Tellurium Chemistry Research Articles

Polytelluride square planar chain-induced anharmonicity results in ultralow thermal conductivity and high thermoelectric efficiency in Al2Te5 monolayers.

Two-dimensional (2D) metal chalcogenides provide rich ground for the development of nanoscale thermoelectrics, although achieving optimal thermoelectric efficiency is still a challenge. Here, we leverage the unique chemistry of tellurium (Te), renowned for its hypervalent bonding and catenation abilities, to tackle this challenge as manifested in Al2Te3 and Al2Te5 monolayers. While the former forms a straightforward covalent Al-Te network, the latter adopts a more intricate bonding mechanism, enabled by eccentric features of Te chemistry, to maintain charge balance. In Al2Te5, a square planar chain (SPC) known as polytelluride [Te3]2- is neutralized by the covalently bonded [Al2Te2]2+ framework. The hypervalent nature of Te results in bizarre Born effective charges of 7 and -4 for adjacent Te atoms within the square planar chain, a feature that induces significant anharmonicity in Al2Te5 monolayers. Enhanced anharmonic lattice vibrations and the accordion pattern bestow glass-like, strongly anisotropic thermal conductivity to the Al2Te5 monolayer. The calculated κL values of 1.8 and 0.5 W m-1 K-1 along the a- and b-axes at 600 K are one order of magnitude lower than those of Al2Te3, and even lower than monolayers that contain heavy cations like Bi2Te3. Moreover, the tellurium chain dominates the valence band maximum and conduction band minimum of Al2Te5, leading to a high valley degeneracy of 10, and thus a high power factor and figure of merit (zT). Using rigorous first-principles calculations of electron relaxation time, the estimated hole-doped and electron-doped zT of, respectively, 1.5 and 0.5 at 600 K is achieved for Al2Te5. The pioneering zT of Al2Te5 compared to that of Al2Te3 is rooted merely in its amorphous-like lattice thermal transport and its polytelluride chain. These findings underscore the importance of aluminum telluride and polymeric-based inorganic compounds as practical and cost-effective thermoelectric materials, pending further experimental validation.

Tellurium with Reversible Six-Electron Transfer Chemistry for High-Performance Zinc Batteries.

Chalcogens, especially tellurium (Te), as conversion-type cathodes possess promising prospects for zinc batteries (ZBs) with potential rich valence supply and high energy density. However, the conversion reaction of Te is normally restricted to the Te2-/Te0 redox with a low voltage plateau at ∼0.59 V (vs Zn2+/Zn) rather than the expected positive valence conversion of Te0 to Ten+, inhibiting the development of Te-based batteries toward high output voltage and energy density. Herein, the desired reversible Te2-/Te0/Te2+/Te4+ redox behavior with up to six-electron transfer was successfully activated by employing a highly concentrated Cl--containing electrolyte (Cl- as strong nucleophile) for the first time. Three flat discharge plateaus located at 1.24, 0.77, and 0.51 V, respectively, are attained with a total capacity of 802.7 mAh g-1. Furthermore, to improve the stability of Ten+ products and enhance the cycling stability, a modified ionic liquid (IL)-based electrolyte was fabricated, leading to a high-performance Zn∥Te battery with high areal capacity (7.13 mAh cm-2), high energy density (542 Wh kgTe-1 or 227 Wh Lcathdoe+anode-1), excellent cycling performance, and a low self-discharge rate based on 400 mAh-level pouch cell. The results enhance the understanding of tellurium chemistry in batteries, substantially promising a remarkable route for advanced ZBs.

Subnano-sized tellurium@nitrogen/phosphorus co-doped carbon nanofibers as anode for potassium-based dual-ion batteries

