K-edge X-ray Absorption Spectroscopy Research Articles

Tracking nuclear motion in single-molecule magnets using femtosecond X-ray absorption spectroscopy

The development of new data storage solutions is crucial for emerging digital technologies. Recently, all-optical magnetic switching has been achieved in dielectrics, proving to be faster than traditional methods. Despite this, single-molecule magnets (SMMs), which are an important class of magnetic materials due to their nanometre size, remain underexplored for ultrafast photomagnetic switching. Herein, we report femtosecond time-resolved K-edge X-ray absorption spectroscopy (TR-XAS) on a Mn(III)-based trinuclear SMM. Exploiting the elemental specificity of XAS, we directly track nuclear dynamics around the metal ions and show that the ultrafast dynamics upon excitation of a crystal-field transition are dominated by a magnetically active Jahn-Teller mode. Our results, supported by simulations, reveal minute bond length changes from 0.01 to 0.05 Å demonstrating the sensitivity of the method. These geometrical changes are discussed in terms of magneto-structural relationships and consequently our results illustrate the importance of TR-XAS for the emerging area of ultrafast molecular magnetism.

Probing Isolated Water Molecules in Aqueous Acetonitrile Solutions Using Oxygen K-Edge X-ray Absorption Spectroscopy.

Oxygen K-edge X-ray absorption spectroscopy (XAS) of an aqueous acetonitrile solution exhibited a sharp peak at approximately 537 eV, which was similar to that of water vapor and was not observed in liquid water. The inner-shell spectra of isolated water molecules and water clusters of different sizes surrounded by acetonitrile molecules were obtained by extracting these water structures from the liquid structures of aqueous acetonitrile solutions, as calculated using molecular dynamics simulations. The sharp peak profiles of the O K-edge XAS spectra were derived not from water clusters but from isolated water molecules surrounded by acetonitrile molecules. The present study proposes that isolated water molecules are easily formed in aqueous acetonitrile solutions and that the electronic structures of the isolated water molecules can be analyzed using O K-edge XAS spectra, which separates the contributions of small water clusters.

Excited-State Identification of a Nickel-Bipyridine Photocatalyst by Time-Resolved X-ray Absorption Spectroscopy.

Photoassisted catalysis using Ni complexes is an emerging field for cross-coupling reactions in organic synthesis. However, the mechanism by which light enables and enhances the reactivity of these complexes often remains elusive. Although optical techniques have been widely used to study the ground and excited states of photocatalysts, they lack the specificity to interrogate the electronic and structural changes at specific atoms. Herein, we report metal-specific studies using transient Ni L- and K-edge X-ray absorption spectroscopy of a prototypical Ni photocatalyst, (dtbbpy)Ni(o-tol)Cl (dtb = 4,4'-di-tert-butyl, bpy = bipyridine, o-tol = ortho-tolyl), in solution. We unambiguously confirm via direct experimental evidence that the long-lived (∼5 ns) excited state is a tetrahedral metal-centered triplet state. These results demonstrate the power of ultrafast X-ray spectroscopies to unambiguously elucidate the nature of excited states in important transition-metal-based photocatalytic systems.

In Solution Identification of the Lysine-Cysteine Redox Switch with a NOS Bridge in Transaldolase by Sulfur K-Edge X-ray Absorption Spectroscopy.

A novel covalent post-translational modification (lysine-NOS-cysteine) was discovered in proteins, initially in the enzyme transaldolase of Neisseria gonorrhoeae (NgTAL) [Nature 2021, 593, 460-464], acting as a redox switch. The identification of this novel linkage in solution was unprecedented until now. We present detection of the NOS redox switch in solution using sulfur K-edge X-ray absorption spectroscopy (XAS). The oxidized NgTAL spectrum shows a distinct shoulder on the low-energy side of the rising edge, corresponding to a dipole-allowed transition from the sulfur 1s core to the unoccupied σ* orbital of the S-O group in the NOS bridge. This feature is absent in the XAS spectrum of reduced NgTAL, where Lys-NOS-Cys is absent. Our experimental and calculated XAS data support the presence of a NOS bridge in solution, thus potentially facilitating future studies on enzyme activity regulation mediated by the NOS redox switches, drug discovery, biocatalytic applications, and protein design.

