In this work, the properties of a novel electrolyte based on the combination of bio-based Æ´-valerolactone (GVL) solvent with lithium bis(oxalato)borate (LiBOB) salt and its use for lithium-ion capacitors (LICs) are presented. It is shown that the 1 m LiBOB in GVL electrolyte displays good transport properties, high thermal stability, and the ability to prevent anodic dissolution. Its impact on the performance of both battery-type and capacitive-type electrodes is evaluated. In this regard, special attention is paid to the filming properties associated with LiBOB and GVL decomposition at the electrode surfaces. To the best of the authors' knowledge, the full-cell devices assembled in this study are the first example of a fluorine-free LIC. These devices exhibit a favorable energy-to-power ratio, delivering 80 Wh kg-1 AM at 10 000 W kg-1 AM along with excellent cycling stability, retaining 80% of the initial capacitance after 25 000 cycles. Furthermore, post-mortem analysis of the LIC electrodes is conducted to gain deeper insights into the degradation mechanisms within the device.
In this work, we report on an improved cell assembly of cylindrical electrochemical cells for 23 Na in-situ solid-state NMR (ssNMR) investigations. The cell set-up is suitable for using powder electrode materials. Reproducibility of our cell assembly is analyzed by preparing two cells containing hard carbon (HC) powder as working electrode and sodium metal as reference electrode. Electrochemical storage properties of HC powder electrode derived from carbonization of sustainable cellulose are studied by ssNMR. 23 Na in-situ ssNMR monitors the sodiation/desodiation of a Na|NaPF6 |HC cell (cell 1) over a period of 22â days, showing high cell stability. After the galvanostatic process, the HC powder material is investigated by high resolution 23 Na ex-situ MAS NMR. The formation of ionic sodium species in different chemical environments is obtained. Subsequently, a second Na|NaPF6 |HC cell (cell 2) is sodiated for 11â days achieving a capacity of 220â mAh/g. 23 Na ex-situ MAS NMR measurements of the HC powder material extracted from this cell clearly indicate the presence of quasi-metallic sodium species next to ionic sodium species. This observation of quasi-metallic sodium species is discussed in terms of the achieved capacity of the cell as well as of side reactions of sodium in this electrode material.
Herein, we present a new heterogeneous catalyst active toward glucose to formic acid methyl ester oxidation. The catalyst was fabricated via electrostatic immobilization of the inorganic polyoxometalate HPA-5 catalyst H8[PMo7V5O40] onto the pore surface of amphiphilic block copolymer membranes prepared via non-solvent-induced phase separation (NIPS). The catalyst immobilization was achieved via wet impregnation due to strong coulombic interactions between protonated tertiary amino groups of the polar poly(2-(dimethylamino)ethyl methacrylate) block and the anionic catalyst. Overall, three sets of five consecutive catalytic cycles were performed in an autoclave under 90 °Ð¡ and 11.5 bar air pressure in methanol, and the corresponding yields of formic acid methyl ester were quantified via head-space gas chromatography. The obtained results demonstrate that the membrane maintains its catalytic activity over multiple cycles, resulting in high to moderate yields in comparison to a homogeneous catalytic system. Nevertheless, presumably due to leaching, the catalytic activity declines over five catalytic cycles. The morphological and chemical changes of the membrane during the prolonged catalysis under harsh conditions were examined in detail using different analytic tools, and it seems that the underlying block copolymer is not affected by the catalytic process.
Electrochemical nitrate reduction to ammonia powered by renewable electricity is not only a promising alternative to the established energy-intense and non-ecofriendly Haber-Bosch reaction for ammonia generation but also a future contributor to the ever-more important denitrification schemes. Nevertheless, this reaction is still impeded by the lack of understanding for the underlying reaction mechanism on the molecular scale which is necessary for the rational design of active, selective, and stable electrocatalysts. Herein, a novel single-site bismuth catalyst (Bi-N-C) for nitrate electroreduction is reported to produce ammonia with maximum Faradaic efficiency of 88.7% and at a high rate of 1.38 mg h-1 mgcat -1 at -0.35 V versus reversible hydrogen electrode (RHE). The active center (described as BiN2 C2 ) is uncovered by detailed structural analysis. Coupled density functional theory calculations are applied to analyze the reaction mechanism and potential rate-limiting steps for nitrate reduction based on the BiN2 C2 model. The findings highlight the importance of model catalysts to utilize the potential of nitrate reduction as a new-generation nitrogen-management technology based on the construction of efficient active sites.
