Boosting the Photocatalytic Hydrogen Evolution Activity for D-π-A Conjugated Microporous Polymers by Statistical Copolymerization.

Recently, great progress has been achieved in the design and preparation of conjugated organic polymer photocatalysts for hydrogen generation. However, it is still challenging to develop an organic polymer photocatalyst with high photoconversion efficiency. Rational structure design of organic polymer photocatalysts holds the key point to realize high photocatalytic performance. Herein, a series of donor-π-acceptor (D-π-A) conjugated organic copolymer photocatalysts is developed using statistical copolymerization by tuning the feed molar ratio of pyrene (donor) to dibenzothiophene-S,S-dioxide (acceptor) units. It reveals that the photocatalytic activity of the resulting copolymers is significantly dependent on the molar ratio of donor to acceptor, which efficiently changes the polymer structure and component. When the monomer feed ratio is 25:75, the random copolymer PyBS-3 of 10 mg with Pt cocatalyst shows a high hydrogen evolution rate of 1.05 mmol h-1 under UV/Vis light irradiation using ascorbic acid as the hole-scavenger, and an external quantum efficiency of 29.3% at 420 nm, which represents the state-of-the-art of organic polymer photocatalysts. This work demonstrates that statistical copolymerization is an efficient strategy to optimize the polymer structure for improving the photocatalytic activity of conjugated organic polymer catalysts.

Dodecacyclic-Fused Electron Acceptors with Multiple Electron-Deficient Units for Efficient Organic Solar Cells.

Fused aromatic cores in non-fullerene electron acceptors (NFEAs) play a significant role in determining their optoelectronic properties and photovoltaic performance. In this work, a dodecacyclic-fused core with three electron-deficient units is synthesized through a double intramolecular Cadogan reduction cyclization. Terminal groups with different halogen substitution (F or Cl) are grafted onto the dodecacyclic-fused core to afford MS-4F and MS-4Cl, both of which showed strong and broad absorption, narrow bandgaps around 1.40 eV, and variable molecular packing model in pristine and blend films. Photovoltaic performance of solar cells containing MS-4F and MS-4Cl as NFEAs were investigated with resultant power conversion efficiencies (PCEs) of 11.75 % and 11.79 %, respectively. The mechanism study indicates that both of PBDB-T : MS-4F- and PBDB-T : MS-4Cl-based devices displayed high hole and electron mobility values, efficient charge transfer, and low charge recombination etc. These results indicate that designing multiple-fused aromatic cores with multiple electron-deficient units is a promising strategy to obtain high-performance NFEAs.

A Truxenone-based Covalent Organic Framework as an All-Solid-State Lithium-Ion Battery Cathode with High Capacity.

All-solid-state lithium ion batteries (LIBs) are ideal for energy storage given their safety and long-term stability. However, there is a limited availability of viable electrode active materials. Herein, we report a truxenone-based covalent organic framework (COF-TRO) as cathode materials for all-solid-state LIBs. The high-density carbonyl groups combined with the ordered crystalline COF structure greatly facilitate lithium ion storage via reversible redox reactions. As a result, a high specific capacity of 268 mAh g-1 , almost 97.5 % of the calculated theoretical capacity was achieved. To the best of our knowledge, this is the highest capacity among all COF-based cathode materials for all-solid-state LIBs reported so far. Moreover, the excellent cycling stability (99.9 % capacity retention after 100 cycles at 0.1 C rate) shown by COF-TRO suggests such truxenone-based COFs have great potential in energy storage applications.

Estimation of the Continuous and Discontinuous Leverage Effects.

This paper examines the leverage effect, or the generally negative covariation between asset returns and their changes in volatility, under a general setup that allows the log-price and volatility processes to be Itô semimartingales. We decompose the leverage effect into continuous and discontinuous parts and develop statistical methods to estimate them. We establish the asymptotic properties of these estimators. We also extend our methods and results (for the continuous leverage) to the situation where there is market microstructure noise in the observed returns. We show in Monte Carlo simulations that our estimators have good finite sample performance. When applying our methods to real data, our empirical results provide convincing evidence of the presence of the two leverage effects, especially the discontinuous one.

Fluorescent Supramolecular Polymers Based on Pillar[5]arene for OLED Device Fabrication.

A series of AA/BB-type supramolecular polymers (SP1-3) based on pillar[5]arene host-guest interactions was developed and their photoelectric properties were further evaluated. The formation of SP1 was confirmed by multiple measurements via nuclear magnetic resonance and specific viscosity studies. The electroluminescence properties of SP1-3 were also investigated. As a result of the efficient energy transfer caused by the exciton trapping on narrow band gap guest G2, by applying a doping strategy, the light-emitting color of the resulting polymers could be easily turned from blue to green. Meanwhile, photoluminescent efficiencies up to 81.6% were obtained. All the supramolecular polymers prepared in this work were utilized as the emissive layers (EMLs) in light-emitting devices and a maximum luminance efficiency (LE) of nearly 5 cd A-1 was achieved.

A series of blue supramolecular polymers with different counterions for polymer light-emitting diodes.

A series of blue supramolecular polymers with different counterions based on host-guest interactions were developed for polymer light-emitting diodes. It was found that the counterions play important roles in the resulting materials' supramolecular interactions as well as the device performance.