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Organic semiconductors, such as carbon nitride, when employed as powders, show attractive photocatalytic properties, but their photoelectrochemical performance suffers from low charge transport capability, charge carrier recombination, and self-oxidation. High film-substrate affinity and well-designed heterojunction structures may address these issues, achieved through advanced film generation techniques. Here, we introduce a spin coating pretreatment of a conductive substrate with a multipurpose polymer and a supramolecular precursor, followed by chemical vapor deposition for the synthesis of dual-layer carbon nitride photoelectrodes. These photoelectrodes are composed of a porous microtubular top layer and an interlayer between the porous film and the conductive substrate. The polymer improves the polymerization degree of carbon nitride and introduces C-C bonds to increase its electrical conductivity. These carbon nitride photoelectrodes exhibit state-of-the-art photoelectrochemical performance and achieve high yield in C-H functionalization. This carbon nitride photoelectrode synthesis strategy may be readily adapted to other reported processes to optimize their performance., (© 2023. The Author(s).)

In addition to causing trillion-dollar economic losses every year, counterfeiting threatens human health, social equity and national security. Current materials for anti-counterfeiting labelling typically contain toxic inorganic quantum dots and the techniques to produce unclonable patterns require tedious fabrication or complex readout methods. Here we present a nanoprinting-assisted flash synthesis approach that generates fluorescent nanofilms with physical unclonable function micropatterns in milliseconds. This all-in-one approach yields quenching-resistant carbon dots in solid films, directly from simple monosaccharides. Moreover, we establish a nanofilm library comprising 1,920 experiments, offering conditions for various optical properties and microstructures. We produce 100 individual physical unclonable function patterns exhibiting near-ideal bit uniformity (0.492 ± 0.018), high uniqueness (0.498 ± 0.021) and excellent reliability (>93%). These unclonable patterns can be quickly and independently read out by fluorescence and topography scanning, greatly improving their security. An open-source deep-learning model guarantees precise authentication, even if patterns are challenged with different resolutions or devices., (© 2023. The Author(s).)

The metal organic framework structure ZIF-8 has been grown directly on vertically aligned carbon nano tubes (VACNT) by a solid vapour transformation of a ZnO@VACNT composite with gaseous 2-methylimidazole. The ZnO@VACNT composite was synthesised by atomic layer deposition (ALD) using diethylzinc and water as precursors resulting in a homogeneous distribution of crystalline ZnO particles with an average size of 13 nm within the 3D VACNT host structure. The ZnO@VACNT composite was transformed to ZIF-8 by reaction with 2-methyl-imidazole (Hmim) while maintaining the 3D VACNT structure employing a solid vapour transformation reaction. Reaction time and temperature were identified as key parameters to control the generated surface area and the degree of conversion of the nanoscaled ZnO particles. 80 °C and 72 h were found to be sufficient for a complete conversion while longer reaction times result in even higher surface areas of the formed ZIF-8@VACNT composite. Surface areas of up to 1569 m 2 g -1 could be achieved. Temperatures below 80 °C led to an incomplete conversion even under longer reaction times of up to 6 weeks. Finally, the CO 2 adsorption properties of the ZIF-8@VACNT composite were evaluated. A composite with a 27 w% content of CNTs and a surface area of 1277 m 2 g -1 shows an adsorption of 6.05 mmol g -1 CO 2 at 30 bar. From the comparison with the pristine materials ZIF-8 and VACNT alone the observed overall CO 2 adsorption behaviour of the composite is a combination of the behaviour of the individual components, ZIF-8 and VACNTs. Namely the typical steep rise of the ZIF-8 in the low-pressure regime with a nearly linear steady progression in the medium pressure size regime, the latter typical for VACNTs, proves that the combination of both components leads to enhanced adsorption properties of the ZIF-8@VACNT composite compared to the sole components ZIF-8 and VACNTs.

Magnesium-Sulfur batteries are one of most appealing options among the post-lithium battery systems due to its potentially high energy density, safe and sustainable electrode materials. The major practical challenges are originated from the soluble magnesium polysulfide intermediates and their shuttling between the electrodes, which cause high overpotentials, low sulfur utilization, and poor Coulombic efficiency. Herein, a functional Mo 6 S 8 modified separator is designed to effectively address these issues. Both the experimental results and density functional theory calculations show that the electrochemically active Mo 6 S 8 layer has a superior adsorption capability of polysulfides and simultaneously acts as a mediator to accelerate the polysulfide conversion kinetics. Remarkably, the magnesium-sulfur cell assembled with the functional separator delivers a high specific energy density (942.9 mA h g -1 in the 1st cycle) and can be cycled at 0.2 C for 200 cycles with a Coulombic efficiency of 96%. This work demonstrates a new design concept toward high-performance metal-sulfur batteries., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Fabrication of hybrid photoelectrodes on a subsecond timescale with low energy consumption and possessing high photocurrent densities remains a centerpiece for successful implementation of photoelectrocatalytic synthesis of fuels and value-added chemicals. Here, we introduce a laser-driven technology to print sensitizers with desired morphologies and layer thickness onto different substrates, such as glass, carbon, or carbon nitride (CN). The specially designed process uses a thin polymer reactor impregnated with transition metal salts, confining the growth of transition metal oxide (TMO) nanostructures on the interface in milliseconds, while their morphology can be tuned by the laser. Multiple nano-p-n junctions at the interface increase the electron/hole lifetime by efficient charge trapping. A hybrid copper oxide/CN photoanode with optimal architecture reaches 10 times higher photocurrents than the pristine CN photoanode. This technology provides a modular approach to build a library of TMO-based composite films, enabling the creation of materials for diverse applications.

