George Tsilomelekis

Molecular structure, morphology and growth mechanisms and rates of 5-hydroxymethyl furfural (HMF) derived humins

We apply ATR-FTIR spectroscopy, Scanning Electron Microscopy (SEM) and Dynamic Light Scattering (DLS) experiments to investigate the molecular structure, morphology and growth mechanism of 5-hydroxymethyl furfural (HMF) derived humins as a function of HMF conversion. Our FTIR data support a reaction pathway in which humins form either through a ring opening mechanism and/or through substitution at the α or β position via nucleophilic attack. The addition of DMSO as a co-solvent leads to significant changes in the FTIR spectra of humins. We find that the nucleophilic attack pathway is suppressed in the presence of DMSO co-solvent and rationalizes the very small humin particles (∼100 nm) observed in SEM images contrary to the large particles (with multimodal size distribution and largest particles of up to 3–4 μm) observed in neat water. DLS experiments under several reaction conditions further confirm the particle size distribution observed via SEM. A plausible reaction network for humin formation, which rationalizes qualitatively our experimental results as well as those reported in the literature, is also postulated.

Origin of 5‐Hydroxymethylfurfural Stability in Water/Dimethyl Sulfoxide Mixtures

In the present work, we combined vibrational spectroscopy with electronic structure calculations to understand the solvation of HMF in DMSO, water, and DMSO/water mixtures and to provide insights into the observed hindrance of HMF rehydration and aldol condensation reactions if it is dissolved in DMSO/water mixtures. To achieve this goal, the attenuated total reflection FTIR spectra of a wide composition range of binary and ternary mixtures were measured, analyzed, and compared to the findings of ab initio DFT calculations. The effect of solvent on the HMF C-O and O-H vibrational modes reveals significant differences that are ascribed to different intermolecular interactions between HMF and DMSO or water. We also found that DMSO binds to HMF more strongly than water, and interactions with the HMF hydroxyl group are stronger than those with the HMF carbonyl group. We also showed the preferential solvation of HMF C-O groups by DMSO if HMF is dissolved in DMSO/water mixed solvent. Frontier molecular orbital theory was used to examine the influence of the solvent on side reactions. The results show that HMF solvation by DMSO increases its LUMO energy, which reduces its susceptibility to nucleophilic attack and minimizes undesirable hydration and humin-formation reactions. This result, together with the preferential solvation of HMF by DMSO, provide an explanation for the enhanced HMF stability in DMSO/water mixtures observed experimentally.

Mechanism of Brønsted Acid‐Catalyzed Glucose Dehydration

We present the first DFT-based microkinetic model for the Brønsted acid-catalyzed conversion of glucose to 5-hydroxylmethylfurfural (HMF), levulinic acid (LA), and formic acid (FA) and perform kinetic and isotopic tracing NMR spectroscopy mainly at low conversions. We reveal that glucose dehydrates through a cyclic path. Our modeling results are in excellent agreement with kinetic data and indicate that the rate-limiting step is the first dehydration of protonated glucose and that the majority of glucose is consumed through the HMF intermediate. We introduce a combination of 1) automatic mechanism generation with isotopic tracing experiments and 2) elementary reaction flux analysis of important paths with NMR spectroscopy and kinetic experiments to assess mechanisms. We find that the excess formic acid, which appears at high temperatures and glucose conversions, originates from retro-aldol chemistry that involves the C6 carbon atom of glucose.

On the configuration, molecular structure and vibrational properties of MoOx sites on alumina, zirconia, titania and silica

The article addresses the critical molecular structural issue of differentiating between the mono-oxo (MoO) and di-oxo [Mo(O)2] configurations as well as the most plausible structures for the oxo-molybdenum [(MoOx)n] sites (including aspects related to coordination number of Mo and extent of association/polymerization) deposited on typical catalyst supports such as γ-Al2O3, monoclinic ZrO2, TiO2-anatase and SiO2. The issue is of topical character and has been the subject of persistent post-2005 research endeavors comprising both theoretical (mainly DFT) work as well as careful experimental/spectroscopic studies (Raman, IR, DR-UV/Vis) that in some cases have also been combined with isotopic labeling experiments. The pertinent vibrational properties are discussed in relation to site configuration (mono-oxo vs. di-oxo), structure and extent of association/polymerization of dispersed oxomolybdates. Vibrational isotope effects and mechanisms for 18O/16O exchange at the molecular level are given special attention.

