New catalyst lowers cost for producing environmentally sustainable hydrogen from water

A plentiful supply of clean energy is lurking in plain sight. It is the hydrogen we can extract from water (H2O) using renewable energy. Scientists are seeking low-cost methods for producing clean hydrogen from water to replace fossil fuels, as part of the quest to combat climate change.

Hydrogen can power vehicles while emitting nothing but water. Hydrogen is also an important chemical for many industrial processes, most notably in steel making and ammonia production. Using cleaner hydrogen is highly desirable in those industries.

A multi-institutional team led by the U.S. Department of Energy's (DOE) Argonne National Laboratory has developed a low-cost catalyst for a process that yields clean hydrogen from water. Other contributors include DOE's Sandia National Laboratories and Lawrence Berkeley National Laboratory, as well as Giner Inc.

"A process called electrolysis produces hydrogen and oxygen from water and has been around for more than a century," said Di-Jia Liu, senior chemist at Argonne. He also holds a joint appointment in the Pritzker School of Molecular Engineering at the University of Chicago.

Proton exchange membrane (PEM) electrolyzers represent a new generation of technology for this process. They can split water into hydrogen and oxygen with higher efficiency at near room temperature. The reduced energy demand makes them an ideal choice for producing clean hydrogen by using renewable but intermittent sources, such as solar and wind.

This electrolyzer runs with separate catalysts for each of its electrodes (cathode and anode). The cathode catalyst yields hydrogen, while the anode catalyst forms oxygen. A problem is that the anode catalyst uses iridium, which has a current market price of around $5,000 per ounce. The lack of supply and high cost of iridium pose a major barrier for widespread adoption of PEM electrolyzers.

The main ingredient in the new catalyst is cobalt, which is substantially cheaper than iridium. "We sought to develop a low-cost anode catalyst in a PEM electrolyzer that generates hydrogen at high throughput while consuming minimal energy," Liu said. "By using the cobalt-based catalyst prepared by our method, one could remove the main bottleneck of cost to producing clean hydrogen in an electrolyzer."

Giner Inc., a leading research and development company working toward commercialization of electrolyzers and fuel cells, evaluated the new catalyst using its PEM electrolyzer test stations under industrial operating conditions. The performance and durability far exceeded that of competitors' catalysts.

Important to further advancing the catalyst performance is understanding the reaction mechanism at the atomic scale under electrolyzer operating conditions. The team deciphered critical structural changes that occur in the catalyst under operating conditions by using X-ray analyses at the Advanced Photon Source (APS) at Argonne. They also identified key catalyst features using electron microscopy at Sandia Labs and at Argonne's Center for Nanoscale Materials (CNM). The APS and CNM are both DOE Office of Science user facilities.

"We imaged the atomic structure on the surface of the new catalyst at various stages of preparation," said Jianguo Wen, an Argonne materials scientist.

In addition, computational modeling at Berkeley Lab revealed important insights into the catalyst's durability under reaction conditions.

The team's achievement is a step forward in DOE's Hydrogen Energy Earthshot initiative, which mimics the U.S. space program's "Moon Shot" of the 1960s. Its ambitious goal is to lower the cost for green hydrogen production to one dollar per kilogram in a decade. Production of green hydrogen at that cost could reshape the nation's economy. Applications include the electric grid, manufacturing, transportation and residential and commercial heating.

"More generally, our results establish a promising path forward in replacing catalysts made from expensive precious metals with elements that are much less expensive and more abundant," Liu noted.

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Catalyst purifies herbicide-tainted water and produces hydrogen

Researchers in the Oregon State University College of Science have developed a dual-purpose catalyst that purifies herbicide-tainted water while also producing hydrogen.

The project, which included researchers from the OSU College of Engineering and HP Inc. is important because water pollution is a major global challenge, and hydrogen is a clean, renewable fuel.

Findings of the study, which explored photoactive catalysts, were published today in the journal ACS Catalysis.

"We can combine oxidation and reduction into a single process to achieve an efficient photocatalytic system," OSU's Kyriakos Stylianou said. "Oxidation happens via a photodegradation reaction, and reduction through a hydrogen evolution reaction."

A catalyst is a substance that increases the rate of a chemical reaction without itself undergoing any permanent chemical change.

