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New class of catalysts could dramatically change playing field in nickel catalysis

Researchers at the University of Illinois Urbana-Champaign have reported a breakthrough in nickel catalysis that harnesses a rare oxidation state of nickel that has proved challenging to control yet is highly valued for its potential to facilitate important chemical reactions.

The researchers, led by Liviu Mirica, a professor of chemistry at Illinois, explain in a recently published paper in Nature Catalysis how they have overcome a long-standing challenge in the field of nickel catalysis by developing a new method for synthesizing thermally stable Ni(I) compounds, opening new avenues for building complex molecules.

New shelf-stable nickel one compounds

"We have developed shelf-stable Ni(I) compounds that could dramatically change the playing field of nickel catalysis. And that's why we have an international patent for it, and we're working with pharmaceutical companies and chemical vendors who want to license it," Mirica said.

Nickel-catalyzed cross-coupling reactions are widely used to form carbon–carbon and carbon heteroatom bonds, essential steps in producing pharmaceuticals, agrochemicals, and advanced materials. Traditionally, these reactions rely on two forms of nickel Ni(0) or Ni(II) as catalysts. Catalytically competent Ni(I) sources have remained elusive, but attractive.

"This form of nickel is highly desirable partly because it may open up new avenues of reactivity that have remained elusive with traditional sources of nickel," said Sagnik Chakrabarti, co-author and former graduate student in the Mirica group who worked on the project with graduate students Jubyeong Chae and Katy A. Knecht.

Isocyanides unlock nickel reactivity

Mirica said previous approaches by chemists have used specialized ligands that limit the generality of Ni(I) in a reaction the way one would use Ni(II) or Ni(0) sources. By tapping into the unique properties of organic compounds called isocyanides, the Mirica group has developed a simple system that gets the chemistry to work.

In their study, they demonstrated how the commercially available isocyanides function as simple supporting ligands, which connect to the nickel atom and form stable, powerful catalysts that can be used to snap molecular pieces together with exceptional speed and precision, opening an untapped chemical space for reaction discovery.

Their Ni(I) complexes are readily available, shelf-stable, easily prepared, and easily handled catalysts that are efficient for a wide variety of chemical reactions. This is unique because most Ni(I) complexes tend to be rather unstable, which has limited their use in catalytic settings.

Performance across key cross-couplings

"We were able to put Ni(I), 'nickel one,' in a bottle so people can use it on a wider scale for various synthetic applications," Mirica said.

In the study, the researchers demonstrate that these new catalysts work in several of the most important reactions used to make pharmaceuticals, electronics, advanced materials, and more. They report the synthesis, characterization, and catalytic activity of two classes of Ni(I) isocyanide complexes: coordinatively saturated homoleptic compounds and coordinatively unsaturated Ni(I)-halide compounds. One is slightly more reactive than the other.

Their complexes exhibit rapid ligand substitution and demonstrate exceptional performance in Kumada, Suzuki–Miyaura, and Buchwald Hartwig cross-coupling reactions, according to the study, and notably, they exhibit chemo-selectivity, displaying their versatility.

Hints of new reaction pathways

According to Mirica and Chakrabarti, this new class of catalysts could be a game changer in nickel catalysis. Chakrabarti said there could be new reactions that could be discovered by directly introducing Ni(I) into reactions.

"And in fact, in the paper, we do talk about a new class of reactions that we developed and that has not been achieved with Ni catalysts before," he said. "It's just a snippet of reactivity, not like a full vignette in itself, but it still shows that by synthesizing something that's different from what's out there, we can maybe coax unique reactivity."

The research team also found that a tiny amount goes a long way.

Broad applicability and future directions

"The interesting thing that we found is that we can use very, very tiny amounts of the nickel catalyst, which is unusual in Ni catalysis, which typically needs higher amounts of the catalyst," Mirica said.

The study also highlights the structural diversity of isocyanides and their potential as spectator ligands for reaction discovery. Their study showed that this chemistry is not limited to just the one class of isocyanide they used, the tert-butyl isocyanide, but it's broadly applicable to other classes of isocyanides as well.