Structural and electronic transformations of GeSe2 glass under high pressures studied by X-ray absorption spectroscopy

Pressure-induced transformations in an archetypal chalcogenide glass (GeSe2) have been investigated up to 157 GPa by X-ray absorption spectroscopy (XAS) and molecular dynamics (MD) simulations. Ge and Se K-edge XAS data allowed simultaneous tracking of the correlated local structural and electronic changes at both Ge and Se sites. Thanks to the simultaneous analysis of extended X-ray absorption fine structure (EXAFS) signals of both edges, reliable quantitative information about the evolution of the first neighbor Ge-Se distribution could be obtained. It also allowed to account for contributions of the Ge-Ge and Se-Se bond distributions (chemical disorder). The low-density to high-density amorphous-amorphous transformation was found to occur within 10 to 30 GPa pressure range, but the conversion from tetrahedral to octahedral coordination of the Ge sites is completed above [Formula: see text] 80 GPa. No convincing evidence of another high-density amorphous state with coordination number larger than six was found within the investigated pressure range. The number of short Ge-Ge and Se-Se "wrong" bonds was found to increase upon pressurization. Experimental XAS results are confirmed by MD simulations, indicating the increase of chemical disorder under high pressure.

Fire simulation effects on the transformation of iron minerals in alpine soils

Heat-induced changes in topsoil iron (Fe) species triggered by the relatively low temperatures (Ts) produced by wildfires (200–300 °C) have not been fully elucidated. Changes in the chemistry of Fe minerals can produce cascading impacts on the environment, and the resulting aftermath may be exacerbated in erosion-prone alpine soils. The aim of this study was to determine - at environmentally realistic conditions - changes in the composition and crystallinity of Fe species, and the dispersible organic matter (OM) pool (evaluated by the pyrophosphate extraction), as a function of rising Ts, native Fe phases and OM in alpine soils. Multiple techniques were employed, including X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), magnetic measurements and Fe K-edge X-ray absorption spectroscopy (XAS). The results demonstrated the dominance of poorly crystalline Fe phases at 300 °C. At the same T, we observed the partial conversion of maghemite to hematite (supporting the involvement of oxidative processes) and, in the presence of high organic carbon (OC) contents, an enrichment in magnetic minerals (suggesting the onset of reducing conditions). The heat-induced modifications in Fe species and organic compounds did not promote the stabilization of the remaining OM, highlighting the weak nature of soil organo-mineral associations in an after-fire scenario. These phenomena can be further aggravated in case of the steep terrain that characterize alpine soils.

Tracking Coordination Environment and Reaction Intermediates in Homogeneous and Heterogeneous Epoxidation Catalysts via Ti L2,3-Edge Near-Edge X-ray Absorption Fine Structures.

Ti-based molecules and materials are ubiquitous and play a major role in both homogeneous and heterogeneous catalytic processes. Understanding the electronic structures of their active sites (oxidation state, local symmetry, and ligand environment) is key to developing molecular-level structure-property relationships. In that context, X-ray absorption spectroscopy (XAS) offers a unique combination of elemental selectivity and sensitivity to local symmetry. Commonly, for early transition metals such as Ti, K-edge XAS is applied for in situ characterization and subsequent structural analysis with high sensitivity toward tetrahedral species. Ti L2,3-edge spectroscopy is in principle complementary and offers specific opportunities to interrogate the electronic structure of five-and six-coordinated species. It is, however, much more rarely implemented because the use of soft X-rays implies ultrahigh vacuum conditions. Furthermore, the interpretation of the data can be challenging. Here, we show how Ti L2,3-edge spectroscopy can help to obtain unique information about both homogeneous and heterogeneous epoxidation catalysts and develop a molecular-level relationship between spectroscopic signatures and electronic structures. Toward this goal, we first establish a spectral library of molecular Ti reference compounds, comprising various coordination environments with mono- and dimeric Ti species having O, N, and Cl ligands. We next implemented a computational methodology based on multiplet ligand field theory and maximally localized Wannier orbitals benchmarked on our library to understand Ti L2,3-edge spectroscopic signatures. We finally used this approach to track and predict the spectra of catalytically relevant intermediates, focusing on Ti-based olefin epoxidation catalysts.

Site-specific electronic structure of covalently linked bimetallic dyads from nitrogen K-edge x-ray absorption spectroscopy.

