Urea susbstitutes noble metal catalysts

… for the photodegradation of organic polluants.

A new laser-based technique developed by the Institute of Materials Science (ICMAB-CSIC) uses urea, a common substance in the chemical industry and a low-cost alternative to noble metal co-catalyst, to enable a more efficient, one-step production of hybrid graphene-based organic-inorganic composite layers for environmental remediation, photodegradation of antibiotic contaminants from wastewater. The composition and chemical bonds of the urea-enriched thin layers were studied in detail using synchrotron light at the ALBA Synchrotron.
Human activity is increasing the amount of pollutants in water and air, as well as in all sorts of materials at home and work place. The existence of antibiotic contamination is undeniably one of the most threatening challenges to date, at a time when antibiotic-resistant bacteria has already been flagged as the next world-wide pandemic crisis.
Semiconductor photocatalysts have long been investigated for environmental remediation because they can degrade or mineralize a wide range of organic contaminants as well as pathogens. Research focuses on addressing some drawbacks that prevent their use on a large scale. On the one hand, many photocatalysts are activated only by UV radiation which represents solely a small fraction of the total available solar emission. On the other hand, the recombination of the photogenerated  electron-hole pairs that enable the decomposition of the pollutant is usually faster than the oxidation reactions that cause the degradation of organic molecules. As a consequence, noble metal co-catalysts acting as electron scavengers, such as gold or platinum, are needed in the process.

Image: Researchers Ángel Pérez  del Pino and Enikö György from the ICMAB-CSIC together with Ibraheem Yousef, scientists responsible of MIRAS beamline at ALBA.

Watching molecules in a light-triggered catalyst ring ‘like an ensemble of bells’

A better understanding of these systems will aid in developing next-generation energy technologies.

Photocatalysts ­– materials that trigger chemical reactions when hit by light – are important in a number of natural and industrial processes, from producing hydrogen for fuel to enabling photosynthesis.
Now an international team has used an X-ray laser at the Department of Energy’s SLAC National Accelerator Laboratory to get an incredibly detailed look at what happens to the structure of a model photocatalyst when it absorbs light.
The researchers used extremely fast laser pulses to watch the structure change and see the molecules vibrating, ringing “like an ensemble of bells,” says lead author Kristoffer Haldrup, a senior scientist at Technical University of Denmark (DTU). This study paves the way for deeper investigation into these processes, which could help in the design of better catalysts for splitting water into hydrogen and oxygen for next-generation energy technologies.
“If we can understand such processes, then we can apply that understanding to developing molecular systems that do tricks like that with very high efficiency,” Haldrup says.

>Read more on the Linac Coherent Light Source at SLAC website

Image: When photocatalyst molecules absorb light, they start vibrating in a coordinated way, like an ensemble of bells. Capturing this response is a critical step towards understanding how to design molecules for the efficient transformation of light energy to high-value chemicals.
Credit: Gregory Stewart/SLAC National Accelerator Laboratory

Platinum forms nano-bubbles

Technologically important noble metal oxidises more readily than expected.

Platinum, a noble metal, is oxidised more quickly than expected under conditions that are technologically relevant. This has emerged from a study jointly conducted by the DESY NanoLab and the Vienna University of Technology. Devices that contain platinum, such as the catalytic converters used to reduce exhaust emissions in cars, can suffer a loss in efficacy as a result of this reaction. The team around principal author Thomas Keller, from DESY and the University of Hamburg, is presenting its findings in the journal Solid State Ionics. The result is also a topic at the users’ meeting of DESY’s X-ray light sources with more than 1000 participants currently taking place in Hamburg.
“Platinum is an extremely important material in technological terms,” says Keller. “The conditions under which platinum undergoes oxidation have not yet been fully established. Examining those conditions is important for a large number of applications.”
The scientists studied a thin layer of platinum which had been applied to an yttria-stabilised zirconia crystal (YSZ crystal), the same combination that is used in the lambda sensor of automotive exhaust emission systems. The YSZ crystal is a so-called ion conductor, meaning that it conducts electrically charged atoms (ions), in this case oxygen ions. The vapour-deposited layer of platinum serves as an electrode. The lambda sensor measures the oxygen content of the exhaust fumes in the car and converts this into an electrical signal which in turn controls the combustion process electronically to minimize toxic exhausts.

