Rational Design of Fluorinated 2D Polymer Film Based on Donor-Accepter Architecture toward Multilevel Memory Device for Neuromorphic Computing.

Fluorine-containing 2D polymer (F-2DP) film is a desired system to regulate the charge transport in organic electronics but rather rarely reports due to the limited fluorine-containing building blocks and difficulties in synthesis. Herein, a novel polar molecule with antiparallel columnar stacking is synthesized and further embedded into an F-2DP system to control over the crystallinity of F-2DP film through self-complementary π-electronic forces. The donor-accepter-accepter'-donor' (D-A-A'-D') structure regulates the charge transportation efficiently, inducing multilevel memory behavior through stepwise charge capture and transfer processes. Thus, the device exhibits ternary memory behavior with low threshold voltage (Vth1 of 1.1 V, Vth2 of 2.0 V), clearly distinguishable resistance states (1:102:104) and ternary yield (83%). Furthermore, the stepwise formation of the charge complex endows the device with a wider range to regulate the conductive state, which allows its application in brain-inspired neuromorphic computing. Modified National Institute of Standards and Technology recognition can reach an accuracy of 86%, showing great potential in neuromorphic computing applications in the post-Moore era.

Synthesis of a covalent organic framework with hetero-environmental pores and its medicine co-delivery application.

The topology type and the functionalization of pores play an important role in regulating the performance of covalent organic frameworks. Herein, we designed and synthesized the covalent organic framework with hetero-environmental pores using predesigned asymmetrical dialdehyde monomer. According to the results of structural characterization, crystallinity investigation, and theoretical calculation, the hetero-environmental pores of the obtained framework are regarded as the alternant arrangement. The distinctive hetero pore structure leads the designed material to show more advantages as compared with control materials in loading both hydrophobic and hydrophilic antibiotics for wound healing. This dual-antibiotic strategy can expand the antibacterial range as compared with the single antibiotic one, and reduce the generation of drug resistance. In summary, this strategy for designing covalent organic frameworks with hetero-environmental pores can extend the structural variety and provide a pathway for improving the practical application performance of these materials.

Linkages Make a Difference in the Photoluminescence of Covalent Organic Frameworks.

Covalent organic frameworks (COFs) with structural designability and tunability of photophysical properties enable them to be a promising class of organic luminescent materials by incorporating well-designed fluorescent units directly into the periodic skeletons. The photophysical properties of COFs are mainly affected by the structural features, which determine the conjugation degree, charge delocalization ability, and exciton dynamics of COFs. To understand the relationship between COF structures and their photophysical properties, two COFs with the same pyrene chromophore units but different linkages (imine or vinylene) were designed and synthesized. Interestingly, different linkages endow COFs with huge differences in solid-state photoluminescence quantum yield (PLQY) for imine- and vinylene-linked pyrene-based COFs, which possess PLQY values of 0.34 % and 15.43 %, respectively. The femtosecond-transient absorption spectra and time-dependent density functional theory reveal the different charge-transfer pathways in imine- and vinylene-linked COFs, which influence the exciton relaxation way and fluorescence intensity. In addition, an effective white-light device was obtained by coating the vinylene-linked COF on a light-emitting diode strip.

A Fully Conjugated Covalent Organic Framework with Oxidative and Reductive Sites for Photocatalytic Carbon Dioxide Reduction with Water.

Constructing a powerful photocatalytic system that can achieve the carbon dioxide (CO2 ) reduction half-reaction and the water (H2 O) oxidation half-reaction simultaneously is a very challenging but meaningful task. Herein, a porous material with a crystalline topological network, named viCOF-bpy-Re, was rationally synthesized by incorporating rhenium complexes as reductive sites and triazine ring structures as oxidative sites via robust -C=C- bond linkages. The charge-separation ability of viCOF-bpy-Re is promoted by low polarized π-bridges between rhenium complexes and triazine ring units, and the efficient charge-separation enables the photogenerated electron-hole pairs, followed by an intramolecular charge-transfer process, to form photogenerated electrons involved in CO2 reduction and photogenerated holes that participate in H2 O oxidation simultaneously. The viCOF-bpy-Re shows the highest catalytic photocatalytic carbon monoxide (CO) production rate (190.6 µmol g-1 h-1 with about 100 % selectivity) and oxygen (O2 ) evolution (90.2 µmol g-1 h-1 ) among all the porous catalysts in CO2 reduction with H2 O as sacrificial agents. Therefore, a powerful photocatalytic system was successfully achieved, and this catalytic system exhibited excellent stability in the catalysis process for 50 hours. The structure-function relationship was confirmed by femtosecond transient absorption spectroscopy and density functional theory calculations.

Numerical Study on Thermal Stress of High Temperature Proton Exchange Membrane Fuel Cells during Start-Up Process.

