The functional chameleon of materials chemistry—combining carbon structures into all-carbon hybrid nanomaterials with intrinsic porosity to overcome the “functionality-conductivity-dilemma” in electrochemical energy storage and electrocatalysis

Nanoporous carbon materials can cover a remarkably wide range of physicochemical properties. They are widely applied in electrochemical energy storage and electrocatalysis. As a matter of fact, all these applications combine a chemical process at the electrode–electrolyte interface with the transport (and possibly the transfer) of electrons. This leads to multiple requirements which can hardly be fulfilled by one and the same material. This “functionality‐conductivity‐dilemma” can be minimized when multiple carbon‐based compounds are combined into porous all‐carbon hybrid nanomaterials. This article is giving a broad and general perspective on this approach from the viewpoint of materials chemists. The problem and existing solutions are first summarized. This is followed by an overview of the most important design principles for such porous materials, a chapter discussing recent examples from different fields where the formation of comparable structures has already been successfully applied, and an outlook over the future development of this field that is foreseen

Who are the ‘dark’ politicians? Insights from self-reports of German state parliament candidates

A growing body of studies is focusing on politicians' personalities, as the personality of political elites has been shown to affect their behavior. Whereas most research uses the big five framework or HEXACO, only a few studies have been able to capture more "aversive," "dark" - yet non-pathological - personality traits of politicians. However, these studies refer to top politicians; information on the distribution and the correlates of dark personality traits in the broad mass of politicians is still lacking. Moreover, information on dark personality traits in politicians is usually based on expert ratings; data using self-placement is missing. Based on data from six surveys with candidates running for German state elections in 2021 and 2022 (N[pooled data set] = 1,632), we, to the best of our knowledge, offer, for the first time, insights into politicians’ self-reported socially aversive personality traits. "Dark" personality traits are measured by the political elites aversive personality scale (PEAPS). Results show that German politicians exhibit moderate levels of aversive personality traits. In addition, the extent of candidates' dark personalities is strongly negatively correlated with honesty-humility, agreeableness vs. anger, and extraversion, while associations with other basic personality traits are much weaker or insignificant. We also find that younger, more right-leaning, and more ideologically extreme candidates report higher levels of aversive personality

“Giant” nitrogen uptake in ionic liquids confined in carbon pores

Ionic liquids are well known for their high gas absorption capacity. It is shown that this is not a solvent constant, but can be enhanced by another factor of 10 by pore confinement, here of the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate (EmimOAc) in the pores of carbon materials. A matrix of four different carbon compounds with micro- and mesopores as well as with and without nitrogen doping is utilized to investigate the influence of the carbons structure on the nitrogen uptake in the pore-confined EmimOAc. In general, the absorption is most improved for IL in micropores and in nitrogen-doped carbon. This effect is so large that it is already seen in TGA and DSC experiments. Due to the low vapor pressure of the IL, standard volumetric sorption experiments can be used to quantify details of this effect. It is reasoned that it is the change of the molecular arrangement of the ions in the restricted space of the pores that creates additional free volume to host molecular nitrogen

Numerical analysis of the light modulation by the frustule of Gomphonema parvulum : the role of integrated optical components

Siliceous diatom frustules present a huge variety of shapes and nanometric pore patterns. A better understanding of the light modulation by these frustules is required to determine whether or not they might have photobiological roles besides their possible utilization as building blocks in photonic applications. In this study, we propose a novel approach for analyzing the near-field light modulation by small pennate diatom frustules, utilizing the frustule of Gomphonema parvulum as a model. Numerical analysis was carried out for the wave propagation across selected 2D cross-sections in a statistically representative 3D model for the valve based on the finite element frequency domain method. The influences of light wavelength (vacuum wavelengths from 300 to 800 nm) and refractive index changes, as well as structural parameters, on the light modulation were investigated and compared to theoretical predictions when possible. The results showed complex interference patterns resulting from the overlay of different optical phenomena, which can be explained by the presence of a few integrated optical components in the valve. Moreover, studies on the complete frustule in an aqueous medium allow the discussion of its possible photobiological relevance. Furthermore, our results may enable the simple screening of unstudied pennate frustules for photonic applications

Influence of pore architecture and chemical structure on the sodium storage in nitrogen-doped hard carbons

Hard carbon is the material of choice for sodium ion battery anodes. Capacities comparable to those of lithium/graphite can be reached, but the understanding of the underlying sodium storage mechanisms remains fragmentary. A two-step process is commonly observed, where sodium first adsorbs to polar sites of the carbon (“sloping region”) and subsequently fills small voids in the material (“plateau region”). To study the impact of nitrogen functionalities and pore geometry on sodium storage, a systematic series of nitrogen-doped hard carbons is synthesized. The nitrogen content is found to contribute to sloping capacity by binding sodium ions at edges and defects, whereas higher plateau capacities are found for materials with less nitrogen content and more extensive graphene layers, suggesting the formation of 2D sodium structures stabilized by graphene-like pore walls. In fact, up to 84% of the plateau capacity is measured at potentials less than 0 V versus metallic Na, that is, quasimetallic sodium can be stabilized in such structure motifs. Finally, gas physisorption measurements are related to charge–discharge data to identify the energy storage relevant pore architectures. Interestingly, these are pores inaccessible to probe gases and electrolytes, suggesting a new view on such “closed pores” required for efficient sodium storage

Toward efficient synthesis of porous all-carbon-based nanocomposites for enantiospecific separation

