chemistry – Page 3 – Lightsources.org

Molecular Anvils Trigger Chemical Reactions

2018/06/202018/06/27

The discovery opens up new possibilities for the high-specificity synthesis of valuable but challenging molecules in an environmentally friendly process.

For about a decade, researchers from the Stanford Institute for Materials and Energy Sciences at Stanford University have pursued a research program involving diamondoids—nanosized diamonds made up of as few as 10 carbon atoms. The diamondoids are extracted from petroleum fluids, sorted by size and shape, and put to work in ingenious ways, such as directing the self-assembly of nanowires made of copper and sulfur.

Initially, the researchers had thought that this nanowire material could be a good superconductor, so they performed experiments and calculations to test their ideas. What they found, however, was completely unexpected: the diamondoid–copper–sulfur building blocks they had synthesized did not make a superconductor, but they could be used to trigger chemical reactions with pressure, as opposed to heat or light.

Image: An animation shows how attaching molecular anvils (gray cages) to softer molecules (red and yellow balls) distributes the pressure from a bigger diamond anvil unevenly, so chemical bonds bend and eventually break around the atom that bears the largest deformation (circled red ball).
Credit: Greg Stewart/SLAC National Accelerator Laboratory

Takeuchi Receives European Inventor Award 2018

2018/06/072018/06/11

Prolific patent-holder won for inventing battery that increases the lifespan of implantable defibrillators fivefold, greatly reducing need for reoccurring surgery.

Esther Sans Takeuchi, PhD, has won the 2018 European Inventor Award in the “Non-EPO countries”, the European Patent Office (EPO) announced today. The award was given to her by the EPO at a ceremony held today in Paris, Saint-Germain-en-Laye. Of the four U.S. scientists nominated for the award, Takeuchi is the only American to bring home Europe’s most prestigious prize of innovation.

Takeuchi is the Chief Scientist of the Energy Sciences Directorate at the U.S. Department of Energy’s Brookhaven National Laboratory, Stony Brook University’s (SBU) William and Jane Knapp Endowed Chair in Energy and the Environment, and a Distinguished Professor of Chemistry in the College of Arts & Sciences and in Materials Science and Chemical Engineering in the College of Engineering and Applied Sciences at SBU. She was honored for developing the compact batteries that power tiny, implantable cardiac defibrillators (ICDs)—devices that detect and correct irregular, potentially fatal, heart rhythms. Her lithium silver vanadium oxide (“Li/SVO”) battery extended the power-source lifetime for ICDs to around five years, considerably longer than its predecessors, thus reducing the number of surgeries patients needed to undergo to replace them. Her invention led not only to an advance in battery chemistry, but also enabled the production and widespread adoption of ICDs and significantly improved patient well-being.

Image: Esther Sans Takeuchi, a joint appointee of Brookhaven National Laboratory and Stony Brook University, has won the 2018 European Inventor Award in the category “Non-EPO countries.”

Perovskites, the rising star for energy harvesting

2018/06/052018/06/18

Perovskites are promising candidates for photovoltaic cells, having reached an energy harvesting of more than 20% while it took silicon three decades to reach an equivalent. Scientists from all over the world are exploring these materials at the ESRF.

Photovoltaic (PV) panels exist in our society since several years now. The photovoltaic market is currently dominated by wafer-based photovoltaics or first generation PVs, namely the traditional crystalline silicon cells, which take a 90% of the market share.

Although silicon (Si) is an abundant material and the price of Si-PV has dropped in the past years, their manufacturing require costly facilities. In addition, their fabrication typically takes place in countries that rely on carbon-intensive forms of electricity generation (high carbon footprint).

But there is room for hope. There is a third generation of PV: those based on thin-film cells. These absorb light more efficiently and they currently take 10% of the market share.

Image: The CEA-CNRS team on ID01. From left to right: Peter Reiss, from CEA-Grenoble/INAC, Tobias Schulli from ID01, Tao Zhou from ID01, Asma Aicha Medjahed, Stephanie Pouget (both from CEA-Grenoble/INAC) and David Djurado, from the CNRS.
Credits: C. Argoud.

Putting CO2 to a good use

2018/04/302018/05/02

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.

Scientists explore how slow release fertilizer behaves in soil

2018/04/252018/04/26

Testing soil samples at the Canadian Light Source has helped a University of Saskatchewan soil scientist understand how tripolyphosphate (TPP), a slow release form of phosphorus fertilizer, works in the soil as a plant nutrient for much longer periods than previously thought.

