A High-Nuclearity Copper Sulfide Nanocluster [S-Cu50] Featuring a Double-Shell Structure Configuration with Cu(II)/Cu(I) Valences.

This work represents an important step in the quest for creating atomically precise binary semiconductor nanoclusters (BS-NCs). Compared with coinage metal NCs, the preparation of BS-NCs requires strict control of the reaction kinetics to guarantee the formation of an atomically precise single phase under mild conditions, which otherwise could lead to the generation of multiple phases. Herein, we developed an acid-assisted thiolate dissociation approach that employs suitable acid to induce cleavage of the S-C bonds in the Cu-S-R (R = alkyl) precursor, spontaneously fostering the formation of the [Cu-S-Cu] skeleton upon the addition of extra Cu sources. Through this method, a high-nuclearity copper sulfide nanocluster, Cu50S12(SC(CH3)3)20(CF3COO)12 (abbreviated as [S-Cu50] hereafter), has been successfully prepared in high yield, and its atomic structure was accurately modeled through single-crystal X-ray diffraction. It was revealed that [S-Cu50] exhibits a unique double-shell structural configuration of [Cu14S12]@[Cu36S20], and the innermost [Cu14] moiety displays a rhombic dodecahedron geometry, which has never been observed in previously synthesized Cu metal, hydride, or chalcogenide NCs. Importantly, [S-Cu50] represents the first example incorporating mixed Cu(II)/Cu(I) valences in reported atomically precise copper sulfide NCs, which was unambiguously confirmed by XPS, EPR, and XANES. In addition, the electronic structure of [S-Cu50] was established by a variety of optical investigations, including absorption, photoluminescence, and ultrafast transient absorption spectroscopies, as well as theoretical calculations. Moreover, [S-Cu50] is air-stable and demonstrates electrocatalytic activity in ORR with a four-electron pathway.

Multi-functional Single-Source Molecular Precursors for Carbon-Coated Mixed-Metal Phosphates.

We introduce a new synthetic concept that can be broadly adopted for the low-temperature preparation of mixed-metal energy storage materials, such as phosphates, silicates, fluorides, fluorophosphates, and fluorosulfates that exhibit intrinsic low electronic conductivity and thus require a carbon modulation. The development of novel low-temperature approaches for assembling energy-related materials with a complex core-shell microstructure is of great importance for expanding their application scope. The traditional definition of single-source precursors refers to their ability to yield a phase-pure material upon thermal decomposition. We have developed a new way for the utilization of heterometallic molecular precursors in synthesis that goes beyond its common delineation as a single-phase maker. The utility of this approach has been demonstrated upon the low-temperature synthesis of lithium-iron phosphate@C, which represents a celebrated cathode material for Li-ion batteries. The first atomically precise carbonaceous molecular precursors featuring a desired Li:Fe:P ratio of 1:1:1, divalent iron, and sufficient oxygen content for the target LiFeIIPO4 phosphate were shown to enable a spontaneous formation of both the olivine core and conductive carbon shell, yielding a carbon-coated mixed-metal phosphate.

Heterotrimetallic Precursor with 2:2:1 Metal Ratio Requiring at Least a Pentanuclear Molecular Assembly.

This work represents an important step in the quest to make heteromultimetallic molecules featuring specific metal types and complicated metal ratios. The rational design, synthesis, and characterization of a complex heterotrimetallic single-source molecular precursor for the next generation sodium-ion battery cathode material, Na2Mn2FeO6, is described. A unique pentametallic platform [MnII(ptac)3-Na-MnIII(acac)3-Na-MnII(ptac)3] (1) was derived from the known polymeric structure of [NaMnII(acac)3]∞, through a series of elaborate design procedures, such as mixed-ligand, unsymmetric ligand, and mixed-valent approaches. Importantly, the application of those techniques results in a molecule with distinctively different transition metal positions in terms of ligand environment and oxidation states. An isovalent substitution of FeIII for the central MnIII ion forms the target heterotrimetallic precursor [MnII(ptac)3-Na-FeIII(acac)3-Na-MnII(ptac)3] (3) with an appropriate metal ratio of Na:Mn:Fe = 2:2:1. The arrangement of metal ions and ligands in this pentametallic assembly was confirmed by single crystal X-ray investigation. The unambiguous assignment of the positions and oxidation states of the Periodic Table neighbors Fe and Mn in 3 has been achieved by a combination of investigative techniques that include synchrotron resonant diffraction, X-ray multiwavelength anomalous diffraction, X-ray fluorescence spectroscopy, Mössbauer spectroscopy, and gas-phase DART mass spectrometry. The heterotrimetallic single-source precursor 3 was shown to exhibit a clean decomposition pattern yielding the phase-pure P2-Na2Mn2FeO6 quaternary oxide with high uniformity of metal ion distribution as confirmed by electron microscopy.

