Transformation of alkali and alkaline-earth metals during coal oxy-fuel combustion in the presence of SO_2 and H_2O

The occurrence modes of alkali and alkaline-earth metals（AAEMs） in coal relate to their release behavior and ash formation during combustion. To better understand the transformation of AAEMs,the release behavior of water-soluble,HCl-soluble,HCl-insoluble AAEMs during Shenmu coal（SM coal） oxy-fuel combustion in the presence of SO2 and H2O in a drop-tube reactor was investigated through serial dissolution using H2O and HCl solutions. The results show that the release rates of AAEMs increase with an increase in temperature under the three atmospheres studied. The high release rates of Mg and Ca from SM coal are dependent on the high content of soluble Mg and Ca in SM coal. SO2 inhibits the release rates of AAEMs,while H2O promotes them. The effects of SO2 and H2O on the Na and K species are more evident than those on Mg and Ca species. All three types of AAEMs in coal can volatilize in the gas phase during coal combustion. The W-type AAEMs release excessively,whereas the release rates of I-type AAEMs are relatively lower. Different types of AAEM may interconvert through different pathways under certain conditions. Both SO2 and H2O promote the transformation reactions. The effect of SO2 was related to sulfate formation and the promotion by H2O occurs because of a decrease in the melting point of the solid as well as the reaction of H2O.

Promotion effects of alkali metals on iron molybdate catalysts for CO_(2)catalytic hydrogenation

CO_(2)hydrogenation is an attractive way to store and utilize carbon dioxide generated by industrial processes,as well as to produce valuable chemicals from renewable and abundant resources.Iron catalysts are commonly used for the hydrogenation of carbon oxides to hydrocarbons.Iron-molybdenum catalysts have found numerous applications in catalysis,but have been never evaluated in the CO_(2)hydrogenation.In this work,the structural properties of iron-molybdenum catalysts without and with a promoting alkali metal(Li,Na,K,Rb,or Cs)were characterized using X-ray diffraction,hydrogen temperatureprogrammed reduction,CO_(2)temperature-programmed desorption,in-situ^(57)Fe Mossbauer spectroscopy and operando X-ray adsorption spectroscopy.Their catalytic performance was evaluated in the CO_(2)hydrogenation.During the reaction conditions,the catalysts undergo the formation of an iron(Ⅱ)molybdate structure,accompanied by a partial reduction of molybdenum and carbidization of iron.The rate of CO_(2)conversion and product selectivity strongly depend on the promoting alkali metals,and electronegativity was identified as an important factor affecting the catalytic performance.Higher CO_(2)conversion rates were observed with the promoters having higher electronegativity,while low electronegativity of alkali metals favors higher light olefin selectivity.

Additive effects of alkaline-earth metals and nickel on the performance of Co/γ-Al_2O_3 in methane catalytic partial oxidation

Nano-sized γ-alumina （γ-Al2O3） was first prepared by a precipitation method. Then, active component of cobalt and a series of alkaline- earth metal promoters or nickel （Ni） with different contents were loaded on the γ-Al2O3 support. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction （XRD） and thermogravimetry analysis （TGA）. The activity and selectivity of the catalysts in catalytic partial oxidation （CPO） of methane have been compared with Co/γ-Al2O3, and it is found that the catalytic activity, selectivity, and stability are enhanced by the addition of alkaline-earth metals and nickel. The optimal loadings of strontium （Sr） and Ni were 6 and 4 wt%, respectively. This finding will be helpful in designing the trimetallic Co-Ni-Sr/γ-Al2O3 catalysts with high performance in CPO of methane

Field emission properties of capped carbon nanotubes doped by alkali metals:a theoretical investigation

The electronic structures and field emission properties of capped CNT55 systems with or without alkali metal atom adsorption were systematically investigated by density functional theory calculation.The results indicate that the adsorption of alkali metal on the center site of a CNT tip is energetically favorable.In addition,the adsorption energies increase with the introduction of the electric field.The excessive negative charges on CNT tips make electron emittance much easier and result in a decrease in work function.Furthermore,the inducing effect by positively charged alkali metal atoms can be reasonably considered as the dominant reason for the improvement in field emission properties.