Jordan Hamilton says the research also has implications for ongoing efforts by U of S soil scientists to use phosphorous-rich materials to clean up contaminated petroleum sites.

Hamilton, now a post-doctoral fellow working within U of S professor Derek Peak’s Environmental Soil Chemistry group, had a chapter of his PhD thesis, “Chemical speciation and fate of tripolyphosphate after application to a calcareous soil,” published earlier this year in the online journal Geochemical Transactions.

TPP needs to break down into a simpler form of phosphate in order to be used as a nutrient by plants. In most types of soil, the belief was that TPP would break down right away, says Hamilton.

“I would definitely say the biggest surprise is how quickly the TPP adsorbed (attached itself) to mineral sources, especially in these calcium-rich soils,” he said. “For the longer term, it was surprising to see it persist.”

Tailoring the surface chemical reactivity of transition‐metal dichalcogenide PtTe2 crystals

2018/03/262018/03/28

Recently, the PtX2 (X=S, Se, Te) class of transition-metal dichalcogenides has emerged as one of the most promising among layered materials “beyond graphene” for the presence of high room-temperature electron mobility and, moreover, bulk type-II Dirac fermions, arising from a tilted Dirac cone.
Information on the ambient stability of PtTe2 is a crucial step in order to evaluate the feasibility of its exploitation in technology. Moreover, the possibility to tune surface chemical reactivity by appropriate surface modification is an essential step for its employment for diverse applications, especially in catalysis.
By means of experiments with several surface-science spectroscopies and density functional theory, an international team of researchers from Italy, Republic of Korea, and Taiwan (coordinated by Graphene Labs of Istituto Italiano di Tecnologia) has investigated the reactivity of the PtTe2 surface toward most common ambient gases (oxygen and water), under the framework of the European Graphene Flagship-Core1 project.
To assess the surface chemical reactivity of PtTe2, X-ray photoelectron spectroscopy (XPS) carried out at the APE-HE beamline has been combined with high-resolution electron energy loss (HREELS) experiments and with density functional theory.
From the analysis of Te 3d core-level spectra in XPS and from the featureless vibrational spectrum in HREELS, it has been demonstrated that as-cleaved defect-free PtTe2 surface is inert toward most common ambient gases (oxygen and water).
In the evaluation of the ambient stability of PtTe2, the possible influence of Te vacancies on surface chemical reactivity deserves particular attention. As a matter of fact, Te vacancies may appear on non-stoichiometric samples during the growth process. To check the influence of Te vacancies on ambient stability of PtTe2, Te vacancies have been intentionally introduced in stoichiometric PtTe2 samples by Ar-ion sputtering. After exposing to O2 the PtTe2 surface defected by ion sputtering, with a Pt:Te ratio of 39:61, spectral features related to Te(IV) species appear, arising from the formation of Te=O bonds in a tellurium-oxide phase. The Te(IV) components are the most intense lines in the Te 3d XPS spectra for the case of air-exposed defected samples (see Figure 1). Concerning reactivity to water, it adsorbs molecularly even at room temperature on defected PtTe2. These findings also imply that the presence of Te vacancies is able to jeopardize the ambient stability of uncapped PtTe2-based devices, with a subsequent necessity to reduce the amount of Te vacancies for a successful technological exploitation of PtTe2.

>Read more on the Elettra website

Figure: XPS spectra of Te-3d core levels acquired for: defected PtTe₂ (green curve), the same surface exposed to 10⁶ L of O₂(black curve) and air-exposed defected PtTe₂ (yellow curve). The photon energy is 745 eV.

COSMIC impact: next-gen X-ray microscopy platform now operational

2018/03/21

A next-generation X-ray beamline now operating at the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) brings together a unique set of capabilities to measure the properties of materials at the nanoscale.

Called COSMIC, for Coherent Scattering and Microscopy, this X-ray beamline at Berkeley Lab’s Berkeley Lab’s Advanced Light Source (ALS) allows scientists to probe working batteries and other active chemical reactions, and to reveal new details about magnetism and correlated electronic materials.
COSMIC has two branches that focus on different types of X-ray experiments: one for X-ray imaging experiments and one for scattering experiments. In both cases, X-rays interact with a sample and are measured in a way that provides, structural, chemical, electronic, or magnetic information about samples.

The beamline is also intended as an important technological bridge toward the planned ALS upgrade, dubbed ALS-U, that would maximize its capabilities.