A nitrogen K-edge x-ray absorption near-edge structure (XANES) survey is presented for tetrapyrido[3,2-a:2',3'-c:3″,2″-h:2‴,3‴-j]phenazine (tpphz)-bridged bimetallic assemblies that couple chromophore and catalyst transition metal complexes for light driven catalysis, as well as their individual molecular constituents. We demonstrate the high N site sensitivity of the N pre-edge XANES features, which are energetically well-separated for the phenazine bridge N atoms and for the individual metal-bound N atoms of the inner coordination sphere ligands. By comparison with the time-dependent density functional theory calculated spectra, we determine the origins of these distinguishable spectral features. We find that metal coordination generates large shifts toward higher energy for the metal-bound N atoms, with increasing shift for 3d < 4d < 5d metal bonding. This is attributed to increasing ligand-to-metal σ donation that increases the effective charge of the bound N atoms and stabilizes the N 1s core electrons. In contrast, the phenazine bridge N pre-edge peak is found at a lower energy due to stabilization of the low energy electron accepting orbital localized on the phenazine motif. While no sensitivity to ground state electronic coupling between the individual molecular subunits was observed, the spectra are sensitive to structural distortions of the tpphz bridge. These results demonstrate N K-edge XANES as a local probe of electronic structure in large bridging ligand motifs, able to distinctly investigate the ligand-centered orbitals involved in metal-to-ligand and ligand-to-ligand electron transfer following light absorption.

Enhanced Strontium Removal through Microbially Induced Carbonate Precipitation by Indigenous Ureolytic Bacteria.

Microbial ureolysis offers the potential to remove metals including Sr2+ as carbonate minerals via the generation of alkalinity coupled to NH4+ and HCO3- production. Here, we investigated the potential for bacteria, indigenous to sediments representative of the U.K. Sellafield nuclear site where 90Sr is present as a groundwater contaminant, to utilize urea in order to target Sr2+-associated (Ca)CO3 formation in sediment microcosm studies. Strontium removal was enhanced in most sediments in the presence of urea only, coinciding with a significant pH increase. Adding the biostimulation agents acetate/lactate, Fe(III), and yeast extract to further enhance microbial metabolism, including ureolysis, enhanced ureolysis and increased Sr and Ca removal. Environmental scanning electron microscopy analyses suggested that coprecipitation of Ca and Sr occurred, with evidence of Sr associated with calcium carbonate polymorphs. Sr K-edge X-ray absorption spectroscopy analysis was conducted on authentic Sellafield sediments stimulated with Fe(III) and quarry outcrop sediments amended with yeast extract. Spectra from the treated Sellafield and quarry sediments showed Sr2+ local coordination environments indicative of incorporation into calcite and vaterite crystal structures, respectively. 16S rRNA gene analysis identified ureolytic bacteria of the genus Sporosarcina in these incubations, suggesting they have a key role in enhancing strontium removal. The onset of ureolysis also appeared to enhance the microbial reduction of Fe(III), potentially via a tight coupling between Fe(III) and NH4+ as an electron donor for metal reduction. This suggests ureolysis may support the immobilization of 90Sr via coprecipitation with insoluble calcium carbonate and cofacilitate reductive precipitation of certain redox active radionuclides, e.g., uranium.

Structural and physical properties of Ni 1−x V x alloys around and away from quantum critical point

We investigate the room temperature structure (global and local), temperature dependent magnetic and transport behaviour of Ni 1−x V x ( 0⩽x⩽0.13 ) alloys. Our Energy Dispersive Analysis of x-rays results show that the prepared compositions are stoichiometric. With increase in V doping, the compounds exhibit a quantum phase transition around x c = 0.12, where the ferromagnetic phase is suppressed. Our results show that all the compounds stabilize in face centred cubic structure at RT and the lattice parameter shows unusual behaviour close to x c . The magnetic and heat capacity studies show signature of Griffiths phase on either side of x c . From 25 K to the lowest collected temperature, we observe a linear T dependence of resistivity at x = 0.1 and around x c , which is separated by a Fermi-liquid region around x = 0.106. This suggests that the origin of the transport behaviour is different around the quantum critical point and away from it. Our Ni K-edge x-ray Absorption Spectroscopy results show that there is a significant reduction in the first coordination number around Ni central atom on doping. Further, with doping, there is distortion in the first coordination shell around Ni. This suggests, with V doping, the local structure around Ni is different from the global structure as obtained from the x-ray Diffraction results. Interestingly, with doping, we observe a direct connection between the extent of distortion at RT and the magnetic disorder obtained at 2 K. We believe our results will motivate the scientific community to further study the interplay between the structural disorder and quantum fluctuations with temperature at the local level.

