Small Molecule Based Organic Photo Signal Receiver for High-Speed Optical Wireless Communications.

The present work describes the development of an organic photodiode (OPD) receiver for high-speed optical wireless communication. To determine the optimal communication design, two different types of photoelectric conversion layers, bulk heterojunction (BHJ) and planar heterojunction (PHJ), are compared. The BHJ-OPD device has a -3 dB bandwidth of 0.65 MHz (at zero bias) and a maximum of 1.4 MHz (at -4 V bias). A 150 Mbps single-channel visible light communication (VLC) data rate using this device by combining preequalization and machine learning (ML)-based digital signal processing (DSP) is demonstrated. To the best of the authors' knowledge, this is the highest data rate ever achieved on an OPD-based VLC system by a factor of 40 over the previous fastest reported. Additionally, the proposed OPD receiver achieves orders of magnitude higher spectral efficiency than the previously reported organic photovoltaic (OPV)-based receivers.

Liquid-like properties of cyclopentadienyl complexes of barium: molecular dynamics simulations of nanoscale droplets.

Cyclopentadienyl complexes of barium have great utility in materials science and engineering, in particular, as precursors in the atomic layer deposition processes, which are required to be fluidic as well as thermally stable and volatile. Here, we investigated the liquid-like properties of cyclopentadienyl barium complexes including (Me5C5)2Ba, (tBu3C5H2)2Ba, (iPr4C5H)2Ba, (iPr5C5)2Ba, and [(SiMe3)3C5H2]2Ba, using molecular dynamics simulations of nanoscale droplets. The compounds were modeled using a recently developed generic force field, GFN-FF. Nanoscale droplets with about 5.0 nm diameters were formed by aggregating 96 molecules of each compound. Simulation results reveal that substituting methyl groups of (Me5C5)2Ba with other alkyl and silyl moieties has a non-negligible effect on the intra- and intermolecular structure and dynamics. In particular, in contrast to more flexible (Me5C5)2Ba, the substitution with five iso-propyl groups to form (iPr5C5)2Ba adds rigidity to the complex with restricted orientational fluctuations for two cyclopentadienyl ligands and arranges molecules parallel to each other with greater probability. In addition, comparison between (tBu3C5H2)2Ba, with three tert-butyl groups, and its silyl analogue, [(SiMe3)3C5H2]2Ba, reveals that intermolecular interactions between the molecules with silyl groups are softer than those with tert-butyl groups and result in broader radial distribution functions, whereas the dynamic properties are similar for both compounds. This work suggests that molecular dynamics simulations contribute to molecular-level understanding of the effect of chemical substitution in organometallic compounds on the intra- and intermolecular properties of molecular liquids.

Autobifunctional Mechanism of Jagged Pt Nanowires for Hydrogen Evolution Kinetics via End-to-End Simulation.

The extraordinary mass activity of jagged Pt nanowires can substantially improve the economics of the hydrogen evolution reaction (HER). However, it is a great challenge to fully unveil the HER kinetics driven by the jagged Pt nanowires with their multiscale morphology. Herein we present an end-to-end framework that combines experiment, machine learning, and multiscale advances of the past decade to elucidate the HER kinetics catalyzed by jagged Pt nanowires under alkaline conditions. The bifunctional catalysis conventionally refers to the synergistic increase in activity by the combination of two different catalysts. We report that monometals, such as jagged Pt nanowires, can exhibit bifunctional characteristics owing to its complex surface morphology, where one site prefers electrochemical proton adsorption and another is responsible for activation, resulting in a 4-fold increase in the activity. We find that the conventional design guideline that the sites with a 0 eV Gibbs free energy of adsorption are optimal for HER does not hold under alkaline conditions, and rather, an energy between -0.2 and 0.0 eV is shown to be optimal. At the reaction temperatures, the high activity arises from low-coordination-number (≤7) Pt atoms exposed by the jagged surface. Our current demonstration raises an emerging prospect to understand highly complex kinetic phenomena on the nanoscale in full by implementing end-to-end multiscale strategies.

Boosting hot electron flux and catalytic activity at metal-oxide interfaces of PtCo bimetallic nanoparticles.