Image: X-rays strike a scintillator material at the COSMIC beamline, causing it to glow.
Credit: Simon Morton/Berkeley Lab

Determining the impact of post-conservation corrosion

2018/03/092018/03/08

When King Henry VIII’s flagship, the Mary Rose, sank off Portsmouth in 1545, it took with it 1248 iron cannonballs. Since the excavation of the shipwreck (from 1979-1983), the cannonballs have been conserved in different ways, offering a unique opportunity to study different conservation methods.

Humans have been using iron to make weapons, tools and ceremonial items for more than 20,000 years, but once these objects have been excavated they are at risk from corrosion, which can be accelerated in the presence of chlorine. Each recovered artefact has to be conserved to prevent it from deteriorating in the presence of air and water. Until now, a comparison of the effectiveness of different conservation methods has been hampered by the variable nature of both the artefacts found, and the environment in which they were buried.

Image: Dr Eleanor Schofield, Dr Giannantonio Cibin and Hayley Simon with iron shot and samples on Diamond’s B18 beamline.
Credit: Diamond Light Source

Possible Path to the Formation of Life’s Building Blocks in Space

2018/03/052018/03/08

Experiments at Berkeley Lab’s Advanced Light Source reveal how a hydrocarbon called pyrene could form near stars

Scientists have used lab experiments to retrace the chemical steps leading to the creation of complex hydrocarbons in space, showing pathways to forming 2-D carbon-based nanostructures in a mix of heated gases.

The latest study, which featured experiments at the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab), could help explain the presence of pyrene, which is a chemical compound known as a polycyclic aromatic hydrocarbon, and similar compounds in some meteorites.

A team of scientists, including researchers from Berkeley Lab and UC Berkeley, participated in the study, published March 5 in the Nature Astronomy journal. The study was led by scientists at the University of Hawaii at Manoa and also involved theoretical chemists at Florida International University.

Image: A researcher handles a fragment and a test tube sample of the Murchison meteorite, which has been shown to contain a a variety of hydrocarbons and amino acids, in this photo from a previous, unrelated study at Argonne National Laboratory. Experiments at Berkeley Lab are helping to retrace the chemical steps by which complex hydrocarbons like pyrene could form in the Murchison meteorite and other meteorites.
Credit: Argonne National Laboratory

Converting CO2 into usable energy

2018/03/01

Scientists show that single nickel atoms are an efficient, cost-effective catalyst for converting carbon dioxide into useful chemicals.

Imagine if carbon dioxide (CO₂) could easily be converted into usable energy. Every time you breathe or drive a motor vehicle, you would produce a key ingredient for generating fuels. Like photosynthesis in plants, we could turn CO₂ into molecules that are essential for day-to-day life. Now, scientists are one step closer.

Researchers at the U.S. Department of Energy’s (DOE) Brookhaven National Laboratory are part of a scientific collaboration that has identified a new electrocatalyst that efficiently converts CO₂ to carbon monoxide (CO), a highly energetic molecule. Their findings were published on Feb. 1 in Energy & Environmental Science.

“There are many ways to use CO,” said Eli Stavitski, a scientist at Brookhaven and an author on the paper. “You can react it with water to produce energy-rich hydrogen gas, or with hydrogen to produce useful chemicals, such as hydrocarbons or alcohols. If there were a sustainable, cost-efficient route to transform CO₂ to CO, it would benefit society greatly.”

>Read more on the NSLS-II website

Image: Brookhaven scientists are pictured at NSLS-II beamline 8-ID, where they used ultra-bright x-ray light to “see” the chemical complexity of a new catalytic material. Pictured from left to right are Klaus Attenkofer, Dong Su, Sooyeon Hwang, and Eli Stavitski.

Scientists confirm speculation on the chemistry of a high-performance battery

2018/02/282018/03/05

X-ray experiments at Berkeley Lab reveal what’s at work in an unconventional electrode.

Scientists have discovered a novel chemical state of the element manganese. This chemical state, first proposed about 90 years ago, enables a high-performance, low-cost sodium-ion battery that could quickly and efficiently store and distribute energy produced by solar panels and wind turbines across the electrical grid.

This direct proof of a previously unconfirmed charge state in a manganese-containing battery component could inspire new avenues of exploration for battery innovations.

X-ray experiments at the U.S. Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) were key in the discovery. The study results were published Feb. 28 in the journal Nature Communications.

