Origin of Intrinsically Low Thermal Conductivity in Talnakhite Cu17.6Fe17.6S32 Thermoelectric Material: Correlations between Lattice Dynamics and Thermal Transport.

Understanding the nature of phonon transport in solids and the underlying mechanism linking lattice dynamics and thermal conductivity is important in many fields, including the development of efficient thermoelectric materials where a low lattice thermal conductivity is required. Herein, we choose the pair of synthetic chalcopyrite CuFeS2 and talnakhite Cu17.6Fe17.6S32 compounds, which possess the same elements and very similar crystal structures but very different phonon transport, as contrasting examples to study the influence of lattice dynamics and chemical bonding on the thermal transport properties. Chemically, talnakhite derives from chalcopyrite by inserting extra Cu and Fe atoms in the chalcopyrite lattice. The CuFeS2 compound has a lattice thermal conductivity of 2.37 W m-1 K-1 at 625 K, while Cu17.6Fe17.6S32 features Cu/Fe disorder and possesses an extremely low lattice thermal conductivity of merely 0.6 W m-1 K-1 at 625 K, approaching the amorphous limit κmin. Low-temperature heat capacity measurements and phonon calculations point to a large anharmonicity and low Debye temperature in Cu17.6Fe17.6S32, originating from weaker chemical bonds. Moreover, Mössbauer spectroscopy suggests that the state of Fe atoms in Cu17.6Fe17.6S32 is partially disordered, which induces the enhanced alloy scattering. All of the above peculiar features, absent in CuFeS2, contribute to the extremely low lattice thermal conductivity of the Cu17.6Fe17.6S32 compound.

Nitrogenase-mimic iron-containing chalcogels for photochemical reduction of dinitrogen to ammonia.

A nitrogenase-inspired biomimetic chalcogel system comprising double-cubane [Mo2Fe6S8(SPh)3] and single-cubane (Fe4S4) biomimetic clusters demonstrates photocatalytic N2 fixation and conversion to NH3 in ambient temperature and pressure conditions. Replacing the Fe4S4 clusters in this system with other inert ions such as Sb(3+), Sn(4+), Zn(2+) also gave chalcogels that were photocatalytically active. Finally, molybdenum-free chalcogels containing only Fe4S4 clusters are also capable of accomplishing the N2 fixation reaction with even higher efficiency than their Mo2Fe6S8(SPh)3-containing counterparts. Our results suggest that redox-active iron-sulfide-containing materials can activate the N2 molecule upon visible light excitation, which can be reduced all of the way to NH3 using protons and sacrificial electrons in aqueous solution. Evidently, whereas the Mo2Fe6S8(SPh)3 is capable of N2 fixation, Mo itself is not necessary to carry out this process. The initial binding of N2 with chalcogels under illumination was observed with in situ diffuse-reflectance Fourier transform infrared spectroscopy (DRIFTS). (15)N2 isotope experiments confirm that the generated NH3 derives from N2 Density functional theory (DFT) electronic structure calculations suggest that the N2 binding is thermodynamically favorable only with the highly reduced active clusters. The results reported herein contribute to ongoing efforts of mimicking nitrogenase in fixing nitrogen and point to a promising path in developing catalysts for the reduction of N2 under ambient conditions.

Enhanced photochemical hydrogen evolution from Fe4S4-based biomimetic chalcogels containing M2+ (M = Pt, Zn, Co, Ni, Sn) centers.