Tellurium (Te) is a high-volumetric-capacity and high-rate electrode material for potassium-ion (K+) storage. However, there is a lack of knowledge about the nanostructure design of electrode and detailed redox process of tellurium. Herein, we fabricated subnano-sized (<1 nm) tellurium encapsulated into nitrogen, phosphorus-codoped porous carbon nanofibers (Te@N,P-codoped PCNFs). Single-atom and small-molecule tellurium allotropes can be first identified within hierarchical porous carbon through the space confinement of micropores and the chemical bonding effect. A multi-step transformation process for K+ storage is disclosed by experimental and theoretical approaches, where tellurium is firstly converted into K2Ten (n = 5 ∼ 7), then reduced to K2Te3/K2Te2, and eventually transformed into K2Te. Importantly, heteroatoms codoping facilitates tellurium immobilization and K2Te adsorption to avoid their detachment from electrode, and meanwhile, the space confinement of micropores effectively alleviates the volume change. This well-designed electrode exhibits high capacity of 2023.13 mAh cm−3 after 700 cycles at 0.5 C and superior cycling performance for 1500 cycles at 5.0 C, which endows graphite cathode-based dual-ion batteries with good cyclability and high energy density of 191.6 Wh kg−1 (based on the total mass of the anode and cathode). Our work demonstrates the feasibility of atomically dispersed tellurium through the structure engineering, and provides new insights for the manipulation of tellurium chemistry.

Mechanism of tellurium induced nickel alloy corrosion in molten LiCl-KCl salt

Fission product tellurium causes severe embrittlement of nickel alloys in nuclear molten fuel salt systems. This paper investigates the tellurium chemistry in molten LiCl-KCl-Li2Te salts and the tellurium reactions at the alloy interface. The reactions for the two-step reduction of Te0 and the electrochemical formation of nickel tellurides have been identified from cyclic voltammograms. The corrosion of UNS N10003 alloy with different tellurium salt chemistries and applied potentials found that tellurium corrosion attack is only present at potentials more positive than the Ni1.43Te/Te2− potential. The critical potential is thus suggested for mitigating tellurium embrittlement using the redox control technique.

Organic Telluride Formation from Paint Solvents Under Gamma Irradiation

The interactions between tellurium and organic material during a nuclear reactor accident are critical to source term estimations because of the possible formation of volatile species. Reactions taking place in the containment sump are of interest since these can lead to re-volatilization and increase the fission product source term. This paper presents results from experiments investigating the interaction of tellurium dioxide with three paint solvents—texanol ester, methyl isobutyl ketone, and toluene—under containment sump conditions. The experiments were performed by irradiating a mixed solution of tellurium dioxide and paint solvents at a dose rate of 4 kGy/h up to 300 kGy. The resulting samples were analyzed for tellurium concentration and speciation. Tellurium(IV) was found to reduce to metallic tellurium under irradiation when paint solvents were present. More importantly, several volatile organic tellurides were identified in the irradiated samples, which suggests that tellurium can form volatile species in sump conditions when in contact with dissolved paint solvents. This paper provides novel evidence of organic telluride formation in the sump and raises further interest in tellurium chemistry during a severe nuclear reactor accident.

Chemistry of tellurium containing macrocycles

Abstract The chemistry of Tellurium containing macrocycles has received great attraction and developed rapidly. Recently inorganic chemists are fascinated by ligands containing macrocycles having tellurium as soft donor and N and O as hard donor atoms. The tellurium atom is more electropositive than carbon due to its large size that resulted in polarisation of Te–C bond. So, tellurium containing macrocycles are explored due to their high reactivity and toxicity. Well-designed macrocycles containing different metals is an interesting field of chemistry as macrocycle with mixed donor atoms can bind two different metal atoms with different nature within the same cavity and thereby ion selectivity increases. Chemistry of macrocycles with tellurium as soft donor atoms also gives rise to very interesting coordination behaviour as addition of Tellurium in macrocycle adds an additional probe (125Te NMR help to monitor their structures in solutions). The chemistry of hard and soft donors in macrocyclic framework makes interesting coordination chemistry and need to be explore. The discussion includes different types of tellurium macrocycles and their chemistry.

Synthesis and Characterization of Tellurium Catecholates and Their N-Oxide Adducts.

