Structural and spectroscopic characterisation of C4 oxygenates relevant to structure/activity relationships of the hydrogenation of α,β-unsaturated carbonyls

In the present work, we have investigated the conformational isomerism and calculated the vibrational spectra of the C4 oxygenates: 3-butyne-2-one, 3-butene-2-one, 2-butanone and 2-butanol using density functional theory. The calculations are validated by comparison to structural data where available and new, experimental inelastic neutron scattering and infrared spectra of the compounds. We find that for 3-butene-2-one and 2-butanol the spectra show clear evidence for the presence of conformational isomerism and this is supported by the calculations. Complete vibrational assignments for all four molecules are provided and this provides the essential information needed to generate structure/activity relationships for the sequential catalytic hydrogenation of 3-butyne-2-one to 2-butanol

Inelastic neutron scattering studies of methyl chloride synthesis over alumina

Not only is alumina the most widely used catalyst support material in the world, it is also an important catalyst in its own right. One major chemical process that uses alumina in this respect is the industrial production of methyl chloride. This is a large scale process (650 000 metric tons in 2010 in the United States), and a key feedstock in the production of silicones that are widely used as household sealants. In this Account, we show how, in partnership with conventional spectroscopic and reaction testing methods, inelastic neutron scattering (INS) spectroscopy can provide additional insight into the active sites present on the catalyst, as well as the intermediates present on the catalyst surface.<p></p> INS spectroscopy is a form of vibrational spectroscopy, where the spectral features are dominated by modes involving hydrogen. Because of this, most materials including alumina are largely transparent to neutrons. Advantageously, in this technique, the entire “mid-infrared”, 0–4000 cm<sup>–1</sup>, range is accessible; there is no cut-off at 1400 cm<sup>–1</sup> as in infrared spectroscopy. It is also straightforward to distinguish fundamental modes from overtones and combinations. <p></p> A key parameter in the catalyst’s activity is the surface acidity. In infrared spectroscopy of adsorbed pyridine, the shifts in the ring stretching modes are dependent on the strength of the acid site. However, there is a very limited spectral range available. We discuss how we can observe the low energy ring deformation modes of adsorbed pyridine by INS spectroscopy. These modes can undergo shifts that are as large as those seen with infrared inspectroscopy, potentially enabling finer discrimination between acid sites. <p></p> Surface hydroxyls play a key role in alumina catalysis, but in infrared spectroscopy, the presence of electrical anharmonicity complicates the interpretation of the O–H stretch region. In addition, the deformations lie below the infrared cut-off. Both of these limitations are irrelevant to INS spectroscopy, and all the modes are readily observable. When we add HCl to the catalyst surface, the acid causes changes in the spectra. We can then deduce both that the surface chlorination leads to enhanced Lewis acidity and that the hydroxyl group must be threefold coordinated. <p></p> When we react η-alumina with methanol, the catalyst forms a chemisorbed methoxy species. Infrared spectroscopy clearly shows its presence but also indicates the possible coexistence of a second species. Because of INS spectroscopy’s ability to discriminate between fundamental modes and combinations, we were able to unambiguously show that there is a single intermediate present on the surface of the active catalyst. This work represents a clear example where an understanding of the chemistry at the molecular level can help rationalize improvements in a large scale industrial process with both financial and environmental benefits. <p></p&gt

Structure/activity relationships applied to the hydrogenation of α,β-unsaturated carbonyls: The hydrogenation of 3-butyne-2-one over alumina-supported palladium catalysts

The gas phase hydrogenation of 3-butyne-2-one, an alkynic ketone, over two alumina-supported palladium catalysts is investigated using infrared spectroscopy in a batch reactor at 373 K. The mean particle size of the palladium crystallites of the two catalysts are comparable (2.4 ± 0.1 nm). One catalyst (Pd(NO3)2/Al2O3) is prepared from a palladium(II) nitrate precursor, whereas the other catalyst (PdCl2/Al2O3) is prepared using palladium(II) chloride as the Pd precursor compound. A three-stage sequential process is observed with the Pd(NO3)2/Al2O3 catalyst facilitating complete reduction all the way through to 2-butanol. However, hydrogenation stops at 2-butanone with the PdCl2/Al2O3 catalyst. The inability of the PdCl2/Al2O3 catalyst to reduce 2-butanone is attributed to the inaccessibility of edge sites on this catalyst, which are blocked by chlorine retention originating from the catalyst’s preparative process. The reaction profiles observed for the hydrogenation of this alkynic ketone are consistent with the site-selective chemistry recently reported for the hydrogenation of crotonaldehyde, an alkenic aldehyde, over the same two catalysts. Thus, it is suggested that a previously postulated structure/activity relationship may be generic for the hydrogenation of α,β-unsaturated carbonyl compounds over supported Pd catalysts

