Alkali Metal Research Articles

Quantitative pre-intercalation of alkali metal ions enables precisely modulating Li+ storage of MXenes

Ion intercalation is crucial for improving energy storage performance, but controlling the content of intercalated ions is challenging for two-dimensional (2D) electrode materials although it enables clarifying individual intercalation behaviors and thereof pinpointing the intercalation mechanism. Herein, the equal‐content alkali metal ions were successfully manipulated to intercalate into Mo2CTx MXene electrodes via an electrochemistry‐driven approach via the anti‐battery principle. Based on a variety of alkali metal ions pre‐intercalation into the Mo2CTx MXene (M+‐Mo2CTx) electrodes, the lithium storage performance was largely improved. Li+‐Mo2CTx electrode exhibits an outstanding capacity of 395.49 mAh g−1 at 200 mA g−1 after 100 cycles due to the enhanced redox activity induced by high-valence Mo and low -F interlayer exposed surface. Besides, the K+‐Mo2CTx electrode delivers excellent rate performance due to faster ion transfer kinetics originating from the pillaring effect of pre-intercalated K+ ions. In a broader sense, our study opens up a new route to accurately improve the electrochemical performance via precisely tuning the content of ions intercalated into 2D intercalation‐type materials.

Controlled Release of Diborane from Alkali Metal Borohydride using Ionic Liquid-Based Lewis Acids.

Alkali metal borohydrides present a rich source of energy dense materials of boron and hydrogen, however their potential in propellants has been hitherto untapped. Potassium borohydride is a promising fuel with high gravimetric energy density and relatively low sensitivity to air and moisture. Problems arise due to the dehydrogenation of the borohydride on heating with minimal energy release. Common methods to extract both boron and hydrogen by means of borane species involve direct reaction of boron trifluoride species with alkali borohydrides. However, these methods face storage and safety issues due to rapid release of diborane on mixing the reactants. We propose a method of diborane release through controlled release of boron trifluoride by means of a tetrafluoroborate based ionic liquid. The trifluoride is released from the ionic liquid at elevated temperatures and enables safe mixture of the reactants at room temperature. It was found that the reaction between borohydride and boron trifluoride proceeds well above room temperature with potassium borohydride releasing diborane and potassium fluoride. The reaction pathway shows a primary reaction releasing diborane and potassium fluoride and a second less energy efficient step leading to the formation of potassium tetrafluoroborate. A 3D printed propellant formulation was also tested.

Controlled Release of Diborane from Alkali Metal Borohydride using Ionic Liquid‐Based Lewis Acids

AbstractAlkali metal borohydrides present a rich source of energy dense materials of boron and hydrogen, however their potential in propellants has been hitherto untapped. Potassium borohydride is a promising fuel with high gravimetric energy density and relatively low sensitivity to air and moisture. Problems arise due to the dehydrogenation of the borohydride on heating with minimal energy release. Common methods to extract both boron and hydrogen by means of borane species involve direct reaction of boron trifluoride species with alkali borohydrides. However, these methods face storage and safety issues due to rapid release of diborane on mixing the reactants. We propose a method of diborane release through controlled release of boron trifluoride by means of a tetrafluoroborate based ionic liquid. The trifluoride is released from the ionic liquid at elevated temperatures and enables safe mixture of the reactants at room temperature. It was found that the reaction between borohydride and boron trifluoride proceeds well above room temperature with potassium borohydride releasing diborane and potassium fluoride. The reaction pathway shows a primary reaction releasing diborane and potassium fluoride and a second less energy efficient step leading to the formation of potassium tetrafluoroborate. A 3D printed propellant formulation was also tested.

