In operando observation of reaction intermediates is crucial for unraveling reaction mechanisms. To address the sensitivity limitations of commercial ReactIR, a flow cell was integrated with a Fourier transform infrared (FTIR) spectrometer yielding a "flow FTIR" device coupled with an NMR spectrometer for the elucidation of reaction mechanisms. The former device detects the low-intensity IR peaks of reaction intermediates by adjusting the path length of the FTIR sample cell, whereas the flow NMR allows the quantitative analysis of reaction species, thus offsetting the limitations of IR spectroscopy resulting from different absorption coefficients of the normal modes. Using the flow NMR and FTIR device, the controversial mechanism of benzoxazole synthesis was conclusively determined by spectroscopic evaluation of the reaction intermediates. This system enabled the accurate acquisition of previously elusive kinetic data, such as the reaction time and rate-determining step. The implementation of reaction flow cells into NMR and FTIR systems could be widely applied to study various reaction mechanisms, including dangerous and harsh reactions, thus avoiding contact with potentially harmful reaction intermediates.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.analchem.0c03852 | DOI Listing |
J Am Chem Soc
January 2025
Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Hydrogen spillover is an important process in catalytic hydrogenation reactions, facilitating H activation and modulating surface chemistry of reducible oxide catalysts. This study focuses on the unveiling of platinum-induced hydrogen spillover on monoclinic tungsten trioxide (γ-WO), employing ambient pressure X-ray photoelectron spectroscopy, density functional theory calculations and microkinetic modeling to investigate the dynamic evolution of surface states at varied temperatures. At room temperature, hydrogen spillover results in the formation of W and hydrogen intermediates (hydroxyl species and adsorbed water), facilitated by Pt metal clusters.
View Article and Find Full Text PDFJ Comp Neurol
January 2025
Institute of Neurobiology, University of Puerto Rico, Medical Sciences Campus, San Juan, Puerto Rico.
Snails belonging to the genus Biomphalaria serve as obligatory intermediate hosts for the trematode Schistosoma mansoni, the causative agent for the most widespread form of schistosomiasis. The simpler nervous systems of gastropod molluscs, such as Biomphalaria, provide advantageous models for investigating neural responses to infection at the cellular and network levels. The present study examined neuropeptides related to cholecystokinin (CCK), a major multifunctional regulator of central nervous system (CNS) function in mammals.
View Article and Find Full Text PDFNat Commun
January 2025
Wuhan National Laboratory for Optoelectronics, School of Optoelectronic Science and Engineering, Huazhong University of Science and Technology, Wuhan, PR China.
Active and stable electrocatalysts are essential for hydrogen production from alkaline water electrolysis. However, precisely controlling the interaction between electrocatalysts and reaction intermediates (HO*, H*, and *OH) remains challenging. Here, we demonstrate an yttrium-doped NiMo-MoO heterogenous electrocatalyst that efficiently promotes water dissociation and accelerates the intermediate adsorption/desorption dynamics in alkaline electrolytes.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Anhui Normal University, School of Chemistry and Materials Science, CHINA.
The space charge effect induced by high-quality heterojunctions is essential for efficient electrocatalytic processes. Herein, we delicately manipulate intermolecular charge transfer by modifying substituents (-g = -CH3, -H, -NO2) with various electron donating/withdrawing capabilities in CoPc-g/CoS organic-inorganic heterostructures. CoPc-CH3, as a typical electron donor, transfers more electrons to CoS due to the presence of -CH3, forming the strongest space electric field and thus regulating the dual active sites at the interface.
View Article and Find Full Text PDFACS Nano
January 2025
Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials, Ministry of Education, School of Materials Science and Engineering, Shandong University, Jinan 250061, P. R. China.
To achieve a long cycle life and high-capacity performance for Li-O batteries, it is critical to rationally modulate the formation and decomposition pathway of the discharge product LiO. Herein, we designed a highly efficient catalyst containing dual catalytic active sites of Pt single atoms (Pt) paired with high-entropy alloy (HEA) nanoparticles for oxygen reduction reaction (ORR) in Li-O batteries. HEA is designed with a moderate d-band center to enhance the surface adsorbed LiO intermediate (LiO(ads)), while Pt active sites exhibit weak adsorption energy and promote the soluble LiO pathway (LiO(sol)).
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!