"So, the generality in using a bunch of different isocyanides bodes well for the future development of this chemistry," Chakrabarti said.

Future work in the Mirica group will explore the fundamental structure and bonding of these unusually stable compounds, their new reactivity, and the differences in reactivity between alkyl and aryl isocyanide-supported complexes, which according to their study exhibit divergent catalytic behavior.

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A breakthrough that turns exhaust CO2 into useful materials

Exhaust gases from home furnaces, fireplaces, and industrial facilities release carbon dioxide (CO2) into the air, contributing to pollution. Scientists reporting in ACS Energy Letters have developed a new type of electrode designed to address this problem by capturing CO2 directly from the air and turning it into a useful chemical called formic acid. In testing, the system outperformed existing electrode technologies when exposed to simulated flue gas and when operating at CO2 levels similar to those found in the atmosphere.

"This work shows that carbon capture and conversion do not need to be treated as separate steps. By integrating both functions into a single electrode, we demonstrate a simpler pathway for CO2 utilization under realistic gas conditions," explains Wonyong Choi, a corresponding author on the study.

Why CO2 Conversion Has Been So Difficult

Pulling carbon dioxide out of the air may seem straightforward, especially since plants do it naturally. The greater challenge lies in transforming that captured gas into something useful, a step that is essential if carbon capture technologies are to be widely adopted. In real industrial exhaust, CO2 is usually mixed with other gases, including nitrogen and oxygen. Most existing conversion systems only work efficiently when carbon dioxide has already been separated and concentrated, which limits their practicality.

To overcome this obstacle, Donglai Pan, Myoung Hwan Oh, Wonyong Choi, and their colleagues set out to build a system that could operate under realistic conditions. Their goal was to create a device capable of handling flue gas as it is actually produced and converting even small amounts of captured CO2 into a valuable product.

Inside the Three Layer Electrode

The research team designed an electrode that allows gas to pass through it, trap carbon dioxide, and convert it at the same time. The device is made up of three layers: a material that captures CO2, a sheet of gas permeable carbon paper, and a catalytic layer of tin(IV) oxide. Together, these components enable the direct conversion of carbon dioxide gas into formic acid.

Formic acid is an important chemical used in a range of applications, including fuel cells and other industrial processes. Producing it directly from exhaust gases could make carbon reuse more practical and cost effective.

Strong Results Under Real World Conditions

When tested with pure CO2 gas, the new electrode showed about 40% higher efficiency than existing carbon conversion electrodes under similar laboratory conditions. The advantage became even clearer when researchers used a simulated flue gas containing 15% CO2, 8% oxygen gas, and 77% nitrogen gas. Under these conditions, the new system continued to generate substantial amounts of formic acid, while other technologies produced very little.

The electrode also proved capable of capturing carbon dioxide at concentrations similar to those found in the atmosphere, showing that it can function in ambient air. According to the researchers, this approach offers a promising path toward integrating carbon capture into real industrial applications. They also suggest that similar designs could eventually be adapted to capture and convert other greenhouse gases, including methane.

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Scientists Found a Platinum Alternative Hiding in Plain Sight

A low-cost industrial metal just proved it can beat platinum at recycling plastic and powering cleaner chemistry.

Many products people use every day, from plastics to detergents, depend on chemical reactions powered by catalysts made from precious metals such as platinum. While platinum is highly effective, it is also expensive and limited in supply. Scientists have spent years searching for alternatives that are both affordable and sustainable. One strong candidate is tungsten carbide, an Earth-abundant material already widely used in industrial machinery, cutting tools, and chisels.

Despite its promise, tungsten carbide has not been easy to apply in chemical manufacturing. Its unique properties have limited its effectiveness in the past. Recent research led by Marc Porosoff, an associate professor in the University of Rochester’s Department of Chemical and Sustainability Engineering, has now addressed several of these challenges, bringing tungsten carbide closer to serving as a realistic substitute for platinum.

Why Atomic Arrangement Matters

According to Sinhara Perera, a chemical engineering PhD student in Porosoff’s lab, one of the main obstacles lies in the way tungsten carbide atoms are arranged.

