Water molecules on the surface of an electrode flip just before they give up electrons to form oxygen – a feat of nanoscale gymnastics that explains why the reaction takes more energy than it theoretically should. After observing this flipping in individual water molecules for the first time, scientists at Northwestern University in the US say that the next step is to find ways of controlling it. Doing so could improve the efficiency of the reaction, making it easier to produce both oxygen and hydrogen fuel from water.
The water splitting process takes place in an electrochemical cell containing water and a metallic electrode. When a voltage is applied to the electrode, the water splits into oxygen and hydrogen via two separate half-reactions.
The problem is that the half-reaction that produces oxygen, known as the oxygen evolution reaction (OER), is difficult and inefficient and takes more energy than predicted by theory. “It should require 1.23 V,” says Franz Geiger, the Northwestern physical chemist who led the new study, “but in reality, it requires more like 1.5 or 1.8 V.” This extra energy cost is one of the reasons why water splitting has not been implemented on a large scale, he explains.
Determining how water molecules arrange themselves
In the new work, Geiger and colleagues wanted to test whether the orientation of the water’s oxygen atoms affects the kinetics of the OER. To do this, they directed an 80-femtosecond pulse of infrared (1034 nm) laser light onto the surface of the electrode, which was in this case made of nickel. They then measured the intensity of the reflected light at half the incident wavelength.
This method, which is known as second harmonic and vibrational sum-frequency generation spectroscopy, revealed that the water molecules’ alignment on the surface of the electrode depended on the applied voltage. By analysing the amplitude and phase of the signal photons as this voltage was cycled, the researchers were able to pin down how the water molecules arranged themselves.
They found that before the voltage was applied, the water molecules were randomly oriented. At a specific applied voltage, however, they began to reorient. “We also detected water dipole flipping just before cleavage and electron transfer,” Geiger adds. “This allowed us to distinguish flipping from subsequent reaction steps.”
An unexplored idea
The researchers’ explanation for this flipping is that at high pH levels, the surface of the electrode is negatively charged due to the presence of nickel hydroxide groups that have lost their protons. The water molecules therefore align with their most positively charged ends facing the electrode. However, this means that the ends containing the electrons needed for the OER (which reside in the oxygen atoms) are pointing away from the electrode. “We hypothesized that water molecules must flip to align their oxygen atoms with electrochemically active nickel oxo species at high applied potential,” Geiger says.
This idea had not been explored until now, he says, because water absorbs strongly in the infrared range, making it appear opaque at the relevant frequencies. The electrodes typically employed are also too thick for infrared light to pass through. “We overcame these challenges by making the electrode thin enough for near-infrared transmission and by using wavelengths where water’s absorbance is low (the so-called ‘water window’),” he says.
Other challenges for the team included designing a spectrometer that could measure the second harmonic generation amplitude and phase and developing an optical model to extract the number of net-aligned water molecules and their flipping energy. “The full process – from concept to publication – took three years,” Geiger tells Physics World.
The team’s findings, which are detailed in Science Advances, suggest that controlling the orientation of water at the interface with the electrode could improve OER catalyst performance. For example, surfaces engineered to pre-align water molecules might lower the kinetic barriers to water splitting. “The results could also refine electrochemical models by incorporating structural water energetics,” Geiger says. “And beyond the OER, water alignment may also influence other reactions such as the hydrogen evolution reaction and CO₂ reduction to liquid fuels, potentially impacting multiple energy-related technologies.”
The researchers are now exploring alternative electrode materials, including NiFe and multi-element catalysts. Some of the latter can outperform iridium, which has traditionally been the best-performing electrocatalyst, but is very rare (it comes from meteorites) and therefore expensive. “We have also shown in a related publication (in press) that water flipping occurs on an earth-abundant semiconductor, suggesting broader applicability beyond metals,” Geiger reveals.
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