Scientists at Berkeley Lab and New York University participated in the study, which was led by researchers at Natron Energy, formerly Alveo Energy, a Santa Clara, California-based battery technology company.

The battery that Natron Energy supplied for the study features an unconventional design for an anode, which is one of its two electrodes. Compared with the relatively mature designs of anodes used in lithium-ion batteries, anodes for sodium-ion batteries remain an active focus of R&D.

Photo: An array of solar panels and windmills.
Credit: PxHere

Unraveling the Complexities of Auto-Oxidation

2018/02/232018/03/07

A better understanding of auto-oxidation reaction mechanisms could lead to better engines, less air pollution, and improved climate models.

Oxygen plays a key role in chemical reactions that produce pollutants in the atmosphere and that fuel combustion engines. In these reactions, auto-oxidation (spontaneous oxidation in air or in the presence of oxygen) produces highly oxygenated molecules.

For example, volatile organic compounds (VOCs)—gas molecules emitted from vehicles, factories, and power plants (as well as living plants)—undergo a sequence of auto-oxidation reactions with the surrounding air, forming highly oxygenated molecules that contribute to air pollution, affecting health and climate. The same highly oxygenated molecules are also produced during the ignition of fuels in advanced combustion engines; controlling their formation and destruction processes can help to develop higher-efficiency engines.

However, because these highly oxygenated molecules are very reactive and decompose quickly, determining their identities has been difficult.

>Read more on the ALS website

Image: Illustration of the jet-stirred reactor used in this experiment. Jet nozzles in the reaction chamber (center) generate turbulence for mixing the incoming fuel molecules with oxidizer (lower right). After the fuels react, the products exit the apparatus (upper left) to be analyzed by advanced mass spectrometry.
Credit: Ahmed Najjar

A comparison of the etch mechanisms of germanium and silicon

2018/02/132018/02/15

Time multiplexed, deep reactive ion etching (DRIE) is a standard silicon microfabrication technique for fabricating MEMS sensors, actuators, and more recently in CMOS development for 2.5D and 3D memory devices.

At CHESS, we have adopted this microfabrication technique to develop novel x-ray optics called,Collimating Channel Arrays (CCAs) [1], for confocal x-ray fluorescence microscopy (CXRF). Because the first CCA optics were fabricated from silicon substrates, the range of x-ray fluorescence energies for which they could be used, and hence the elements they could be used to study, was limited. Unwanted x-rays above about 11 keV could penetrate through the silicon, showing up as background and interfering with the measurement.

To solve the background problem, germanium substrates were used to fabricate the CCA optics. Germanium, which is much denser and therefore x-ray opaque than silicon, is also etch compatible with the fluorine etch chemistry for silicon DRIE. However, small differences in etch behavior between germanium and silicon can cause big differences in the outcome. Here, Genova et al JVST B [2] report a systematic comparison of the etch mechanisms of silicon and germanium, performed with the Plasma Therm Versaline deep silicon etcher at the Cornell NanoScale Science & Technology Facility (CNF). The etch rates of silicon and germanium were compared by varying critical parameters in the DRIE process, especially the applied power and voltage used for each of 3 steps in the etch process, on custom-designed wafers with a variety of features with systematically varying dimensions.

>Read more on the CHESS website

Image: (extract, full image here) SEM of high aspect ratio (>13:1) etched features in Si at 3.7 μm/min (a) and Ge at 3.4 μm/min (b)

High coherence and intensity at FERMI enables new X-ray interfacial probe

2018/02/052018/03/14

Interfaces are involved in a wide range of systems and have significant implications in many fields of scientific and technological advancement, often determining device performance or chemical reactivity. Vital examples include solar cells, protein folding, and computer chips. A class of commonly used surface science techniques are comprised of even-ordered nonlinear spectroscopies (i.e., second harmonic and sum frequency generation) which exhibit no response in centrosymmetric media due to symmetry constraints.As a result, they have been widely used at optical wavelengths to explore physical and chemical properties of interfaces, where centrosymmetry is broken. Extending this to x-ray wavelengths would effectively combine the element specificity and spectral sensitivity of x-ray spectroscopy with the rigorous interfacial/surface specificity of optical even-ordered nonlinear spectroscopies. Unfortunately, at hard x-ray energies (x-ray wavelength order of the spacing between atoms) these even-ordered nonlinear spectroscopies are effectively bulk probes, as each individual atom breaks inversion symmetry. As soft x-ray wavelengths fall in between the UV and hard x-ray regimes, there has been uncertainty regarding the interface specificity of soft x-ray second harmonic generation.