Chiral separation and asymmetric synthesis and catalysis are crucial processes for obtaining enantiopure compounds, which are especially important in the pharmaceutical industry. The efficiency of the separation processes is readily increased by using porous materials as the active material can interact with a larger surface area. Silica, metal–organic frameworks, or chiral polymers are versatile porous materials that are established in chiral applications, but their instability under certain conditions in some cases requires the use of more stable porous materials such as carbons. In addition to their stability, porous carbon materials can be tailored for their ability to adsorb and catalytically activate different chemical compounds from the liquid and the gas phase. The difficulties imposed by the functionalization of carbons with chiral species were tackled in the past by carbonizing chiral ionic liquids (CILs) together with a template to create pores, which results in the entire body of a material that is built up from the precursor. To increase the atomic efficiency of ionic liquids for better economic utilization of CILs, the approach presented here is based on the formation of a composite between CIL-derived chiral carbon and a pristine carbon material obtained from carbohydrate precursors. Two novel enantioselective carbon composite materials are applied for the chiral recognition of molecules in the gas phase, as well as in solution. The enantiomeric ratio of the l-composite for phenylalanine from the solution was (L/D) = 8.4, and for 2-butanol from the gas phase, it was (S/R) = 1.3. The d-composite showed an opposite behavior, where the enantiomeric ratio for phenylalanine was (D/L) = 2.7, and for 2-butanol from the gas phase, it was (R/S) = 1.3

Synthesis of polymer Janus particles with tunable wettability profiles as potent solid surfactants to promote gas delivery in aqueous reaction media

Janus particles exhibit a strong tendency to directionally assemble and segregate to interfaces and thus offer advantages as colloidal analogues of molecular surfactants to improve the stability of multiphasic mixtures. Investigation and application of the unique adsorption properties require synthetic procedures that enable careful design and reliable control over the particles’ asymmetric chemistry and wettability profiles with high morphological uniformity across a sample. Herein, we report on a novel one-step synthetic approach for the generation of amphiphilic polymer Janus particles with highly uniform and tunable wettability contrasts, which is based on using reconfigurable bi-phasic Janus emulsions as versatile particle scaffolds. Two phase-separated acrylate oils were used as the constituent droplet phases and transformed into their solidified Janus particle replicas via UV-induced radical polymerization. Using Janus emulsions as particle precursors offers the advantage that their internal droplet geometry can be fine-tuned by changing the force balance of surface tensions acting at the individual interfaces via surfactants or the volume ratio of the constituent phases. In addition, preassembled functional surfactants at the droplet interfaces can be locked in position upon polymerization, which enables both access toward postfunctionalization reaction schemes and the generation of highly uniform Janus particles with adjustable wettability profiles. Depending on the particle morphology and wettability, their interfacial position can be adjusted, which allows us to stabilize either air bubbles-in-water or water droplets-in-air (liquid marbles). Motivated by the interfacial activity of the particles and particularly the longevity of the resulting particle-stabilized air-in-water bubbles, we explored their ability to promote the delivery of oxygen inside a liquid-phase reaction medium, namely, for the heterogeneous Au-NP-mediated catalytic oxidation of d-glucose. We observed a 2.2-fold increase in the reaction rate attributed to the increase of the local concentration of oxygen around catalysts, thus showcasing a new strategy to overcome the limited solubility of gases in aqueous reaction media

Insights into the sodiation mechanism of hard carbon-like materials from electrochemical impedance spectroscopy

To render the sodium ion battery (SIB) competitive among other technologies, the processes behind sodium storage in hard carbon anodes must be understood. For this purpose, electrochemical impedance spectroscopy (EIS) is usually undervalued, since fitting the spectra with equivalent circuit models requires an a-priori knowledge about the system at hand. The analysis of the distribution of relaxation times (DRT) is an alternative, which refrains from fitting arbitrarily nested equivalent circuits. In this paper, the sodiation and desodiation of a hard carbon anode is studied by EIS at different states of charge (SOC). By reconstructing the DRT function, highly resolved information on the number and relative contribution of individual electrochemical processes is derived. During the sloping part of the sodiation curve, mass transport is found to be the most dominant source of resistance but rapidly diminishes when the plateau phase is reached. An equivalent circuit model, qualitatively reproducing the experimental data of the sloping region was built upon the DRT results, which is particularly useful for future EIS studies on hard carbon SIB anodes. More importantly, this work contributes to establish EIS as a practical tool to directly study electrode processes without the bias of a previously assumed model

Understanding structure-property relationships under experimental conditions for the optimization of lithium ion capacitor anodes based on all-carbon-composite materials

The nanoscale combination of a conductive carbon and a carbon-based material with abundant heteroatoms is a promising method to overcome the common limitation that the latter have high affinity to alkali metal ions but low electronic conductivity. The synthetic protocol for their combination as well as the individual ratios and structures are all important aspects influencing the properties of such multifunctional compounds. Their interplay is herein investigated by infiltration of a porous ZnO-templated carbon (ZTC) with nitrogen-rich carbon obtained by condensation of hexaazatripenylene-hexacarbonitile (HAT-CN) at 550-1000°C. The density of lithiophilic sites can be controlled by HAT-CN content and condensation temperature. Lithium storage properties are significantly improved in comparison to those of the individual compounds and their physical mixtures. Depending on the uniformity of the formed composite, loading ratio and condensation temperature have different influence. Most stable operation at high capacity per used monomer is achieved with a slowly dried composite with a HAT-CN:ZTC mass ratio of 4:1, condensed at 550°C, providing more than 400 mAh g−1 discharge capacity at 0.1 A g−1 and a capacity retention of 72% after 100 cycles of operation at 0.5 A g−1 due to the homogeneity of the composite and high content of lithophilic sites. This article is protected by copyright. All rights reserved