Part of what makes tungsten carbide difficult to use as a catalyst, she explains, is that its atoms can organize themselves into many different configurations, known as phases.

“There’s been no clear understanding of the surface structure of tungsten carbide because it’s really difficult to measure the catalytic surface inside the chambers where these chemical reactions take place,” says Perera.

To overcome this limitation, the research team developed a way to control the material’s structure while reactions were actively occurring. In a study published in ACS Catalysis, Porosoff, Perera, and chemical engineering undergraduate student Eva Ciuffetelli ’27 carefully engineered tungsten carbide particles at the nanoscale inside a chemical reactor, where temperatures can exceed 700 degrees Celsius.

Using a method called temperature-programmed carburization, they created tungsten carbide catalysts in specific phases directly inside the reactor. The researchers then carried out chemical reactions and analyzed which versions delivered the best performance.

“Some of the phases are more thermodynamically stable, so that’s where the catalyst inherently wants to end up,” says Porosoff. “But other phases that are less thermodynamically stable are more effective as catalysts.”

Through this process, the team identified a specific phase, β-W2C, that performed especially well in reactions that convert carbon dioxide into essential building blocks for fuels and other valuable chemicals. With further optimization by industry, Porosoff and his colleagues believe this phase could rival platinum while avoiding its high cost and limited availability.

Using Tungsten Carbide to Upcycle Plastic Waste

The researchers also examined how tungsten carbide could help address another major challenge: plastic waste. Porosoff and his collaborators studied its use as a catalyst for plastic upcycling, a process that transforms discarded plastics into higher-quality materials.

In a study published in the Journal of the American Chemical Society, led by Linxao Chen from the University of North Texas and supported by Porosoff and University of Rochester Assistant Professor Siddharth Deshpande, the team demonstrated how tungsten carbide can drive a chemical process known as hydrocracking.

Hydrocracking breaks large molecules into smaller ones that can be reused to make new products. In this case, the researchers focused on polypropylene, which is commonly used in water bottles and many other plastic items.

Although hydrocracking is widely used in oil and gas refining, applying it to plastic waste has been difficult. Most single-use plastics contain long polymer chains that are extremely stable, and contaminants in waste streams can quickly deactivate traditional catalysts. Platinum-based catalysts also rely on microporous supports that are too small for large polymer chains to access.

“Tungsten carbide, when made with the correct phase, has metallic and acidic properties that are good for breaking down the carbon chains in these polymers,” says Porosoff. “These big bulky polymer chains can interact with the tungsten carbide much easier because they don’t have micropores that cause limitations with typical platinum-based catalysts.”

The results showed that tungsten carbide was not only significantly cheaper than platinum catalysts for hydrocracking, but also more than 10 times as efficient. The researchers say these findings could lead to better catalyst designs and new ways to convert plastic waste into valuable materials, supporting a circular economy.

Measuring Temperature With Greater Precision

Accurate temperature measurement plays a crucial role in developing efficient catalysts. Chemical reactions either absorb heat (endothermic) or release heat (exothermic), and controlling temperature at the catalyst surface allows scientists to coordinate multiple reactions more effectively.

However, traditional temperature measurements rely on bulk readings that average conditions across a reactor. These measurements often fail to capture the precise environment at the catalyst surface, making it difficult to study reactions accurately.

To solve this problem, the research team adopted optical measurement techniques developed in the lab of Andrea Pickel, a visiting professor in the Department of Mechanical Engineering. They described this new approach in a study published in EES Catalysis.

“We learned from this study that depending on the type of chemistry, the temperature measured with these bulk readings can be off by 10 to 100 degrees Celsius,” says Porosoff. “That’s a really significant difference in catalytic studies where you’re trying to ensure that measurements are reproducible and that multiple reactions can be coupled.”

Using this method, the team studied tandem catalyst systems in which heat released by one reaction is used to drive another reaction that requires heat input. Pairing these reactions more precisely can reduce wasted energy and improve overall efficiency in chemical processes.

Porosoff says this technique could also influence how catalysis research is conducted more broadly, leading to better measurements, stronger reproducibility, and more reliable results across the field.

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