>Read more on the DESY (PETRA III) website

Image: Electron microscope view into the interior of a platinum bubble. The cross-section was exposed with a focused ion beam. Below the hollow Pt bubble the angular YSZ crystal can be seen.
Credit: DESY, Satishkumar Kulkarni

Single atoms can make more efficient catalysts

Detailed observations of iridium atoms at work could help make catalysts that drive chemical reactions smaller, cheaper and more efficient.

Catalysts are chemical matchmakers: They bring other chemicals close together, increasing the chance that they’ll react with each other and produce something people want, like fuel or fertilizer.

Since some of the best catalyst materials are also quite expensive, like the platinum in a car’s catalytic converter, scientists have been looking for ways to shrink the amount they have to use.

Now scientists have their first direct, detailed look at how a single atom catalyzes a chemical reaction. The reaction is the same one that strips poisonous carbon monoxide out of car exhaust, and individual atoms of iridium did the job up to 25 times more efficiently than the iridium nanoparticles containing 50 to 100 atoms that are used today.

>Read more on the SSRL at SLAC website

Image: Scientists used a combination of four techniques, represented here by four incoming beams, to reveal in unprecedented detail how a single atom of iridium catalyzes a chemical reaction.
Credit: Greg Stewart/SLAC National Accelerator Laboratory

Illuminating nanoparticle growth with X-rays

Ultrabright x-rays at NSLS-II reveal key details of catalyst growth for more efficient hydrogen fuel cells

Hydrogen fuel cells are a promising technology for producing clean and renewable energy, but the cost and activity of their cathode materials is a major challenge for commercialization. Many fuel cells require expensive platinum-based catalysts—substances that initiate and speed up chemical reactions—to help convert renewable fuels into electrical energy. To make hydrogen fuel cells commercially viable, scientists are searching for more affordable catalysts that provide the same efficiency as pure platinum.

“Like a battery, hydrogen fuel cells convert stored chemical energy into electricity. The difference is that you’re using a replenishable fuel so, in principle, that ‘battery’ would last forever,” said Adrian Hunt, a scientist at the National Synchrotron Light Source II (NSLS-II), a U.S. Department of Energy (DOE) Office of Science User Facility at DOE’s Brookhaven National Laboratory. “Finding a cheap and effective catalyst for hydrogen fuel cells is basically the holy grail for making this technology more feasible.”

>Read more on the NSLS-II website

Image: Brookhaven Lab scientists Mingyuan Ge, Iradwikanari Waluyo, and Adrian Hunt are pictured left to right at the IOS beamline, where they studied the growth pathway of an efficient catalyst for hydrogen fuel cells.

Light-activated, single- ion catalyst breaks down carbon dioxide

X-ray studies reveal structural details that may point the way to designing better catalysts for converting pollutant gas into useful products

A team of scientists has discovered a single-site, visible-light-activated catalyst that converts carbon dioxide (CO2) into “building block” molecules that could be used for creating useful chemicals. The discovery opens the possibility of using sunlight to turn a greenhouse gas into hydrocarbon fuels.

The scientists used the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science user facility at Brookhaven National Laboratory, to uncover details of the efficient reaction, which used a single ion of cobalt to help lower the energy barrier for breaking down CO2. The team describes this single-site catalyst in a paper just published in the Journal of the American Chemical Society.

Converting CO2 into simpler parts—carbon monoxide (CO) and oxygen—has valuable real-world applications. “By breaking CO2, we can kill two birds with one stone—remove CO2 from the atmosphere and make building blocks for making fuel,” said Anatoly Frenkel, a chemist with a joint appointment at Brookhaven Lab and Stony Brook University. Frenkel led the effort to understand the activity of the catalyst, which was made by Gonghu Li, a physical chemist at the University of New Hampshire.

>Read more on the NSLS-II at Brookhaven National Laboratory website

Image: National Synchrotron Light Source II (NSLS-II) QAS beamline scientist Steven Ehrlich, Stony Brook University (SBU) graduate student Jiahao Huang, and Brookhaven Lab-SBU joint appointee Anatoly Frenkel at the QAS beamline at NSLS-II.

