Crystal Chemistry Research Articles

The iron oxidation state of Ryugu samples

AbstractThe Hayabusa2 mission sampled Ryugu, an asteroid that did not suffer extensive thermal metamorphism, and returned rocks to the Earth with no significant air exposure. It therefore offers a unique opportunity to study the redox state of carbonaceous Cb‐type asteroids and evaluate the overall redox state of the most primitive rocks of the solar system. An analytical framework was developed to investigate the iron mineralogy and valence state in extraterrestrial material at the micron scale by combining x‐ray diffraction, conventional Mössbauer (MS), and nuclear forward scattering (NFS) spectroscopies. An array of standard minerals was analyzed and cross‐calibrated between MS and NFS. Then, MS and NFS spectra on three Ryugu grains were collected at the bulk and the micron scales. In Ryugu samples, iron is essentially accommodated in magnetite, clay minerals (serpentine–smectite), and sulfides. Only a single set of Mössbauer parameters was necessary to account for the entire variability observed in MS and NFS spectra, at all spatial scales investigated. These parameters therefore make up a fully consistent iron mineralogical model for the Ryugu samples. As far as MS and NFS spectroscopies are concerned, Ryugu grains are overall similar to each other and share most of their mineralogical features with CI‐type chondrites. In detail however, no ferrihydrite is found in Ryugu particles even at the very sensitive scale of Mössbauer spectroscopy. The typical Fe3+/Fetot of clay minerals is much lower than typical redox ratios measured in CI chondrites (Fe3+/Fetot = 85%–90%). Furthermore, magnetite from Ryugu is stoichiometric with no significant maghemite component, whereas up to 12% of maghemite was previously identified in the Orgueil's so‐called magnetite. These differences suggest that most CI meteorites suffered terrestrial alteration and that the preterrestrial composition of these carbon‐rich samples was less oxidized than previously measured. However, it is not clear yet whether or not the parent bodies of CI chondrites were as reduced as Ryugu. Finally, the high spatial resolution of NFS allows to disentangle the redox state and the crystal chemistry of iron accommodated in serpentine and smectite. The most likely polytype of serpentine is lizardite, containing <35% of Fe3+, a fraction of which being tetrahedrally coordinated. Smectite is more oxidized (Fe3+/Fetot > 65%) and mainly contains octahedral ferric iron. This finding implies that these clays formed from highly alkaline fluids and the spatial variability highlighted here may suggest a temporal evolution or a spatial variability of the nature of this fluid.

Synthesis and Crystal and Electronic Structures of the Zintl Phase Sr21Cd4Sb18

Reported herein are the synthesis and crystal chemistry analysis of the Zintl phase Sr21Cd4Sb18. Single crystals of this compound were grown using the Sn-flux method, and structural characterization was carried out using single-crystal X-ray diffraction. Crystal data: Monoclinic space group C2/m (No. 12, Z = 4); a = 18.2536(6) Å, b = 17.4018(5) Å, and c = 17.8979(6) Å, β = 92.024(1)°. The structure is based on edge- and corner-shared CdSb4 tetrahedra, which ultimately form octameric [Cd8Sb22] fragments, where two symmetry-equivalent subunits are connected via a homoatomic Sb–Sb interaction. The electronic band structure calculations contained herein reveal the emergence of a direct gap between the valence and the conduction bands.

Crystal chemistry and origin of epidote-(Sr) in alkaline rocks of the teschenite association (Silesian Unit, Outer Western Carpathians, Czech Republic)

Crystal chemistry and origin of epidote-(Sr) in alkaline rocks of the teschenite association (Silesian Unit, Outer Western Carpathians, Czech Republic)

Tetrahedrite-(Cd), Cu6(Cu4Cd2)Sb4S13, from Radětice near Příbram, Czech Republic: the new Cd member of the tetrahedrite group