Naturally abundant enzymes often feature active sites comprising transition metal cluster units that catalyze chemical processes and reduce small molecules as well as protons. We introduce a family of new chalcogenide aerogels (chalcogels), aiming to model the function of active sites and the structural features of a larger protective framework. New metal incorporated iron sulfur tin sulfide chalcogels referred to as ternary chalcogels and specifically the chalcogels M-ITS-cg3, fully integrate biological redox-active Fe4S4 clusters into a semiconducting porous framework by bridging them with Sn4S10 linking units. In the M-ITS-cg3 system we can tailor the electro- and photocatalytic properties of chalcogels through the control of spatial distance of redox-active Fe4S4 centers using additional linking metal ions, M(2+) (Pt, Zn, Co, Ni, Sn). The presence of a third metal does not change the structural properties of the biomimetic chalcogels but modifies and even enhances their functional performance. M-ITS-cg3s exhibit electrocatalytic activity in proton reduction that arises from the Fe4S4 clusters but is tuned inductively by M(2+). The metal ions alter the reduction potential of Fe4S4 in a favorable manner for photochemical hydrogen production. The Pt incorporated ITS-cg3 shows the greatest improvement in the overall hydrogen yield compared to the binary ITS-cg3. The ability to manipulate the properties of biomimetic chalcogels through synthetic control of the composition, while retaining both structural and functional properties, illustrates the chalcogels' flexibility and potential in carrying out useful electrochemical and photochemical reactions.

Field-induced spin-flop in antiferromagnetic semiconductors with commensurate and incommensurate magnetic structures: Li2FeGeS4 (LIGS) and Li2FeSnS4 (LITS).

Li2FeGeS4 (LIGS) and Li2FeSnS4 (LITS), which are among the first magnetic semiconductors with the wurtz-kesterite structure, exhibit antiferromagnetism with TN ≈ 6 and 4 K, respectively. Both compounds undergo a conventional metamagnetic transition that is accompanied by a hysteresis; a reversible spin-flop transition is dominant. On the basis of constant-wavelength neutron powder diffraction data, we propose that LIGS and LITS exhibit collinear magnetic structures that are commensurate and incommensurate with propagation vectors km = [1/2, 1/2, 1/2] and [0, 0, 0.546(1)], respectively. The two compounds exhibit similar magnetic phase diagrams, as the critical fields are temperature-dependent. The nuclear structures of the bulk powder samples were verified using time-of-flight neutron powder diffraction along with synchrotron X-ray powder diffraction. (57)Fe and (119)Sn Mössbauer spectroscopy confirmed the presence of Fe(2+) and Sn(4+) as well as the number of crystallographically unique positions. LIGS and LITS are semiconductors with indirect and direct bandgaps of 1.42 and 1.86 eV, respectively, according to optical diffuse-reflectance UV-vis-NIR spectroscopy.

Tunable biomimetic chalcogels with Fe4S4 cores and [Sn(n)S(2n+2)](4-)(n = 1, 2, 4) building blocks for solar fuel catalysis.

Biology sustains itself by converting solar energy in a series of reactions between light harvesting components, electron transfer pathways, and redox-active centers. As an artificial system mimicking such solar energy conversion, porous chalcogenide aerogels (chalcogels) encompass the above components into a common architecture. We present here the ability to tune the redox properties of chalcogel frameworks containing biological Fe(4)S(4) clusters. We have investigated the effects of [Sn(n)S(2n+2)](4-) linking blocks ([SnS(4)](4-), [Sn(2)S(6)](4-), [Sn(4)S(10)](4-)) on the electrochemical and electrocatalytic properties of the chalcogels, as well as on the photophysical properties of incorporated light-harvesting dyes, tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)). The various thiostannate linking blocks do not alter significantly the chalcogel surface area (90-310 m(2)/g) or the local environment around the Fe(4)S(4) clusters as indicated by (57)Fe Mössbauer spectroscopy. However, the varying charge density of the linking blocks greatly affects the reduction potential of the Fe(4)S(4) cluster and the electronic interaction between the clusters. We find that when the Fe(4)S(4) clusters are bridged with the adamantane [Sn(4)S(10)](4-) linking blocks, the electrochemical reduction of CS(2) and the photochemical production of hydrogen are enhanced. The ability to tune the redox properties of biomimetic chalcogels presents a novel avenue to control the function of multifunctional chalcogels for a wide range of electrochemical or photochemical processes relevant to solar fuels.