Transition metal complexes: mixed works better

A team at BESSY II has investigated how various iron-complex compounds process energy from incident light. They were able to show why certain compounds have the potential to convert light into electrical energy. 

The results are important for the development of organic solar cells. The study has now been published in the journal PCCP, and its illustration selected for the cover.
Transition-metal complexes – that is a cumbersome word for a class of molecules with important properties: An element from the group of transition metals sits in the centre. The outer electrons of the transition-metal atom are located in cloverleaf-like extended d-orbitals that can be easily influenced by external excitation. Some transition-metal complexes act as catalysts to accelerate certain chemical reactions, and others can even convert sunlight into electricity. The well-known dye solar cell developed by Michael Graetzel (EPFL) in the 1990s is based on a ruthenium complex.

Why not Iron?
However, it has not yet been possible to replace the rare and expensive transition metal ruthenium with a less expensive element, such as iron. This is astonishing, because the same number of electrons is found on extended outer d-orbitals of iron. However, excitation with light from the visible region does not release long-lived charge carriers in most of the iron complex compounds investigated so far.

>Read more on the Bessy II at HZB website

Image: The illustration shows a molecule with an iron atom at its centre, bound to 4 CN groups and a bipyridine molecule. The highest occupied iron orbital is shown as a green-red cloud. As soon as a cyan group is present, the outer iron orbitals are observed to delocalize so that electrons are also densely present around the nitrogen atoms.
Credit: T. Splettstoesser/HZB

The search for clean hydrogen fuel

The world is transitioning away from fossil fuels and hydrogen is poised to be the replacement.

Two things are needed if we are to make the transition to a low carbon, “hydrogen economy” they are clean and high yielding sources of hydrogen, as well as efficient means of producing and storing energy using hydrogen.

Hydrogen powered cars are the perfect case study for how a hydrogen-fuelled future would look. While they work and show a great deal of promise, the best examples of hydrogen being used in fuel require very clean sources of hydrogen. If the source of hydrogen is mixed with contaminants like carbon monoxide, the efficiency of the fuel goes down and causes downstream problems in the fuel cell.

A team from KTH led by Jonas Weissenrieder is visiting MAX IV this week to try and solve this exact problem, how can we generate clean hydrogen for fuel cells? The team is working on a process to catalyse the oxidation of carbon monoxide, which adversely affects fuel cell performance, to harmless carbon dioxide. The catalysis reaction must be selective, and not affect the hydrogen gas that could be oxidised to water which is not great for running car engines.

>Read more on the MAX IV Laboratory website

Single atoms break carbon’s strongest bond

Scientists discovered that single atoms of platinum can break the bond between carbon and fluorine, one of the strongest known chemical bonds.

An international team of scientists including researchers at Yale University and the U.S. Department of Energy’s (DOE) Brookhaven National Laboratory have developed a new catalyst for breaking carbon-fluorine bonds, one of the strongest chemical bonds known. The discovery, published on Sept. 10 in ACS Catalysis, is a breakthrough for efforts in environmental remediation and chemical synthesis.

“We aimed to develop a technology that could degrade polyfluoroalkyl substances (PFAS), one of the most challenging pollutant remediation problems of the present day,” said Jaehong Kim, a professor in the department of chemical and environmental engineering at Yale University. “PFAS are widely detected all over the world, from Arctic biota to the human body, and concentrations in contaminated groundwater significantly exceed the regulatory limit in many areas. Currently, there are no energy-efficient methods to destroy these contaminants. Our collaboration with Brookhaven Lab aims to solve this problem by taking advantage of the unique properties of single atom catalysts.”

>Read more on the NSLS-II at Brookhaven National Laboratory website

Image: Brookhaven scientist Eli Stavitski is shown at NSLS-II’s Inner Shell Spectroscopy beamline, where researchers imaged the physical and chemical complexity of a single-atom catalyst that breaks carbon-fluorine bonds.

Highly efficient single-atom catalyst could help auto industry

A longer-lasting, higher-efficiency platinum catalyst has been developed by a Dalhousie University-led team, a result with major implications for the automobile industry.