Abstract. Tetrahedrite-(Cd), Cu6(Cu4Cd2)Sb4S13, is a new IMA-approved mineral species from Radětice near the Příbram deposit, Czech Republic. It occurs as black metallic anhedral grains, up to 200 µm in size in quartz–calcite gangue, associated with galena, bournonite, sphalerite, pyrite, geocronite, silver, stromeyerite, tetrahedrite-(Zn), tetrahedrite-(Fe), tetrahedrite-(Cu), and an unknown Pb-rich tetrahedrite-like phase. In reflected light, tetrahedrite-(Cd) is isotropic and grey with greenish tints. Reflectance data for the four COM wavelengths in air are as follows (λ (nm) : R (%)): 470 : 30.8, 546 : 31.1, 589 : 31.1 and 650 : 28.8. Electron microprobe analysis gave (in wt % – average of 13 spot analyses) Cu 34.85, Ag 2.09, Fe 0.18, Zn 0.26, Cd 11.03, Hg 0.75, Pb 0.31, Sb 28.07, and S 23.38, with a total of 100.92. On the basis of ΣMe = 16 atoms per formula unit, the empirical formula of tetrahedrite-(Cd) is Cu9.65Ag0.34Cd1.73Zn0.07Hg0.07Fe0.06Pb0.03Sb4.06S12.84. Tennantite-(Cd) is cubic, I4‾3m, with unit-cell parameters a=10.504(3) Å, V=1158.9(9) Å3, and Z=2. Its crystal structure was refined by single-crystal X-ray diffraction data to a final R1=0.0252 on the basis of 257 unique reflections with Fo>4σ(Fo) and 23 refined parameters. Tetrahedrite-(Cd) is isotypic with other tetrahedrite-group minerals. Its crystal chemistry is discussed, and previous findings of Cd-rich tetrahedrite-group minerals are briefly reviewed.

Crystal chemistry of type paulkerrite and establishment of the paulkerrite group nomenclature

Abstract. A single-crystal structure determination and refinement has been conducted for the type specimen of paulkerrite. The structure analysis showed that the mineral has monoclinic symmetry, space group P21/c, not orthorhombic, Pbca, as originally reported. The unit-cell parameters are a=10.569(2), b=20.590(4), c=12.413(2) Å, and β=90.33(3)∘. The results from the structure refinement were combined with electron microprobe analyses to establish the empirical structural formula A1[(H2O)0.98K0.02]Σ1.00 A2K1.00 M1(Mg1.02Mn0.982+)Σ2.00 M2(Fe1.203+Ti0.544+Al0.24Mg0.02)Σ2.00 M3(Ti0.744+ Fe0.263+)Σ1.00 (PO4)4.02 X[O1.21F0.47(OH)0.32]Σ2.00(H2O)10 ⋅ 3.95H2O, which leads to the end-member formula (H2O)KMg2Fe2Ti(PO4)4(OF)(H2O)10 ⋅ 4H2O. A proposal for a paulkerrite group, comprising orthorhombic members benyacarite, mantiennéite, pleysteinite, and hochleitnerite and monoclinic members paulkerrite and rewitzerite, has been approved by the International Mineralogical Association's Commission for New Minerals, Nomenclature and Classification. The general formulae are A2M12M22M3(PO4)4X2(H2O)10 ⋅ 4H2O and A1A2M12M22M3(PO4)4X2(H2O)10 ⋅ 4H2O for orthorhombic and monoclinic species, respectively, where A= K, H2O, □ (= vacancy); M1 = Mn2+, Mg, Fe2+, Zn (rarely Fe3+); M2 and M3 = Fe3+, Al, Ti4+ (and very rarely Mg); X= O, OH, F. In monoclinic species, K and H2O show an ordering at the A1 and A2 sites, whereas O, (OH), and F show a disordering over the two non-equivalent X1 and X2 sites, which were hence merged as X2 in the general formula. In both monoclinic and orthorhombic species, a high degree of mixing of Fe3+, Al, and Ti occurs at the M2 and M3 sites of paulkerrite group members, making it difficult to get unambiguous end-member formulae from the structural determination of the constituents at individual sites. To deal with this problem an approach has been used that involves merging the compositions at the M2 and M3 sites and applying the site-total-charge method. The merged-site approach allows end-member formulae to be obtained directly from the chemical analysis without the need to conduct crystal-structure refinements to obtain the individual site species.

Chiral spiral cyclic twins. II. A two-parameter family of cyclic twins composed of discrete circle involute spirals.