Coupled Experimental-Theoretical Characterization of a Carbon Electrode in Vanadium Redox Flow Batteries using X-ray Absorption Spectroscopy.

Vanadium redox flow batteries (VRFBs) have emerged as promising solutions for stationary grid energy storage due to their high efficiency, scalability, safety, near room-temperature operation conditions, and the ability to independently size power and energy capacities. The performance of VRFBs heavily relies on the redox couple reactions of V2+/V3+ and VO2+/VO2+ on carbon electrodes. Therefore, a thorough understanding of the surface functionality of carbon electrodes and their propensity for degradation during electrochemical cycles is crucial for designing VRFBs with extended lifespans. In this study, we present a coupled experimental-theoretical approach based on carbon K edge X-ray absorption spectroscopy (XAS) to characterize carbon electrodes prepared under different conditions and identify relevant functional groups that contribute to unique spectroscopic features. Atomic models were created to represent functional groups, such as hydroxyl, carboxyl, methyl, and aldehyde, bonded to carbon atoms in either sp2 or sp3 environments. The interactions between functionalized carbon and various solvated vanadium complexes were modeled using density functional theory. A library of carbon K-edge XAS spectra was generated for distinct carbon atoms in different functional groups, both before and after interacting with solvated vanadium complexes. We demonstrate how these simulated spectra can be used to deconvolve ex situ experimental spectra measured from carbon electrodes and to track changes in the electrode composition following immersion in different electrolytes or extended cycling within a functional VRFB. By doing so, we identify the active species present on the carbon electrodes, which play a crucial role in determining their electrochemical performance.

Spectroscopic Characterization of Mn1+ Low Oxidation State in Prussian Blue-Based Battery Anodes.

Stabilization of ions in exotic oxidation states is beneficial for the development of new materials for green energy technologies. Exotic Mn1+ was proposed to play a role in the function of sodium-based Prussian blue analogues (PBA) batteries, a highly sought-out technology for industrial energy storage. Here, we report the detailed electronic structure characterization of uncharged and charged sodium-based manganese hexacyanomanganate anodes via Mn K-edge X-ray absorption spectroscopy (XAS), Kβ nonresonant X-ray emission (XES), and resonant inelastic X-ray scattering (RIXS). The latter allowed us to obtain site-selective XANES information about two distinct Mn centers. The obtained spectroscopic data represent the first electronic structure characterization of low-spin Mn1+ using hard X-ray RIXS and XES and allowed us to confirm its role in anode reduction. Our experimental approach can be expanded to analysis of analogues with other 3d transition metals broadening the application of exotic ionic states in materials engineering.

Incorporation of iron(III) into nanoporous silica spheres

Iron(III) containing silica spheres with the average diameter of 800 nm were prepared by the hydrolysis and the condensation of tetraethoxysilane in the presence of hexadecyltrimethylammonium chloride and subsequent reaction with aqueous or ethanol solution of iron(III) nitrate. The iron(III)-containing silica spheres were calcined in air at 400 °C to obtain nanoporous silica spheres containing iron(III). The location and the states of the iron in the nanoporous silica spheres were examined using scanning electron microscopy, transmission electron microscopy, elemental mapping, diffuse reflectance ultraviolet-visible absorption as well as Fe K-edge X-ray absorption spectroscopy. Iron(III) was located at the surface of the spheres as octahedrally coordinated species when iron(III) was adsorbed from ethanol solution of iron(III) nitrate. When the incorporation of iron(III) was done from the aqueous solution of iron(III) nitrate, tetrahedrally coordinated iron(III) was dispersed homogeneously through the spherical silica particles. Both of the silica spheres were microporous with the large BET surface area (ca. 1000 m2/g). The iron(III) containing silica spheres absorbed UV and were inactive for the photocatalytic degradation of methylene blue.

Are 4f-Orbitals Engaged in Covalent Bonding Between Lanthanides and Triphenylphosphine Oxide? An Oxygen K-Edge X-ray Absorption Spectroscopy and Density Functional Theory Study.