Particle Conditioning for Improving Blockage Resistance of Denitration Catalysts in Sintering Flue Gas

The stability and safety of selective catalytic reduction (SCR) systems are threatened by potential catalyst blockages caused by fly ash deposition. This paper proposes to improve the blockage resistance of denitration catalysts for sintered fly ash through particle conditioning. X-ray fluorescence spectroscopy, scanning electron microscopy, and laser particle analyzer were combined with laboratory heating experiments and field tests for systematic research. The results indicate that the composition and morphology of sintered fly ash are intrinsic factors contributing to catalyst blockage, while heating conditions act as external triggers. The sintered fly ash primarily exhibits a fluffy, branched cotton-like structure. Its main components are K2O, Fe2O3, Na2O, and CaO, with the alkali metal oxides of potassium and sodium comprising 20% to 50%. At ambient temperature, sintered fly ash presents no agglomeration, but significant agglomeration occurs as temperature increases. Particle conditioning effectively inhibits the agglomeration tendency of sintered fly ash. Field tests show that catalyst activity remains unaffected even under severe blockage conditions. The pressure drop across the catalyst layers increases progressively, with the first layer displaying the least pressure drop and the third displaying the most. After particle conditioning, the pressure drop across the catalyst is stabilized at values below 600 Pa, effectively mitigating the blockage issue in the denitrification catalyst for sintering flue gas. This research provides critical technical support for the stable ultra-low emission of NOx from sintering flue gas.

Structural Study on Alkali‐Carboxylate Functionalized Late‐Transition Metal Bis(dithiocarbamate) Complexes

AbstractLithium, sodium, and potassium derivatives of amino‐acid derived bis(dithiocarbamate) complexes of bivalent nickel, palladium, platinum, and copper are readily available by treatment of the carboxylic‐acid functionalized complexes with the respective alkali metal hydroxide. Representative derivatives of the types A4[M(L1)2], A2[M(HL1)2], A[M(HL1)(H2L1)] (N‐dithioato‐iminodiacetate, L1), and A2[M(L2,3)2] (N‐dithioato‐l‐prolinate, L2, and ‐N‐benzylglycinate, L3; A=Li, Na, K; M=Ni, Pd, Pt, Cu) were isolated and characterized by spectroscopic and thermal methods. Six entries were accessible to single‐crystal X‐ray structure determination, revealing the presence of different coordination‐polymeric structures and hydrogen‐bonded assemblies comprising solvent‐separated cations in the solid state. While the transition metal always retains its all‐sulfur coordination with defined geometry, the alkali metals are structurally more flexible. The latter are usually coordinated by carboxylate and water, but additional interactions with sulfur donors are also relevant in some cases.

Conversion of Cellobiose to Formic Acid as a Biomass-Derived Renewable Hydrogen Source Using Solid Base Catalysts.

Formic acid is considered a promising hydrogen carrier. Biomass-derived formic acid can be obtained by oxidative decomposition of sugars. This study explored the production of formic acid from cellobiose, a disaccharide consisting of d-glucose linked by β-glycosidic bonds using heterogeneous catalysts under mild reaction conditions. The use of alkaline earth metal oxide solid base catalysts like CaO and MgO in the presence of hydrogen peroxide could afford formic acid from cellobiose at 343 K. While CaO gave 14 % yield of formic acid, the oxide itself was converted to a harmful metal peroxide, CaO2 after the reaction. In contrast, MgO could produce formic acid without the formation of the metal peroxide. The difficulty in selectively synthesizing formic acid from cellobiose using these solid base catalysts was due to the poor conversion of cellobiose to glucose. Using a combination of solid acid and base catalysts, a high formic acid yield of 33 % was obtained under mild reaction conditions due to the quantitative hydrolysis of cellobiose to glucose by a solid acid followed by the selective decomposition of glucose to formic acid by a solid base.

In the LiCl-KCl melt at 500<sup>о</sup>С depending on the content of Li<sub>2</sub>О и LiOH

Molten alkali metal chlorides used in pyrotechnologies are aggressive corrosive agents. The high operating temperature of the process, the heterogeneity of the environment, and the significant corrosion activity of the molten salt necessitate both the search for stable structural materials and the development of methods for protecting the structural elements of high-temperature technological devices. Corrosion loss reduction techniques traditionally used in low temperature environments are not applicable at high temperatures. The article examines the influence of oxygen-containing impurities (lithium oxide and hydroxide) on the corrosion behavior of metallic nickel (grade NP1) – the main component of candidate structural alloys, a thermodynamically and structurally stable material in the melt for the process of electrolytic refining of spent nuclear fuel. A method for preparing the LiCl–KCl salt electrolyte and obtaining lithium oxide by thermal decomposition of anhydrous lithium hydroxide under vacuum is described, and the concentrations of impurities in the electrolyte and the synthesized lithium oxide are determined. An installation for conducting corrosion tests in an inert atmosphere of a glove box is presented. To assess the corrosion resistance of the material, the following were used: gravimetric analysis, X-ray diffraction analysis of the surface and cross-sectional sections, and X-ray diffraction analysis of the surface of the samples. The dependences of the corrosion rate of the material on the concentration of oxygen-containing additives Li2O and LiOH were obtained. Based on a combination of gravimetric, X-ray microspectral and X-ray phase analysis data, it was established that metallic nickel samples demonstrate high corrosion resistance in the studied melts with the introduction of Li2O and LiOH additives.

