Thiophene-Based Conjugated Acetylenic Polymers with Dual Active Sites for Efficient Co-Catalyst-Free Photoelectrochemical Water Reduction in Alkaline Medium

Although being attractive materials for photoelectrochemical hydrogen evolution reaction (PEC HER) under neutral or acidic conditions, conjugated polymers still show poor PEC HER performance in alkaline medium due to the lack of water dissociation sites. Herein, we demonstrate that tailoring the polymer skeleton from poly(diethynylthieno[3,2-b]thiophene) (pDET) to poly(2,6-diethynylbenzo[1,2-b:4,5-b′]dithiophene (pBDT) and poly(diethynyldithieno[3,2-b:2′,3′-d]thiophene) (pDTT) in conjugated acetylenic polymers (CAPs) introduces highly efficient active sites for water dissociation. As a result, pDTT and pBDT, grown on Cu substrate, demonstrate benchmark photocurrent densities of 170 μA cm−2 and 120 μA cm−2 (at 0.3 V vs. RHE; pH 13), which are 4.2 and 3 times higher than that of pDET, respectively. Moreover, by combining DFT calculations and electrochemical operando resonance Raman spectroscopy, we propose that the electron-enriched Cβ of the outer thiophene rings of pDTT are the water dissociation active sites, while the −C≡C− bonds function as the active sites for hydrogen evolution

Biobased chiral semi-crystalline or amorphous high-performance polyamides and their scalable stereoselective synthesis

The use of renewable feedstock is one of the twelve key principles of sustainable chemistry. Unfortunately, bio-based compounds often suffer from high production cost and low performance. To fully tap the potential of natural compounds it is important to utilize their functionalities that could make them superior compared to fossil-based resources. Here we show the conversion of (+)-3-carene, a by-product of the cellulose industry into ε-lactams from which polyamides. The lactams are selectively prepared in two diastereomeric configurations, leading to semi-crystalline or amorphous, transparent polymers that can compete with the thermal properties of commercial high-performance polyamides. Copolyamides with caprolactam and laurolactam exhibit an increased glass transition and amorphicity compared to the homopolyamides, potentially broadening the scope of standard polyamides. A four-step one-vessel monomer synthesis, applying chemo-enzymatic catalysis for the initial oxidation step, is established. The great potential of the polyamides is outlined