Photocatalytic hydrogen evolution from FeMoS-based biomimetic chalcogels.

The naturally abundant elements used to catalyze photochemical processes in biology have inspired many research efforts into artificial analogues capable of proton reduction or water oxidation under solar illumination. Most biomimetic systems are isolated molecular units, lacking the protective encapsulation afforded by a protein's tertiary structure. As such, advances in biomimetic catalysis must also be driven by the controlled integration of molecular catalysts into larger superstructures. Here, we present porous chalcogenide framework materials that contain biomimetic catalyst groups immobilized in a chalcogenide network. The chalcogels are formed via metathesis reaction between the clusters [Mo(2)Fe(6)S(8)(SPh)(3)Cl(6)](3-) and [Sn(2)S(6)](4-) in solution, yielding an extended, porous framework structure with strong optical absorption, high surface area (up to 150 m(2)/g), and excellent aqueous stability. Using [Ru(bpy)(3)](2+) as the light-harvesting antenna, the chalcogels are capable of photocatalytically producing hydrogen from mixed aqueous solutions and are stable under constant illumination over a period of at least 3 weeks. We also present improved hydrogen yields in the context of the energy landscape of the chalcogels.

Biomimetic multifunctional porous chalcogels as solar fuel catalysts.

Biological systems that can capture and store solar energy are rich in a variety of chemical functionalities, incorporating light-harvesting components, electron-transfer cofactors, and redox-active catalysts into one supramolecule. Any artificial mimic of such systems designed for solar fuels production will require the integration of complex subunits into a larger architecture. We present porous chalcogenide frameworks that can contain both immobilized redox-active Fe(4)S(4) clusters and light-harvesting photoredox dye molecules in close proximity. These multifunctional gels are shown to electrocatalytically reduce protons and carbon disulfide. In addition, incorporation of a photoredox agent into the chalcogels is shown to photochemically produce hydrogen. The gels have a high degree of synthetic flexibility, which should allow for a wide range of light-driven processes relevant to the production of solar fuels.

Light-Induced Bistability in Iron(III) Spin-Transition Compounds of 5 X-Salicylaldehyde Thiosemicarbazone (X=H, Cl, Br).

The iron(III) spin-crossover compounds [Fe(Hthsa)(thsa)]⋅H2 O (1), [Fe(Hth5Clsa)(th5Clsa)2 ]⋅H2 O (2), and [Fe(Hth5Brsa)(th5Brsa)2 ]⋅H2 O (3) (H2 thsa=salicylaldehyde thiosemicarbazone, H2 th5Clsa=5-chlorosalicylaldehyde thiosemicarbazone, and H2 th5Brsa=5-bromosalicylaldehyde thiosemicarbazone) have been synthesized and their spin-transition properties investigated by magnetic susceptibility, Mössbauer spectroscopy, and differential scanning calorimetry measurements. The three compounds exhibit an abrupt spin transition with a thermal hysteresis effect. The more polarizable the substituent on the salicylaldehyde moiety, the more complete is the transition at room temperature with an increased degree of cooperativity. The molecular structures of 1 and 2 in the high-spin state are revealed. The occurrence of the light-induced excited-spin-state trapping phenomenon appears to be dependent on the substituent incorporated into the 5-position of the salicylaldehyde subunit. Whereas the compounds with an electron-withdrawing group (-Br or -Cl) exhibit light-induced trapped excited high-spin states with great longevity of metastability, the halogen-free compound does not, even though strong intermolecular interactions (such as hydrogen-bonding networks and π stacking) operate in the system. For compound 2, the surface level of photoconversion is less than 35 %. In contrast, compound 3 displays full photoexcitation.

Novel nanohybrids derived from the attachment of FePt nanoparticles on carbon nanotubes.