A mathematical toy model of chiral spiral cyclic twins is presented, describing a family of deterministically generated aperiodic point sets. Its individual members depend solely on a chosen pair of integer parameters, a modulus m and a multiplier μ. By means of their specific parameterization they comprise local features of both periodic and aperiodic crystals. In particular, chiral spiral cyclic twins are composed of discrete variants of continuous curves known as circle involutes, each discrete spiral being generated from an integer inclination sequence. The geometry of circle involutes does not only provide for a constant orthogonal separation distance between adjacent spiral branches but also yields an approximate delineation of the intrinsically periodic twin domains as well as a single aperiodic core domain interconnecting them. Apart from its mathematical description and analysis, e.g. concerning its circle packing densities, the toy model is studied in association with the crystallography and crystal chemistry of α-uranium and CrB-type crystal structures.

Crystal chemistry and thermal behavior of B-, S- and Na-bearing spurrite

Crystal chemistry and thermal behavior of B-, S- and Na-bearing spurrite

Ultrahigh-Density Superhard Hexagonal BN and SiC with Quartz Topology from Crystal Chemistry and First Principles

Based on superdense C6 with a quartz (qtz) topology, new ultrahigh-density hexagonal binary phases, qtz BN and qtz SiC, were identified via full geometry structure relaxations and ground state energies using calculations based on the quantum density functional theory (DFT) with a gradient GGA exchange–correlation XC functional. Like qtz C6, with respect to diamond, the resulting binary qtz BN and qtz SiC were found to be less cohesive than cubic BN and cubic SiC, respectively, but were confirmed to be mechanically (elastic constants) and dynamically (phonon band structures) stable. Higher densities of the new phases correlate with higher hardness values compared to cubic BN and cubic SiC. In contrast to the regular tetrahedra that characterize the cubic BN and SiC phases, the corner-sharing tetrahedra in the new phases are distorted, which accounts for their exceptional density and hardness. All three qtz phases were found to be semiconducting to insulators, with reduced band gaps compared to diamond, cubic BN, and cubic SiC.

Oxide growth characteristics, kinetics and mechanism of rutile formation on pure titanium

Isothermal oxidation of titanium results in the formation of rutile (TiO2) at temperatures of 600 °C – 1200 °C. Initial growth of TiO2 occurs linearly with an activation energy of 53 kJ/mol. Subsequent growth happens parabolically with an activation energy of 155 kJ/mol determined through a proposed quantitative oxide growth model. Inert particles were located at air/oxide interface, indicating oxygen ions to be dominant component for growth of TiO2. Crystal structure and defect chemistry of TiO2 suggests that oxygen diffuses through TiO2 via oxygen vacancies primarily. Temperature-dependent isothermal oxidation mechanism of titanium is proposed considering experimental results and thermodynamic arguments.

Comparative crystal chemistry of monovalent cation-exchanged birnessite

Birnessite (ideally, Na0.54Mn2O4∙1.5H2O) is a layered manganese oxide mineral formed by edge-sharing of MnO6 octahedral sheets stacked in ∼7 Å spacing where variable amounts of water molecules and Na+ cations are occupied in a loosely disordered fashion. As such, the interlayer cations can be mixed with or substituted by other cations to contain diverse rare metals and chemical species to endow unique sensitivity on natural environments. To understand comparative crystal chemistry of birnessite as a function of interlayer cation substitution, a series of monovalent cation-exchanged forms, i.e., H-, Li-, K-, NH4-, Rb-, and Cs-exchanged birnessite, were produced from the original Na-birnessite under ambient conditions and analyzed using synchrotron X-ray powder diffraction, thermo-gravimetry, and X-ray photoluminescence spectroscopy. The (001) interplanar spacing generally expands as a function of ionic radius while it contracts as a function of the water content. Compared to the original Na-birnessite, MnO6 octahedral sheets of cation-exchanged forms become generally reduced and show higher MnIII to MnIV ratio, which affects the interlayer cation and water population. Based on the Rietveld structural refinements, the interlayer structural models are categorized into two groups depending on the distribution fashion of cations and water molecules, i.e., water molecules and cations in the Li-, K-, Rb-, Cs-birnessite models occupy separate interlayer sites whereas those are statistically mixed in the H-, Na-, NH4-birnessite models. The interlayer bonding between water molecules and oxygen atoms of the MnO6 layer appears to be a controlling factor for the interlayer spacing. The complex interplay among cation type, water content, Mn oxidation state, and related structural and chemical parameters are discussed to understand the comparative crystal chemistry of birnessite, which would serve as a basis to understanding its potential role in the geochemical cycle of cationic species in aqueous terrestrial environments.