Tellurium catecholate complexes were investigated to probe the redox chemistry of tellurium, whose oxidation state can span from -2 to +6. Treating TeO2 with catechols resulted in tellurium coordination complexes in high yields within minutes to hours at room temperature or with extended heating, depending on the ligand substituents, giving Te(IV) complexes of the form Te(C)2, where C = 3,5-di-tert-butylcatecholate, o-catecholate, or tetrachlorocatecholate. The redox behavior of these complexes was investigated through addition of organic oxidants, giving nearly quantitative adducts of pyridine N-oxide or N-methylmorpholine N-oxide with each tellurium complex, the latter set leading to ligand oxidation upon heating. Each compound was characterized crystallographically and computationally, providing data consistent with a mostly electrostatic interaction and very little covalent character between the N-oxide and Te complex. The Te N-oxide bond orders are consistently lower than those with the catechol derivatives, as characterized with the Mayer, Gopinathan-Jug (G-J), and first Nalewajski-Mrozek (N-M1) bond indices. The tellurium lone pair is energetically buried by 1.93-2.81 eV, correlating with the observation that the ligands are more reactive than the tellurium center toward oxidation. This combined experimental and theoretical study finds structure-property relationships between ligand design and reactivity that will aid in future efforts for the recovery of tellurium.

Tellurium-Polysulfide Chemistry Enables Stable Operation of Lithium-Sulfur Batteries with Limited Lithium Inventory and Electrolyte Supply

The practical realization of lithium-sulfur (Li-S) batteries with high energy density is currently limited by the poor cyclability of the lithium-metal anode. Lithium plating and stripping in the liquid ether-based electrolyte is irreversible over long-term cycling and this leads to rapid capacity fade. Due to the reducing nature of lithium, parasitic side reactions with the electrolyte also occur with considerable severity during cell operation. This eliminates a significant portion of the available lithium inventory and electrolyte supply, and the cell fails prematurely. These problems can be sidestepped by employing surplus lithium and electrolyte in the cell, but this compromises the stack-level energy density. Stabilizing lithium deposition and reducing electrolyte decomposition is of critical importance to enabling commercially viable Li-S batteries with high energy density and long cycle life.The chemistry of Li-S batteries is unique due to the generation of polysulfide intermediates at the cathode that are soluble in the electrolyte. The polysulfides migrate to the anode side, which fundamentally alters its interfacial chemistry by forming reduced sulfide species (Li2S/Li2S2) on the lithium surface. These species are known to have an intrinsically stabilizing effect on lithium deposition, although it is not sufficient to enable stable operation of Li-S batteries at reasonable current densities. Nevertheless, the modification of electrolyte-soluble polysulfide species offers a unique opportunity for tuning the interfacial chemistry of the lithium-metal anode towards stabilizing lithium deposition and reducing electrolyte decomposition.Tellurium, which sits two position below sulfur in Group 16 of the periodic table, is an excellent candidate element for modifying the composition of polysulfide intermediates in Li-S batteries and forming potentially favorable components in the lithium SEI layer. It was found that elemental tellurium (Te0) could be facilely assimilated into polysulfide species to form soluble mixed polytellurosulfide species when left in an ethereal solution of Li2S6. This was confirmed by the characteristic isotopic signature of tellurium using mass spectrometry. The polytellurosulfide species were found to reduce on the surface of lithium metal to form red-colored lithium thiotellurate (Li2TeS3), which was confirmed by X-ray techniques. In contrast to Li2S, Li2TeS3 is expected to be a significantly better ionic conductor due to the reduced electron density around the sulfur atoms. This would help engender a uniform lithium-ion flux on the lithium surface, enabling homogenous lithium deposition.Based on the results above, elemental tellurium was simply added in a 1 : 10 molar ratio to the sulfur/Li2S cathode to modify the chemistry of Li-S batteries. During cell operation, the generated polysulfides (Li2Sn) reacted with the Te0 additive in the cathode to form polytellurosulfide (Li2TexSy) species in-situ. The crossover of these tellurium-containing species to the anode side was confirmed by the detection of a significant amount of Li2TeS3 on the lithium surface. The favorable properties of Li2TeS3 as a lithium SEI component enabled the formation of dense and uniform lithium deposits and significantly improved lithium cycling efficiency. In the anode-free full cell configuration, which pairs a Li2S cathode with a bare anode current collector and contains zero excess lithium (N/P ratio = 1), the addition of tellurium improved cycle life by a factor of 7. The loss of the limited lithium inventory in the anode-free cell was reduced from 2% per cycle to 0.25% per cycle.Time-of-flight secondary ion mass spectrometry (ToF-SIMS) revealed the drastically reduced electrolyte decomposition on lithium surface due to tellurium-stabilized lithium deposition. The reduced electrolyte decomposition could allow a limited electrolyte supply to be retained for a longer number of cycles, thus enabling extended cyclability under lean-electrolyte conditions. This was confirmed using large-area pouch cells employing a high-loading sulfur cathode (5.2 mg cm-2), a lithium-foil anode, and a low electrolyte/sulfur (E/S) ratio of 4.5 µl mg-1. Under such stringent cell design conditions, the pouch cells could be cycled stably for nearly 100 cycles with the addition of tellurium. In contrast, the control cell failed within 25 cycles.This work demonstrates a novel, effective, and robust strategy of adding tellurium to the sulfur/Li2S cathode for stabilizing lithium deposition and reducing electrolyte decomposition in Li-S batteries. This improves cycle life in energy-dense cell configurations operating with a limited lithium inventory or electrolyte supply. Importantly, this approach is scalable as no expensive or complicated pre-treatments or coatings of the lithium-metal anode are necessary. The unique chemistry of tellurium in the polysulfide-rich environment of Li-S batteries opens a new frontier in research in Li-S batteries, bringing them one step closer to reality. Figure 1

