Scientists at the Department of Energy’s Oak Ridge National Laboratory have developed an electrochemical process that uses tiny spikes of carbon and copper to turn carbon dioxide, a greenhouse gas, into ethanol. Their finding, which involves nanofabrication and catalysis science, was serendipitous. 

“We discovered somewhat by accident that this material worked,” said ORNL’s Adam Rondinone, lead author of the team’s study published in ChemistrySelect. “We were trying to study the first step of a proposed reaction when we realized that the catalyst was doing the entire reaction on its own.”

The team used a catalyst made of carbon, copper and nitrogen and applied voltage to trigger a complicated chemical reaction that essentially reverses the combustion process. With the help of the nanotechnology-based catalyst which contains multiple reaction sites, the solution of carbon dioxide dissolved in water turned into ethanol with a yield of 63 percent. Typically, this type of electrochemical reaction results in a mix of several different products in small amounts.

“We’re taking carbon dioxide, a waste product of combustion, and we’re pushing that combustion reaction backwards with very high selectivity to a useful fuel,” Rondinone said. “Ethanol was a surprise -- it’s extremely difficult to go straight from carbon dioxide to ethanol with a single catalyst.”

The catalyst’s novelty lies in its nanoscale structure, consisting of copper nanoparticles embedded in carbon spikes. This nano-texturing approach avoids the use of expensive or rare metals such as platinum that limit the economic viability of many catalysts.

ORNL researchers developed a catalyst made of copper nanoparticles (seen as spheres) embedded in carbon nanospikes that can convert carbon dioxide into ethanol. 



Chemistry Select- High-Selectivity Electrochemical Conversion of CO2 to Ethanol using a Copper Nanoparticle/N-Doped Graphene Electrode



“By using common materials, but arranging them with nanotechnology, we figured out how to limit the side reactions and end up with the one thing that we want,” Rondinone said.

The researchers’ initial analysis suggests that the spiky textured surface of the catalysts provides ample reactive sites to facilitate the carbon dioxide-to-ethanol conversion.

“They are like 50-nanometer lightning rods that concentrate electrochemical reactivity at the tip of the spike,” Rondinone said.

Given the technique’s reliance on low-cost materials and an ability to operate at room temperature in water, the researchers believe the approach could be scaled up for industrially relevant applications. For instance, the process could be used to store excess electricity generated from variable power sources such as wind and solar.

“A process like this would allow you to consume extra electricity when it’s available to make and store as ethanol,” Rondinone said. “This could help to balance a grid supplied by intermittent renewable sources.” 

The researchers plan to refine their approach to improve the overall production rate and further study the catalyst’s properties and behavior.

They report an electrocatalyst which operates at room temperature and in water for the electroreduction of dissolved CO2 with high selectivity for ethanol. The overpotential (which might be lowered with the proper electrolyte, and by separating the hydrogen production to another catalyst) probably precludes economic viability for this catalyst, but the high selectivity for a 12-electron reaction suggests that nanostructured surfaces with multiple reactive sites in close proximity can yield novel reaction mechanisms. This suggests that the synergistic effect from interactions between Cu and CNS presents a novel strategy for designing highly selective electrocatalysts. While the entire reaction mechanism has not yet been elucidated, further details would be revealed from conversion of potential intermediates (e. g. CO, formic acid and acetaldehyde) in future work.

Abstract

Though carbon dioxide is a waste product of combustion, it can also be a potential feedstock for the production of fine and commodity organic chemicals provided that an efficient means to convert it to useful organic synthons can be developed. Herein we report a common element, nanostructured catalyst for the direct electrochemical conversion of CO2 to ethanol with high Faradaic efficiency (63 % at −1.2 V vs RHE) and high selectivity (84 %) that operates in water and at ambient temperature and pressure. Lacking noble metals or other rare or expensive materials, the catalyst is comprised of Cu nanoparticles on a highly textured, N-doped carbon nanospike film. Electrochemical analysis and density functional theory (DFT) calculations suggest a preliminary mechanism in which active sites on the Cu nanoparticles and the carbon nanospikes work in tandem to control the electrochemical reduction of carbon monoxide dimer to alcohol.

SOURCES - Oak Ridge National Lab, Chemistry Select