Analysis of thermodynamics, kinetics, and reaction pathways in the amination of secondary alcohols over Ru/SiO2

Xin Gao, Dia Sahsah, Andreas Heyden, Jesse Q. Bond

Research output: Contribution to journalArticlepeer-review

3 Scopus citations


This work considers the Ru-mediated amination of secondary alcohols with ammonia in vapor and liquid media. We map thermodynamic constraints, and we probe the impacts of species partial pressure, residence time, and reaction temperature on rate, selectivity, and catalyst stability. Alcohol amination consumes no H2, and H2 has no significant impact on amination kinetics; however, operating under H2 benefits Ru stability. Primary amine selectivity increases with ammonia pressure and alcohol conversion, and the latter observation is consistent with the formation of primary amines through a network of sequential reactions. Unfortunately, primary amines are susceptible to secondary deamination to form hydrocarbons. As is typical of processes that seek to isolate a reactive intermediate, the main selectivity challenge here is identifying residence times that are long enough to accumulate high substrate conversion but short enough to avoid secondary deamination. In general, moderate residence times will maximize the production of primary amines. Insights extend across a broad substrate scope, and we observe 70 – 90% yield of primary amines from linear, cyclic, and heterocyclic alcohols. That said, heterocyclic alcohols appear susceptible to product inhibition, so achieving high conversions requires longer residence times and/or increased ammonia pressures.

Original languageEnglish (US)
Pages (from-to)74-90
Number of pages17
JournalJournal of Catalysis
StatePublished - Aug 2023
Externally publishedYes


  • Alcohol amination
  • Amination kinetics
  • Ammonia
  • Heterogeneous
  • Primary amines
  • Ru

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry


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