Tellurium Behavior in the Containment Sump: Dissolution, Redox, and Radiolysis Effects

In the event of a severe nuclear accident, one major concern is the release of radioactive material into the environment causing potential exposure of the general public to radiation. Among the volatile radionuclides are a range of tellurium isotopes. Due to the radioactivity and the volatility of tellurium, it has to be taken into account when assessing the overall effects of an accident. The interest in tellurium is not limited only to its release but also to the fact that some tellurium isotopes decay to iodine, and thus affect the iodine release behavior. The release and transport behavior of tellurium has been investigated over the past decades, however, the aqueous chemistry of tellurium in the complex containment sump system is still unclear. This study presents the behavior of tellurium dioxide in simplified containment sump conditions in relation to dissolution, redox reactions, and interactions with water radiolysis products. The results indicate that radiolysis products have a significant effect on tellurium chemistry in both a reducing and oxidizing manner depending on the solution composition. The redox reactions also affect the solubility of tellurium. The results show that the current information used to assess tellurium source term needs to be reevaluated for both severe accident management and for code validation purposes.

Selenium &amp; tellurium chemistry at the beginning of the 3rd millennium: a celebration of ICCST

Vito Lippolis and Claudio Santi introduce theNew Journal of Chemistrythemed collection on selenium &amp; tellurium chemistry at the beginning of the 3rd millennium: a celebration of ICCST.

The aqueous chemistry of tellurium: critically-selected equilibrium constants for the low-molecular-weight inorganic species

Environmental contextEquilibrium constants are required in many scientific disciplines such as biology, medicine, engineering, and in particular chemistry. Lack of reliable equilibrium constants for tellurium has restricted our understanding of its speciation and behaviour in the environment. This study presents a reliable set of equilibrium constants for tellurium, thereby providing a more coherent basis for future experimental investigations of the geochemistry, biochemistry and toxicology of this element. AbstractRelatively little information is available in the literature regarding the speciation and solubility of tellurium in aqueous solutions. The available thermodynamic data have been critically evaluated and entered into a thermodynamic database. The Joint Expert Speciation System suite of computer programs has been used to achieve thermodynamic consistency and provide a critically-selected set of equilibrium constants that can later be used for modelling purposes.

Selenium– and tellurium–halogen reagents

Abstract Selenium and tellurium form binary halides in which the chalcogen can be in formal oxidation states (IV), (II) or (I). They are versatile reagents for the preparation of a wide range of inorganic and organic selenium and tellurium compounds taking advantage of the reactivity of the chalcogen–halogen bond. With the exception of the tetrafluorides, the tetrahalides are either commercially available or readily prepared. On the other hand, the low-valent species, EX2 (E = Se, Te; X = Cl, Br) and E2X2 (E = Se, Te; X = Cl, Br) are unstable with respect to disproportionation and must be used as in situ reagents. Organoselenium and tellurium halides are well-known in oxidation states (IV) and (II), as exemplified by REX3, R2EX2 and REX (R = alkyl, aryl; E = Se, Te; X = F, Cl, Br, I); mixed-valent (IV/II) compounds of the type RTeX2TeR are also known. This chapter surveys the availability and/or preparative methods for these widely used reagents followed by examples of their applications in synthetic inorganic and organic selenium and tellurium chemistry. For both the binary halides and their organic derivatives, the discussion is subdivided according to the formal oxidation state of the chalcogen.