>Read more on the FERMI webpage

Figure: (extract) Experimental Design. X-ray pulses are passed through a 2 mm iris and focused onto the graphite sample at normal incidence. The transmitted beam is then passed through a 600 nm aluminum filter and onto a spectrometer grating, spatially resolving the second harmonic signal from the fundamental. Inset: A schematic energy level diagram of the second harmonic generation process. (entire figure here)

Magnetic trick triples the power of SLAC’s X-ray laser

2018/01/312018/02/01

The new technique will allow researchers to observe ultrafast chemical processes previously undetectable at the atomic scale.

Scientists at the Department of Energy’s SLAC National Accelerator Laboratory have discovered a way to triple the amount of power generated by the world’s most powerful X-ray laser. The new technique, developed at SLAC’s Linac Coherent Light Source (LCLS), will enable researchers to observe the atomic structure of molecules and ultrafast chemical processes that were previously undetectable at the atomic scale.

The results, published in a Jan. 3 study in Physical Review Letters (PRL), will help address long-standing mysteries about photosynthesis and other fundamental chemical processes in biology, medicine and materials science, according to the researchers.

“LCLS produces the world’s most powerful X-ray pulses, which scientists use to create movies of atoms and molecules in action,” said Marc Guetg, a research associate at SLAC and lead author of the PRL study. “Our new technique triples the power of these short pulses, enabling higher contrast.”

>Read more on the LCSL website

Picture: The research team, from left: back row, Yuantao Ding, Matt Gibbs, Nora Norvell, Alex Saad, Uwe Bergmann, Zhirong Huang; front row, Marc Guetg and Timothy Maxwell.
Credit: Dawn Harmer/SLAC

Molecular dynamics on the femtosecond timescale

2018/01/252018/02/01

A photochemical reaction in its becoming has been observed with unprecedented detail at the Free Electron Laser FERMI in Trieste.

The result of the experiment published in Nature Communications paves the way for investigations that can shed new light on photochemical processes.

“Shooting the movie” of a photochemical reaction, interpreting its hidden details with the help of a computer: this is what has been done, thanks to the extraordinary capabilities of the FERMI free electron laser source in Trieste, by a research team composed of the Universities of Uppsala and Gothenburg in Sweden, the Institut Ruđer Bošković of Zagreb, the Elettra-FERMI Laboratory, the University of Trieste and the Laboratory of Physical Chemistry, Matter and Radiation in Paris. The study was published in Nature Communications.

The researchers wanted to capture the details of a chemical reaction promoted by the absorption of light (photochemical process), to understand how the excitation generated by a light beam induces changes on a target molecule. The first steps in a photochemical process involve changes in the electronic and geometric structure of a molecule over extremely short times measured in femtoseconds (1 fs = 10-15 s), which had so far hindered the accurate reconstruction of the entire sequence of the reaction.

The combination of intensity, energy resolution and very short pulse duration of the FERMI seeded free-electron laser source can now for the first time provide exceptionally detailed information on photoexcitation-deexcitation and fragmentation processes of isolated molecules in pump-probe experiments on the 50-femtosecond time scale.

Photoelectron spectroscopy with high resolution in energy and time, combined with accurate electronic structure and molecular dynamics calculations, has allowed to visualize in its entirety the temporal evolution of the prototype system chosen for the experiment: acetylacetone—a stable molecule used in environmental and medical applications.

“Besides revealing the dynamics of the reaction—explains Maria Novella Piancastelli of the University of Uppsala, principal investigator—a strong point of the experiment lies in the general applicability of the method, which leads us to consider it as the best way to investigate fundamental photochemical processes such as photosynthesis, photovoltaic energy production and vision. The stairway that goes from simple to complex molecules, and from the understanding of phenomena to practical applications is of course a long one, and we are specifically interested in its ‘first step’.

>Read more on the FERMI website

Figure: A pictorial representation of the potential energy surfaces involved in the relaxation mechanism of acetylacetone: the ground state S₀ (darker blue), two singlet S₂ (ππ*) (light blue) and S₁ (nπ*) (orange), and two triplet T₂ (nπ*) (light green) and T₁ (ππ*) (green) states. This approach based on high-resolution valence spectra backed by high-level calculations is the ultimate way to shed light on fundamental, basic photo processes such as photosynthesis, photovoltaic energy production, and vision.