Selective separation of industrial important C8 , C6 and C3 hydrocarbon pairs by physisorbents can greatly reduce the energy intensity related to the currently used cryogenic distillation techniques. The achievement of size-sieving based on carbonaceous materials is desirable, but commonly hindered by the random structure of carbons often with a broad pore size distribution. Herein, a pH-regulated pre-condensation strategy was introduced to control the carbon pore architecture by the sp2 /sp3 hybridization of precursor. The lower pH value during pre-condensation of glucose facilitates the growth of aromatic nanodomains, rearrangement of stacked layers and a concomitant transition from sp3 -C to sp2 -C. The subsequent pyrolysis endows the pore size manipulated from 6.8 to 4.8â Å and narrowly distributed over a range of 0.2â Å. The refined pores enable effective size-sieving of C8 , C6 and C3 hydrocarbon pairs with high separation factor of 1.9 and 4.9 for C8 xylene (X) isomers para-X/meta-X and para-X/ortho-X, respectively, 5.1 for C6 alkane isomers n-hexane/3-methylpentane, and 22.0 for C3 H6 /C3 H8 . The excellent separation performance based-on size exclusion effect is validated by static adsorption isotherms and dynamic breakthrough experiments. This synthesis strategy provides a means of exploring advanced carbonaceous materials with controlled hybridized structure and pore sizes for challenging separation needs.
A comprehensive study on the properties and implementation of glyoxylic-acetals in sodium-ion energy storage systems is presented. Electrolytes containing 1,1,2,2-tetramethoxyethane (tetramethoxyglyoxal, TMG), 1,1,2,2-tetraethoxyethane (tetraethoxyglyoxal, TEG) and a mixture of the latter with propylene carbonate (PC) exhibit increased thermal stabilities and higher flash points compared to classical electrolytes based on carbonates as solvents. Due to its favorable properties, 1â m NaTFSI in TEG/PC (3 : 7), has been selected and used for sodium-ion energy storage systems based on a Prussian Blue (PB) positive electrode and a hard carbon (HC) negative electrode. Compared to conventional electrolyte (based on a 1 : 1 mixture of ethylene carbonate, EC, and dimethyl carbonate, DMC), this glyoxylic-acetal electrolyte provides competitive capacity and prolonged cycle life. Postmortem XPS analysis indicates that the electrode-electrolyte interphases formed in presence of TEG are thicker and presumably more protective, inhibiting typical degradation processes of the electrodes. Furthermore, it is demonstrated that the suitable properties of TEG on the cycling stability can also be exploited for the construction of highly stable sodium-ion capacitors.
Acetals , Sodium , Electrolytes , Solvents , Carbonates
Sorption-based water capture is an attractive solution to provide potable water in arid regions. Heteroatom-decorated microporous carbons with hydrophilic character are promising candidates for water adsorption at low humidity, but the strong affinity between the polar carbon pore walls and water molecules can hinder the water transport within the narrow pore system. To reduce the limitations of mass transfer, C2 N-type carbon materials obtained from the thermal condensation of a molecular hexaazatriphenylene-hexacarbonitrile (HAT-CN) precursor were treated mechanochemically via ball milling. Scanning electron microscopy as well as static light scattering reveal that large pristine C2 N-type particles were split up to a smaller size after ball milling, thus increasing the pore accessibility which consequently leads to faster occupation of the water vapor adsorption sites. The major aim of this work is to demonstrate the applicability of thermal response measurements to track these enhanced kinetics of water adsorption. The adsorption rate constant of a C2 N material condensed at 700 °C remarkably increased from 0.026â s-1 to 0.036â s-1 upon ball milling, while maintaining remarkably high water vapor capacity. This work confirms the advantages of small particle sizes in ultramicroporous materials on their vapor adsorption kinetics. It is demonstrated that thermal response measurements are a valuable and time-saving method to investigate water adsorption kinetics, capacities, and cycling stability.
