Triazine Frameworks for the Photocatalytic Selective Oxidation of Toluene.

Investigations into the selective oxidation of inert sp3 C-H bonds using polymer photocatalysts under mild conditions have been limited. Additionally, the structure-activity relationship of photocatalysts often remains insufficiently explored. Here, a series of thiophene-based covalent triazine frameworks (CTFs) are used for the efficient and selective oxidation of hydrocarbons to aldehydes or ketones under ambient aerobic conditions. Spectroscopic methods conducted in situ and density functional theory (DFT) calculations revealed that the sulfur atoms within the thiophene units play a pivotal role as oxidation sites due to the generation of photogenerated holes. The effect of photogenerated holes on photocatalytic toluene oxidation was investigated by varying the length of the spacer in a CTF donor-acceptor based photocatalyst. Furthermore, the manipulation of reactive oxygen species was employed to enhance selectivity by weakening the peroxidative capacity. As an illustrative example, this study successfully demonstrated the synthesis of a precursor of the neurological drug AMG-579 using a photocatalytic protocol.

Covalent Triazine Framework Nanoparticles via Size-Controllable Confinement Synthesis for Enhanced Visible-Light Photoredox Catalysis.

For metal-free, organic conjugated polymer-based photocatalysts, synthesis of defined nanostructures is still highly challenging. Here, we report the formation of covalent triazine framework (CTF) nanoparticles via a size-controllable confined polymerization strategy. The uniform CTF nanoparticles exhibited significantly enhanced activity in the photocatalytic formation of dibenzofurans compared to the irregular bulk material. The optoelectronic properties of the nanometer-sized CTFs could be easily tuned by copolymerizing small amounts of benzothiadiazole into the conjugated molecular network. This optimization of electronic properties led to a further increase in observed photocatalytic efficiency, resulting in total an 18-fold enhancement compared to the bulk material. Full recyclability of the heterogeneous photocatalysts as well as catalytic activity in dehalogenation, hydroxylation and benzoimidazole formation reactions demonstrated the utility of the designed materials.

Enriching and Quantifying Porous Single Layer 2D Polymers by Exfoliation of Chemically Modified van der Waals Crystals.

2D polymer sheets with six positively charged pyrylium groups at each pore edge in a stacked single crystal can be transformed into a 2D polymer with six pyridines per pore by exposure to gaseous ammonia. This reaction furnishes still a crystalline material with tunable protonation degree at regular nano-sized pores promising as separation membrane. The exfoliation is compared for both 2D polymers with the latter being superior. Its liquid phase exfoliation yields nanosheet dispersions, which can be size-selected using centrifugation cascades. Monolayer contents of ≈30 % are achieved with ≈130 nm sized sheets in mg quantities, corresponding to tens of trillions of monolayers. Quantification of nanosheet sizes, layer number and mass shows that this exfoliation is comparable to graphite. Thus, we expect that recent advances in exfoliation of graphite or inorganic crystals (e.g. scale-up, printing etc.) can be directly applied to this 2D polymer as well as to covalent organic frameworks.

Dual-Responsive Photocatalytic Polymer Nanogels.

Selective activation of photocatalysts under constant light conditions has recently been targeted to produce multi-responsive systems. However, controlled activation, with easy recovery of the photocatalysts, induced by external stimuli remains a major challenge. Mimicking the responsiveness of biological systems to multiple triggers can offer a promising solution. Herein, we report dual-responsive polymer photocatalysts in the form of nanogels consisting of a cross-linked poly-N-isopropylacrylamide nanogel, copolymerised with a photocatalytically active monomer. The dual-responsive polymer nanogels undergo a stark decrease in diameter with increasing temperature, which shields the photocatalytic sites, decreasing the activity. Temperature-dependent photocatalytic formation of NAD+ in water demonstrates the ability to switch photocatalysis on and off. Moreover, the photocatalysed syntheses of several fine chemicals were carried out to demonstrate the utility of the designed material.

Recycling Perovskite Solar Cells To Avoid Lead Waste.

Methylammonium lead iodide (MAPbI3) perovskite based solar cells have recently emerged as a serious competitor for large scale and low-cost photovoltaic technologies. However, since these solar cells contain toxic lead, a sustainable procedure for handling the cells after their operational lifetime is required to prevent exposure of the environment to lead and to comply with international electronic waste disposal regulations. Herein, we report a procedure to remove every layer of the solar cells separately, which gives the possibility to selectively isolate the different materials. Besides isolating the toxic lead iodide in high yield, we show that the PbI2 can be reused for the preparation of new solar cells with comparable performance and in this way avoid lead waste. Furthermore, we show that the most expensive part of the solar cell, the conductive glass (FTO), can be reused several times without any reduction in the performance of the devices. With our simple recycling procedure, we address both the risk of contamination and the waste disposal of perovskite based solar cells while further reducing the cost of the system. This brings perovskite solar cells one step closer to their introduction into commercial systems.

Control of Perovskite Crystal Growth by Methylammonium Lead Chloride Templating.

State-of-the-art solar cells based on methylammonium lead iodide (MAPbI3 ) now reach efficiencies over 20 %. This fast improvement was possible with intensive research in perovskite processing. In particular, chloride-based precursors are known to have a positive influence on the crystallization of the perovskite. Here, we used a combination of in-situ X-ray diffraction and charge-transport measurements to understand the influence of chloride during perovskite crystallization in planar heterojunction solar cells. We show that MAPbCl3 crystallizes directly after the deposition of the starting solution and acts as a template for the formation of MAPbI3 . Additionally, we show that the charge-carrier mobility doubles by extending the time for the template formation. Our results give a deeper understanding of the influence of chloride in the synthesis of MAPbI3 and illustrate the importance of carefully controlling crystallization for reproducible, high-efficiency solar cells.