Synthesis of Se–N+ and Te–N+ bond-containing heterocycles

Elaboration of novel synthetic methods in the field of selenium and tellurium chemistry is actual due to their possible further utilization both in development of new medicines and materials, as well as intermediates and catalysts in organic synthesis. This review is a survey of the synthetic methods toward formation of Se–N+ and Te–N+ bonds from 1975 until present.

Tellurium-Impregnated Porous Cobalt-Doped Carbon Polyhedra as Superior Cathodes for Lithium-Tellurium Batteries.

Lithium-tellurium (Li-Te) batteries are attractive for energy storage owing to their high theoretical volumetric capacity of 2621 mAh cm-3. In this work, highly nanoporous cobalt and nitrogen codoped carbon polyhedra (C-Co-N) derived from a metal-organic framework (MOF) is synthesized and employed as tellurium host for Li-Te batteries. The Te@C-Co-N cathode with a high Te loading of 77.2 wt % exhibits record-breaking electrochemical performances including an ultrahigh initial capacity of 2615.2 mAh cm-3 approaching the theoretical capacity of Te (2621 mAh cm-3), a superior cycling stability with a high capacity retention of 93.6%, a ∼99% Columbic efficiency after 800 cycles as well as rate capacities of 2160, 1327.6, and 894.8 mAh cm-3 at 4, 10, and 20 C, respectively. The redox chemistry of tellurium is revealed by in operando Raman spectroscopic analysis and density functional theory simulations. The results illustrate that the performances are attributed to the highly conductive C-Co-N matrix with an advantageous structure of abundant micropores, which provides highly efficient channels for electron transfer and ionic diffusion as well as sufficient surface area to efficiently host tellurium while mitigating polytelluride dissolution and suppressing volume expansion.

Thorium Chemistry in Oxo-Tellurium System under Extreme Conditions.

Through the use of a high-temperature/high-pressure synthesis method, four thorium oxo-tellurium compounds with different tellurium valence states were isolated. The novel inorganic phases illustrate the intrinsic complexity of the actinide tellurium chemistry under extreme conditions of pressure and temperature. Th2Te3O11 is the first instance of a mixed-valent oxo-tellurium compound, and at the same time, Te exhibits three different coordination environments (TeIVO3, TeIVO4, and TeVIO6) within a single structure. These three types of Te polyhedra are further fused together, resulting in a [Te3O11]8- fragment. Na4Th2(TeVI3O15) and K2Th(TeVIO4)3 are the first alkaline thorium tellurates described in the literature. Both compounds are constructed from ThO9 tricapped trigonal prisms and TeVIO6 octahedra. Na4Th2(TeVI3O15) is a three-dimensional framework based on Th2O15 and Te2O10 dimers, while K2Th(TeVIO4)3 contains tungsten oxide bronze like Te layers linked by ThO9 polyhedra. The structure of β-Th(TeIVO3)(SO4) is built from infinite thorium chains cross-linked by TeIVO32- and SO42- anions. Close structural analysis suggests that β-Th(TeIVO3)(SO4) is highly related to the structure of α-Th(SeO4)2. Additionally, the Raman spectra are recorded and the characteristic peaks are assigned based on a comparison of reported tellurites or tellurates.