Platinum catalysts help deactivate toxic exhaust gases from traditional car engines. Platinum is also used to help drive the chemical reactions that make zero-emissions hydrogen fuel cells possible – a technology that could transform automobiles as we know them.

The new catalyst combines gold and platinum to form what’s known as a single-atom catalyst, resulting in nearly 100-fold increases in efficiency over market platinum catalysts, says Peng Zhang, the Dalhousie professor who led this research.
Not only is efficiency improved at the outset, but it is maintained through the catalyst’s lifetime: normally, a platinum catalyst works less well over time as carbon monoxide molecules tightly bond to and block platinum from helping reactions along.
Improvements come from two properties: the single atom structure, which maximizes platinum’s active surface area, and the unique electronic properties that adding gold to create an alloy helps to achieve.

>Read more on the Canadian Light Source website

Image: The blue balls represent platinum atoms, surrounded by gold atoms (yellow). This structure maximizes the platinum catalyst’s efficiency.

Insight into catalysis through novel study of X-ray absorption spectroscopy

An international team has made a breakthrough at BESSY II.

For the first time, they succeeded in investigating electronic states of a transition metal in detail and drawing reliable conclusions on their catalytic effect from the data. These results are helpful for the development of future applications of catalytic transition-metal systems. The work has now been published in Chemical Science, the Open Access journal of the Royal Society of Chemistry.

Many important processes in nature depend on catalysts, which are atoms or molecules that facilitate a reaction, but emerge from it themselves unchanged. One example is photosynthesis in plants, which is only possible with the help of a protein complex comprising four manganese atom sites at its centre. Redox reactions, as they are referred to, often play a pivotal role in these types of processes. The reactants are reduced through uptake of electrons, or oxidized through their release. Catalytic redox processes in nature and industry often only succeed thanks to suitable catalysts, where transition metals supply an important function.

>Read more about on the BESSY II at HZB website

Image: Manganese compounds also play a role as catalysts in photosynthesis.
Credit: HZB

Fuel cells from plants

Using elements in plants to increase fuel cell efficiency while reducing costs

Researchers from the Institut National de la Recherche Scientifique, Québec are looking into reeds, tall wetlands plants, in order to make cheaper catalysts for high-performance fuel cells.

Due to rising global energy demands and the threat caused by environmental pollution, the search for new, clean sources of energy is on.

Unlike a battery, which stores electricity for later use, a fuel cell generates electricity from stored materials, or fuels.

Hydrogen-based fuel is a very clean fuel source that only produces water as a by-product, and could effectively replace fossil fuels. In order to make hydrogen fuel viable for everyday use, high-performance fuel cells are needed to convert the energy from the hydrogen into electricity.

Hydrogen fuel cells use platinum catalysts to drive energy conversion, but the platinum is expensive, accounting for almost half of a fuel cell’s total cost according to Qiliang Wei, a PhD student in Shuhui Sun’s group from the Institut National de la Recherche Scientifique – Énergie, Matériaux et Télécommunications who studies lower-cost alternatives to platinum catalysts.

>Read more on the Canadian Light Source website

An electrifying view on catalysis

The future of chemistry is ‘electrifying’: With increasing availability of cheap electrical energy from renewables, it will soon become possible to drive many chemical processes by electrical power. In this way, chemical products and fuels can be produced via sustainable routes, replacing current processes which are based on fossil fuels.

In most cases, such electrically driven reactions make use of so-called electrocatalysts, complex materials which are assembled from a large number of chemical componentAs. The electrocatalyst plays an essential role: It helps to run the chemical reaction while keeping the loss of energy minimal, thereby saving as much renewable energy as possible. In most cases, electrocatalysts are developed empirically and the chemical reactions at their interfaces are poorly understood. A better understanding of these processes is essential, however, for fast development of new electrocatalysts and for a directed improvement of their lifetime, one of the most important factors that currently limit their applicability.

>Read more on the Elettra website

Figure:  Introducing well-defined model electrocatalysts into the field of electrochemistry.

Putting CO2 to a good use

One of the biggest culprits of climate change is an overabundance of carbon dioxide in the atmosphere.

