NiAu Single Atom Alloys for the Non-oxidative Dehydrogenation of Ethanol to Acetaldehyde and Hydrogen

• Published in: Topics in catalysis Vol. 61; no. 5-6; pp. 475 - 486
• Main Authors: Giannakakis, Georgios, Trimpalis, Antonios, Shan, Junjun, Qi, Zhen, Cao, Sufeng, Liu, Jilei, Ye, Jianchao, Biener, Juergen, Flytzani-Stephanopoulos, Maria
• Format: Journal Article
• Language: English
• Published: New York Springer US 01.05.2018; Springer Nature B.V; Springer
• Subjects: Acetaldehyde; Catalysis; catalysis (heterogeneous), mesostructured materials, materials and chemistry by design, synthesis (novel materials); Catalytic activity; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Clusters; Dehydrogenation; Dispersion; Dynamic stability; Ethanol; Gold; Hydrogen storage; Industrial Chemistry/Chemical Engineering; Original Paper; Pharmacy; Physical Chemistry; Selectivity; Stability tests; Gold; Nickel; Hydrogen; Single atom alloys; Ethanol dehydrogenation; Acetaldehyde
• ISSN: 1022-5528; 1572-9028
• DOI: 10.1007/s11244-017-0883-0

Gold is examined here as an alternative to copper for the selective dehydrogenation of ethanol to acetaldehyde and hydrogen. Despite its high selectivity, gold is only active at temperatures higher than 250 °C for this reaction. We demonstrate that addition of a small amount of Ni on either supported or unsupported Au surfaces induces resistance to sintering, along with a beneficial effect on the catalytic activity. NiAu alloys prepared here with Ni as the minority component to the limit of atomic dispersion in the gold surfaces, catalyze the reaction beginning below 150 °C. A significant decrease of the apparent activation energy from 96 ± 3 kJ/mol for the monometallic Au to 59 ± 5 kJ/mol for the alloy was found. The Ni dispersion and concentration as a function of gas environment was followed by in situ DRIFTS and by XPS. The stability of the catalyst morphology was investigated through post-reaction microscopy imaging and long-term stability tests under reaction conditions. As shown via dynamic reaction experiments, acetaldehyde and H 2 were selectively produced up to 280 °C. A small drop of selectivity at higher temperatures is attributed to the formation of Ni clusters, as proven by CO-DRIFTS on the used sample. Comparison with samples of higher Ni loading, where Ni clusters are formed, clearly shows that they catalyze the undesired full decomposition of ethanol to CO, CH 4 , and H 2 .