Invited for the cover of this issue is Jörg J. Schneider and co-workers at Technical University Darmstadt, Helmholtz-Zentrum Dresden-Rossendorf and KIT Karlsruhe. The image depicts the application of high energy generated electron/positron couples which are able to detect defects sites in semiconducting zinc oxide thin films. Read the full text of the article at 10.1002/chem.202004270., (© 2021 Wiley-VCH GmbH.)

Zinc oxide thin films are fabricated by controlled oxidation of sputtered zinc metal films on a hotplate in air at temperatures between 250 and 450 °C. The nanocrystalline films possess high relative densities and show preferential growth in (100) orientation. Integration in thin-film transistors reveals moderate charge carrier mobilities as high as 0.2 cm 2  V -1 s -1 . The semiconducting properties depend on the calcination temperature, whereby the best performance is achieved at 450 °C. The defect structure of the thin ZnO film can be tracked by Doppler-broadening positron annihilation spectroscopy as well as positron lifetime studies. Comparably long positron lifetimes suggest interaction of zinc vacancies (V Zn ) with one or more oxygen vacancies (V O ) in larger structural entities. Such V O -V Zn defect clusters act as shallow acceptors, and thus, reduce the overall electron conductivity of the film. The concentration of these defect clusters decreases at higher calcination temperatures as indicated by changes in the S and W parameters. Such zinc oxide films obtained by conversion of metallic zinc can also be used as seed layers for solution deposition of zinc oxide nanowires employing a mild microwave-assisted process. The functionality of the obtained nanowire arrays is tested in a UV sensor device. The best results with respect to sensor sensitivity are achieved with thinner seed layers for device construction., (© 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The high-theoretical-capacity (∼170 mAh/g) Prussian white (PW), Na x Fe[Fe(CN) 6 ] y · n H 2 O, is one of the most promising candidates for Na-ion batteries on the cusp of commercialization. However, it has limitations such as high variability of reported stable practical capacity and cycling stability. A key factor that has been identified to affect the performance of PW is water content in the structure. However, the impact of airborne moisture exposure on the electrochemical performance of PW and the chemical mechanisms leading to performance decay have not yet been explored. Herein, we for the first time systematically studied the influence of humidity on the structural and electrochemical properties of monoclinic hydrated (M-PW) and rhombohedral dehydrated (R-PW) Prussian white. It is identified that moisture-driven capacity fading proceeds via two steps, first by sodium from the bulk material reacting with moisture at the surface to form sodium hydroxide and partial oxidation of Fe 2+ to Fe 3+ . The sodium hydroxide creates a basic environment at the surface of the PW particles, leading to decomposition to Na 4 [Fe(CN) 6 ] and iron oxides. Although the first process leads to loss of capacity, which can be reversed, the second stage of degradation is irreversible. Over time, both processes lead to the formation of a passivating surface layer, which prevents both reversible and irreversible capacity losses. This study thus presents a significant step toward understanding the large performance variations presented in the literature for PW. From this study, strategies aimed at limiting moisture-driven degradation can be designed and their efficacy assessed.

The European Union has proposed the value of 1 ng L - 1 as a drinking water quality standard for estradiol. With conventional technologies only partially removing estradiol, the investigation of novel alternatives is more than ever required. Tagliavini and Schäfer proposed that the use of a thin activated carbon layer combined with a membrane is worth considering. In this work, the process was further advanced through a systematic investigation of the role of activated carbon size, activation and surface chemistry on the removal of estradiol. The use of smaller carbon particles allows reaching the ambitious target value of 1 ng L - 1 in a millimetric layer. Further, adsorption kinetic enhancement by increasing the oxygen content on the carbon improves the removal from 96 to 99 % (for a layer of 2 mm) for OH-containing pollutants such as estradiol. High removal, together with low pressure and no by-product formation, are characteristics that make the UF-PBSAC a promising and competitive approach., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier Ltd.)

