Structure Low Dimensionality and Lone-Pair Stereochemical Activity: the Key to Low Thermal Conductivity in the Pb-Sn-S System.

Recently, metal sulfides have begun to receive attention as potential cost-effective materials for thermoelectric applications beyond optoelectronic and photovoltaic devices. Herein, based on a comparative analysis of the structural and transport properties of 2D PbSnS2 and 1D PbSnS3, we demonstrate that the intrinsic effects that govern the low lattice thermal conductivity (κL) of these sulfides originate from the combination of the low dimensionality of their crystal structures with the stereochemical activity of the lone-pair electrons of cations. The presence of weak bonds in these materials, responsible for phonon scattering, results in inherently low κL of 1.0 W/m K in 1D PbSnS3 and 0.6 W/m K in 2D PbSnS2 at room temperature. However, the nature of the thermal transport is quite distinct. 1D PbSnS3 exhibits a higher thermal conductivity with a crystalline-like peak at low temperatures, while 2D PbSnS2 demonstrates glassy thermal conductivity in the entire temperature range investigated. First-principles density functional theory calculations reveal that the presence of antibonding states below the Fermi level, especially in PbSnS2, contributes to the very low κL. In addition, the calculated phonon dispersions exhibit very soft acoustic phonon branches that give rise to soft lattices and very low speeds of sounds.

Three-Fold Coordination of Copper in Sulfides: A Blockade for Hole Carrier Delocalization but a Driving Force for Ultralow Thermal Conductivity.

Copper-rich sulfides are very promising for energy conversion applications due to their environmental compatibility, cost effectiveness, and earth abundance. Based on a comparative analysis of the structural and transport properties of Cu3BiS3 with those of tetrahedrite (Cu12Sb4S13) and other Cu-rich sulfides, we highlight the role of the cationic coordination types and networks on the electrical and thermal properties. By precession-assisted 3D electron diffraction analysis, we find very high anisotropic thermal vibration of copper attributed to its 3-fold coordination, with an anisotropic atomic displacement parameter up to 0.09 Å2. Density functional theory calculations reveal that these Cu atoms are weakly bonded and give rise to low-energy Einstein-like vibrational modes that strongly scatter heat-carrying acoustic phonons, leading to ultralow thermal conductivity. Importantly, we demonstrate that the 3-fold coordination of copper in Cu3BiS3 and in other copper-rich sulfides constituted of interconnected CuS3 networks causes a hole blockade. This phenomenon hinders the possibility of optimizing the carrier concentration and electronic properties through mixed valency Cu+/Cu2+, differently from tetrahedrite and most other copper-rich chalcogenides, where the main interconnected Cu-S network is built of CuS4 tetrahedra. The comparison with various copper-rich sulfides demonstrates that seeking for frameworks characterized by the coexistence of tetrahedral and 3-fold coordinated copper is very attractive for the discovery of efficient thermoelectric copper-rich sulfides. Considering that lattice vibrations and carrier concentration are key factors for engineering transport phenomena (electronic, phonon, ionic, etc.) in copper-rich chalcogenides for various types of applications, our findings improve the guidelines for the design of materials enabling sustainable energy solutions with wide-ranging applications.

Cs2Ln3CuS8 (Ln = La-Nd, Sm-Tb): Synthesis, Crystal Structure, and Magnetic and Optical Properties.

This work reports the preparation of new quaternary sulfides Cs2Ln3CuS8 (Ln = La-Nd, Sm-Tb), their original crystal and electronic structures, and their magnetic properties. The sulfides were prepared using a reactive flux method from mixtures of Ln2S3 (EuS), Cs2S6, Cu2S, and S. They crystallize in a new type of structure (C2/m space group) and exhibit a layer-like crystal structure, which is a hybrid of those of the ACe2CuS6 series (A = Cs, K) and that of K2CeCu2S4. The values of the optical band gap calculated by the Kubelka-Munk equation are in the range of 1.2-2.62 eV depending on the nature of the Ln ion. The Cs2Gd3CuS8 compound displays relatively great magnetic refrigerating properties at cryogenic temperature with the mass entropy change (-ΔSM) reaching 19.5 J kg-1 K-1 at 3.5 K for ΔH = 5 T.