Emerging Carbon Nanotube-Based Nanomaterials for Stable and Dendrite-Free Alkali Metal Anodes:Challenges,Strategies,and Perspectives

Alkali metals(Li,Na,and K)are promising candidates for high-performance rechargeable alkali metal battery anodes due to their high theoretical specific capacity and low electrochemical potential.However,the actual application of alkali metal anodes is impeded by the challenges of alkali metals,including their high chemical reactivity,uncontrolled dendrite growth,unstable solid electrolyte interphase,and infinite volume expansion during cycling processes.Introducing carbon nanotube-based nanomaterials in alkali metal anodesis an effective solution to these issues.These nanomaterials have attracted widespread attention owing to their unique properties,such as their high specific surface area,superior electronic conductivity,and excellent mechanical stability.Considering the rapidly growing research enthusiasm for this topic in the last several years,we review recent progress on the application of carbon nanotube-based nanomaterials in stable and dendrite-free alkali metal anodes.The merits and issues of alkali metal anodes,as well as their stabilizing strategies are summarized.Furthermore,the relationships among methods of synthesis,nano-or microstructures,and electrochemical properties of carbon nanotube-based alkali metal anodes are systematically discussed.In addition,advanced characterization technologies on the reaction mechanism of carbon nanotube-based nanomaterials in alkali metal anodes are also reviewed.Finally,the challenges and prospects for future study and applications of carbon nanotube-based AMAs in high-performance alkali metal batteries are discussed.

Effects of inherent alkali and alkaline earth metals on nitrogen transformation during steam gasification of Shengli lignite

This work evaluated the effects of inherent alkali and alkaline earth metals on nitrogen transformation during steam gasification of Shengli lignite at the temperature of 873-1173 K in a fluidized-bed/fixed-bed quartz reactor. The results indicated that the alkali metal Na and alkaline earth metals Ca, Mg in coal have different effects on inherent nitrogen transformation to NH3, HCN and char-N during the lignite steam gasification. Specifically during the steam gasification of Shengli lignite, Na and Ca, Mg not only catalyze the inherent nitrogen conversions to NH3, but also promote the secondary reactions of the nascent char-N as well as the generation of NH3 from the generated HCN, meanwhile they also inhibited the inherent nitrogen conversion to HCN and char-N. The presence of Na, Ca and Mg hindered the formation of oxidized nitrogen (N-X) functional groups, but enhanced pyridinic nitrogen (N-6) and quaternary nitrogen's (N-Q) formation in char.

Study of Spectral Character of Alkali Metals Using Microwave Plasma Torch Simultaneous Spectrometer

A microwave plasma torch （MPT） simultaneous spectrometer was used to study the spectral character and the matrix effect on alkali metal ions in solution. The main parameters were optimized. The microwave forward power was 100 W. The argon flow rate that was used to sustain the Ar-MPT included the flow rate of carrier gas and the flow rate of support gas, which were 0. 8 and 1.0 L/min, respectively. The HC1 concentration in the solution was 0.02 mol/L. The observation height was 9. 0 ram. The detection limits of Li, Na, K, Rb, and Cs were 0. 0003, 0. 0004, 0. 009, 0.07 and 2.4 mg/L, respectively, and the resuhs obtained by the Ar-MPT were compared with those obtained by argon inductively coupled plasma（Ar-ICP） and argon microwave induced plasma（Ar-MIP）. The interference effects of several matrix elements were also studied.

Designing Advanced Liquid Electrolytes for Alkali Metal Batteries:Principles,Progress,and Perspectives

The ever-growing pursuit of high energy density batteries has triggered extensive efforts toward developing alkali metal(Li,Na,and K)battery(AMB)technologies owing to high theoretical capacities and low redox potentials of metallic anodes.Typically,for new battery systems,the electrolyte design is critical for realizing the battery electrochemistry of AMBs.Conventional electrolytes in alkali ion batteries are generally unsuitable for sustaining the stability owing to the hyper-reactivity and dendritic growth of alkali metals.In this review,we begin with the fundamentals of AMB electrolytes.Recent advancements in concentrated and fluorinated electrolytes,as well as functional electrolyte additives for boosting the stability of Li metal batteries,are summarized and discussed with a special focus on structure-composition-performance relationships.We then delve into the electrolyte formulations for Na-and K metal batteries,including those in which Na/K do not adhere to the Li-inherited paradigms.Finally,the challenges and the future research needs in advanced electrolytes for AMB are highlighted.This comprehensive review sheds light on the principles for the rational design of promising electrolytes and offers new inspirations for developing stable AMBs with high performance.

A comprehensive overview of the electrochemical mechanisms in emerging alkali metal-carbon dioxide batteries

Alkali metal-carbon dioxide(Li/Na/K-CO_(2))batteries are emerging electrochemical energy storage technologies in the context of the energy crisis and the urgent demand for carbon neutrality.Alkali metal-CO_(2) batteries offer a new strategy for CO_(2) fixation and utilization,and thus has been receiving considerable attention in recent years.Considerable progress has been achieved since alkali metal-CO_(2) batteries were invented,especially in terms of development of new electrode materials,and yet,research is lacking on the underlying mechanisms of the systems.This is the first typical review focusing on the electrochemical mechanisms of metal-CO_(2) batteries that summarizes the current understanding of and provides insights into the thermodynamic reaction pathways,the kinetic characteristics,and the crucial factors determining the reaction mechanisms in alkali metal-CO_(2) batteries.The review starts with the fundamental concepts of alkali metal-CO_(2) batteries,followed by a comprehensive discussion of the working mechanisms on cathodes and anodes.Moreover,the operation mechanisms of state-of-the-art electrolytes,including liquid and(quasi-)solid-state electrolytes,are also described.Finally,we identify the unsolved problems in current alkali metal-CO_(2) batteries and propose potential topics for future research.