Li2NaB3S2O12: A Deep-UV Transparent Borosulfate with Moderate Birefringence Derived from the [B3S2O12]∞ Infinite Chain Designed by the High Boron-to-Sulfur Ratio Strategy.

The first mixed alkali metal borosulfate compound, Li2NaB3S2O12 (LNBSO), which contains [BO3] groups, was designed and synthesized by using a high boron-to-sulfur ratio strategy through the high temperature solution method. LNBSO exhibits a birefringence of 0.057@546.1 nm in experiments, which was mainly contributed by the [BO3] groups, and possesses a short absorption edge at 184 nm, and the space group of LNBSO is P21/c. This newly synthesized borosulfate compound holds potential as a promising birefringent material within the deep-ultraviolet wavelength range. Moreover, the investigation on the relationship among the ratio of boron to sulfur, the dimensionality of the anionic framework, and the formation of [BO3] groups has been conducted on available borosulfate, providing insights for the synthesis of borosulfate with desirable performances.

A novel trialkyl phosphate – Ionic liquid mixture for an efficient separation of Lithium ion from its acidic feed solution

Separation of Lithium ion (Li+) using conventional non-crown type ligands through solvent extraction process is a challenging task and can only be feasible by tuning the organic phase with an additional polar environment. In this context, we have projected an extracting system containing a traditional trialkyl phosphate (T(alk)P): Tri-iso-amyl phosphate (TiAP) containing a minimal amount of ionic liquid (IL): [C4mpip][NTf2] (1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide) for the efficient extraction and separation of Li+ from its hydrochloric acid feed. The extraction performances pertaining various experimental parameters were realized to explore the solvent potentiality of TiAP/[C4mpip][NTf2] towards Li+ coordination. Involvement of two ligand molecules in extraction in presence of 10 % (v/v) IL diluent offers fast extraction kinetics and turns the extraction mechanism into a cation exchange pathway, which was further examined by using different classes of ILs in conjunction with TiAP for Li+ uptake. The selectivity of Li+ over other alkali (or alkaline earth) metal ions was investigated to highlight the affinity of the proposed IL system towards Li+. Extraction scenario in TiAP phase was compared with that in TBP phase containing same IL to bring out the efficacy of the proposed IL system. The stripping performance of Li+ from the loaded organic phase was studied using an acid solution to establish the sustainability of the proposed extraction process.

FEATURES AND EXPERIENCE OF CONVERTING GAS-OIL BOILERS OF INDUSTRIAL CHP PLANTS TO BURNING BIOMASS AND SUB-BITUMINOUS COAL

The paper examines the features of biomass as a fuel and substantiates that for agrobiomass waste with a high content of alkali metal oxides and slag properties of ash, it is more appropriate to burn it in a dense bed in the form of pellets, which ensures a temperature at the exit from the furnace of no more than 900 °C, a low part of fly ash and low content of unburned carbon in it, and so eliminates the risk of smoldering deposits with their melting and slagging. Technical solutions are given and the experience is presented of gas and oil boilers of CHP plants of sugar factories reconstruction with their transfer to the burning of biomass and/or coal in a dense bed on a direct-flow grate with the replacement of the air heater with air-water heater, with the addition of stages of the boiling economizer to compensate for the decrease in the heat perception of the furnace screens, maintaining the overall height of the boiler and the plane of the boiler cell. The reconstruction of boilers according to the developed technical solutions is possible to perform in the interval between production seasons, its implementation on boilers BKZ-75 GMA of Radekhiv and Chortkiv sugar factories allowed to achieve acceptable technical, economic and environmental indicators and ensured payback due to the difference in commercial prices of gas and of agrobiomass pellets. It is proposed to replicate the positive experience in the creation of decentralized regulating thermal generation capacities of the country. Bibl. 30, Fig. 3, Tab. 4.

