MIT Researchers Boost Common Catalytic Reactions

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While there has typically been little interaction between electrochemical and thermochemical catalysis researchers, Surendranath says, “this study shows the community that there’s really a blurring of the line between the two, and that there is a huge opportunity in cross-fertilization between these two communities.”

Published: Wednesday, February 28, 2024 – 11:58

Rate increases of that magnitude have been seen before but in a different class of catalytic reactions known as redox half-reactions, which involve the gain or loss of an electron. The dramatically increased rates reported in the new study “have never been observed for reactions that don’t involve oxidation or reduction,” Surendranath says.

Surendranath says these new findings “raise tantalizing possibilities: Is this a more general phenomenon? Does electrochemical potential play a key role in other reaction classes as well? In our mind, this reshapes how we think about designing catalysts and promoting their reactivity.”

People working on thermochemical catalysis, Surendranath says, usually don’t consider the role of the electrochemical potential at the catalyst surface, “and they often don’t have good ways of measuring it. And what this study tells us is that relatively small changes, on the order of a few hundred millivolts, can have huge impacts—orders of magnitude changes in the rates of catalyzed reactions at those surfaces.

“The results are really striking,” says Surendranath, a professor of chemistry and chemical engineering.

Chemists traditionally think about surface catalysis based on the chemical binding energy of molecules to active sites on the surface, which influences the amount of energy needed for the reaction. But the new findings show that the electrostatic environment is “equally important in defining the rate of the reaction,” Surendranath says.

While their experiments so far were done with a two-dimensional planar electrode, most industrial reactions are run in three-dimensional vessels filled with powders. Catalysts are distributed through those powders, providing a lot more surface area for the reactions to take place. Westendorff says, “We’re looking at how catalysis is currently done in industry and how we can design systems that take advantage of the already existing infrastructure.”

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“This research is of the highest quality,” says Costas Vayenas, a professor of engineering at the university of Patras, in Greece, who was not associated with the study. The work “is very promising for practical applications, particularly since it extends previous related work in redox catalytic systems.”

Roman-Leshkov says “Traditionally, people who work in thermochemical catalysis would not associate these reactions with electrochemical processes at all. However, introducing this perspective to the community will redefine how we can integrate electrochemical characteristics into thermochemical catalysis. It will have a big impact on the community in general.”

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The non-redox chemical reactions studied by the MIT team are catalyzed by acids. “If you’re a first-year chemistry student, probably the first type of catalyst you learn about is an acid catalyst,” Surendranath says. There are many hundreds of such acid-catalyzed reactions, “and they’re super important in everything from processing petrochemical feedstocks to making commodity chemicals to doing transformations in pharmaceutical products. The list goes on and on.”

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In practice, the findings could lead to far more efficient production of a wide variety of chemical materials, the team says. “You get orders of magnitude changes in rate with very little energy input,” Surendranath says. “That’s what’s amazing about it.”

“This overlooked parameter of surface potential is something we should pay a lot of attention to because it can have a really, really outsized effect. It changes the paradigm of how we think about catalysis.”

(MIT: Cambridge, MA) — A simple technique that uses small amounts of energy could boost the efficiency of some key chemical processing reactions up to a factor of 100,000, MIT researchers report. These reactions are at the heart of petrochemical processing, pharmaceutical manufacturing, and many other industrial chemical processes.

The team included MIT postdoc Max Hulsey, Ph.D.2022, and graduate student Thejas Wesley, Ph.D. 2023, and was supported by the U.S. Air Force Office of Scientific Research and the U.S. Department of Energy Basic Energy Sciences.