The bonding covalency between trivalent lanthanides (Ln = La, Pr, Nd, Eu, Gd) and triphenylphosphine oxide (TPPO) is studied by X-ray absorption spectra (XAS) and density functional theory (DFT) calculations on the LnCl3(TPPO)3 complexes. The O, P, and Cl K-edge XAS for the single crystals of LnCl3(TPPO)3 were collected, and the spectra were interpreted based on DFT calculations. The O and P K-edge XAS spectra showed no significant change across the Ln series in the LnCl3(TPPO)3 complexes, unlike the Cl K-edge XAS spectra. The experimental O K-edge XAS spectra suggest no mixing between the Ln 4f- and the O 2p-orbitals in the LnCl3(TPPO)3 complexes. DFT calculations indicate that the amount of the O 2p character per Ln-O bond is less than 0.1% in the Ln 4f-based orbitals in all of the LnCl3(TPPO)3 complexes. The experimental spectra and theoretical calculations demonstrate that Ln 4f-orbitals are not engaged in the covalent bonding of lanthanides with TPPO, which contrasts the involvement of U 5f-orbitals in covalent bonding in the UO2Cl2(TPPO)2 complex. Results in this work reinforce our previous speculation that bonding covalency is potentially responsible for the extractability of monodentate organophosphorus ligands toward metal ions.

Structural Distortion in the Wadsley-Roth Niobium Molybdenum Oxide Phase Triggering Extraordinarily Stable Battery Performance.

Wadsley-Roth niobium oxide phases have attracted extensive research interest recently as promising battery anodes. We have synthesized the niobium-molybdenum oxide shear phase (Nb, Mo)13 O33 with superior electrochemical Li-ion storage performance, including an ultralong cycling lifespan of at least 15000 cycles. During electrochemical cycling, a reversible single-phase solid-solution reaction with lithiated intermediate solid solutions is demonstrated using in situ X-ray diffraction, with the valence and short-range structural changes of the electrode probed by in situ Nb and Mo K-edge X-ray absorption spectroscopy. This work reveals that the superior stability of niobium molybdenum oxides is underpinned by changes in octahedral distortion during electrochemical reactions, and we report an in-depth understanding of how this stabilizes the oxide structure during cycling with implications for future long-life battery material design.

X-ray absorption spectroscopic studies of Fe environments in borosilicate waste glasses synthesized under a variety of redox conditions

Fe K-edge X-ray absorption spectroscopy (XAS) was performed on two borosilicate waste glass series to determine Fe valence and coordination changes over a wide range of redox synthesis conditions. Data were also collected on eight Fe-silicate standards, including the rare phase, pellyite, that was used as a tetrahedral Fe2+O4 standard. X-ray absorption near-edge structure (XANES) linear combination fits of the Fe2+O4, Fe2+O5, and Fe3+O4 standards data to the glass spectra determined Fe2+/Fetotal ratios from 0.07 to 0.90 that are within 10 % of Mössbauer findings. As the glasses become reduced, XANES indicates Fe3+O4 tetrahedra are being replaced by Fe2+O4 tetrahedra, and possibly, Fe2+O5 sites, while extended X-ray absorption fine structure analyses show average Fe-O distances increase from 1.88 to 1.96 Å. The XANES-determined three Fe-site population distributions in the glasses are similar to findings reported in a recent molecular dynamics study of Fe redox effects in waste glass.

Impact of Local Structure in Supported CaO Catalysts for Soft-Oxidant-Assisted Methane Coupling Assessed through Ca K-Edge X-ray Absorption Spectroscopy.