Experimental and theoretical investigation on pre-deposited precursor as growth sites for monolayer MoS2 growth by supercritical fluid deposition

The assistance of promoters, Molybdates or alkali metal salts can regulate the nucleation site of MoS2 in chemical vapor deposition. However, the introduction of impurities inevitably reduces the MoS2 quality. Here, we present the growth of monolayer MoS2 by supercritical fluid deposition to pre-deposit Mo(CO)6 precursors as nucleation sites, replacing difficult to clean conventional promoters. Domain-limited homogeneous and heterogeneous reactions occur at nucleation sites, and through optimization of sulfurization parameters, high-quality monolayer MoS2 with about 20 μm domain size can be obtained by growing at 760 °C and 40 sccm argon for 20 min. Monolayer MoS2 coverage ranged from 2.6 % to 39.1 % by regulating dissolution mass in range of 100–400 mg, utilizing the highly soluble Mo(CO)6 in supercritical CO2. Density functional theory calculations show that decarbonylated Mo(CO)6 possesses higher sulfide reactivity. This study provides new insights into the impurity-free controlled site growth of two-dimensional materials.

Optical and electronic properties of RENiO3 doped with alkali earth metals (Be, Mg, Ca, Sr and Ba): Combining first principles calculations and machine learning

The perovskite rare earth nickelate (RENiO3) has attracted significant attention owing to its peculiar physical properties and promising potential for diverse applications. It is reported that introducing H or Li might change the electronic and optical properties of RENiO3. However, little is known about multi-electrons doping in RENiO3. In this study, the bandgaps, optical and electronic properties were investigated in RENiO3 with alkaline earth metal (AEM) elements (Be, Mg, Ca, Sr and Ba) doping. For the atomic configurations of doped RENiO3, the interstitial sites of RENiO3 are more likely to be occupied by Be, Mg and Ca atoms, whereas Sr and Ba atoms tend to replace RE atoms in RENiO3. The band gap of RENiO3 decreases after AEM doping. Moreover, the machine learning results found that the formation energy of the AEM, the relative atomic mass of the AEM, and the doping position significantly influence the band gap. Furthermore, the infrared light blocking capability, the visible light transmission, and the electronic conductivity are enhanced in AEM doped RENiO3. This study may contribute to the experimental modulation of the optical and electronic properties of RENiO3 through AEM doping.

Ash Interaction with Two Cu-Based Magnetic Oxygen Carriers during Biomass Combustion by the Chemical Looping with Oxygen Uncoupling Process.

Chemical-looping combustion (CLC) stands out as a promising method for carbon capture and storage for the purpose of mitigating climate change. The process involves the conversion of fuel facilitated by an oxygen carrier, with the resulting CO2 inherently separated from other air components. Notably, when applied to biomass combustion this process offers a pathway to achieving negative CO2 emissions. However, a significant challenge for CLC, particularly in its application to biomass, is the management of interactions between ash and oxygen carriers. Biomass-derived ashes typically contain substantial quantities of reactive ash-forming substances, such as alkaline and alkali earth elements. These interactions can impact the performance and longevity of the oxygen carrier, necessitating careful consideration and mitigation strategies in CLC systems utilizing biomass feedstocks. This study examined the interaction between biomass ash components and two recently developed oxygen carriers, Cu30MnFekao7.5 and Cu30MnFe, during combustion in a 1.5 kWth continuous unit. Both oxygen carriers achieved 100% combustion efficiency and a CO2 capture efficiency of 95% at 900 °C. Although the copper in both oxygen carriers did not exhibit any noticeable interaction with ash components, the accumulative presence of potassium and magnesium in Cu30MnFekao7.5 was identified by inductively coupled plasma and scanning electron microscopy with energy dispersive X-ray analysis, indicating an increase in the amount of both elements in the particles after combustion operation. No problems of agglomeration or fluidization were observed in any of the experiments.

