Modifying Proton Relay into Bioinspired Dye-Based Coordination Polymer for Photocatalytic Proton-Coupled Electron Transfer.

Proton-coupled electron transfer (PCET) imparts an energetic advantage over single electron transfer in activating inert substances. Natural PCET enzyme catalysis generally requires tripartite preorganization of proton relay, substrate-bound active center, and redox mediator, making the processes efficient and precluding side reactions. Inspired by this, a heterogeneous photocatalytic PCET system was established to achieve higher PCET driving forces by modifying proton relays into anthraquinone-based anionic coordination polymers.

Confinement Effect in Metal-Organic Framework Cu() for Enhancing Shape Selectivity of Radical Difunctionalization of Alkenes.

The radical difunctionalization of alkenes plays a vital role in pharmacy, but the conventional homogeneous catalytic systems are challenging in selectivity and sustainability to afford the target molecules. Herein, the famous readily available metal-organic framework (MOF), Cu(), has been applied to cyano-trifluoromethylation of alkenes as a high-performance and recyclable heterogeneous catalyst, which possesses copper(II) active sites residing in funnel-like cavities. Under mild conditions, styrene derivatives and various unactivated olefins could be smoothly transformed into the corresponding cyano-trifluoromethylation products.

A tri-functional self-supported electrocatalyst featuring mostly NiTeO perovskite for H production methanol-water co-electrolysis.

A self-supported NiTeO perovskite is made by deploying an extended hydrothermal tellurization strategy with a restricted Te content, which was found to be exceptionally active towards the oxidation of water and methanol and the reduction of water in 1.0 M KOH where it delivered -10 mA cm at just -1.54 V for a full cell featuring MOR‖HER.

Harnessing Radicals in Confined Supramolecular Environments Made Possible by MOFs.

Researching and utilizing radical intermediates in organic synthetic chemistry have innovated discoveries in methodology and theory. Reactions concerning free radical species opened new pathways beyond the frame of the two-electron mechanism while commonly characterized as rampant processes lacking selectivity. As a result, research in this field has always focused on the controllable generation of radical species and determining factors of selectivity.

A Diode-Like Dye-Cu Anisotropic Junction in a Coordination Polymer as a Logic State Ratchet for Intratumor Redox Photomodulation.

Redox logic materials offer new avenues to modulate intracellular pathologic redox environment area-specifically, but the unambiguity of redox logic states and their unidirectional and repetitive switchability are challenging to realize. By merging a bistable diisophthalic phenazine dye ligand with Cu salt, a multistable coordination polymer (CP) was constructed, of which the dye-Cu anisotropic junction achieved the diode-like unidirectional electron transfer and logic state ratchet for the first time. Radical cationic CP maintained OFF status with low toxicity in healthy tissues, but was reduced to the neutral SERVO state by the overexpressed glutathione (GSH) in hypoxic tumors.

All-Soft Supercapacitors Based on Liquid Metal Electrodes with Integrated Functionalized Carbon Nanotubes.

Soft energy storage devices, such as supercapacitors, are an essential component for powering integrated soft microsystems. However, conventional supercapacitors are mainly manufactured using hard/brittle materials that easily crack and eventually delaminate from the current collector by mechanical deformation. Therefore, to realize all-soft supercapacitors, the electrodes should be soft, stretchable, and highly conductive without compromising the electrochemical performance.

Preparation and application of N-doped carbon nanotube arrays on graphene fibers.

A new kind of carbon hybrid material with a unique structure and outstanding mechanical and functional properties is reported in this article. Nitrogen-doped carbon nanotube (CNT) arrays with inside located Ni particles are in situ grown on the surface of phenolic carbon modified graphene fibers during their conversion from graphene oxide fibers. The carbon hybrid fibers exhibit not only high tensile strength and elongation at the break, but also excellent flexibility since the CNT arrays cover all the surface of the highly strong graphene fiber.

Ultrastrong Graphene-Based Fibers with Increased Elongation.

A new method to prepare graphene-based fibers with ultrahigh tensile strength, conductivity, and increased elongation is reported. It includes wet-spinning the mixture of GO aqueous dispersion with phenolic resin solution in a newly developed coagulation bath, followed by annealing. The introduced phenolic carbon increased densification of graphene fibers through reducing defects and increased interfacial interaction among graphene sheets by forming new C-C bonds, thus resulting in the increasing of stiffness, toughness, and conductivity simultaneously.

Phenolic resin-grafted reduced graphene oxide as a highly stable anode material for lithium ion batteries.

A novel and effective route for preparing phenol formaldehyde resin grafted reduced graphene oxide (rGO-g-PF) electrode materials with highly enhanced electrochemical properties is reported. In order to prepare rGO-g-PF, hydroxymethyl-terminated PF is initially grafted to graphene oxide (GO) via esterification reaction. Subsequently, the grafted GO is reduced by the carbonization process under an inert gas atmosphere.