Surface Modulation and Chromium Complexation: All-in-One Solution for the Cr(VI) Sequestration with Bifunctional Molecules.

The sulfidation of zero valent iron (ZVI) to an Fe@FeSx (S-ZVI) composite has been intensively explored in the ZVI field. Yet, further benefits from the FeSx coating layer are seldom realized, especially those effectively using its intrinsic physical and chemical properties for elaborate design. Here, we demonstrate that in a traditional Cr(VI) sequestration reaction, the FeSx layer displays a great utility in immobilizing molecules containing hydroxyl groups (-OH) and hence, attracting Cr(VI) complexes chelated with carboxyl organics (RCOOH). Such intermolecular attraction readily promotes the diffusion of the Cr(VI) complexes to the S-ZVI surface, affording a higher reaction rate for the Cr(VI) sequestration process. In addition, the above mechanism was used to guide a rational selection of molecules incorporating both hydroxyl and carboxyl functional groups with a proper ratio and thereby, a significantly improved reaction efficiency was achieved. Furthermore, the FeSx phase was revealed to be consumed in the reaction, acting as a supplementary reductant. This work is the first to unveil the relationship between molecules with specific functionalization and the FeSx phase, providing a general rule in choosing appropriate reaction media for Cr(VI) sequestration and related reactions.

Heterotrimetallic Mixed-Valent Molecular Precursors Containing Periodic Table Neighbors: Assignment of Metal Positions and Oxidation States.

A known trinuclear structure was used to design the heterobimetallic mixed-valent, mixed-ligand molecule [CoII (hfac)3 -Na-CoIII (acac)3 ] (1). This was used as a template structure to develop heterotrimetallic molecules [CoII (hfac)3 -Na-FeIII (acac)3 ] (2) and [NiII (hfac)3 -Na-CoIII (acac)3 ] (3) via isovalent site-specific substitution at either of the cobalt positions. Diffraction methods, synchrotron resonant diffraction, and multiple-wavelength anomalous diffraction were applied beyond simple structural investigation to provide an unambiguous assignment of the positions and oxidation states for the periodic table neighbors in the heterometallic assemblies. Molecules of 2 and 3 are true heterotrimetallic rather than a statistical mixture of two heterobimetallic counterparts. Trinuclear platform 1 exhibits flexibility in accommodating a variety of di- and trivalent metals, which can be further utilized in the design of molecular precursors for the NaMM'O4 functional oxide materials.

Phase evolution of the surface iron (hydr)oxides to the iron sulfide through anion exchange during sulfidation of zero valent iron.

The naturally-formed iron (hydr)oxides on the surface of zero valent iron (ZVI) have long been considered as passivation layer and inert phases which significantly reduce the reaction activities when they are employed in environmental remediation. Although it seems there are no direct benefits to keep these passivation layers, here, we show that such phases are necessary intermediates for the transformation to iron sulfides through an anion exchange pathway during sulfidation of ZVI. The pre-formed (hydr)oxides undergo a phase evolution upon aging and specific phases can be effectively trapped, which can be confirmed by a combination of different characterization techniques including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRPD), and X-ray absorption near edge structure (XANES) spectroscopy. Interestingly, after sulfidation, the resultant samples originated from different (hydr)oxides demonstrate different activities in the Cr(VI) sequestration. The XANES investigation of Fe K edge and Fe L2,3 edge indicates Fe remains the same after sulfidation, suggesting a non-redox, anion exchange reaction pathway for the production of iron sulfides, where O2- anions are directly replaced with S2-. Consequently, the structural characteristics of the parent (hydr)oxides are inherited by the as-formed iron sulfides, which make them behave differently because of their different structural natures.

Protective Spinel Coating for Li1.17Ni0.17Mn0.50Co0.17O2 Cathode for Li-Ion Batteries through Single-Source Precursor Approach.

The Li1.17Ni0.17Mn0.50Co0.17O2 Li-rich NMC positive electrode (cathode) for lithium-ion batteries has been coated with nanocrystals of the LiMn1.5Co0.5O4 high-voltage spinel cathode material. The coating was applied through a single-source precursor approach by a deposition of the molecular precursor LiMn1.5Co0.5(thd)5 (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate) dissolved in diethyl ether, followed by thermal decomposition at 400 °C inair resulting in a chemically homogeneous cubic spinel. The structure and chemical composition of the coatings, deposited on the model SiO2 spheres and Li-rich NMC crystallites, were analyzed using powder X-ray diffraction, electron diffraction, high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and energy-dispersive X-ray (EDX) mapping. The coated material containing 12 wt.% of spinel demonstrates a significantly improved first cycle Coulombic efficiency of 92% with a high first cycle discharge capacity of 290 mAhg-1. The coating also improves the capacity and voltage retention monitored over 25 galvanostatic charge-discharge cycles, although a complete suppression of the capacity and voltage fade is not achieved.