Self-protected Chlorella@Mn catalyst with excellent resistance to alkali/alkaline earth metal for NOx reduction by NH3

In the selective catalytic reduction of NOx by NH3 (NH3-SCR), conventional Mn-based denitration catalysts often suffered from susceptibility to poisoning by alkali and alkaline earth metals, this paper presented an innovative self-protected Chlorella@Mn denitration catalyst. Remarkably, in the presence of high concentrations (2 wt%) of alkali and alkaline earth metal oxides, the Chlorella@Mn catalyst sustained a NOx conversion exceeding 96 % at 175 °C. At an even higher concentration (4 wt%), NOx conversion above 90 % at 175 °C, surface analysis revealed that POMn sites acted as sacrificial sites, binding to the alkali and alkaline earth metals, the Chlorella@Mn catalyst surface naturally carried a spectrum of acidic species (such as SO42−, PO3−, SiO32−), proficient in capturing alkali/alkaline earth metal effectively, elements such as S, P, and Si formed bonds with K, Na, Ca, and Mg. The synergistic protection of the active sites and the surface elements avoided the deactivation of the catalyst. The detrimental effects of high concentrations of alkali and alkaline earth metals were primarily due to promoting an excessively high valence state of Mn on the catalyst surface and the reduction or loss of NH3 adsorption and activation at Brønsted acid sites. This research provided valuable insights for advancing the development of low-temperature denitration catalysts with improved resistance to alkali and alkaline earth metal poisoning.

Surface Chemical Effects on Fischer–Tropsch Iron Oxide Catalysts Caused by Alkali Ion (Li, Na, K, Cs) Doping

Among the alkali metals, potassium is known to significantly shift selectivity toward value-added, heavier alkanes and olefins in iron-based Fischer–Tropsch synthesis catalysts. The aim of the present contribution is to shed light on the mechanism of action of alkaline promoters through a systematic study of the structure–reactivity relationships of a series of Fe oxide FTS catalysts promoted with Group I (Li, Na, K, Cs) alkali elements. Reactivity data are compared to structural data based on in situ, synchrotron-based XRD and XPS, as well as temperature-programmed studies (TPR-H2, TPC-CO, TPD-CO2, and TPD-H). It has been observed that the alkali elements induced higher carburization rates, higher basicities, and lower adsorbed hydrogen coverages. Catalyst stability followed the trend Na-Fe > unpromoted > Li-Fe > K-Fe > Cs-Fe, being consistent with the ability of the alkali (Na) to prevent active site loss by catalyst reoxidation. Potassium was the most active in promoting high α hydrocarbon formation. It is active enough to promote CO dissociative adsorption (and the formation of FeCx active phases) and decrease the surface coverage of H-adsorbed species, but it is not so active as to cause premature catalyst deactivation by the formation of a carbon layer resulting in the blocking active sites.

Ammonothermal Synthesis of Luminescent Imidonitridophosphate Ba4P4N8(NH)2:Eu2.

The structural variability of a compound class is an important criterion for the research into phosphor host lattices for phosphor-converted light-emitting diodes (pc-LEDs). Especially, nitridophosphates and the related class of imidonitridophosphates are promising candidates. Recently, the ammonothermal approach has opened a systematic access to this substance class with larger sample quantities. We present the successful ammonothermal synthesis of the imidonitridophosphate Ba4P4N8(NH)2:Eu2+. Its crystal structure is solved by X-ray diffraction and it crystallizes in space group Cc (no.9) with lattice parameters a=12.5250(3), b=12.5566(4), c=7.3882(2)Å and β=102.9793(10)°. For the first time, adamantane-type (imido)nitridophosphate anions [P4N8(NH)2]8- are observed next to metal ions other than alkali metals in a compound. The presence of imide groups in the structure and the identification of preferred positions for the hydrogen atoms are performed using a combination of quantum chemical calculations, Fourier-transform infrared, and solid-state NMR spectroscopy. Eu2+ doped samples exhibit cyan emission (λmax=498nm, fwhm=50nm/1981cm-1) when excited with ultraviolet light with an impressive internal quantum efficiency (IQE) of 41%, which represents the first benchmark for imidonitridophosphates and is promising for potential industrial application of this compound class.