Crystal chemistry and compressibility of Fe0.5Mg0.5Al0.5Si0.5O3 and FeMg0.5Si0.5O3 silicate perovskites at pressures up to 95GPa.

Silicate perovskite, with the mineral name bridgmanite, is the most abundant mineral in the Earth's lower mantle. We investigated crystal structures and equations of state of two perovskite-type Fe3+-rich phases, FeMg0.5Si0.5O3 and Fe0.5Mg0.5Al0.5Si0.5O3, at high pressures, employing single-crystal X-ray diffraction and synchrotron Mössbauer spectroscopy. We solved their crystal structures at high pressures and found that the FeMg0.5Si0.5O3 phase adopts a novel monoclinic double-perovskite structure with the space group of P21/n at pressures above 12GPa, whereas the Fe0.5Mg0.5Al0.5Si0.5O3 phase adopts an orthorhombic perovskite structure with the space group of Pnma at pressures above 8GPa. The pressure induces an iron spin transition for Fe3+ in a (Fe0.7,Mg0.3)O6 octahedral site of the FeMg0.5Si0.5O3 phase at pressures higher than 40GPa. No iron spin transition was observed for the Fe0.5Mg0.5Al0.5Si0.5O3 phase as all Fe3+ ions are located in bicapped prism sites, which have larger volumes than an octahedral site of (Al0.5,Si0.5)O6.

Triple-conducting Zn-doped Pr1.8Ba0.2NiO4+δ air electrodes for proton ceramic electrolysis cells

Proton ceramic electrolysis cells (PCECs), electrochemical devices that convert electrical energy into chemical energy, have attracted increasing interest; however, their development has been severely limited by the slow kinetics of the air electrodes. Therefore, this paper reports a novel Zn-doped Pr1.8Ba0.2NiO4+δ (PBN) air electrode material in terms of crystal structure, phases, surface chemistry, hydration and conduction behaviors, and electrochemical performance in PCECs. The results show that the optimal Zn doping amount is 0.1 mol replacing Ni (Pr1.8Ba0.2Ni0.9Zn0.1O4+δ, PBNZ1). The PBNZ1 cell achieves a maximum power density of 1.36 W cm−2 in fuel cell mode at 700 °C, while it exhibits an electrolysis current density of 2.95 A cm−2 at 700 °C and 1.3 V, which is 30% higher than that of the PBN cell. This improvement can be attributed to the acceleration of charge transfer processes in the air electrode through Zn doping.

Eu2MGe2OS6 (M = Mn, Fe, Co): Three Melilite-Type Rare-Earth Oxythiogermanates Exhibiting Balanced Nonlinear-Optical Behaviors.

Metal oxychalcogenides as candidates for novel mid-infrared nonlinear-optical materials have attracted great interest due to the distinctive advantages of oxides and chalcogenides in this field. Herein, the first melilite-type rare-earth (RE) oxythiogermanates Eu2MGe2OS6 [M = Mn (1), Fe (2), Co (3)] are obtained by combining RE metals with localized f electrons, magnetic transition metals with delocalized d electrons, and the highly distorted mixed anionic group [GeOS3] into one structure. They belong to the tetragonal P4̅21m space group, and highly distorted [EuOS7] bicapped trigonal prisms bridge adjacent {[MGe2OS6]4-}∞ layers to build the three-dimensional network. Their optical band gaps are determined as 2.40, 2.11 and 2.14 eV, and they show moderate second-harmonic-generation (SHG) responses (0.3, 0.3 and 0.5 × AGS) and large laser-induced damage thresholds (2.77-8.31 × AGS). Theoretical calculation results indicate that the synergistic effect of [EuOS7] and [MS4] units acts on the SHG effect. This work enriches the crystal chemistry of melilite-structure materials.

Ultra-hard hexagonal C12 with C3 cyclopropane-like moiety from first principles

An original carbon allotrope, hexagonal C12, is proposed from crystal chemistry and quantum density functional theory DFT calculations of ground state and physical properties. The structure exhibits corner sharing distorted tetrahedra with the presence of C3 triangular cyclopropane-like moiety connecting planar carbon. Hex.C12 is found cohesive and stable both mechanically (elastic constants and their combinations) and dynamically (phonons band structures) and presents ultra-hardness with HVickers = 70 GPa. The temperature dependence of the heat capacity CV shows close magnitudes to experimental results of diamond. The electronic band structure reveals insulating behavior with 4 eV band gap, smaller than diamond's.

