After 150 Years, a Breakthrough in Understanding the Conversion of CO2 to Electrofuels

Recent research in electrocatalytic CO₂ conversion points the way to using CO₂ as a feedstock and renewable electricity as an energy supply for the synthesis of different types of fuel and value-added chemicals such as ethylene, ethanol, and propane. But scientists still do not understand even the first step of these reactions—CO₂ activation, or the transformation of the linear CO₂ molecule at the catalyst surface upon accepting the first electron. Knowing the exact structure of the activated CO₂ is essential because its structure dictates both the end product of the reaction and its energy cost. This reaction can start from many initial steps and go through many pathways, giving typically a mixture of products. If scientists figure out how the process works, they will be better able to selectively promote or inhibit certain pathways, which will lead to the development of a commercially viable catalyst for this technology.

Columbia Engineering researchers announced today that they solved the first piece of the puzzle—they have proved that CO₂ electroreduction begins with one common intermediate, not two as was commonly thought. They applied a comprehensive suite of experimental and theoretical methods to identify the structure of the first intermediate of CO₂ electroreduction: carboxylate CO₂− that is attached to the surface with C and O atoms. Their breakthrough, published online today in PNAS, came by applying surface enhanced Raman scattering (SERS) instead of the more frequently used surface enhanced infrared spectroscopy (SEIRAS). The spectroscopic results were corroborated by quantum chemical modeling.

“Our findings about CO₂ activation will open the door to an incredibly broad range of possibilities: if we can fully understand CO₂ electroreduction, we’ll be able to reduce our dependence on fossil fuels, contributing to the mitigation of climate change,” says the paper’s lead author Irina Chernyshova, associate research scientist, Department of Earth and Environmental Engineering. “In addition, our insight into CO₂ activation at the solid-water interface will enable researchers to better model the prebiotic scenarios from CO₂ to complex organic molecules that may have led to the origin of life on our planet.”

They decided to use SERS rather than SEIRAS for their observations because they found that SERS has several significant advantages that enable more accurate identification of the structure of the reaction intermediate. Most importantly, the researchers were able to measure the vibrational spectra of species formed at the electrode-electrolyte interface along the entire spectral range and on an operating electrode (in operandi). Using both quantum chemical simulations and conventional electrochemical methods, the researchers were able to get the first detailed look at how CO₂ is activated at the electrode-electrolyte interface.

Understanding the nature of the first reaction intermediate is a critical step toward commercialization of the electrocatalytic CO₂ conversion to useful chemicals. It creates a solid foundation for moving away from the trial-and-error paradigm to rational catalyst design. “With this knowledge and computational power,” says the paper’s co-author Sathish Ponnurangam, a former graduate student and postdoc in Somasundaran’s lab who is now an assistant professor of chemical and petroleum engineering at the University of Calgary, Canada, “researchers will be able to predict more accurately the reaction on different catalysts and specify the most promising ones, which can further be synthesized and tested.”

“The Columbia Engineering experiments provide such detail that we should be able to obtain very definitive validation of the computational models,” says William Goddard, Charles and Mary Ferkel Professor of Chemistry, Materials Science, and Applied Physics at Caltech, who was not involved with the study. “I expect that together with our theory, the Columbia Engineering experiments will provide precise mechanisms to be established and that examining how the mechanisms change for different alloys, surface structures, electrolytes, additives, should enable optimization of the electrocatalysts for water spitting (solar fuels), CO₂ reduction to fuels and organic feedstocks, N₂ reduction to NH₃ to obtain much less expensive fertilizers, all the key problems facing society to obtain the energy and food to accommodate our exploding population.”

Electrocatalysis and photocatalysis (the so-called artificial photosynthesis) are among the most promising ways to achieve effective storage for renewable energy. CO₂ electroreduction has been capturing the imagination of researchers for more than 150 years because of its similarity to photosynthesis. Just as a plant converts sunlight into chemical energy, a catalyst converts electrons supplied by renewable energy into chemical energy that is stored in reduced products of CO₂. In addition to its application for renewable energy, electrocatalysis technology may also enable manned Mars missions and colonies by providing fuel for the return trip and carbonaceous chemicals from the CO₂ that makes up 95 percent of that planet’s atmosphere.

“We expect our findings and methodology will spur work on how to make go faster and at a lower energy cost not only electrocatalytic but also photocatalytic CO₂ reduction,” says Ponisseril Somasundaran, LaVon Duddleson Krumb Professor of Mineral Engineering, Department of Earth and Environmental Engineering. “In the latter case, a catalyst reduces CO₂ using direct sunlight. Even though these two approaches are experimentally different they are microscopically similar—both start with activation of CO₂ upon electron transfer from a catalyst surface. At this point, I believe that both these approaches will dominate the future.”

The team is now working to uncover the subsequent reaction steps—to see how CO₂ is further transformed—and to develop superior catalysts based on earth-abundant elements such as copper and tin.

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Columbia Engineering
Columbia Engineering, based in New York City, is one of the top engineering schools in the U.S. and one of the oldest in the nation. Also known as The Fu Foundation School of Engineering and Applied Science, the School expands knowledge and advances technology through the pioneering research of its more than 250 faculty, while educating undergraduate and graduate students in a collaborative environment to become leaders informed by a firm foundation in engineering. The School’s faculty are at the center of the University’s cross-disciplinary research, contributing to the Data Science Institute, Earth Institute, Zuckerman Mind Brain Behavior Institute, Precision Medicine Initiative, and the Columbia Nano Initiative. Guided by its strategic vision, “Columbia Engineering for Humanity,” the School aims to translate ideas into innovations that foster a sustainable, healthy, secure, connected, and creative humanity.