From K6[Re6-xMoxS8(CN)5] Solid Solution to Individual Cluster Complexes: Separation and Investigation of [Re4Mo2S8(CN)6]n- and [Re3Mo3S8(CN)6]n- Heterometallic Clusters.

A series of new cluster compounds with {Re4Mo2S8} and {Re3Mo3S8} cores has been obtained and investigated. The clusters with different Re/Mo ratios were isolated as individual compounds, which made it possible to study their spectroscopic and electrochemical properties. The geometry of the new clusters was studied using a combination of X-ray diffraction analysis, XAS and quantum chemical DFT calculations. It was shown that the properties of the new clusters, such as the number and position of electrochemical transitions, electronic structure and change in geometry with a change in charge, are similar to the properties of clusters based on the {Re4Mo2Se8} and {Re3Mo3Se8} cores described earlier.

A Tunable Structural Family with Ultralow Thermal Conductivity: Copper-Deficient Cu1-x□xPb1-xBi1+xS3.

Understanding the mechanism that connects heat transport with crystal structures and order/disorder phenomena is crucial to develop materials with ultralow thermal conductivity (κ), for thermoelectric and thermal barrier applications, and requires the study of highly pure materials. We synthesized the n-type sulfide CuPbBi5S9 with an ultralow κ value of 0.6-0.4 W m-1 K-1 in the temperature range 300-700 K. In contrast to prior studies, we show that this synthetic sulfide does not exhibit the ordered gladite mineral structure but instead forms a copper-deficient disordered aikinite structure with partial Pb replacement by Bi, according to the chemical formula Cu1/3□2/3Pb1/3Bi5/3S3. By combining experiments and lattice dynamics calculations, we elucidated that the ultralow κ value of this compound is due to very low energy optical modes associated with Pb and Bi ions and, to a smaller extent, Cu. This vibrational complexity at low energy hints at substantial anharmonic effects that contribute to enhance phonon scattering. Importantly, we show that this aikinite-type sulfide, despite being a poor semiconductor, is a potential matrix for designing novel, efficient n-type thermoelectric compounds with ultralow κ values. A drastic improvement in the carrier concentration and thermoelectric figure of merit have been obtained upon Cl for S and Bi for Pb substitution. The Cu1-x□xPb1-xBi1+xS3 series provides a new, interesting structural prototype for engineering n-type thermoelectric sulfides by controlling disorder and optimizing doping.

Crystal Structure Classification of Copper-Based Sulfides as a Tool for the Design of Inorganic Functional Materials.

Research focusing on the interplay between structural features and transport properties of inorganic materials is of paramount importance for the identification, comprehension, and optimisation of functional materials. In this respect, Earth-abundant copper sulfides have been receiving considerable attention from scientists as the urgency remains to discover and improve the efficiency of sustainable materials for energy applications. This proposed classification of copper sulfides, associated with p- and/or d-block elements, is based on their crystallographic features and an analysis of their transport properties. It provides guidelines to help estimate some properties of new materials (type of main charge carriers, thermal conductivity, transport mechanisms, etc.) from consideration of only their chemical composition and crystal structure. The classification relies primarily on recent studies in the fields of thermoelectricity and photovoltaics as well as on crystal-structure investigations.

Synergistic Effect of Chemical Substitution and Insertion on the Thermoelectric Performance of Cu26V2Ge6S32 Colusite.