Twists and Puckers: Tuning Crystal Chemistry in the La(AuxGe1-x)2 Compositional Series.

The physical properties of solid-state materials are closely tied to their crystal structure, yet our understanding of how competing structural arrangements energetically compare is limited. In this work, we explore how small differences in composition affect the structure in the La(AuxGe1-x)2 series of compounds, which comprises four unique structure types between LaGe2 and LaAu2. This family includes the previously unknown AlB2-type compound with stoichiometry La(Au0.375Ge0.625)2 as well as La(Au0.25Ge0.75)2, an intergrowth of the AlB2 and ThSi2 structure types. We then study the chemical forces driving the structure changes and use phonon band structure calculations and DFT-Chemical Pressure to evaluate atomic-size effects. These calculations show that the parent AlB2 structure type is disfavored in Au-rich compounds due to soft atomic motions along the c axis. The instability of AlB2-type LaAuGe is confirmed by the presence of imaginary modes in the phonon band structure that correspond to a "puckering" of the hexagonal AlB2-type lattice, resulting in the experimentally observed LiGaGe structure type. The impact of size effects is less clear for Au-poor compositions; instead, twisting the AlB2 structure type to form the ThSi2 type opens a pseudogap at the Fermi level in the electronic density of states. This investigation demonstrates how crystal structure in solid-state materials can be compositionally tuned based on balancing size and electronics when multiple structure types are in close thermodynamic competition.

Protonated Organic Diamines as Templates for Layered and Microporous Structures: Synthesis, Crystal Chemistry, and Structural Trends among the Compounds Formed in Aqueous Systems Transition Metal Halide or Nitrate-Diamine-Selenious Acid.

Systematic studies of crystalline compounds formed in aqueous systems containing aliphatic diamines, divalent transition metal halides, and selenious acid resulted in the discovery of a large family of new complex species corresponding to several new structure types. With ethylenediamine (en), layered (enH2)[M(HSeO3)2X2] compounds are the most commonly formed species which constitute a significant contribution to the family of layered hydrogen selenites containing neutral [M(HSeO3)2] (M = Mg, Mn, Co, Ni, Cu, Zn, Cd) 2D building blocks. In contrast to some previous suggestions, piperazine (pip), as well as its homologue N-methylpiperazine, mostly give rise to quite different, sometimes more complex, structures of varied dimensionality while the (pipH2)[M(HSeO3)2X2] compounds are formed only with M = Cu and Cd. In addition, metal-, halide-, or selenium-free by-product species are observed. The SeIV can be present in a multitude of forms, including H2SeO3, HSeO3-, SeO32-, and Se2O52-, reflecting amazing adaptability to the shape of the templating cations.

The crystal chemistry and reactivity of ternary Na2Fe3Cl8 from the NaCl-FeCl2 system and its potential application as coating layer for cathode in sodium ion batteries

This report explores theoretical and experimental methods to characterize the ternary phases arising from the NaCl + FeCl2 system at both low (150 °C) and high temperatures (550 °C), through milling and evaporation processing techniques. We found that Na2Fe3Cl8 is the only metastable ternary compound produced in either case and only at high temperatures, which is in good qualitative agreement with density functional theory calculations performed with the recent r2SCAN metaGGA functional. The elementary, crystallographic, and grain structure information on Na2Fe3Cl8 collected using a combination of x-ray diffraction, scanning electron microscopy, energy dispersive and Mössbauer spectroscopy is described and discussed in detail. Na2Fe3Cl8 is determined to have a layered trigonal structure in the R3̅m space group. Other ternary stable or metastable ternary phases such as Na6FeCl8 and Na2FeCl4 were not observed, which is likely the result of decomposition occurring beyond 400 °C. While the structure of Na2Fe3Cl8 makes it inadequate as a potential cathode in Na-ion batteries, Na2Fe3Cl8 may operate as suitable coating layer to regulate the passage of ions from electrolytes to active electrode materials without interfacial degradation.

