One‐pot chemical vapor deposition (CVD) growth of large‐area Janus SeMoS monolayers is reported, with the asymmetric top (Se) and bottom (S) chalcogen atomic planes with respect to the central transition metal (Mo) atoms. The formation of these 2D semiconductor monolayers takes place upon the thermodynamic‐equilibrium‐driven exchange of the bottom Se atoms of the initially grown MoSe₂ single crystals on gold foils with S atoms. The growth process is characterized by complementary experimental techniques including Raman and X‐ray photoelectron spectroscopy, transmission electron microscopy, and the growth mechanisms are rationalized by first principle calculations. The remarkably high optical quality of the synthesized Janus monolayers is demonstrated by optical and magneto‐optical measurements which reveal the strong exciton–phonon coupling and enable an exciton g‐factor of −3.3.

A novel fluorine‐free electrolyte comprising a solution of lithium bis(oxalato)borate in ethyl isopropyl sulfone is presented. It is characterized by its safety and non‐toxic properties, along with the capability to effectively suppress the anodic dissolution of aluminum. Successful high‐temperature application of this electrolyte in combination with various capacitor‐ and battery‐like electrode materials is shown. Further utilization in a lithium‐ion capacitor and a lithium‐ion battery is demonstrated. To the best of the knowledge, the lithium‐ion capacitor presented in this work represents the first entirely fluorine‐free device suitable for high‐temperature applications. When operating at 60 °C, this device delivers a maximum energy output of 169 Wh kg⁻¹_AM at a power of 200 W kg⁻¹_AM and even 80 Wh kg¹_AM at 10 kW kg^‐1_AM, along with the ability to retain 80% of its initial capacitance after 3500 cycles at 5 A g⁻¹. As such, this novel electrolyte is a promising alternative to conventional fluorine‐containing configurations since its performance is capable to match or even surpass that of most similar laboratory‐scale LICs.

The anion-intercalation chemistries of graphite have the potential to construct batteries with promising energy and power breakthroughs. Here, we report the use of an ultrathin, positively charged two-dimensional poly(pyridinium salt) membrane (C2DP) as the graphite electrode skin to overcome the critical durability problem. Large-area C2DP enables the conformal coating on the graphite electrode, remarkably alleviating the electrolyte. Meanwhile, the dense face-on oriented single crystals with ultrathin thickness and cationic backbones allow C2DP with high anion-transport capability and selectivity. Such desirable anion-transport properties of C2DP prevent the cation/solvent co-intercalation into the graphite electrode and suppress the consequent structure collapse. An impressive PF₆⁻-intercalation durability is demonstrated for the C2DP-covered graphite electrode, with capacity retention of 92.8% after 1000 cycles at 1 C and Coulombic efficiencies of > 99%. The feasibility of constructing artificial ion-regulating electrode skins with precisely customized two-dimensional polymers offers viable means to promote problematic battery chemistries.

Light-driven production of hydrogen peroxide via selective dioxygen reduction is an attractive “green” alternative to the conventionally used anthraquinone process. One of the most promising classes of photocatalytic materials for this conversion that excels by high selectivity, chemical stability and low cost is represented by polymeric carbon nitrides, and particularly by various types of poly(heptazine imide) (PHI), i.e., ionic variants of carbon nitride. A crucial challenge highlighted by recent studies is the problem of separation of formed H₂O2 from the reaction medium and especially from the suspended photocatalyst particles since photocatalytically generated H₂O2 can undergo light-driven reductive or oxidative decomposition, as well as disproportionation on the surface of the photocatalyst in the dark. Herein, we report an elegant solution to this problem by implementing a biphasic reaction system in which the hydrophobic photocatalyst oxidizes a lipophilic electron donor in the organic phase, while the produced H₂O₂ is instantaneously extracted into the aqueous layer. To this end, we have achieved an effective hydrophobization of ionic carbon nitride (PHI) nanoparticles in the form of a composite with alkylated silica. The hydrophobized composite effectively photocatalyzes the reduction of dioxygen to H₂O₂ with concurrent oxidation of a model fatty alcohol (1-octanol) in the organic phase under visible light irradiation (406 nm LED), and enables, at the same time, facile separation of the high-value H₂O₂/water mixture from the reaction medium at H₂O₂ concentrations (~0.12 mol L^-1) that are unprecedentedly high for light-driven systems reported in the literature. Notably, fatty alcohols are readily available from vegetable waxes and as pulping sub-products, and the products of their partial oxidation represent a valuable feedstock for the synthesis of pharmaceuticals and cosmetic products. This work thus showcases a rational design of a high-performance photocatalytic system for H₂O₂ production that enables easy separation of the product from electron donors and its recovery at high concentrations, and paves the way for sustainable and economically viable light-driven H₂O₂ production from easily available feedstock.

Aromatic self-assembled monolayers (SAMs) can be cross-linked into molecular nanosheets – carbon nanomembranes (CNMs) – via low-energy electron irradiation. Due to their favorable mechanical stability and tunable functional properties, they possess a high potential for various applications including nanosensors and separation membranes for osmosis or energy conversion devices. Despite this potential, the mechanistic details of the electron irradiation induced cross-linking process still need to be understood in more detail. Here, we studied the cross-linking of 4′-nitro-1,1′-biphenyl-4-thiol SAM on gold. The SAM samples were irradiated with different electron energies ranging from 2.5 to 100 eV in ultra-high vacuum and subsequently analysed by complementary techniques. We present results obtained via spectroscopy and microscopy characterization by high-resolution X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction with micrometre sized electron beams (μLEED) and low-energy electron microscopy (LEEM). To demonstrate the formation of CNMs, the formed two-dimensional molecular materials were transferred onto grids and oxidized wafer and analyzed by optical, scanning electron microscopy (SEM) and atomic force microscopy (AFM). We found a strong energy dependence for the cross section for the cross-linking process, the rate of which decreases exponentially towards lower electron energies by about four orders of magnitude. We conduct a comparative analysis of the cross sections for the C–H bond scission via electron impact ionization and dissociative electron attachment and find that these different ionization mechanisms are responsible for the variation of the cross-linking cross section with electron energy.

In spite of the enormous promise that polymeric carbon nitride (PCN) materials hold for various applications, the fabrication of high‐quality, binder‐free PCN films and electrodes has been a largely elusive goal to date. Here, we tackle this challenge by devising, for the first time, a water‐based sol−gel approach that enables facile preparation of thin films based on poly(heptazine imide) (PHI), a polymer belonging to the PCN family. The sol−gel process capitalizes on the use of a water‐soluble PHI precursor that allows formation of a non‐covalent hydrogel. The hydrogel can be deposited on conductive substrates, resulting in formation of mechanically stable polymeric thin layers. The resulting photoanodes exhibit unprecedented photoelectrochemical (PEC) performance in alcohol reforming and highly selective (∼100 %) conversions with very high photocurrents (>0.25 mA cm⁻² under 2 sun) down to <0 V vs. RHE. This enables even effective PEC operation under zero‐bias conditions and represents the very first example of a ‘soft matter’‐based PEC system capable of bias‐free photoreforming. The robust binder‐free films derived from sol−gel processing of water‐soluble PCN thus constitute a new paradigm for high‐performance ‘soft matter’ photoelectrocatalytic systems and pave the way for further applications in which high‐quality PCN films are required.