Multiwalled carbon nanotubes (MWCNTs) were used as nanotemplates for the dispersion and stabilization of FePt nanoparticles (NPs). Pre-formed capped FePt NPs were connected to the MWCNTs external surface via covalent binding through organic linkers. Free FePt NPs and MWCNTs-FePt hybrids were annealed in vacuum at 700 degrees C in order to achieve the L1(0) ordering of the FePt phase. Both as prepared and annealed samples were characterized and studied using a combination of experimental techniques, such as Raman and Mössbauer spectroscopies, powder X-ray Diffraction (XRD), magnetization and transmittion electron microscopy (TEM) measurements. TEM measurements of the hybrid sample before annealing show that a fine dispersion of NPs along the MWCNTs surface is achieved, while a certain amount of free particles attached to each other in well connected dense assemblies of periodical or non-periodical particle arrangements is also observed. XRD measurements reveal that the FePt phase has the face-centered cubic (fcc) disordered crystal structure in the as prepared samples, which is transformed to the face-centered tetragonal (fct) L1(0) ordered crystal structure after annealing. An increase in the average particle size is observed after annealing, which is higher for the free NPs sample. Superparamagnetic phenomena due to the small FePt particle size are observed in the Mössbauer spectra of the as prepared samples. Mössbauer and magnetization measurements of the MWCNTs-FePt hybrids sample reveal that the part of the FePt particles attached to the MWCNTs surface shows superparamagnetic phenomena at RT even after the annealing process. The hard magnetic L1(0) phase characteristics are evident in the magnetization measurements of both samples after annealing, with the coercivity of the hybrid sample over-scaling that of the free NPs sample by a factor of 1.25.

Iron-substituted cubic silsesquioxane pillared clays: Synthesis, characterization and acid catalytic activity.

Novel pillared structures were developed from the intercalation of iron-substituted cubic silsesquioxanes in a sodium and an acid-activated montmorillonite nanoclay and evaluated as acid catalysts. Octameric cubic oligosiloxanes were formed upon controlled hydrolytic polycondensation of the corresponding monomer (a diamino-alkoxysilane) and reacted with iron cations to form complexes that were intercalated within the layered nanoclay matrices. Upon calcination iron oxide nanoparticles are formed which are located on the silica cubes (pillars) and on the surfaces of the clay platelets. Acid activation of the nanoclay was performed in order to increase the number of acid active sites in the pristine clay and thus increase its catalytic activity. A plethora of analytical techniques including X-ray diffraction, thermal analyses, Fourier transform infrared, electron paramagnetic resonance, Raman, Mössbauer and X-ray photoelectron spectroscopies and porosimetry measurements were used in order to follow the synthesis steps and to fully characterize the final catalysts. The resulting pillared clays exhibit a high specific area and show significant acid catalytic activity that was verified using the catalytic dehydration of isopropanol asa probe reaction.

Zero-valent iron/iron oxide-oxyhydroxide/graphene as a magnetic sorbent for the enrichment of polychlorinated biphenyls, polyaromatic hydrocarbons and phthalates prior to gas chromatography-mass spectrometry.

A composite magnetic material consisting of zero-valent iron, iron oxide-oxyhydroxide and graphene was synthesized and used successfully as a sorbent for the micro solid-phase extraction of PAHs, PCBs and phthalic acid esters. The components endow the composite with multiple characteristics such as adsorption capability and facile removal due to its magnetic properties. Due to the π-π electrostatic stacking property of graphene, the high specific surface area and the adsorption capability of both components, the resulting black flaky Fe(0)/iron oxide-oxyhydroxide/graphene composite showed high extraction efficiency for the target analytes from water samples. Compared with the neat graphene, the composite material has improved properties in terms of microextraction capabilities as both the hydrophobic graphene and zero-valent iron participate in the adsorption of the hydrophobic molecules. The precision from the extraction of all three groups of compounds was lower than 7% and the recoveries were from 90 to 93% from a spiked lake water sample. The high recoveries in relation to the low final volume of the desorption solvent ensure high preconcentration efficiency and a promising sorbent for analytical applications.