The electrochemical nitrogen reduction reaction (NRR) to ammonia (NH3 ) is a potentially carbon-neutral and decentralized supplement to the established Haber-Bosch process. Catalytic activation of the highly stable dinitrogen molecules remains a great challenge. Especially metal-free nitrogen-doped carbon catalysts do not often reach the desired selectivity and ammonia production rates due to their low concentration of NRR active sites and possible instability of heteroatoms under electrochemical potential, which can even contribute to false positive results. In this context, the electrochemical activation of nitrogen-doped carbon electrocatalysts is an attractive, but not yet established method to create NRR catalytic sites. Herein, a metal-free C2 N material (HAT-700) is electrochemically etched prior to application in NRR to form active edge-sites originating from the removal of terminal nitrile groups. Resulting activated metal-free HAT-700-A shows remarkable catalytic activity in electrochemical nitrogen fixation with a maximum Faradaic efficiency of 11.4% and NH3 yield of 5.86 µg mg-1 cat h-1 . Experimental results and theoretical calculations are combined, and it is proposed that carbon radicals formed during activation together with adjacent pyridinic nitrogen atoms play a crucial role in nitrogen adsorption and activation. The results demonstrate the possibility to create catalytically active sites on purpose by etching labile functional groups prior to NRR.
Carbon , Nitrogen Fixation , Carbon/chemistry , Ammonia , Catalytic Domain , Nitrogen/chemistry , Metals , Nitriles
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.
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.
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.
Covalent organic frameworks (COFs) have emerged as an important class of organic semiconductors and photocatalysts for the hydrogen evolution reaction (HER)from water. To optimize their photocatalytic activity, typically the organic moieties constituting the frameworks are considered and the most suitable combinations of them are searched for. However, the effect of the covalent linkage between these moieties on the photocatalytic performance has rarely been studied. Herein, we demonstrate that donor-acceptor (D-A) type imine-linked COFs can produce hydrogen with a rate as high as 20.7â mmol g-1 h-1 under visible light irradiation, upon protonation of their imine linkages. A significant red-shift in light absorbance, largely improved charge separation efficiency, and an increase in hydrophilicity triggered by protonation of the Schiff-base moieties in the imine-linked COFs, are responsible for the improved photocatalytic performance.
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.
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.
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.
The quest for more efficient ways to store electrical energy prompted the development of different storage devices over the last decades. This includes but is not limited to different battery concepts and supercapacitors. However, modern batteries rely on electrochemical principles that often involve transition metals which can for instance suffer from toxicity or limited availability. More sustainable alternatives are needed. This sparked the search for organic electrode materials. Nevertheless, compared to their inorganic counterparts, organic electrode materials remain less intensely investigated. Besides the often more complicated electrochemical principles, one likely reason for that are the complex synthetic skills required to develop novel organic materials. Here we review materials synthesized by an old and comparably simple reaction from the field of organic chemistry, namely Schiff-base formation. This reaction can often yield materials under relatively mild conditions, making them especially interesting for the formation of sustainable electrodes. The main weakness of Schiff-base materials, susceptibility to hydrolysis, is of limited concern in most of the battery systems as they mostly anyways require water-free conditions. This review gives an overview of some selected nanomaterials obtained from Schiff-base formation as well as their carbonized derivatives which are of interest for energy storage. Firstly, the general chemistry of Schiff-bases is introduced, followed by an in-depth survey of the most important breakthroughs in the formation of organic battery electrodes that involve materials based on Schiff-base reaction. Lastly, an outlook considering the main hurdles as well as future perspectives of this research area is given.