Despite numerous studies, the origin of the enhanced catalytic performance of bimetallic nanoparticles (NPs) remains elusive because of the ever-changing surface structures, compositions, and oxidation states of NPs under reaction conditions. An effective strategy for obtaining critical clues for the phenomenon is real-time quantitative detection of hot electrons induced by a chemical reaction on the catalysts. Here, we investigate hot electrons excited on PtCo bimetallic NPs during H2 oxidation by measuring the chemicurrent on a catalytic nanodiode while changing the Pt composition of the NPs. We reveal that the presence of a CoO/Pt interface enables efficient transport of electrons and higher catalytic activity for PtCo NPs. These results are consistent with theoretical calculations suggesting that lower activation energy and higher exothermicity are required for the reaction at the CoO/Pt interface.

Single-atom catalysts for CO2 electroreduction with significant activity and selectivity improvements.

A single-atom catalyst (SAC) has an electronic structure that is very different from its bulk counterparts, and has shown an unexpectedly high specific activity with a significant reduction in noble metal usage for CO oxidation, fuel cell and hydrogen evolution applications, although physical origins of such performance enhancements are still poorly understood. Herein, by means of density functional theory (DFT) calculations, we for the first time investigate the great potential of single atom catalysts for CO2 electroreduction applications. In particular, we study a single transition metal atom anchored on defective graphene with single or double vacancies, denoted M@sv-Gr or M@dv-Gr, where M = Ag, Au, Co, Cu, Fe, Ir, Ni, Os, Pd, Pt, Rh or Ru, as a CO2 reduction catalyst. Many SACs are indeed shown to be highly selective for the CO2 reduction reaction over a competitive H2 evolution reaction due to favorable adsorption of carboxyl (*COOH) or formate (*OCHO) over hydrogen (*H) on the catalysts. On the basis of free energy profiles, we identified several promising candidate materials for different products; Ni@dv-Gr (limiting potential UL = -0.41 V) and Pt@dv-Gr (-0.27 V) for CH3OH production, and Os@dv-Gr (-0.52 V) and Ru@dv-Gr (-0.52 V) for CH4 production. In particular, the Pt@dv-Gr catalyst shows remarkable reduction in the limiting potential for CH3OH production compared to any existing catalysts, synthesized or predicted. To understand the origin of the activity enhancement of SACs, we find that the lack of an atomic ensemble for adsorbate binding and the unique electronic structure of the single atom catalysts as well as orbital interaction play an important role, contributing to binding energies of SACs that deviate considerably from the conventional scaling relation of bulk transition metals.

Adsorption of Carbon Dioxide on Unsaturated Metal Sites in M2 (dobpdc) Frameworks with Exceptional Structural Stability and Relation between Lewis Acidity and Adsorption Enthalpy.

A series of metal-organic frameworks (MOFs) M2 (dobpdc) (M=Mn, Co, Ni, Zn; H4 dobpdc=4,4'-dihydroxy-1,1'-biphenyl-3,3'-dicarboxylic acid), with a highly dense arrangement of open metal sites along hexagonal channels were prepared by microwave-assisted or simple solvothermal reactions. The activated materials were structurally expanded when guest molecules including CO2 were introduced into the pores. The Lewis acidity of the open metal sites varied in the order MnZn, as confirmed by C=O stretching bands in the IR spectra, which are related to the CO2 adsorption enthalpy. DFT calculations revealed that the high CO2 binding affinity of transition-metal-based M2 (dobpdc) is primarily attributable to the favorable charge transfer from CO2 (oxygen lone pair acting as a Lewis base) to the open metal sites (Lewis acid), while electrostatic effects, the underlying factor responsible for the particular order of binding strength observed across different transition metals, also play a role. The framework stability against water coincides with the order of Lewis acidity. In this series of MOFs, the structural stability of Ni2 (dobpdc) is exceptional; it endured in water vapor, liquid water, and in refluxing water for one month, and the solid remained intact on exposure to solutions of pH 2-13. The DFT calculations also support the experimental finding that Ni2 (dobpdc) has higher chemical stability than the other frameworks.