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1. Simultaneous tracking of ultrafast surface and gas-phase dynamics in solid–gas interfacial reactions

   https://doi.org/10.1063/5.0217441  

   Blackman, Keith; Segrest, Eric; Turner, George; Machamer, Kai; Gupta, Aakash; Khan_Pathan, Md Afjal; Berriel, S Novia; Banerjee, Parag; Vaida, Mihai E (August 2024, Review of Scientific Instruments)

   Real-time detection of intermediate species and final products at the surface and near-surface in interfacial solid–gas reactions is critical for an accurate understanding of heterogeneous reaction mechanisms. In this article, an experimental method that can simultaneously monitor the ultrafast dynamics at the surface and above the surface in photoinduced heterogeneous reactions is presented. This method relies on a combination of mass spectrometry and femtosecond pump–probe spectroscopy. As a model system, the photoinduced reaction of methyl iodide on and above a cerium oxide surface is investigated. The species that are simultaneously detected from the surface and gas-phase present distinct features in the mass spectra, such as a sharp peak followed by an adjacent broad shoulder. The sharp peak is attributed to the species detected from the surface, while the broad shoulder is due to the detection of gas-phase species above the surface, as confirmed by multiple experiments. By monitoring the evolution of the sharp peak and broad shoulder as a function of the pump–probe time delay, transient signals are obtained that describe the ultrafast photoinduced reaction dynamics of methyl iodide on the surface and in the gas-phase. Finally, SimION simulations are performed to confirm the origin of the ions produced on the surface and in the gas-phase. 

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2. Flow Electrolyzer Mass Spectrometry with a Gas‐Diffusion Electrode Design

   https://doi.org/10.1002/anie.202013713  

   Hasa, Bjorn; Jouny, Matthew; Ko, Byung Hee; Xu, Bingjun; Jiao, Feng (December 2020, Angewandte Chemie International Edition)

   Abstract Operando mass spectrometry is a powerful technique to probe reaction intermediates near the surface of catalyst in electrochemical systems. For electrochemical reactions involving gas reactants, conventional operando mass spectrometry struggles in detecting reaction intermediates because the batch‐type electrochemical reactor can only handle a very limited current density due to the low solubility of gas reactant(s). Herein, we developed a new technique, namely flow electrolyzer mass spectrometry (FEMS), by incorporating a gas‐diffusion electrode design, which enables the detection of reactive volatile or gaseous species at high operating current densities (>100 mA cm⁻²). We investigated the electrochemical carbon monoxide reduction reaction (eCORR) on polycrystalline copper and elucidated the oxygen incorporation mechanism in the acetaldehyde formation. Combining FEMS and isotopic labelling, we showed that the oxygen in the as‐formed acetaldehyde intermediate originates from the reactant CO, while ethanol and n‐propanol contained mainly solvent oxygen. The observation provides direct experimental evidence of an isotopic scrambling mechanism. 

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3. Transient Absorption Microscopy Using Widefield Lock-in Camera Imaging

   https://doi.org/10.1021/acs.jpcc.4c02984  

   Wilson, Kelly S; Volek, Tanner S; Gross, Niklas; Link, Stephan; Baiz, Carlos R; Roberts, Sean T (July 2024, The Journal of Physical Chemistry C)

   Over the past decade, the proliferation of pulsed laser sources with high repetition rates has facilitated a merger of ultrafast time-resolved spectroscopy with imaging microscopy. In transient absorption microscopy (TAM), the excited-state dynamics of a system are tracked by measuring changes in the transmission of a focused probe pulse following photoexcitation of a sample. Typically, these experiments are done using a photodiode detector and lock-in amplifier synchronized with the laser and images highlighting spatial heterogeneity in the TAM signal are constructed by scanning the probe across a sample. Performing TAM by instead imaging a spatially defocused widefield probe with a multipixel camera could dramatically accelerate the acquisition of spatially resolved dynamics, yet approaches for such widefield imaging generally suffer from reduced signal-to-noise due to an incompatibility of multipixel cameras with high-frequency lock-in detection. Herein, we describe implementation of a camera capable of high-frequency lock-in detection, thereby enabling widefield TAM imaging at rates matching those of high repetition rate lasers. Transient images using a widefield probe and two separate pump pulse configurations are highlighted. In the first, a widefield probe was used to image changes in the spatial distribution of photoexcited molecules prepared by a tightly focused pump pulse, while in the second, a widefield probe detected spatial variations in photoexcited dynamics within a heterogeneous organic crystal excited by a defocused pump pulse. These results highlight the ability of high-sensitivity lock-in detection to enable widefield TAM imaging, which can be leveraged to further our understanding of excited-state dynamics and excitation transport within spatially heterogeneous systems. 