A new capacitive sensor for displacement measurement in a surface force apparatus

We present a new capacitive sensor for displacement measurement in a Surface Forces Apparatus (SFA) which allows dynamical measurements in the range of 0-100 Hz. This sensor measures the relative displacement between two macroscopic opaque surfaces over periods of time ranging from milliseconds to in principle an indefinite period, at a very low price and down to atomic resolution. It consists of a plane capacitor, a high frequency oscillator, and a high sensitivity frequency to voltage conversion. We use this sensor to study the nanorheological properties of dodecane confined between glass surfaces.Comment: 7 pages, 8 figure

Vibrational spectroscopy and DFT calculations of 1,​3-​dibromo-​2,​4,​6-​trimethylbenzene: Anharmonicity, coupling and methyl group tunneling

International audienceThe Raman, IR and INS spectra of 1,3-dibromo-2,4,6-trimethylbenzene (DBMH) were recorded in the 80-3200 cm-1 range. The molecular conformation and vibrational spectra of DBMH were computed at the MPW1PW91/LANL2DZ level. Except for the methyl 2 environment, the agreement between the DFT calculations and the neutron diffraction structure is almost perfect (deviations < 0.01 Å for bond lengths, < 0.2° for angles). The frequencies of the internal modes of vibration were calculated with the harmonic and anharmonic approximations; the later method yields results that are in remarkable agreement with the spectroscopic data, resulting in a confident assignment of the vibrational bands. Thus, no scaling is necessary. The coupling, in phase or anti-phase, of the motions of symmetrical C-Br and C-Me bonds is highlighted. Our DFT calculations suggest that the torsion of methyl groups 4 and 6 is hindered in deep wells, whereas methyl group 2 is a quasi-free rotor. The failure of the calculations to determine the frequencies of the methyl torsional modes is explained as follows: DFT does not consider the methyl spins and assumes localization of the protons, whereas the methyl groups must be treated as quantum rotors

The effect of cation substitution on the local coordination of protons in Ba2In1.85M0.15O6H2 (M = In, Ga, Sc and Y)

We report on an investigation of the local structure and vibrational dynamics in the brownmillerite-based proton conductors Ba2In1.85M0.15O6H2 with M = In, Ga, Sc and Y. The aim is to determine the effect of the cation (M) substitution on the local coordination environment of the protons. The techniques used are infrared spectroscopy and inelastic neutron scattering. The materials are characterized by two main types of proton sites, denoted as H (1) and H(2), which are featured by different local structures. We establish that the relative population of these two proton sites varies as a function of M. Specifically, it is found that, with respect to Ba2In2O6H2, the relative population of H(1) protons increases upon the substitution of In with any of the three different cations. The strongest effect is observed for M = Ga and Sc, whereas the effect observed for M = Y is minor. This new insight motivates efforts to unravel the mobility of the two types of protons, since then cation modification would offer a rational route for improving the proton conductivity of these types of materials

The reaction of formic acid with RaneyTM copper

The interaction of formic acid with RaneyTM Cu proves to be complex. Rather than the expected generation of a monolayer of bidentate formate, we find the formation of a Cu(II) compound. This process occurs by direct reaction of copper and formic acid; in contrast, previous methods are by solution reaction. This is a rare example of formic acid acting as an oxidant rather than, as more commonly found, a reductant. The combination of diffraction, spectroscopic and computational methods has allowed this unexpected process to be characterized

The use of direct geometry spectrometers in molecular spectroscopy

The advantages and disadvantages of the use of direct geometry spectrometers for molecular spectroscopy and catalysis studies are described. We show that both direct and indirect geometry INS spectrometers are important tools for the study of industrially relevant areas such as catalysis, proton conductors and gas separation. We propose a novel hybrid instrument, Cerberus, that would offer high sensitivity and high-to-reasonable resolution across the entire 'mid-infrared' spectral range that would effectively advance research in these areas

Inelastic neutron scattering spectroscopy of amino acids

A combination of infrared, Raman and inelastic neutron scattering (INS) spectroscopies are used to provide complete vibrational spectra of several amino acids and dipeptides. The amino acids studied were glycine, alanine, glutamine, cysteine, methionine and phenylalanine and the dipeptides studied were Gly–Gln and Gly–Ala. The findings of this study have shown how the complementarity of infrared, Raman and INS spectroscopies can be exploited to provide complete vibrational spectra of amino acids and peptides. In particular, the strengths of INS spectroscopy are highlighted: the absence of selection rules, that hydrogenic motions are emphasised, the ready access to the low energy regime (&lt;400 cm−1) and the straightforward calculation of intensities. In the future, it should be possible to apply this approach to the study of larger peptides as well as proteins.</jats:p