High-temperature proton-exchange membrane fuel cells (HT-PEMFCs) with phosphoric-doped polybenzimidazole (PBI) membranes have a higher operating temperature compared to the PEMFCs operating below 373.15 K. The fuel cell is first heated from room temperature to the minimum operating temperature to avoid the generation of liquid water. The existence of liquid water can result in the loss of phosphoric acid and then affect the cell performance. In this study, the start-up process of HT-PEMFCs is numerically studied by establishing a three-dimensional non-isothermal mathematical model. Preheated gas is supplied into gas flow channels to heat the fuel cell, and then voltage load is applied to accelerate the start-up process. Effects of voltage (0.9 V, 0.7 V and 0.5 V) and flow arrangement (co-flow and counter flow) on temperature, current density, proton conductivity and stress distributions of fuel cells are examined. It is found that the maximum stress is increased when a lower voltage is adopted, and the counter-flow arrangement provides a more uniform stress distribution than that of co-flow arrangement.

Fluorine-Containing Covalent Organic Frameworks: Synthesis and Application.

Covalent organic frameworks (COFs) are a type of crystalline porous polymers that possess ordered structures and eternal pores. Because of their unique structural characteristics and diverse functional groups, COFs have been used in various application fields, such as adsorption, catalysis, separation, ion conduction, and energy storage. Among COFs, the fluorine-containing COFs (fCOFs) have been developed for special applications by virtue of special physical and chemical properties resulting from fluorine element, which is a nonmetallic halogen element and possesses strong electronegativity. In the organic chemistry field, introducing fluorine into chemicals enables those chemicals to exhibit many interesting properties, and fluorine chemistry increasingly plays an important role in the history of chemical development. The introduction of fluorine in COFs can enhance the crystallinity, porosity, and stability of COFs, making COFs having superior performances and some new applications. In this review, the synthesis and application of fCOFs are systematically summarized. The application involves photocatalytic production of hydrogen peroxide, photocatalytic water splitting, electrocatalytic CO2 reduction, adsorption for different substances (H2 , pesticides, per-/polyfluoroalkyl substances, polybrominated diphenyl ethers, bisphenols, and positively charged organic dye molecules), oil-water separation, energy storage (e.g., zinc-ion batteries, lithium-sulfur batteries), and proton conduction. Perspectives of remaining challenges and possible directions for fCOFs are also discussed.

Impact of Membrane Phosphoric Acid Doping Level on Transport Phenomena and Performance in High Temperature PEM Fuel Cells.

In this work, a three-dimensional mathematical model including the fluid flow, heat transfer, mass transfer, and charge transfer incorporating electrochemical reactions was developed and applied to investigate the transport phenomena and performance in high-temperature proton exchange membrane fuel cells (HT-PEMFCs) with a membrane phosphoric acid doping level of 5, 7, 9, 11. The cell performance is evaluated and compared in terms of the polarization curve. The distributions of temperature, oxygen mass fraction, water mass fraction, proton conductivity, and local current density of four cases are given and compared in detail. Results show that the overall performance and local transport characteristics are significantly affected by the membrane phosphoric acid doping level.

Bimetallic PdCu Nanoparticles for Electrocatalysis: Multiphase or Homogeneous Alloy?

Crystal phase structure of bimetallic alloy is an important factor determining the electrocatalytic activity toward oxidation of energy molecules. In this paper, PdCu bimetallic NPs with similar element composition and different crystal phase structural features have been synthesized hydrothermally by adjusting the content of ethylenediaminetetraacetic acid disodium salt (EDTA-2Na). Multiphase PdCu NPs composed of pure Pd and alloy phase are obtained with a low concentration (even as low as zero) of EDTA-2Na in synthetic systems while homogeneous PdCu alloy NPs are formed in the presence of EDTA-2Na with a high concentration. The catalytic activity of ethanol electrooxidation is increased from 3.1 mA·cm-2 of pure Pd NPs, to 3.6 mA·cm-2 of multiphase PdCu NPs, and to 5.0 mA·cm-2 of homogeneous PdCu alloy NPs (about 2360 mA mgPd-1). The surface composition and structural stability of homogeneous PdCu NPs were much less damaged during electrochemical measurements. Based on the experimental data, the formation mechanism of multiphase and homogeneous PdCu NPs and their structure-property relationship have been discussed.

Preparation of Hierarchical Highly Ordered Porous Films of Brominated Poly(phenylene oxide) and Hydrophilic SiO2/C Membrane via the Breath Figure Method.

Porous permeable films materials have very broad prospects in the treatment of sludge-containing waste water due to their large surface area and good microfiltration. In this work, highly ordered porous membranes have been prepared successfully on ice substrates using a poly(phenylene oxide) (BPPO)-SiO2 nanoparticle (NP) mixture by the brePorous permeable films materials have very broad prospects in the treatment of sludge-containing waste water due to their large surface area and good microfiltration. In this work, highly ordered porous membranes have been prepared successfully on ice substrates using aath figure method. Based on the theory of Pickering emulsion system and capillary flow, particle assisted membrane formation was analyzed. Another two sorts of new membranes SiO2/C membrane and hierarchical porous polymer (HPP) membrane, which were obtained by modification of the BPPO-SiO2 membrane by calcination and etching, were set up in a further study. Their properties were investigated through the methods of scanning electron microscopy (SEM), fourier transform infrared spectrometry (FTIR), ultraviolet spectrum (UV), capillary electrophoresis (CE), contact angle, and water flux tests. All these results demonstrate that both surface hydrophilicity and fouling resistance of the membrane would be improved by using SiO2 as a filler. The membranes with high permeability and antifouling properties were used for microfiltration applications.