Photocatalysts are materials that absorb light to reach a higher energy level and can use that energy to break down organic contaminants through oxidation. Among photocatalysts' many applications are self-cleaning coatings for stain- and odor-resistant walls, floors, ceilings and furniture.

Stylianou, assistant professor of chemistry, led the study, which involved titanium dioxide photocatalysts derived from a metal-organic framework, or MOF.

Made up of positively charged metal ions surrounded by organic "linker" molecules, MOFs are crystalline, porous materials with tunable structural properties and nanosized pores. They can be designed with a variety of components that determine the MOF's properties.

Upon MOFs' calcination -- high heating without melting -- semiconducting materials like titanium dioxide can be generated. Titanium dioxide is the most commonly used photocatalyst, and it's found in the minerals anatase, rutile and brookite.

Stylianou and collaborators including Líney Árnadóttir of the OSU College of Engineering and William Stickle of HP discovered that anatase doped with nitrogen and sulfur was the best "two birds, one stone" photocatalyst for simultaneously producing hydrogen and degrading the heavily used herbicide glyphosate.

Glyphosate, also known as N-phosphonomethyl glycine or PMG, has been widely sprayed on agricultural fields over the last 50 years since first appearing on the market under the trade name Roundup.

"Only a small percentage of the total amount of PMG applied is taken up by crops, and the rest reaches the environment," Stylianou said. "That causes concerns regarding the leaching of PMG into soil and groundwater, as well it should -- contaminated water can be detrimental to the health of every living thing on the planet. And herbicides leaching into water channels are a primary cause of water pollution."

Among an array of compounds in which hydrogen is found, water is the most common, and producing hydrogen by splitting water via photocatalysis is cleaner and more sustainable than the conventional method of deriving hydrogen -- from natural gas via a carbon-dioxide-producing process known as methane-steam reforming.

Hydrogen serves many scientific and industrial purposes in addition to its energy-related roles. It's used in fuel cells for cars, in the manufacture of many chemicals including ammonia, in the refining of metals and in the production of plastics.

"Water is a rich hydrogen source, and photocatalysis is a way of tapping into the Earth's abundant solar energy for hydrogen production and environmental remediation," Stylianou said. "We are showing that through photocatalysis, it is possible to produce a renewable fuel while removing organic pollutants, or converting them into useful products."

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How a record-breaking copper catalyst converts CO2 into liquid fuels

Since the 1970s, scientists have known that copper has a special ability to transform carbon dioxide into valuable chemicals and fuels. But for many years, scientists have struggled to understand how this common metal works as an electrocatalyst, a mechanism that uses energy from electrons to chemically transform molecules into different products.

Now, a research team led by Lawrence Berkeley National Laboratory (Berkeley Lab) has gained new insight by capturing real-time movies of copper nanoparticles (copper particles engineered at the scale of a billionth of a meter) as they convert CO2 and water into renewable fuels and chemicals: ethylene, ethanol, and propanol, among others. The work was reported in the journal Nature last week.

"This is very exciting. After decades of work, we're finally able to show -- with undeniable proof -- how copper electrocatalysts excel in CO2 reduction," said Peidong Yang, a senior faculty scientist in Berkeley Lab's Materials Sciences and Chemical Sciences Divisions who led the study. Yang is also a professor of chemistry and materials science and engineering at UC Berkeley. "Knowing how copper is such an excellent electrocatalyst brings us steps closer to turning CO2 into new, renewable solar fuels through artificial photosynthesis."

The work was made possible by combining a new imaging technique called operando 4D electrochemical liquid-cell STEM (scanning transmission electron microscopy) with a soft X-ray probe to investigate the same sample environment: copper nanoparticles in liquid. First author Yao Yang, a UC Berkeley Miller postdoctoral fellow, conceived the groundbreaking approach under the guidance of Peidong Yang while working toward his Ph.D. in chemistry at Cornell University.

Scientists who study artificial photosynthesis materials and reactions have wanted to combine the power of an electron probe with X-rays, but the two techniques typically can't be performed by the same instrument.