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4. Formation of sodium-bearing species in the interstellar medium

   https://doi.org/10.1093/mnras/stad3262  

   Acharyya, Kinsuk; Woon, David E.; Herbst, Eric (October 2023, Monthly Notices of the Royal Astronomical Society)

   ABSTRACT Sodium-bearing species such as NaCl in the gas phase have been observed in an assortment of carbon-rich and oxygen-rich stellar atmospheres and interstellar environments such as the high-mass protostellar disc surrounding Orion Src1 and the proto-binary system, IRAS 16547−4247. Their detection in relatively low-temperature regions is yet to be made. In this paper, we consider the synthesis of sodium-bearing species with an emphasis on NaCl, via both gas-phase and grain-surface chemistry under assorted interstellar conditions. We also consider the chemistry leading to the gas-phase species NaH and NaOH. Two classes of numerical simulations were run: models under isothermal conditions at temperatures from 10 to 800 K with varied intervals, and three-phase warm-up models that consist of an initial isothermal collapse at 10 K, followed by a warm-up phase in which temperature rises linearly to 200 K, and finally a hot core phase. We have included reactive desorption for both models to produce gaseous NaCl, NaH, and NaOH. We found that for isothermal models over a broad parameter space, the fractional abundances of gaseous NaCl and NaOH can reach above 2 × 10−10 and approx. 1 × 10−10, respectively, are in the detection range of observational facilities such as Atacama Large Millimeter/Submillimeter Array and JWST. For warm-up models, we found that if we consider molecules to be co-desorbed with water, gaseous NaCl can have a sufficiently large abundance for detection. We then conclude that both gaseous NaCl and NaOH can be detected; however, more experiments and quantum mechanical calculations are needed to constrain the relevant reaction rates better. 

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5. Heterogeneous chemistry of methyl ethyl ketone on mineral oxide surfaces: impacts of relative humidity and nitrogen dioxide on product formation

   https://doi.org/10.1039/D3EA00023K  

   Hettiarachchi, Eshani; Grassian, Vicki H. (May 2023, Environmental Science: Atmospheres)

   Despite their atmospheric abundance, heterogeneous and multiphase reactions of carbonyl compounds are poorly understood. In this study, we investigate the surface adsorption and surface chemistry of methyl ethyl ketone (MEK), the second most abundant ketone in the atmosphere, with several mineral oxide surfaces including SiO 2 , α-Fe 2 O 3 and TiO 2 . In particular, the chemistry of MEK with these common components of mineral dust, under both dry and high relative humidity (RH%) conditions, has been investigated. Furthermore, reactions of adsorbed MEK with gas-phase NO 2 were also examined. We show that MEK molecularly and reversibly adsorbs on SiO 2 whereas irreversible adsorption occurs on both α-Fe 2 O 3 and TiO 2 surfaces, followed by the formation of higher molar mass species resulting from dimerization and oligomerization reactions. Isotope labeling experiments confirmed the incorporation of H atoms from surface hydroxyl groups and strongly adsorbed water into these oligomer products. Most interesting is that at 80% RH, oligomer formation on α-Fe 2 O 3 shifts toward a higher relative abundance of MEK tetramer relative to the dimer while on TiO 2 there was no change in product distribution. In the presence of gas-phase NO 2 , MEK undergoes degradation to formaldehyde and acetaldehyde, followed by the formation of aldol condensation products of these aldehydes on the α-Fe 2 O 3 surface. Overall, this study provides mechanistic insights on mineralogy-specific heterogeneous chemistry of a prevalent and atmospherically abundant ketone. 

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