The electrochemical nitrogen reduction reaction (NRR) to ammonia (NH3) is a promising alternative route for an NH3 synthesis at ambient conditions to the conventional high temperature and pressure Haber-Bosch process without the need for hydrogen gas. Single metal ions or atoms are attractive candidates for the catalytic activation of non-reactive nitrogen (N2), and for future targeted improvement of NRR catalysts, it is of utmost importance to get detailed insights into structure-performance relationships and mechanisms of N2 activation in such structures. Here, we report density functional theory studies on the NRR catalyzed by single Au and Fe atoms supported in graphitic C2N materials. Our results show that the metal atoms present in the structure of C2N are the reactive sites, which catalyze the aforesaid reaction by strong adsorption and activation of N2. We further demonstrate that a lower onset electrode potential is required for Fe-C2N than for Au-C2N. Thus, Fe-C2N is theoretically predicted to be a potentially better NRR catalyst at ambient conditions than Au-C2N owing to the larger adsorption energy of N2 molecules. Furthermore, we have experimentally shown that single sites of Au and Fe supported on nitrogen-doped porous carbon are indeed active NRR catalysts. However, in contrast to our theoretical results, the Au-based catalyst performed slightly better with a Faradaic efficiency (FE) of 10.1% than the Fe-based catalyst with an FE of 8.4% at -0.2 V vs. RHE. The DFT calculations suggest that this difference is due to the competitive hydrogen evolution reaction and higher desorption energy of ammonia.
Polymeric carbon nitride materials have been used in numerous light-to-energy conversion applications ranging from photocatalysis to optoelectronics. For a new application and modelling, we first refined the crystal structure of potassium poly(heptazine imide) (K-PHI)-a benchmark carbon nitride material in photocatalysis-by means of X-ray powder diffraction and transmission electron microscopy. Using the crystal structure of K-PHI, periodic DFT calculations were performed to calculate the density-of-states (DOS) and localize intra band states (IBS). IBS were found to be responsible for the enhanced K-PHI absorption in the near IR region, to serve as electron traps, and to be useful in energy transfer reactions. Once excited with visible light, carbon nitrides, in addition to the direct recombination, can also undergo singlet-triplet intersystem crossing. We utilized the K-PHI centered triplet excited states to trigger a cascade of energy transfer reactions and, in turn, to sensitize, for example, singlet oxygen (1 O2 ) as a starting point to synthesis up to 25â different N-rich heterocycles.
The potassium salt of polyheptazine imide (K-PHI) is a promising photocatalyst for various chemical reactions. From powder X-ray diffraction data an idealized structural model of K-PHI has been derived. Using atomic coordinates of this model we defined an energetically optimized K-PHI structure, in which the K ions are present in the pore and between the PHI-planes. The distance between the anion framework and K+ resembles a frustrated Lewis pair-like structure, which we denote as frustrated Coulomb pair that results in an interesting adsorption environment for otherwise non-adsorbing, non-polar gas molecules. We demonstrate that even helium (He) gas molecules, which are known to have the lowest boiling point and the lowest intermolecular interactions, can be adsorbed in this polarized environment with an adsorption energy of - 4.6 kJ mol-1 per He atom. The interaction between He atoms and K-PHI is partially originating from charge transfer, as disclosed by our energy decomposition analysis based on absolutely localized molecular orbitals. Due to very small charge transfer interactions, He gas adsorption saturates at 8 at%, which however can be subject to further improvement by cation variation.
Efficient and low-cost anode materials for the sodium-ion battery are highly desired to enable more economic energy storage. Effects on an ultrathin carbon nitride film deposited on a copper metal electrode are presented. The combination of effects show an unusually high capacity to store sodium metal. The g-C3 N4 film is as thin as 10â nm and can be fabricated by an efficient, facile, and general chemical-vapor deposition method. A high reversible capacity of formally up to 51â Ah g-1 indicates that the Na is not only stored in the carbon nitride as such, but that carbon nitride activates also the metal for reversible Na-deposition, while forming at the same time an solid electrolyte interface layer avoiding direct contact of the metallic phase with the liquid electrolyte.