Electron microscopes (such as STEM or TEM) use beams of electrons and excel at characterizing the atomic structure in parts of a material. In recent years, 4D STEM (or "2D raster of 2D diffraction patterns using scanning transmission electron microscopy") instruments, such as those at Berkeley Lab's Molecular Foundry, have pushed the boundaries of electron microscopy even further, enabling scientists to map out atomic or molecular regions in a variety of materials, from hard metallic glass to soft, flexible films.

On the other hand, soft (or lower-energy) X-rays are useful for identifying and tracking chemical reactions in real time in an operando, or real-world, environment.

But now, scientists can have the best of both worlds. At the heart of the new technique is an electrochemical "liquid cell" sample holder with remarkable versatility. A thousand times thinner than a human hair, the device is compatible with both STEM and X-ray instruments.

The electrochemical liquid cell's ultrathin design allows reliable imaging of delicate samples while protecting them from electron beam damage. A special electrode custom-designed by co-author Cheng Wang, a staff scientist at Berkeley Lab's Advanced Light Source, enabled the team to conduct X-ray experiments with the electrochemical liquid cell. Combining the two allows researchers to comprehensively characterize electrochemical reactions in real time and at the nanoscale.

Getting granular

During 4D-STEM experiments, Yao Yang and team used the new electrochemical liquid cell to observe copper nanoparticles (ranging in size from 7 nanometers to 18 nanometers) evolve into active nanograins during CO2 electrolysis -- a process that uses electricity to drive a reaction on the surface of an electrocatalyst.

The experiments revealed a surprise: copper nanoparticles combined into larger metallic copper "nanograins" within seconds of the electrochemical reaction.

To learn more, the team turned to Wang, who pioneered a technique known as "resonant soft X-ray scattering (RSoXS) for soft materials," at the Advanced Light Source more than 10 years ago.

With help from Wang, the research team used the same electrochemical liquid cell, but this time during RSoXS experiments, to determine whether copper nanograins facilitate CO2 reduction. Soft X-rays are ideal for studying how copper electrocatalysts evolve during CO2 reduction, Wang explained. By using RSoXS, researchers can monitor multiple reactions between thousands of nanoparticles in real time, and accurately identify chemical reactants and products.

The RSoXS experiments at the Advanced Light Source -- along with additional evidence gathered at Cornell High Energy Synchrotron Source (CHESS) -- proved that metallic copper nanograins serve as active sites for CO2 reduction. (Metallic copper, also known as copper(0), is a form of the element copper.)

During CO2 electrolysis, the copper nanoparticles change their structure during a process called "electrochemical scrambling." The copper nanoparticles' surface layer of oxide degrades, creating open sites on the copper surface for CO2 molecules to attach, explained Peidong Yang. And as CO2 "docks" or binds to the copper nanograin surface, electrons are then transferred to CO2, causing a reaction that simultaneously produces ethylene, ethanol, and propanol along with other multicarbon products.

"The copper nanograins essentially turn into little chemical manufacturing factories," Yao Yang said.

Further experiments at the Molecular Foundry, the Advanced Light Source, and CHESS revealed that size matters. All of the 7-nanometer copper nanoparticles participated in CO2 reduction, whereas the larger nanoparticles did not. In addition, the team learned that only metallic copper can efficiently reduce CO2 into multicarbon products. The findings have implications for "rationally designing efficient CO2 electrocatalysts," Peidong Yang said.

The new study also validated Peidong Yang's findings from 2017: That the 7-nanometer-sized copper nanoparticles require low inputs of energy to start CO2 reduction. As an electrocatalyst, the 7-nanometer copper nanoparticles required a record-low driving force that is about 300 millivolts less than typical bulk copper electrocatalysts. The best-performing catalysts that produce multicarbon products from CO2 typically operate at high driving force of 1 volt.

The copper nanograins could potentially boost the energy efficiency and productivity of some catalysts designed for artificial photosynthesis, a field of research that aims to produce solar fuels from sunlight, water, and CO2. Currently, researchers within the Department of Energy-funded Liquid Sunlight Alliance (LiSA) plan to use the copper nanograin catalysts in the design of future solar fuel devices.

"The technique's ability to record real-time movies of a chemical process opens up exciting opportunities to study many other electrochemical energy conversion processes. It's a huge breakthrough, and it would not have been possible without Yao and his pioneering work," Peidong Yang said.

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