A novel approach to explore organochalcogen chemistry of tellurium based receptor for selective determination of silver ions in aqueous medium

In due consideration of the growing importance of chemical sensors for the detection and quantification of toxic heavy metal ions to counter water pollution, a novel class of tellurium-based organic receptors has been investigated as a potentially sensitive and selective silver-ion probe in the present work. The new tellurium-incorporated Schiff base ligand (R1) was chemically synthesized and characterized using various spectroscopic techniques. Upon an exposure of organic nanoparticles (N1) of the title receptor ligand (R1) to a pool of select heavy metal ions, the former displayed high sensitivity and selectivity towards silver ions, in aqueous medium, with a detection limit of 2.34nM. Interestingly, the presence of metal ions bearing close physico-chemical resemblance to silver exerted negligible interference in the ultra-sensitive detection of silver ions by the title probe N1. Furthermore, the precision and accuracy of the potential silver-ion sensor (N1) in aqueous medium was established across a wide pH range as well as under saline conditions. The analytical utility of this potential silver-ion probe R1 was further investigated for real sample analysis of objects of environmental applicability. The results of the same were authenticated by using atomic absorption spectroscopy. In summary, an investigation into the utility of a new class of tellurium-based organic receptors as potential metal-ion sensors opens a new avenue into the rather poorly-comprehended environmental relevance of organotellurium chemistry.

Tellurium Chemistry in Brazil: Origin and Development

Tellurium Chemistry in Brazil: Origin and Development

Chemistry and Occurrences of Native Tellurium from Epithermal Gold Deposits in Japan

AbstractThe chemistry and mode of occurrences of native tellurium in the epithermal gold ores from Teine, Kobetsuzawa, Mutsu, Kawazu, Suzaki and Iriki in Japan are examined. Mineral assemblages in contact with native tellurium are: quartz‐sylvanite at Teine, quartz‐hessite‐sylvanite‐tellurantimony at Kobetsuzawa, quartz at Mutsu, quartz‐stutzite‐hessite‐sylvanite‐tetradymite at Kawazu, quartz at Suzaki, and quartz‐goldfieldite at Iriki. The peak patterns of XRD for native tellurium from these six ores are nearly identical to that of JCPDS 4–554. Their chemical compositions of Te range from 98.16 to 100.73 wt.%, showing nearly pure tellurium. Other elements detected are: Se of 0–0.85 and Cu of 0–0.74 at Teine, Sb of 0.45–0.47 and Se of 0.19–0.27 at Kawazu, Se of 0.22–1.11 and Sb of 0–0.49 at Suzaki, and Cu of 0.69–0.98, As of 0.22–0.28 and Bi of 0–0.22 wt.% at Iriki. No other elements are detected in the ores of Kobetsuzawa and Mutsu. The ranges of associated minor compositions are consistent with those of the experimental phase. The differences would be related to associate minerals. The mineral assemblages in these ores agree well with the previously proposed experimental phase relations in Au‐Ag‐Te ternary system for 120–280°C. The Suzaki ore has high Te‐Au assemblage: from calaverite‐sylvanite‐krennerite via native tellurium to petzite, with changing mineralization stage, whereas the Kobetsuzawa and the Kawazu ores have high Te‐Ag assemblage of tellurium‐hessite, and native tellurium‐stutzite‐hessite‐sylvanite, respectively. The Teine ore has intermediate assemblage of native tellurium‐sylvanite. The mineral assemblages in the Au‐Ag‐Te system are related to the hydrothermal environment especially to the pH condition, i.e. Au rich assemblages under acidic and Ag rich assemblages under intermediate pH conditions, being supported by alteration mineral species. The other telluriferous epithermal gold deposits not in association with native tellurium such as Agawa, Date, Takeno, Chugu, Chitose, Sado and Kushikino are estimated to have been formed under higher pH conditions as adularia and calcite occur in these deposits. The pH‐Eh diagram for aqueous tellurium species and tellurium minerals at 250°C indicates that the region of native tellurium occurs between those of aqueous telluride and tellurous species at lower pH, being consistent with their mineral assemblages in ores and alteration envelopes.

ChemInform Abstract: (PhTe)3-: The Anionic Tellurium Analogue of I3-.

The missing link between solid-state tellurium chemistry and polyhalide ions is provided by the synthesis of the almost linear (PhTe)(3)(-) ion, whose structure is shown. Tritelluride units are a recurring motif in the solid state and are related to the structures of polyhalides.

Editorial: III Brazilian meeting on the selenium and tellurium chemistry

Editorial: III Brazilian meeting on the selenium and tellurium chemistry