Structural analysis of humins formed in the Brønsted acid catalyzed dehydration of fructose

We use infrared (IR) spectroscopy, gel permeation chromatography (GPC), and liquid chromatography-mass spectrometry (LC-MS) in multistage dissolution experiments in various solvents to investigate the solubility and molecular structure of humins formed during fructose dehydration. We demonstrate that the soluble fraction of humins correlates positively with the donor number of solvents resulting in significant dissolution at room temperature in solvents with high donor number. Most of the solubilized humins fragments have relatively low molecular weight (Mw), and the same species are present in different quantities as the residual solid is repeatedly dissolved in the same solvent. In contrast to the common belief of humins consisting of polymers of large Mw, we postulate for the first time that they are spatially and chemically heterogeneous and consist of insoluble macromolecules and small soluble species that are weakly associated within the structure. The solubility profiles of dissolved species in acetonitrile and methanol are different in terms of Mw but possess similar IR spectra, indicative of similar functional groups in dissolved species. Furthermore, we hypothesize that the identified humins fragments form through aldol condensation between 5-hydroxymethylfurfural and its hydrated products and through condensation of furanic species.

Short-time microscopic dynamics of aqueous methanol solutions

In this paper we present the picosecond vibrational dynamics of a series of methanol aqueous solutions over a wide concentration range from dense to dilute solutions. We studied the vibrational dephasing and vibrational frequency modulation by calculating the time correlation functions of vibrational relaxation by fits in the frequency domain. This method is applied to aqueous methanol solutions xMeOH–(1 − x)H2O, where x = 0, 0.2, 0.4, 0.6, 0.8 and 1. The important finding is that the vibrational dynamics of the system become slower with increasing methanol concentration. The removal of many-body effects by having the molecules in less-crowded environments seems to be the key factor. The interpretation of the vibrational correlation function in the context of Kubo theory, which is based on the assumption that the environmental modulation arises from a single relaxation process and applied to simple liquids, is inadequate for all solutions studied. We found that the vibrational correlation functions of the solutions over the whole concentration range comply with the Rothschild approach, assuming that the environmental modulation is described by a stretched exponential decay. The evolution of the dispersion parameter α with dilution indicates the deviation of the solutions from the model simple liquid and the results are discussed in the framework of the current phenomenological status of the field.

Molybdenum(VI) Oxosulfato Complexes in MoO3-K2S2O7-K2SO4 Molten Mixtures: Stoichiometry, Vibrational Properties, and Molecular Structures

The structural and vibrational properties of molybdenum(VI) oxosulfato complexes formed in MoO(3)–K(2)S(2)O(7) and MoO(3)–K(2)S(2)O(7)–K(2)SO(4) molten mixtures under an O(2) atmosphere and static equilibrium conditions were studied by Raman spectroscopy at temperatures of 400–640 °C. The corresponding composition effects were explored in the X(MoO)(3)(0) = 0–0.5 range. MoO(3) undergoes a dissolution reaction in molten K(2)S(2)O(7), and the Raman spectra point to the formation of molybdenum(VI) oxosulfato complexes. The Mo═O stretching region of the Raman spectrum provides sound evidence for the occurrence of a dioxo Mo(═O)(2) configuration as a core. The stoichiometry of the dissolution reaction MoO(3) + nS(2)O(7)(2–) → C(2n–) was inferred by exploiting the Raman band intensities, and it was found that n = 1. Therefore, depending on the MoO(3 content, monomeric MoO(2)(SO(4))(2)(2–) and/or associated [MoO(2)(SO(4))(2)](m)(2m–) complexes are formed in the binary MoO(3)–K(2)S(2)O(7) molten system, and pertinent structural models are proposed in full consistency with the Raman data. A 6-fold coordination around Mo is inferred. Adjacent MoO(2)(2+) cores are linked by bidentate bridging sulfates. With increasing temperature at concentrated melts (i.e., high X(MoO)(3)(0)), the observed spectral changes can be explained by partial dissociation of [MoO(2)(SO(4))(2)](m)(2m–) by detachment of S(2)O(7)(2–) and formation of a Mo—O—Mo bridge. Addition of K(2)SO(4) in MoO(3)–K(2)S(2)O(7) results in a “follow-up” reaction and formation of MoO(2)(SO(4))(3)(4–) and/or associated [MoO(2)(SO(4))(3)](m)(4m–) complexes in the ternary MoO(3)–K(2)S(2)O(7)–K(2)SO(4) molten system. The 6-fold Mo coordination comprises two oxide ligands and four O atoms linking to coordinated sulfate groups in various environments of reduced symmetry. The most characteristic Raman bands for the molybdenum(VI) oxosulfato complexes pertain to the Mo(═O)(2) stretching modes: (1) at 957 (polarized) and 918 (depolarized) cm(–1) for the ν(s) and ν(as) Mo(═O)(2) modes of MoO(2)(SO(4))(2)(2–) and [MoO(2)(SO(4))(2)](m)(2m–) and (2) at 935 (polarized) and 895 (depolarized) cm(–1) for the respective modes of MoO(2)(SO(4))(3)(4–) and [MoO(2)(SO(4))(3)](m)(4m–). The results were tested and found to be in accordance with ab initio quantum chemical calculations carried out on [MoO(2)(SO(4))(3)](4–) and [{MoO(2)}(2)(SO(4))(4)(μ-SO(4))(2)](8–) ions, in assumed isolated gaseous free states, at the DFT/B3LYP (HF) level and with the 3-21G basis set. The calculations included determination of vibrational infrared and Raman spectra, by use of force constants in the Gaussian 03W program.