From lithium to sodium: design of heterometallic molecular precursors for the NaMO2 cathode materials.

Based on the well-established model structure of Li2M2(tbaoac)6, the first series of heterometallic molecular precursors Na2M2(tbaoac)6(THF)2 (M = Fe, Co, and Ni) have been designed and successfully utilized for the preparation of NaMO2 oxide cathode materials of sodium-ion batteries.

Three to tango requires a site-specific substitution: heterotrimetallic molecular precursors for high-voltage rechargeable batteries.

Design of heterotrimetallic molecules, especially those containing at least two different metals with close atomic numbers, radii, and the same coordination number/environment is a challenging task. This quest is greatly facilitated by having a heterobimetallic parent molecule that features multiple metal sites with only some of those displaying substitutional flexibility. Recently, a unique heterobimetallic complex LiMn2(thd)5 (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate) has been introduced as a single-source precursor for the preparation of a popular spinel cathode material, LiMn2O4. Theoretical calculations convincingly predict that in the above trinuclear molecule only one of the Mn sites is sufficiently flexible to be substituted with another 3d transition metal. Following those predictions, two heterotrimetallic complexes, LiMn2-x Co x (thd)5 (x = 1 (1a) and 0.5 (1b)), that represent full and partial substitution, respectively, of Co for Mn in the parent molecule, have been synthesized. X-ray structural elucidation clearly showed that only one transition metal position in the trinuclear molecule contains Co, while the other site remains fully occupied by Mn. A number of techniques have been employed for deciphering the structure and composition of heterotrimetallic compounds. Synchrotron resonant diffraction experiments unambiguously assigned 3d transition metal positions as well as provided a precise "site-specific Mn/Co elemental analysis" in a single crystal, even in an extremely difficult case of severely disordered structure formed by the superposition of two enantiomers. DART mass spectrometry and magnetic measurements clearly confirmed the presence of heterotrimetallic species LiMnCo(thd)5 rather than a statistical mixture of two heterobimetallic LiMn2(thd)5 and LiCo2(thd)5 molecules. Heterometallic precursors 1a and 1b were found to exhibit a clean decomposition yielding phase-pure LiMnCoO4 and LiMn1.5Co0.5O4 spinels, respectively, at the relatively low temperature of 400 °C. The latter oxide represents an important "5V spinel" cathode material for the lithium ion batteries. Transmission electron microscopy confirmed a homogeneous distribution of transition metals in quaternary oxides obtained by pyrolysis of single-source precursors.

A three body problem: a genuine heterotrimetallic molecule vs. a mixture of two parent heterobimetallic molecules.

This work raises a fundamental question about the "real" structure of molecular compounds containing three different metals: whether they consist of genuine heterotrimetallic species or of a mixture of parent heterobimetallic species. Heterotrimetallic complex Li2CoNi(tbaoac)6 (1, tbaoac = tert-butyl acetoacetate) has been designed based on the model tetranuclear structure featuring two transition metal sites in order to be utilized as a molecular precursor for the low-temperature preparation of the LiCo0.5Ni0.5O2 battery cathode material. An investigation of the structure of 1 appeared to be very challenging, since the Co and Ni atoms have very similar atomic numbers, monoisotopic masses, and radii as well as the same oxidation state and coordination number/environment. Using a statistical analysis of heavily overlaid isotope distribution patterns of the [Li2MM'L5]+ (M/M' = Co2, Ni2, and CoNi) ions in DART mass spectra, it was concluded that the reaction product 1 contains both heterotrimetallic and bimetallic species. A structural analogue approach has been applied to obtain Li2MMg(tbaoac)6 (M = Co (2) and Ni (3)) complexes that contain lighter, diamagnetic magnesium in the place of one of the 3d transition metals. X-ray crystallography, mass spectrometry, and NMR spectroscopy unambiguously confirmed the presence of three types of molecules in the reaction mixture that reaches an equilibrium, Li2M2L6 + Li2Mg2L6 ↔ 2Li2MMgL6, upon prolonged reflux in solution. The equilibrium mixture was shown to have a nearly statistical distribution of the three molecules, and this is fully supported by the results of theoretical calculations revealing that the stabilization energies of heterotrimetallic assemblies fall exactly in between those for the parent heterobimetallic species. The LiCo0.5Ni0.5O2 quaternary oxide has been obtained in its phase-pure form by thermal decomposition of heterometallic precursor 1 at temperatures as low as 450 °C. Its chemical composition, structure, morphology, and transition metal distribution have been studied by X-ray and electron diffraction techniques and compositional energy-dispersive X-ray mapping with nanometer resolution. The work clearly illustrates the advantages of heterometallic single-source precursors over the corresponding multi-source precursors.