Soft-oxidant-assisted methane coupling has emerged as a promising pathway to upgrade methane from natural gas sources to high-value commodity chemicals, such as ethylene, at selectivities higher than those associated with oxidative (O2) methane coupling (OCM). To date, few studies have reported investigations into the electronic structure and the microscopic physical structure of catalytic active sites present in the binary metal oxide catalyst systems that are known to be effective for this reaction. Correlating the catalyst activity to specific active site structures and electronic properties is an essential aspect of catalyst design. Here, we used X-ray absorption spectroscopy at the Ca K-edge to ascertain the most probable local environment of Ca in the ZnO-supported Ca oxide catalysts. These catalysts are shown here to be active for N2O-assisted methane coupling (N2O-OCM) and have previously been reported to be active for CO2-assisted methane coupling (CO2-OCM). X-ray absorption near edge structure features at multiple Ca loadings are interpreted through simulated spectra derived from ab initio full multiple scattering calculations. These simulations included consideration of CaO structures organized in multiple spatial arrangements-linear, planar, and cubic-with separate analyses of Ca atoms in the surfaces and bulk of the three-dimensional structures. The morphology of the oxide clusters was found to influence the various regions of the X-ray absorption spectrum differently. Experiment and theory show that for low-Ca-loading catalysts (≤1 mol %), which contain sites particularly active for methane coupling, Ca primarily exists in an oxidized state that is consistent with the coordination environment of Ca ions in one- and two-dimensional clusters. In addition to their unique nanoscale structures, the spectra also indicate that these clusters have varying degrees of undercoordinated surface Ca atoms that could further influence their catalytic activities. The local Ca structure was correlated to methane coupling activity from N2O-OCM and previously reported CO2-OCM reactor studies. This study provides a unique perspective on the relationship between the catalyst physical and electronic structure and active sites for soft-oxidant-assisted methane coupling, which can be used to inform future catalyst development.

Mechanism of poly(N-isopropylacrylamide) cononsolvency in aqueous methanol solutions explored via oxygen K-edge X-ray absorption spectroscopy.

The cononsolvency mechanism of poly(N-isopropylacrylamide) (PNIPAM), dissolving in pure methanol (MeOH) and water (H2O) but being insoluble in MeOH-H2O mixtures, was investigated by O K-edge X-ray absorption spectroscopy (XAS). The cononsolvency emerges from the aggregation of PNIPAM with MeOH clusters, leading to the collapse of the hydrophobic hydration of PNIPAM.

X-ray absorption and emission spectroscopy of N2S2 Cu(II)/(III) complexes.

This study investigates the influence of ligand charge on transition energies in a series of CuN2S2 complexes based on dithiocarbazate Schiff base ligands using Cu K-edge X-ray absorption spectroscopy (XAS) and Kβ valence-to-core (VtC) X-ray emission spectroscopy (XES). By comparing the formally Cu(II) complexes [CuII(HL1)] (HL12- = dimethyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and [CuII(HL2)] (HL22- = dibenzyl pentane-2,4-diylidenebis[carbonodithiohydrazonate]) and the formally Cu(III) complex [CuIII(L2)], distinct changes in transition energies are observed, primarily attributed to the metal oxidation state. Density functional theory (DFT) calculations demonstrate how an increased negative charge on the deprotonated L23- ligand stabilizes the Cu(III) center through enhanced charge donation, modulating the core transition energies. Overall, significant shifts to higher energies are noted upon metal oxidation, emphasizing the importance of scrutinizing ligand structure in XAS/VtC XES analysis. The data further support the redox-innocent role of the Schiff base ligands and underscore the criticality of ligand protonation levels in future spectroscopic studies, particularly for catalytic intermediates. The combined XAS-VtC XES methodology validates the Cu(III) oxidation state assignment while offering insights into ligand protonation effects on core-level spectroscopic transitions.

Quantitative in situ synchrotron X-ray analysis of the ALD/MLD growth of transition metal dichalcogenide TiS2 ultrathin films.

We present the results of a full quantitative analysis of X-ray absorption spectroscopy (XAS) performed in situ during the growth of ultrathin titanium disulfide (TiS2) films via an innovative two-step process, i.e. atomic layer deposition/molecular layer deposition (ALD/MLD) followed by annealing. This growth strategy aims at separating the growth process from the crystallization process by first creating an amorphous Ti-thiolate that is converted later to crystalline TiS2via thermal annealing. The simultaneous analysis of Ti and S K-edge XAS spectra, exploiting the insights from density functional theory calculations, allows us to shed light on the chemical and structural mechanisms underlying the main steps of growth. The nature of the bonding at the base of the interface creation with the SiO2 substrate is disclosed in this study. Evidence of a progressive incorporation of S in the amorphous Ti-thiolate is given. Finally, it is shown that the annealing step plays a critical role since the transformation of the Ti-thiolate into nanocrystalline TiS2 and the loss of S are simultaneously induced, validating the two-step synthesis approach, which entails distinct growth and crystallization steps. These observations contribute to a deeper understanding of the bonding mechanism at the interface and provide insights for future research in this field and the generation of ultra-thin layered materials.