Surprise discovery could lead to improved catalysts for industrial reactions

The process of catalysis — in which a material speeds up a chemical reaction — is crucial to the production of many of the chemicals used in our everyday lives. But even though these catalytic processes are widespread, researchers often lack a clear understanding of exactly how they work.A new analysis by researchers at MIT has shown that an important industrial synthesis process, the production of vinyl acetate, requires a catalyst to take two different forms, which cycle back and forth from one to the other as the chemical process unfolds.Previously, it had been thought that only one of the two forms was needed. The new findings are published today in the journal Science, in a paper by MIT graduate students Deiaa Harraz and Kunal Lodaya, Bryan Tang PhD ’23, and MIT professor of chemistry and chemical engineering Yogesh Surendranath.There are two broad classes of catalysts: homogeneous catalysts, which consist of dissolved molecules, and heterogeneous catalysts, which are solid materials whose surface provides the site for the chemical reaction. “For the longest time,” Surendranath says, “there’s been a general view that you either have catalysis happening on these surfaces, or you have them happening on these soluble molecules.” But the new research shows that in the case of vinyl acetate — an important material that goes into many polymer products such as the rubber in the soles of your shoes — there is an interplay between both classes of catalysis.“What we discovered,” Surendranath explains, “is that you actually have these solid metal materials converting into molecules, and then converting back into materials, in a cyclic dance.”He adds: “This work calls into question this paradigm where there’s either one flavor of catalysis or another. Really, there could be an interplay between both of them in certain cases, and that could be really advantageous for having a process that’s selective and efficient.”The synthesis of vinyl acetate has been a large-scale industrial reaction since the 1960s, and it has been well-researched and refined over the years to improve efficiency. This has happened largely through a trial-and-error approach, without a precise understanding of the underlying mechanisms, the researchers say.While chemists are often more familiar with homogeneous catalysis mechanisms, and chemical engineers are often more familiar with surface catalysis mechanisms, fewer researchers study both. This is perhaps part of the reason that the full complexity of this reaction was not previously captured. But Harraz says he and his colleagues are working at the interface between disciplines. “We’ve been able to appreciate both sides of this reaction and find that both types of catalysis are critical,” he says.The reaction that produces vinyl acetate requires something to activate the oxygen molecules that are one of the constituents of the reaction, and something else to activate the other ingredients, acetic acid and ethylene. The researchers found that the form of the catalyst that worked best for one part of the process was not the best for the other. It turns out that the molecular form of the catalyst does the key chemistry with the ethylene and the acetic acid, while it’s the surface that ends up doing the activation of the oxygen.They found that the underlying process involved in interconverting the two forms of the catalyst is actually corrosion, similar to the process of rusting. “It turns out that in rusting, you actually go through a soluble molecular species somewhere in the sequence,” Surendranath says.The team borrowed techniques traditionally used in corrosion research to study the process. They used electrochemical tools to study the reaction, even though the overall reaction does not require a supply of electricity. By making potential measurements, the researchers determined that the corrosion of the palladium catalyst material to soluble palladium ions is driven by an electrochemical reaction with the oxygen, converting it to water. Corrosion is “one of the oldest topics in electrochemistry,” says Lodaya, “but applying the science of corrosion to understand catalysis is much newer, and was essential to our findings.”By correlating measurements of catalyst corrosion with other measurements of the chemical reaction taking place, the researchers proposed that it was the corrosion rate that was limiting the overall reaction. “That’s the choke point that’s controlling the rate of the overall process,” Surendranath says.The interplay between the two types of catalysis works efficiently and selectively “because it actually uses the synergy of a material surface doing what it’s good at and a molecule doing what it’s good at,” Surendranath says. The finding suggests that, when designing new catalysts, rather than focusing on either solid materials or soluble molecules alone, researchers should think about how the interplay of both may open up new approaches.“Now, with an improved understanding of what makes this catalyst so effective, you can try to design specific materials or specific interfaces that promote the desired chemistry,” Harraz says. Since this process has been worked on for so long, these findings may not necessarily lead to improvements in this specific process of making vinyl acetate, but it does provide a better understanding of why the materials work as they do, and could lead to improvements in other catalytic processes.Understanding that “catalysts can transit between molecule and material and back, and the role that electrochemistry plays in those transformations, is a concept that we are really excited to expand on,” Lodaya says.Harraz adds: “With this new understanding that both types of catalysis could play a role, what other catalytic processes are out there that actually involve both? Maybe those have a lot of room for improvement that could benefit from this understanding.”This work is “illuminating, something that will be worth teaching at the undergraduate level,” says Christophe Coperet, a professor of inorganic chemistry at ETH Zurich, who was not associated with the research. “The work highlights new ways of thinking. … [It] is notable in the sense that it not only reconciles homogeneous and heterogeneous catalysis, but it describes these complex processes as half reactions, where electron transfers can cycle between distinct entities.”The research was supported, in part, by the National Science Foundation as a Phase I Center for Chemical Innovation; the Center for Interfacial Ionics; and the Gordon and Betty Moore Foundation.