Effect of Alkali Treatment on Heavy Metals Adsorption Capacity of Sewage Sludge

Sewage sludge is the promising raw material for biosorbent preparation. In this work, we evaluated the heavy metals adsorption characteristics of alkali treated sewage sludge (ATSS) by equilibrium studies. The adsorption isotherms were fitted with Langmuir and Freundlich models. Comparing with untreated sewage sludge, the total adsorption capacity (qm) of ATSS (prepared with 0.125 mol/L NaOH) for Cd, Pb, Ni, increased by 0.51, 0.70 and 0.32 mmol/g, respectively. When the NaOH concentration for ATSS preparation increased from 0.125 mol/L to 0.25 mol/L, the qm of ATSS for Pb decreased from 1.05 mmol/g to 0.84 mmol/g. However, when the NaOH concentration increased from 0.25 mol/L to 7.5 mol/L, it showed increasing trend. According to the IR spectra data, the adsorption effect of biosorbent for heavy metals was mainly due to the complexation of -N-H groups and -COOH groups.

Blue-emissions Modulated by Packing Forces in Alkaline-earth Metal OrganicFrameworks Based on Thiophene-2,5-dicarboxylic: Structures and Theoretical Calculations

Solvothermal reactions of Ca(NO), Sr(NO)with thiophene-2,5-dicarboxylic in DMF afforded two new inorganic-organic hybrid frameworks, [M(TDC)(DMF)]n(M = Ca(1), Sr(2), TDC = thiophene-2,5-dicarboxylic, DMF = N,N?-dimethylformamide), which have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis and IR spectra. Both compounds feature three-dimensional(3D) frameworks based on the versatile coordinated modes(μ-η~2:η~2, μ-η~2:η~1, μ-η~2:η~1) of carboxylic groups in tdc ligands. C–H···S hydrogen bonds and C–H···π interactions contribute to the stabilization of the structures. They exhibit weaker packing force compared with their literature isomers. Consequently, blue and blue/green luminescence of two compounds has been observed. Their luminescence mechanism can be ascribed to ligand-to-metal charge transfer(LMCT) compared with the ligand-centered luminescence in their isomers. Electronic structural calculations illustrate that under the condition of weaker packing forces, larger gaps can be achieved, which facilitate the LMCT. This work suggests that the introduction of S-heteroatom can result in more electrons rich in the metal centers, thus giving rise to metal-involved luminescence.

Recent progress in rechargeable alkali metal-air batteries

Rechargeable alkali metal-air batteries are considered as the most promising candidate for the power source of electric vehicles(EVs) due to their high energy density. However, the practical application of metal-air batteries is still challenging. In the past decade, many strategies have been purposed and explored, which promoted the development of metal-air batteries. The reaction mechanisms have been gradually clarified and catalysts have been rationally designed for air cathodes. In this review, we summarize the recent development of alkali metal-air batteries from four parts: metal anodes, electrolytes, air cathodes and reactant gases, wherein we highlight the important achievement in this filed. Finally problems and prospective are discussed towards the future development of alkali metal-air batteries.

Alkali metal cation doping of metal-organic framework for enhancing carbon dioxide adsorption capacity

Metal-organic frameworks （MOFs） have attracted much attention as adsorbents for the separation of CO2 from flue gas or natural gas. Here, a typical metal-organic framework HKUST-I（also named Cu-BTC or MOF-199） was chemically reduced by doping it with alkali metals （Li, Na and K） and they were further used to investigate their CO2 adsorption capacities. The structural information, surface chemistry and thermal behavior of the prepared adsorbent samples were characterized by X-ray powder diffraction （XRD）, thermo-gravimetric analysis （TGA） and nitrogen adsorption-desorption isotherm analysis. The results showed that the CO2 storage capacity of HKUST-1 doped with moderate quantities of Li＋, Na＋ and K＋, individually, was greater than that of unmodified HKUST-1. The highest CO2 adsorption uptake of 8.64 mmol/g was obtained with 1K-HKUST-1, and it was ca. 11% increase in adsorption capacity at 298 K and 18 bar as compared with HKUST- 1. Moreover, adsorption tests showed that HKUST-1 and 1K-HKUST-1 displayed much higher adsorption capacities of CO2 than those of N2. Finally, the adsorption/desorption cycle experiment revealed that the adsorption performance of 1K-HKUST-1 was fairly stable, without obvious deterioration in the adsorption capacity of CO2 after 10 cycles.