Glass-forming ability of TeO2 and temperature induced changes on the structure of the glassy, supercooled, and molten states

Polarized (VV) and depolarized (VH) Raman spectra are obtained for glassy, supercooled, and molten TeO2 at temperatures up to 1000 K in order to elucidate the temperature evolution of the pertinent structural and vibrational properties. The intrinsic tendency of the system for crystallization is avoided by means of a newly applied protocol, thereby enabling the recording of Raman spectra of pure TeO2 on going from the molten to the supercooled liquid and to the room temperature glass states. Following an appropriate fitting procedure, the revealed bands are assigned to specific modes of structural polymorphs. A weak polarised band at ∼880 cm(-1) is assigned to Te=O terminal stretching in agreement with the literature ab initio molecular orbital calculations. Subtle changes to the relative band intensities within the 550-900 cm(-1) stretching region are caused by temperature increase. The network-like structure of the glass/melt is composed by TeO4 trigonal bipyramid and TeO3 trigonal pyramid units. With increasing temperature, TeO4 units convert to TeO3 units with a concurrent increase in the number of Te=O sites resulting from cleavages within the network structure. The fraction of such terminal oxygen atoms has been directly estimated from the spectroscopic data. The relative populations of the basic building blocks and the average number of O atoms around Te have been estimated for a wide temperature range directly from the Raman spectra, implying a gradual transformation of TeO(4/2) to TeO(2/2)(= O) trigonal pyramid units. The results are discussed in the context of the current phenomenological and theoretical status of the field.

Solvent-Induced Frequency Shifts of 5-Hydroxymethylfurfural Deduced via Infrared Spectroscopy and ab Initio Calculations

Solvent-induced frequency shifts (SIFS) of the carbonyl stretching vibration ν(C═O) of 5-hydroxymethylfurfural were measured in protic, polar aprotic, and nonpolar solvents. The Gutmann acceptor number (AN) was found to correlate with the measured frequency shifts. The SIFS in six solvents were investigated using ab initio electronic structure calculations, treating the solvent implicitly and with an explicit solvent ligand interacting with the carbonyl. The conductor-polarizable continuum model (CPCM) of solvation predicted that ν(C═O) shifted according with the dielectric constant as (ε - 1)/(2ε + 1), in agreement with the analytical predictions of the Kirkwood-Bauer-Magat (KBM) theory for a dipole in a dielectric continuum, but in disagreement with the experimental trend. The experimental SIFS were best predicted using gas-phase complexes of HMF and explicit solvent-ligand. Natural bond orbital (NBO) analysis and Baders atoms in molecules theory were used to investigate the electronic structure of these complexes. Strong SIFS were found to arise from stronger H-bonding interactions, as observed in delocalization of carbonyl lone-pair electrons by H-bonding solvent σ*(X-H) orbitals, and an increase in charge density and a decrease in local potential energy at the H-bond (3, -1) critical point. Consequently, by predicting the experimental SIFS and examining the electronic structure, we find the first theoretical evidence for treating Gutmanns solvent AN as a measure of solvent Lewis acidity.