Copper-based sulfides are promising materials for thermoelectric applications, which can convert waste heat into electricity. This study reports the enhanced thermoelectric performance of Cu26V2Ge6S32 colusite via substitution of antimony (Sb) for germanium (Ge) and introduction of copper (Cu) as an interstitial atom. The crystal structure of the solid solutions and Cu-rich compounds were analyzed by powder X-ray diffraction and scanning transmission electron microscopy. Both chemical approaches decrease the hole carrier concentration, which leads to a reduction in the electronic thermal conductivity while keeping the thermoelectric power factor at a high value. Furthermore, the interstitial Cu atoms act as phonon scatterers, thereby decreasing the lattice thermal conductivity. The combined effects increase the dimensionless thermoelectric figure of merit ZT from 0.3 (Cu26V2Ge6S32) to 0.8 (Cu29V2Ge5SbS32) at 673 K.

Local-Disorder-Induced Low Thermal Conductivity in Degenerate Semiconductor Cu22Sn10S32.

S-based semiconductors are attracting attention as environmentally friendly materials for energy-conversion applications because of their structural complexity and chemical flexibility. Here, we show that the delicate interplay between the chemical composition and cationic order/disorder allows one to stabilize a new sphalerite derivative phase of cubic symmetry in the Cu-Sn-S diagram: Cu22Sn10S32. Interestingly, its crystal structure is characterized by a semiordered cationic distribution, with the Cu-Sn disorder being localized on one crystallographic site in a long-range-ordered matrix. The origin of the partial disorder and its influence on the electronic and thermal transport properties are addressed in detail using a combination of synchrotron X-ray diffraction, Mössbauer spectroscopy, transmission electron microscopy, theoretical modeling, and transport property measurements. These measurements evidence that this compound behaves as a pseudogap, degenerate p-type material with very low lattice thermal conductivity (0.5 W m-1 K-1 at 700 K). We show that localized disorder is very effective in lowering κL without compromising the integrity of the conductive framework. Substituting pentavalent Sb for tetravalent Sn is exploited to lower the hole concentration and doubles the thermoelectric figure of merit ZT to 0.55 at 700 K with respect to the pristine compound. The discovery of this semiordered cubic sphalerite derivative Cu22Sn10S32 furthers the understanding of the structure-property relationships in the Cu-Sn-S system and more generally in ternary and quaternary Cu-based systems.

Tailoring Heterometallic Cluster Functional Building Blocks: Synthesis, Separation, Structural and DFT Studies of [Re6-x Mox Se8 (CN)6 ]n.

Influence of the metal core composition and geometry on the structure, spectroscopic properties and redox potentials was investigated for the first time for heterometallic (Re/Mo)6 octahedral clusters. The discrete anionic clusters [Re6-x Mox Se8 (CN)6 ]n- (x=2, 3; n=4, 5) were obtained as individual salts. Their isomeric composition and bond-length distribution were inspected using a combination of single-crystal X-ray structure analysis, NMR, EXAFS, and DFT calculations.

Supramolecular Anchoring of Octahedral Molybdenum Clusters onto Graphene and Their Synergies in Photocatalytic Water Reduction.

Dihydrogen (H2) production from sunlight should become one of the most important energy production means in the future. To reach this goal, low-cost and efficient photocatalysts still need to be discovered. Here we show that red near-IR luminescent metal cluster anions, once combined with pyrene-containing cations, are able to photocatalytically produce molecular hydrogen from water. The pyrene moieties act simultaneously as energy transmitters and as supramolecular linkers between the cluster anions and graphene. This association results in a hybrid material combining the emission abilities of pyrene and cluster moieties with the electronic conduction efficiency of graphene. Hydrogen evolution reaction (HER) studies show that this association induces a significant increase of H2 production compared to that produced separately by clusters or graphene. Considering the versatility of the strategy described to design this photocatalytic hybrid material, transition-metal clusters are promising candidates to develop new, environmentally friendly, and low-cost photocatalysts for HER.

Copper-Rich Thermoelectric Sulfides: Size-Mismatch Effect and Chemical Disorder in the [TS4 ]Cu6 Complexes of Cu26 T2 Ge6 S32 (T=Cr, Mo, W) Colusites.