Enhancing Aniline Condensation Reaction Efficiency Using Alkali and Rare Earth Element Modified USY Zeolite Catalyst: Synergistic Effects and Mechanistic Insights

Enhancing Aniline Condensation Reaction Efficiency Using Alkali and Rare Earth Element Modified USY Zeolite Catalyst: Synergistic Effects and Mechanistic Insights

Effect of CaCO3, SrCO3 and BaCO3 additions on the microstructure and electrical characteristics of SnO2-based varistor ceramics

The ceramic varistors SnO2–Co3O4–Nb2O5–Cr2O3 with the addition of CaCO3, SrCO3 or BaCO3 were sintered at temperatures 1250 and 1350°C, then their structures and electrical properties were studied. In all samples, the SnO2 cassiterite phase with a rutile-type structure and the Co2SnO4 phase with a spinel-type structure were observed. All materials exhibited a highly nonlinear dependence of the current density on the electric field with the nonlinearity coefficient 24–50. When alkaline earth metal carbonates were added, the grain size of all samples decreased and the electric field E1 increased. The addition of CaCO3 lead to the decrease of the low-field electrical conductivity of varistors. The lowest low-field conductivities 4·10-13 and 6·10-13 Ω-1 cm-1 were found in the samples with CaCO3 addition baked at 1250 and 1350°C, respectively. The observed effect is due to the increase of the potential barrier height at the SnO2 grain boundaries by 7 and 13%, respectively, and the decrease of the grain size by 26 and 28% compared to SnO2-based varistor ceramics without CaCO3 addition.

Effectively Sieving Alkali Metal Ions Using Functionalized Graphene Oxide Membranes by Exploiting Water-Repellent Interactions.

Sieving membranes capable of discerning different alkali metal ions are important for many technologies, such as energy, environment, and life science. Recently, two-dimensional (2D) materials have been extensively explored for the creation of sieving membranes with angstrom-scale channels. However, because of the same charge and similar hydrated sizes, mostly laminated membranes typically show low selectivity (<10). Herein, we report a facile and scalable method for functionalizing graphene oxide (GO) laminates by dually grafting cations and water-repellent dimethylsiloxane (DMDMS) molecules to achieve high selectivities of ∼50 and ∼20 toward the transport of Cs+/Li+ and K+/Li+ ion pairs, surpassing many of the state-of-the-art laminated membranes. The enhanced selectivity for alkali metal ions can be credited to a dual impact: (i) strong hydrophobic interactions between the incident cations' hydration shells and the water-repellent DMDMS; (ii) the efficient screening of electrostatic interactions that hamper selectivity.

Alkali metal cation adsorption–induced surface polarization in polymeric carbon nitride for enhanced photocatalytic hydrogen peroxide production

Photocatalytic hydrogen peroxide (H2O2) generation on the catalyst surface from oxygen is an electron-demanding process, making the construction of an electron-rich surface highly advantageous. In this study, a localized electric field was observed on the surface of polymeric carbon nitride (g-C3N4) when alkali metal cations were adsorbed onto it. These fields effectively inhibited surface carrier recombination and extended their lifespan, thereby enhancing H2O2 production. As a result, g-C3N4 achieved a superior H2O2 yield of 2.25 mM after 1 h in a 0.25 M K+ solution, which was 2.06 times greater than that (1.09 mM) achieved in a pure solvent. Notably, the increase in photocatalytic efficiency showed a remarkable dependence on ion species. At low concentrations, H2O2 generation efficiency was in the order of Li+ < Na+ < K+ < Rb+ < Cs+. However, after optimizing the ion concentration, the highest H2O2 production was achieved in a solution containing K+ instead of Cs+. Molecular dynamics simulations and temperature-dependent photocatalysis experiments revealed that the synergistic interaction between adsorption energy and adsorption distance was crucial in governing the extent to which alkali metal cation adsorption enhanced g-C3N4 photocatalytic H2O2 production. This study provides theoretical insights for the design of materials for electron-demanding photocatalysis and aids in understanding variations in photocatalytic behavior in natural waters.