Low-bandgap polymers are widely used as p-type components in photoactive layers of organic solar cells, due to their ability to capture a large portion of the solar spectrum. The comprehension of their supramolecular assembly is crucial in achieving high-performance organic electronic devices. Here we synthezed two exemplar low-bandgap cyclopentadithiophene (CPDT):diketopyrrolopyrrole (DPP)-based polymers, with either a twelve carbon (C12) or a tri etyleneglycol (TEG) side chains on the DPP units (respectively denoted PCPDTDPP_C12 and PCPDTDPP_TEG). We deposited Langmuir-Schaefer films of these polymers blended with the widely used electron donor material [6,6]-phenyl-C61-butyric-acid methyl ester (PCBM). We then characterized the conformational, optical and morphological properties of these films. From the monolayers to the solid films, we observed distinct self-organization and surface properties for each polymer due to the distinct nature of their side chains. Emphasizing their attraction interactions with PCBM and the phase transitions according to the surface pressure. The elements amount on the surface, calculated through the XPS, gave us a good insight on the polymers' conformations. Through UV-visible absorption spectroscopy, the improvement in the PCPDTDPP film ordering upon PCBM addition is evident and we saw the contribution of the polymer units on the optical response. Chemical attributions of the polymers were assigned using FTIR Spectroscopy and Raman Scattering, revealing the physical interaction after mixing the materials. We showed that it is possible to build nanostructured PCPDTDPPs films with a high control of their molecular properties through an understanding of their self-assembly and interactions with an n-type material.

The development of multivalent metal (such as Mg and Ca) based battery systems is hindered by lack of suitable cathode chemistry that shows reversible multi-electron redox reactions. Cationic redox centres in the classical cathodes can only afford stepwise single-electron transfer, which are not ideal for multivalent-ion storage. The charge imbalance during multivalent ion insertion might lead to an additional kinetic barrier for ion mobility. Therefore, multivalent battery cathodes only exhibit slope-like voltage profiles with insertion/extraction redox of less than one electron. Taking VS 4 as a model material, reversible two-electron redox with cationic-anionic contributions is verified in both rechargeable Mg batteries (RMBs) and rechargeable Ca batteries (RCBs). The corresponding cells exhibit high capacities of >300 mAh g -1 at a current density of 100 mA g -1 in both RMBs and RCBs, resulting in a high energy density of >300 Wh kg -1 for RMBs and >500 Wh kg -1 for RCBs. Mechanistic studies reveal a unique redox activity mainly at anionic sulfides moieties and fast Mg 2+ ion diffusion kinetics enabled by the soft structure and flexible electron configuration of VS 4 ., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

The deposition of polyelectrolyte multilayers, obtained by the layer-by-layer (LbL) method, is a well-established technology to design biocompatible and antibacterial coatings aimed at preventing implant-associated infections. Several types of LbL films have been reported to exhibit antiadhesive and/or antibacterial (contact-killing or release-killing) properties governed not only by the incorporated compounds but also by their buildup conditions or their postbuildup treatments. Tannic acid (TA), a natural polyphenol, is known to inhibit the growth of several bacterial strains. In this work, we developed TA/collagen (TA/COL) LbL films built in acetate or citrate buffers at pH 4. Surprisingly, the used buffer impacts not only the physicochemical but also the antibacterial properties of the films. When incubated in physiological conditions, both types of TA/COL films released almost the same amount of TA depending on the last layer and showed an antibacterial effect against Staphylococcus aureus only for citrate-built films. Because of their granular topography, TA/COL citrate films exhibited an efficient release-killing effect with no cytotoxicity toward human gingival fibroblasts. Emphasis is put on a comprehensive evaluation of the physicochemical parameters driving the buildup and the antibacterial property of citrate films. Specifically, complexation strengths between TA and COL are different in the presence of the two buffers affecting the LbL deposition. This work constitutes an important step toward the use of polyphenols as an antibacterial agent when incorporated in LbL films.

Metallic lithium is considered to be one of the most promising anode materials since it offers high volumetric and gravimetric energy densities when combined with high-voltage or high-capacity cathodes. However, the main impediment to the practical applications of metallic lithium is its unstable solid electrolyte interface (SEI), which results in constant lithium consumption for the formation of fresh SEI, together with lithium dendritic growth during electrochemical cycling. Here we present the electrochemical performance of a fluorinated reduced graphene oxide interlayer (FGI) on the metallic lithium surface, tested in lithium symmetrical cells and in combination with two different cathode materials. The FGI on the metallic lithium exhibit two roles, firstly it acts as a Li-ion conductive layer and electronic insulator and secondly, it effectively suppresses the formation of high surface area lithium (HSAL). An enhanced electrochemical performance of the full cell battery system with two different types of cathodes was shown in the carbonate or in the ether based electrolytes. The presented results indicate a potential application in future secondary Li-metal batteries.