Herein, we investigate the Mo and W substitution for Cr in synthetic colusite, Cu26 Cr2 Ge6 S32 . Primarily, we elucidate the origin of extremely low electrical resistivity which does not compromise the Seebeck coefficient and leads to outstanding power factors of 1.94 mW m-1 K-2 at 700 K in Cu26 Cr2 Ge6 S32 . We demonstrate that the abnormally long iono-covalent T-S bonds competing with short metallic Cu-T interactions govern the electronic transport properties of the conductive "Cu26 S32 " framework. We address the key role of the cationic size-mismatch at the core of the mixed tetrahedral-octahedral complex over the transport properties. Two essential effects are identified: 1) only the tetrahedra that are directly bonded to the [TS4 ]Cu6 complex are significantly distorted upon substitution and 2) the major contribution to the disorder is localized at the central position of the mixed tetrahedral-octahedral complex, and is maximized for x=1, i.e. for the highest cationic size-variance, σ2 .

High-Performance Thermoelectric Bulk Colusite by Process Controlled Structural Disordering.

High-performance thermoelectric bulk sulfide with the colusite structure is achieved by controlling the densification process and forming short-to-medium range structural defects. A simple and powerful way to adjust carrier concentration combined with enhanced phonon scattering through point defects and disordered regions is described. By combining experiments with band structure and phonons calculations, we elucidate, for the first time, the underlying mechanism at the origin of intrinsically low thermal conductivity in colusite samples as well as the effect of S vacancies and antisite defects on the carrier concentration. Our approach provides a controlled and scalable method to engineer high power factors and remarkable figures of merit near the unity in complex bulk sulfide such as Cu26V2Sn6S32 colusites.

Unexpected Magnetic Ordering on the Cr Substructure in UCr2Si2C and Structural Relationships in Quaternary U-Cr-Si-C Compounds.

Previous experimental and theoretical studies revealed that carbon insertion into the RCr2Si2 compounds drastically affects the magnetic behavior, since chromium does not carry any magnetic moment in RCr2Si2C (R = Y, La-Sm, Gd-Er) compounds in contrast to RCr2Si2 (R = Y, Sm, Gd-Lu, Th) compounds. In this study, we report on the unexpected magnetic ordering of chromium atoms in the isotype quaternary UCr2Si2C compound. While specific heat and magnetic measurements suggest a Pauli paramagnetic behavior, neutron powder diffraction reveals an antiferromagnetic ordering of the chromium substructure at high temperature ( TN > 300 K), while that of uranium remains nonmagnetically ordered down to 2 K. Its magnetic behavior, inverse in comparison to the RCr2Si2C carbides involving a magnetic lanthanide, is discussed in relation with the singularity of its crystal structure among the series. Moreover, the crystallographic structures and the structural stability of UCr2Si2C and of two other quaternary U-Cr-Si-C compounds (i.e., UCr3Si2C and U2Cr3Si2C3), based on the full occupancy of interstitial sites by carbon atoms, are discussed and compared to those of the related ternary intermetallics. Finally, the low-temperature form of UCr2Si2, corresponding to a displacive transformation around 210 K of the ThCr2Si2-type structure, is reinvestigated by considering a higher symmetry monoclinic unit cell ( C2/ m) instead of the previously reported triclinic cell ( P1̅). The antiferromagnetic ordering at low temperature ( TN = 30(2) K) of the uranium substructure is confirmed, and its magnetic structure is reanalyzed and discussed considering the monoclinic crystal structure.

Metal Atom Clusters as Building Blocks for Multifunctional Proton-Conducting Materials: Theoretical and Experimental Characterization.

