Getting Ready for the Hydrogen Evolution Reaction: The Infrared Spectrum of Hydrated Aluminum Hydride–Hydroxide HAlOH+(H2O)n−1, n=9–14

Published on Angewandte Chemie (19 May 2021)


Author(s): Jakob Heller, Dr. Wai Kit Tang, Dr. Ethan M. Cunningham, Ephrem G. Demissie, Dr. Christian van der Linde, Wing Ka Lam, Dr. Milan Ončák, Dr. Chi-Kit Siu*, Prof. Dr. Martin K. Beyer*



Hydrated singly charged aluminum ions eliminate molecular hydrogen in a size regime from 11 to 24 water molecules. Here we probe the structure of HAlOH+(H2O)n−1, n=9–14, by infrared multiple photon spectroscopy in the region of 1400–2250 cm−1. Based on quantum chemical calculations, we assign the features at 1940 cm−1 and 1850 cm−1 to the Al−H stretch in five- and six-coordinate aluminum(III) complexes, respectively. Hydrogen bonding towards the hydride is observed, starting at n=12. The frequency of the Al−H stretch is very sensitive to the structure of the hydrogen bonding network, and the large number of isomers leads to significant broadening and red-shifting of the absorption of the hydrogen-bonded Al−H stretch. The hydride can even act as a double hydrogen bond acceptor, shifting the Al−H stretch to frequencies below those of the water bending mode. The onset of hydrogen bonding and disappearance of the free Al−H stretch coincides with the onset of hydrogen evolution.



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