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Title: Moving to Sustainable Metals. Multifunctional Ligands in Catalytic, Outer Sphere C-H, N-H and O-H Activation

Much of our work during this grant period has emphasized green chemistry and sustainability. For example, we were able to convert glycerine, a waste byproduct of biodiesel production, into lactic acid, a compound with numerous applications, notably in the food and cosmetics industry, as well as being a source material for a biodegradable plastic. This work required a catalyst, that ceases to work after a certain lapse of time. We were able to identify the way in which this deactivation occurs by identifying some of the metal catalyst deactivation products. These proved to be multimetallic clusters containing up to six metals and up to 14 hydrogen atoms. Both the catalytic reaction itself and the deactivation structures are novel and unexpected. We have previously proposed that nitrogen heterocycles could be good energy carriers in a low CO2 future world. In another part of our study, we found catalysts for introduction of hydrogen, an energy carrier that is hard to store, into nitrogen heterocycles. The mechanism of this process proved to be unusual in that the catalyst transfers the H2 to the heterocycle in the form of H+ and H-, first transferring the H+ and only then the H-. In a thirdmore » area of study, some of our compounds, originally prepared for DOE catalysis purposes, also proved useful in hydrocarbon oxidation and in water oxidation. The latter is important in solar-to-fuel work, because, by analogy with natural photosynthesis, the goal of the Yale Solar Group of four PIs is to convert sunlight to hydrogen and oxygen, which requires water splitting catalysts. The catalysts that proved useful mediate the latter reaction: water oxidation to oxygen. In a more technical study, we developed methods for distinguishing the case where catalysis is mediated by a soluble catalyst from cases where catalysis arises from a deposit of finely divided solid. One particular application involved electrocatalysis, where catalysis is driven by application of a voltage to electrodes dipped in the reactant mixture. We measured the mass increase of an electrode as material is deposited, and were able to see how this process is affected by the voltage supplied to the electrode. Our work continues to be well cited and we often receive requests for information or samples from fellow researchers.« less
  1. Yale Univ., New Haven, CT (United States)
Publication Date:
OSTI Identifier:
Report Number(s):
DOE Contract Number:
Resource Type:
Technical Report
Research Org:
Yale Univ., New Haven, CT (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
25 ENERGY STORAGE; 08 HYDROGEN; 09 BIOMASS FUELS sustainable metals; multifunctional ligands; homogeneous catalysis; and aqueous electrochemistry