The search for new multifunctional materials displaying proton-conducting properties is of paramount necessity for the development of electrochromic devices and supercapacitors as well as for energy conversion and storage. In the present study, proton conductivity is reported for the first time in three molybdenum cluster-based materials: (H)4[Mo6Br6S2(OH)6]-12H2O and (H)2[Mo6X8(OH)6]-12H2O (X = Cl, Br). We show that the self-assembling of the luminescent [Mo6L8i(OH)6a]2-/4- cluster units leads to both luminescence and proton conductivity (σ = 1.4 × 10-4 S·cm-1 in (H)2[Mo6Cl8(OH)6]-12H2O under wet conditions) in the three materials. The latter property results from the strong hydrogen-bond network that develops between the clusters and the water molecules and is magnified by the presence of protons that are statistically shared by apical hydroxyl groups between adjacent clusters. Their role in the proton conduction is highlighted at the molecular scale by ab initio molecular dynamics simulations that demonstrate that concerted proton transfers through the hydrogen-bond network are possible. Furthermore, thermogravimetric analysis also shows the ability of the compounds to accommodate more or less water molecules, which highlights that vehicular (or diffusion) transport probably occurs within the materials. An infrared fingerprint of the mobile protons is finally proposed based on both theoretical and experimental proofs. The present study relies on a synergic computational/experimental approach that can be extended to other proton-conducting materials. It thus paves the way to the design and understanding of new multifunctional proton-conducting materials displaying original and exciting properties.

Lattice and Valence Electronic Structures of Crystalline Octahedral Molybdenum Halide Clusters-Based Compounds, Cs2[Mo6X14] (X = Cl, Br, I), Studied by Density Functional Theory Calculations.

The electronic and crystal structures of Cs2[Mo6X14] (X = Cl, Br, I) cluster-based compounds were investigated by density functional theory (DFT) simulations and experimental methods such as powder X-ray diffraction, ultraviolet-visible spectroscopy, and X-ray photoemission spectroscopy (XPS). The experimentally determined lattice parameters were in good agreement with theoretically optimized ones, indicating the usefulness of DFT calculations for the structural investigation of these clusters. The calculated band gaps of these compounds reproduced those experimentally determined by UV-vis reflectance within an error of a few tenths of an eV. Core-level XPS and effective charge analyses indicated bonding states of the halogens changed according to their sites. The XPS valence spectra were fairly well reproduced by simulations based on the projected electron density of states weighted with cross sections of Al Kα, suggesting that DFT calculations can predict the electronic properties of metal-cluster-based crystals with good accuracy.

Designing a Thermoelectric Copper-Rich Sulfide from a Natural Mineral: Synthetic Germanite Cu22Fe8Ge4S32.

This study shows that the design of copper-rich sulfides by mimicking natural minerals allows a new germanite-type sulfide Cu22Fe8Ge4S32 with promising thermoelectric properties to be synthesized. The Mössbauer spectroscopy and X-ray diffraction analyses provide evidence that the structure of our synthetic compound differs from that of the natural germanite mineral Cu26Fe4Ge4S32 by its much higher Cu+/Cu2+ ratio and different cationic occupancies. The coupled substitution Cu/Fe in the Cu26-xFe4+xGe4S32 series also appears as a promising approach to optimize the thermoelectric properties. The electrical resistivity, which decreases slightly as the temperature increases, shows that these materials exhibit a semiconducting behavior, but are at the border of a metallic state. The magnitudes of the electrical resistivity and Seebeck coefficient increase with x, which suggests that Fe for Cu substitution decreases the hole concentration. The thermal conductivity decreases as the temperature increases leading to a moderately low value of 1.2 W m-1 K-1 and a maximum ZT value of 0.17 at 575 K.

Pushing thermal conductivity to its lower limit in crystals with simple structures.

Materials with low thermal conductivity usually have complex crystal structures. Herein we experimentally find that a simple crystal structure material AgTlI2 (I4/mcm) owns an extremely low thermal conductivity of 0.25 W/mK at room temperature. To understand this anomaly, we perform in-depth theoretical studies based on ab initio molecular dynamics simulations and anharmonic lattice dynamics. We find that the unique atomic arrangement and weak chemical bonding provide a permissive environment for strong oscillations of Ag atoms, leading to a considerable rattling behaviour and giant lattice anharmonicity. This feature is also verified by the experimental probability density function refinement of single-crystal diffraction. The particularly strong anharmonicity breaks down the conventional phonon gas model, giving rise to non-negligible wavelike phonon behaviours in AgTlI2 at 300 K. Intriguingly, unlike many strongly anharmonic materials where a small propagative thermal conductivity is often accompanied by a large diffusive thermal conductivity, we find an unusual coexistence of ultralow propagative and diffusive thermal conductivities in AgTlI2 based on the thermal transport unified theory. This study underscores the potential of simple crystal structures in achieving low thermal conductivity and encourages further experimental research to enrich the family of materials with ultralow thermal conductivity.