Ferric iron in chrome-bearing spinels: implications for microprobe correction procedures

AbstractWe investigated the compositions of a suite of 361 chrome-bearing spinels from spinel peridotites, ophiolitic mantle chromitites and from layered igneous intrusions in which the Fe2+/Fe3+ ratio has been determined by Mössbauer spectroscopy. We explore the crystal-chemical controls on the distribution of Fe3+ and on mineral stoichiometry with regard to electron-probe correction procedures for estimating Fe3+ in spinel. We find that chrome-bearing spinels can be subdivided into three groups: a Cr–Al-rich group; a high-Fe group; and a highly oxidised group. Spinels of the Cr–Al group are found in spinel peridotites and ophiolitic mantle chromitites. They are normal spinels with a low Fe3+ content and compositions that are close to stoichiometric. Spinels in the high-Fe group are found in layered igneous intrusions. They are also normal spinels which have higher concentrations of Fe3+ on the octahedrally coordinated site than is found for the Cr–Al group. Stoichiometric calculations tend to overestimate the Fe3+ content and their compositions do not conform to the MgO–cr# correlation found in the Cr–Al group. Spinels in the highly oxidised group are found in layered intrusions and ophiolitic mantle chromitites. They have (Fe3+/ΣFe)Möss > 0.4 and high Cr (cr# > 0.5), but relatively low Fe2+ (fe# 0.24–0.56). Stoichiometric calculations tend to underestimate the Fe3+ content. They represent normal spinels in which tetrahedrally coordinated Fe2+ has been oxidised to Fe3+.Our data show that spinels with greater Cr and Fe are sufficiently different in their crystal chemistry from the aluminous spinels to indicate that the EPMA correction procedures developed for Fe3+ in aluminous spinels on the basis of the Cr/Al ratio, and used in oxy-thermobarometry, are inappropriate for Cr-rich and Fe-rich compositions.

The selective adsorption and flotation separation of spodumene from feldspar using a novel iron-group multiple ligand collector

Spodumene and feldspar have little difference in flotability due to their similar crystal chemistry properties. Fe-octyl hydroxamic acid (OHA) (iron complexes of octyl hydroxamic acid) demonstrates excellent selectivity but restricted collecting performance in spodumene flotation. In this work, we added sodium dodecyl sulfate (SDS) into Fe-OHA to obtain a novel multiple ligand collector, which was named Fe-OHA-SDS to enhance the collection ability of Fe-OHA. The efficient separation of spodumene from feldspar (the recovery difference was about 84 %) was achieved by Fe-OHA-SDS without adding depressants and foaming agents at pH 6.2. The separation mechanisms were explored by Zeta potential, contact angle, in-situ microcalorimetric, Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) measurements. The findings revealed that Fe-OHA-SDS was more easily bonded to the spodumene surface than the feldspar surface. Meanwhile, the adsorption of Fe-OHA-SDS significantly expanded the hydrophobicity differences on these two mineral surfaces. The Fe-OHA-SDS was adsorbed on the spodumene surface through the Fe-O bond, which differed from the interaction mechanism of traditional mixed collectors on mineral surfaces. Therefore, Fe-OHA-SDS was an efficient collector with potential application value in spodumene flotation.

Etching Strategy for Photocatalysis: The Evolution of Structures and Properties

This review emphasizes the pivotal role of etching strategies in refining structures and properties crucial to photocatalysis, a sustainable solution for energy and environmental remediation. As fossil fuel‐related environmental concerns rise, photocatalysis emerges as a vital alternative. Yet, maximizing its efficacy is an ongoing challenge. Etching strategies, by creating structural vacancies and revealing active crystal facets, enhance light absorption and the catalyst's efficiency. This process effectively reshapes nanostructures, elevating their surface specificity and subsequently their catalytic properties. Despite advancements, few comprehensive reviews detail etching's influence on photocatalysts. This work, therefore, sheds light on how different etching methodologies affect photocatalyst structures and functions, covering mechanisms such as morphology control, surface area boosting, defect engineering, and more. Furthermore, the impact of etching on light absorption, charge dynamics, and reactant interactions is explored. The review concludes by pointing out challenges and the prospective growth of etching in photocatalysis. By deepening the understanding of etching modification, this review aims to drive progress in developing superior photocatalytic materials, thus fostering advances in renewable energy technologies.