As the world tries to find solutions to reverse the problem, scientists from Swansea University have found a way of using CO2 to create ethylene, a key chemical precursor. They have used ID03 to test their hypotheses.

Carbon dioxide is essential for the survival of animals and plants. However, people are the biggest producers of CO2 emissions. The extensive use of fossil fuels such as coal, oil, or natural gas has created an excess of CO2 in the atmosphere, leading to global warming. Considerable research focuses on capturing and storing harmful carbon dioxide emissions. But an alternative to expensive long-term storage is to use the captured CO2 as a resource to make useful materials.

>Read more on the European Synchrotron wesbite

New class of single atoms catalysts for carbon nanotubes

They exhibit outstanding electrochemical reduction of CO2 to CO.

Experiments using X-rays on two beamlines at the Australian Synchrotron have helped characterise a new class of single atom catalysts (SACs) supported on carbon nanotubes that exhibit outstanding electrochemical reduction of CO2 to CO. A weight loading of 20 wt% for the new class, nickel single atom nitrogen doped carbon nanotubes (NiSA-N-CNTs), is believed to be the highest metal loading for SACs reported to date.

Single atoms of nickel, cobalt and iron were supported on nitrogen doped carbon nanotubes via a one-pot pyrolysis method and compared in the study.

A large international collaboration, led by Prof San Ping Jiang, Deputy Director of the Fuels and Energy Technology Institute at the Curtin University of Technology and associates from the Department of Chemical Engineering, have developed a new synthesis and development process for nitrogen-doped carbon nanotubes with a nickel ligand that demonstrate high catalytic activity.

The study was published in Advanced Materials and featured on the inside cover of the publication.

Dr Bernt Johannessen, instrument scientist on the X-ray absorption spectroscopy (XAS) beamline at the Australian Synchrotron was a co-author on the paper, which also included lead investigators from Curtin University of Technology and collaborators at the University of Western Australia, Institute of Metal Research (China), Oak Ridge National Laboratory (US), University of the Sunshine Coast, University of Queensland, Tsinghua University (China) and King Abdulaziz University (Saudi Arabia). Technical support and advice on the soft X-ray spectroscopy experiments was provided by Australian Synchrotron instrument scientist Dr Bruce Cowie.

>Read more on the Australian Synchrotron website

Image: extract of the cover of Advanced Materials.

Edges and corners increase efficiency of catalytic converters

X-rays reveal oxide islands on noble metal nanoparticles

Catalytic converters for cleaning exhaust emissions are more efficient when they use nanoparticles with many edges. This is one of the findings of a study carried out at DESY’s X-ray source PETRA III. A team of scientists from the DESY NanoLab watched live as noxious carbon monoxide (CO) was converted into common carbon dioxide (CO2) on the surface of noble metal nanoparticles like those used in catalytic converters of cars. The scientists are presenting their findings in the journal Physical Review Letters. Their results suggest that having a large number of edges increases the efficiency of catalytic reactions, as the different facets of the nanoparticles are often covered by growing islands of a nano oxide, finally rendering these facets inactive. At the edges, the oxide islands cannot connect, leaving active sites for the catalytic reaction and an efficient oxygen supply.
Catalytic converters usually use nanoparticles because these have a far greater surface area for a given amount of the material, on which the catalytic reaction can take place. For the study presented here, the scientists at DESY’s NanoLab grew platinum-rhodium nanoparticles on a substrate in such a way that virtually all the particles were aligned in the same direction and had the same shape of truncated octahedrons (octahedrons resemble double pyramids). The scientists then studied the catalytic properties of this sample under the typical working conditions of an automotive catalytic converter, with different gaseous compositions in a reaction chamber that was exposed to intense X-rays from PETRA III on the P09 beamline.

>Read more on the PETRA III at DESY website

Image: With increasing oxygen (red) concentration, an oxide sandwich forms on the surface of the metallic nanoparticles, inhibiting the desired reaction of carbon monoxide to carbon dioxide. At the edges, however, the oxide sandwich brakes up, leaving free active sites for catalysis. The more edges the nanoparticles posses, the more efficient will the catalytic converter work.
Credit: DESY, Lucid Berlin