y6-Based Nonfullerene Acceptors: In-Depth Study on Molecular Structure-Property Relation, Molecular Dynamics Simulation, and Charge Dynamics.

Two new Y6 derivatives of symmetrical YBO-2O and asymmetrical YBO-FO nonfullerene acceptors (NFAs) are prepared with a simplified synthetic procedure by incorporating octyl and fluorine substituents onto the terminal 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (INCN) moiety. By moving the alkyl substituents on the Y6 core to the terminal INCN moiety, the lowest unoccupied molecular orbital of the YBO NFAs increases without decreasing solubility, resulting in high open-circuit voltages of the devices. Molecular dynamics simulation shows that YBO-2O/-FO preferentially form core-core and terminal-terminal dimeric interactions, demonstrating their tighter packing structure and higher electron mobility than Y6, which is consistent with 2D grazing incidence X-ray scattering and space charge limited current measurements. In blend films, the hole transfer (HT) from YBO-2O/-FO to the polymer donor PM6 is studied in detail by transient absorption spectroscopy, demonstrating efficient HT from YBO-FO to PM6 with their suitable energy level alignment. Despite the simplified synthesis, YBO-FO demonstrates photovoltaic performance similar to that of Y6, exhibiting a power conversion efficiency of 15.01%. Overall, this design strategy not only simplifies the synthetic procedures but also adjusts the electrical properties by modifying the intermolecular packing and energy level alignment, suggesting a novel simplified molecular design of Y6 derivatives.

Intrachain photophysics of a donor-acceptor copolymer.

By taking advantage of bulk-heterojunction structures formed by blending conjugated donor polymers and non-fullerene acceptors, organic photovoltaic devices have recently attained promising power conversion efficiencies of above 18%. For optimizing organic photovoltaic devices, it is essential to understand the elementary processes that constitute light harvesters. Utilising femtosecond-resolved spectroscopic techniques that can access the timescales of locally excited (LE) state and charge-transfer (CT)/-separated (CS) states, herein we explored their photophysics in single chains of the top-notch performance donor-acceptor polymer, PM6, which has been widely used as a donor in state-of-the-art non-fullerene organic photovoltaic devices, in a single LE state per chain regime. Our observations revealed the ultrafast formation of a CT state and its equilibrium with the parent LE state. From the chain-length dependence of their lifetimes, the equilibrated states were found to idle until they reach a chain folding. At the chain folding, the CT state transforms into an interchain CT state that bifurcates into forming a CS state or annihilation within a picosecond. The observation of prevalent nonexponential behaviour in the relaxation of the transient species is attributed to the wide chain-length distribution that determines the emergence of the chain foldings in a single chain, thus, the lifetime of a LE and equilibrated CT states. Our findings indicate that the abundance of chain folding, where the generation of the "reactive" CS state is initiated from the interchain CT state, is essential for maximising charge carriers in organic photovoltaic devices based on PM6.

Fullerene-Based Triads with Controlled Alkyl Spacer Length as Photoactive Materials for Single-Component Organic Solar Cells.

Two kinds of dumbbell-shaped acceptor-donor-acceptor (A-D-A)-type triad single-component (SC) photovoltaic molecules based on a benzodithiophene-rhodanine (BDTRh) core and [6,6]-phenyl-C61 butyric acid (PC61BA) termini, BDTRh-C2-PC61BA and BDTRh-C10-PC61BA, were synthesized by modulating the alkyl (C2 and C10) spacer lengths. Both SC photovoltaic structures had similar UV-vis spectra in solution, but BDTRh-C10-PC61BA showed a significantly higher absorption coefficient as a thin film. In films, a more facile intermolecular photo-induced charge transfer was observed for BDTRh-C10-PC61BA in the broad-band transient absorption measurements. BDTRh-C10-PC61BA also exhibited a higher hole mobility (by 25 times) and less bimolecular recombination than BDTRh-C2-PC61BA. By plotting the normalized external quantum efficiency data, a higher charge-transfer state was measured for BDTRh-C10-PC61BA, reducing its voltage loss. A higher power conversion efficiency of ∼2% was obtained for BDTRh-C10-PC61BA, showing higher open-circuit voltage, short-circuit current density, and fill factor than those of BDTRh-C2-PC61BA devices. The different carrier dynamics, voltage loss, and optical and photoelectrical characteristics depending on the spacer length were interpreted in terms of the film morphology. The longer decyl spacer in BDTRh-C10-PC61BA afforded a significantly enhanced intermolecular ordering of the p-type core compared to BDTRh-C2-PC61BA, suggesting that the alkyl spacer length plays a critical role in controlling the intermolecular packing interaction.

Hydrogen-Bond Dynamics and Energetics of Biological Water.

Water molecules in the immediate vicinity of biomacromolecules and biomimetic organized assemblies often exhibit a markedly distinct behavior from that of their bulk counterparts. The overall sluggish behavior of biological water substantially affects the stability and integrity of biomolecules, as well as the successful execution of various crucial water-mediated biochemical phenomena. In this Minireview, insights are provided into the features of truncated hydrogen-bond networks that grant biological water its unique characteristics. In particular, experimental results and theoretical investigations, based on chemical kinetics, are presented that have shed light on the dynamics and energetics governing such characteristics. It is emphasized how such details help us to understand the energetics of biological water, an aspect relatively less explored than its dynamics. For instance, when biological water at hydrophilic or charged protein surfaces was explored, the free energy of H-bond breakage was found to be of the order of 0.4 kcal mol-1 higher than that of bulk water.

Hydrogen-Bond Free Energy of Local Biological Water.

Here, we propose an experimental methodology based on femtosecond-resolved fluorescence spectroscopy to measure the hydrogen (H)-bond free energy of water at protein surfaces under isothermal conditions. A demonstration was conducted by installing a non-canonical isostere of tryptophan (7-azatryptophan) at the surface of a coiled-coil protein to exploit the photoinduced proton transfer of its chromophoric moiety, 7-azaindole. The H-bond free energy of this biological water was evaluated by comparing the rates of proton transfer, sensitive to the hydration environment, at the protein surface and in bulk water, and it was found to be higher than that of bulk water by 0.4 kcal mol-1 . The free-energy difference is dominated by the entropic cost in the H-bond network among water molecules at the hydrophilic and charged protein surface. Our study opens a door to accessing the energetics and dynamics of local biological water to give insight into its roles in protein structure and function.

Synergistic Configuration of Diols as Brønsted Bases.

As viscous hydroxylic organic compounds, diols are of interest for their functional molecular conformation, which is based on inter- and intramolecular hydrogen (H)-bonds. By utilising steady-state electronic and vibrational spectroscopy, time-resolved fluorescence spectroscopy, and computational analyses, we report the association of the hydroxyl groups of diols via intra- or intermolecular H-bonds to enhance their reactivity as a base. Whereas the formation of an intermolecularly H-bonded dimer is requisite for diols of weak intramolecular H-bond to extract a proton from a model strong photoacid, a well-configured single diol molecule with an optimised intramolecular H-bond is revealed to serve as an effective Brønsted base with increased basicity. This observation highlights the collective role of H-bonding in acid-base reactions, and provides mechanistic backgrounds to understand the reactivity of polyols in the acid-catalysed dehydration for the synthesis of cyclic ethers at the molecular level.