EAM APPROACH TO ENTHALPY OF FORMATION OF ALKALI METAL ALLOYS

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Influence of alkali metal doping on surface properties and catalytic activity/selectivity of CaO catalysts in oxidative coupling of methane

Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidative coupling of methane （OCM） to higher hydrocarbons at different reaction conditions （viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1） have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties （viz. surface area, basicity/base strength distribution） and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity （strong basic sites） and the C2＋ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO （Na/Ca = 0.1, before calcination） catalyst （calcined at 750 ℃）, showed best performance （C2＋ selectivity of 68.8% with 24.7% methane conversion）, whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.

Selective exchange of alkali metal ions on EAB zeolite

EAB zeolite was successfully prepared and applied to selective adsorption of Li^(+),Na^(+)and K^(+)ions.The physical and chemical properties of the adsorbent were characterized by X-ray diffraction(XRD),X-ray fluorescence(XRF),scanning electron microscope(SEM)and thermogravimetry(TG)methods.The ion exchange behaviours for Li^(+),Na^(+)and K^(+)ions in monomcomponent and multicomponent solutions were studied.In independent ion exchange,the ion exchange capacities ratiosα(/Na/Li)andα(K/Li)were 3.8 and 6.2,respectively.In competitive ion exchange,the selectivitiesβ(Na/Li)andβ(K/Li)increased with the initial concentrations and reached 409 and 992 when the initial concentrations was 100 mmol/L.The thermodynamic study results showed that Gibbs free energy change(ΔGΘ)of ion exchange reaction between Li-EAB and K^(+)was-34.96 kJ/mol,indicating that ion exchange of K^(+)ions was more energetically favourable than Li^(+)ions.The calculation results showed that the energy barriers of ion exchange increased in the order K^(+)Na^(+)<Li^(+).The study shows that EAB zeolite is potential to be used in the separation of alkali ions.

Investigate the kinetics of coke solution loss reaction with an alkali metal as a catalyst based on the improved genetic algorithm

The kinetics of coke solution loss reaction with and without sodium carbonate were investigated under the reaction atmosphere of carb on dioxide. The variables of gas flow rate and coke particle size were explored to eliminate the external and inteirial diffusion, respectively. Then, the improved method combining with the least square and the genetic algorithm was proposed to solve the homogeneous model and the shrinking core model. It was found that the improved genetic algorithm method has good stability by studying the fitness function at each generation. In the homogeneous model, the activation energy with and without sodium carbonate was 54.89 and 95.56 kJ/mol, respectively. And. the activation energy with and without sodium carbonate in the shrinking core model was 49.83 and 92.18 kJ/mol, respectively. Therefore, it was concluded that the sodium carbonate has the catalytic action. In addition, results showed that the estimated conversions were agreed well with the experimental ones, which indicated that the calculated kinetic parameters were valid and the proposed method was successfully developed.

Calculations on polarization properties of alkali metal atoms using Dirac–Fock plus core polarization method

A semi-empirical atomic structure model method is developed in the framework of a relativistic case. This method starts from Dirac-Fock calculations using B-spline basis set. The core-valence electron correction is then treated in a semiempirical core polarization potential. As an application, the polarization properties of alkali metal atoms, including the static polarizabilities and long-range two-body dispersion coefficients, have been calculated. Our results are in good agreement with the results obtained from ab initio relativistic many-body perturbation method and the available experimental measurements.

Alkali Metal-incorporated Mesoporous Smectites:Crystallinity and Textural Properties

A series of mesoporous smectite like materials incorporated with alkali metals such as Li, Na, K and Cs has been synthesized with the hydrothermal method. The crystalline and the pore structures of the materials synthesized significantly change with the introduction of alkali metals. The addition of Li gives highly ordered layer phases, while the incorporation of Cs yields much less crystalline structures. Although Na or K has little effect on the crystalline structure, they modify the pore structure.

Temporal Characteristics of GaAs NEA and Alkali Metal Photocathodes

The temporal characteristics of GaAs NEA and alkali metal photocathodes are studied using Monte Carlo simulation method. The electron transit time and its distribution functions in the photocathodes are calculated. Based on the results, the time modulation transfer functions and temporal resolutions of the photocathodes are obtained. The results show that the response time and temporal resolution of alkali metal photocathode is in femitosecond order and those of GaAs NEA photocathode are in picosecond order.