Revisiting properties of edge-bridged bromide tantalum clusters in the solid-state, in solution and vice versa: an intertwined experimental and modelling approach.

Edge-bridged halide tantalum clusters based on the {Ta6Br12}4+ core have been the topic of many physicostructural investigations both in solution and in the solid-state. Despite a large number of studies, the fundamental correlations between compositions, local symmetry, electronic structures of [{Ta6Bri12}La6]m+/n- cluster units (L = Br or H2O, in solution and in the solid-state), redox states, and vibrational and absorption properties are still not well established. Using K4[{Ta6Bri12}Bra6] as a starting precursor (i: inner and a: apical), we have investigated the behavior of the [{Ta6Bri12}Bra6]4- cluster unit in terms of oxidation properties and chemical modifications both in solution (water and organic solvent) and after recrystallization. A wide range of experimental techniques in combination with quantum chemical simulations afford new data that allow the puzzling behavior of the cluster units in response to changes in their environment to be revealed. Apical ligands undergo changes like modifications of interatomic distances to complete substitutions in solution that modify noticeably the cluster physical properties. Changes in the oxidation state of the cluster units also occur, which modify significantly their physical properties, including optical properties, which can thus be used as fingerprints. A subtle balance exists between the number of substituted apical ligands and the cluster oxidation state. This study provides new information about the exact nature of the species formed during the transition from the solid-state to solutions and vice versa. This shows new perspectives on optimization protocols for the design of Ta6 cluster-based materials.

Promoted crystallisation and cationic ordering in thermoelectric Cu26V2Sn6S32 colusite by eccentric vibratory ball milling.

A pristine colusite Cu26V2Sn6S32 was successfully synthesised on a 100 g scale via a mechanochemical reaction in an industrial eccentric vibratory ball mill followed by spark plasma sintering (SPS) at 873 K. The milling of elemental precursors from 1 up to 12 hours was performed and the prepared samples were investigated in detail by X-ray powder diffraction, Mössbauer spectroscopy, scanning electron microscopy, and thermoelectric property measurements. The results point to the formation of a high purity and high crystallinity non-exsoluted colusite phase after the SPS process (P4[combining macron]3n, a = 10.7614(1) Å) in the case of a 12 h milled sample. In comparison, samples milled for 1-6 h displayed small quantities of binary Cu-S phases and vanadium core-shell inclusions, leading to a V-poor/Sn-rich colusite with a higher degree of structural disorder. These samples exhibit lower electrical conductivity and Seebeck coefficient while an increase in the total thermal conductivity is observed. This phenomenon is explained by a higher reactivity and grain size reduction upon prolonged milling and by a weak evolution of the chemical composition from a partly disordered V-poor/Sn-rich colusite phase to a well-ordered stoichiometric Cu26V2Sn6S32 colusite, which leads to a decrease in carrier concentration. For all samples, the calculated PF values, around 0.7-0.8 mW m-1 K-2 at 700 K, are comparable to the values previously achieved for mechanochemically synthesised Cu26V2Sn6S32 in laboratory mills. This approach thus serves as an example of scaling-up possibility for sulphur-based TE materials and supports their future large-scale deployment.

The Ouzo effect to selectively assemble molybdenum clusters into nanomarbles or nanocapsules with increased HER activity.

Metal cluster nanoparticles are obtained by simple solvent shifting called the Ouzo effect. Remarkably, the assembly of [{Mo6Br8}L6]2- (L = Br- or NCS-) cluster units can be directed into nanomarbles or nanocapsules depending on the cluster chemistry. When deposited on electrodes, these nanoparticles show good activities in electrochemical water splitting under mild conditions.