The local structure of water on chemically and structurally different surfaces is a subject of ongoing research. In particular, confined spaces as found in mesoporous silica have a pronounced effect on the interplay between the adsorbate–adsorbate and adsorbate–surface interactions. Mid-infrared spectroscopy is ideally suited to quantitatively and qualitatively study such systems as the probed molecular vibrations are highly sensitive to intermolecular interactions. Here, the quantity and structure of water adsorbed from the gas phase into silica mesopores at different water vapor pressures was monitored using mid-infrared attenuated total reflection (ATR) spectroscopy. Germanium ATR crystals were coated with different mesoporous silica films prepared by evaporation-induced self-assembly. Quantitative analysis of the water bending vibration at 1640 cm^–1 at varying vapor pressure allows for retrieving porosity and pore size distribution of the mesoporous films. The results were in excellent agreement with those obtained from ellipsometric porosimetry. In addition, different degrees of hydrogen bonding of water as reflected in the band position and shape of the stretching vibrations (3000–3800 cm^–1) were analyzed and attributed to high-density, unordered bulk, low-density, and surface-induced ordered water. Thereby, the progression of surface-induced ordered water and bulk water as a function of water vapor pressure was studied for different pore sizes. Small pores of 5 nm diameter showed a number of two-ordered monolayers, whereas for pores >12 nm diameter, the number of ordered monolayers is significantly larger and agrees with the number observed on planar SiO₂ surfaces.

Adsorption of molecules on high-surface-area materials is a fundamental process critical to many fields of basic and applied chemical research; for instance, it is among the simplest and most efficient principles for separating and remediating polluted water. However, established experimental approaches for investigating this fundamental process preclude in situ monitoring and thus obtaining real-time information about the ongoing processes. In this work, mid-infrared attenuated total reflection (ATR) spectroscopy is introduced as a powerful technique for quantitative in situ monitoring of adsorption processes and thus enrichment of traces of organic pollutants from aqueous solution in ordered mesoporous silica films. The synthesis, functionalization, and characterization of two silica films with 3D hexagonal and cubic pore structure on silicon ATR crystals are presented. Benzonitrile and valeronitrile as model compounds for aromatic and aliphatic water pollutants are enriched in hydrophobic films, while the matrix, water, is excluded from the volume probed by the evanescent field. Enrichment times of 200 and >100, respectively, yielding detection limits in the low ppm range. Furthermore, fast and complete desorption of the analyte, ensuring reliable regeneration of the sensor, was verified. Lastly, we derive and experimentally validate equations for ATR spectroscopy with thin film adsorption layers to quantify the absolute mass of adsorbed pollutant in the film. The excellent agreement between recorded absorptions at target wavenumbers of the target analytes and corresponding simulations corroborates the validity of the chosen approach.

We employ a novel spectroscopic setup based on an external cavity quantum cascade laser and a Mach–Zehnder interferometer to simultaneously record spectra of absorption and dispersion of liquid samples in the mid-infrared. We describe the theory underlying the interferometric measurement and discuss its implications for the experiment. The capability of simultaneously recording a refractive index and absorption spectrum is demonstrated for a sample of acetone in cyclohexane. The recording of absorption spectra is experimentally investigated in more detail to illustrate the method’s capabilities as compared to direct absorption spectroscopy. We find that absorption signals are recorded with strongly suppressed background, but with smaller absolute sensitivity. A possibility of optimizing the setup’s performance by unbalancing the interferometer is presented.

Water affects the amplitude of photoacoustic signals from many gas phase molecules. In quartz-enhanced photoacoustic (QEPAS) measurements of CO excited at the fundamental vibrational resonance of CO, the photoacoustic signal decreases with increasing humidity, reaches a pronounced minimum at ~0.19%_V, and increases with humidity for higher water contents. This peculiar trend is explained by competing endothermal and exothermal pathways of the vibrational relaxation of CO in N₂ and H₂O. Near-resonant vibrational–vibrational transfer from CO to N₂, whose vibrational frequency is 188 cm⁻¹ higher than in CO, consumes thermal energy, yielding a kinetic cooling effect. In contrast, vibrational relaxation via H₂O is fast and exothermal, and hence counteracts kinetic cooling, explaining the observed trend. A detailed kinetic model for collisional relaxation of CO in N₂ and H₂O is presented. Simulations using rate constants obtained from literature were performed and compared to humidity dependent QEPAS experiments at varying pressure. Agreement between the experiments and simulations confirmed the validity of the model. The kinetic model can be used to identify optimized experimental conditions for sensing CO and can be readily adapted to include further collision partners.

The sensitivity of quartz-enhanced photoacoustic spectroscopy (QEPAS) can be drastically increased using the power enhancement in high-finesse cavities. Here, low noise resonant power enhancement to 6.3 W was achieved in a linear Brewster window cavity by exploiting optical feedback locking of a quantum cascade laser. The high intracavity intensity of up to 73 W mm⁻² in between the prongs of a custom tuning fork resulted in strong optical saturation of CO at 4.59 µm. Saturated absorption is discussed theoretically and experimentally for photoacoustic measurements in general and intracavity QEPAS (I-QEPAS) in particular. The saturation intensity of CO’s R9 transition was retrieved from power-dependent I-QEPAS signals. This allowed for sensing CO independently from varying degrees of saturation caused by absorption induced changes of intracavity power. Figures of merit of the I-QEPAS setup for sensing of CO and H₂O are compared to standard wavelength modulation QEPAS without cavity enhancement. For H₂O, the sensitivity was increased by a factor of 230, practically identical to the power enhancement, while the sensitivity gain for CO detection was limited to 57 by optical saturation.