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.

The Molecular Scale Structure of Electrolyte-Metal Oxide Interface

Li-ion batteries (LIBs) are key components of portable electronic devices, as well as in electric vehicles, military and medical equipment, backup power supplies, and even grid storage. However, the energy storage capacity and rate capability of current LIBs is still too low to meet the increasing demand of key markets. For the latter, the properties of the electrolyte-electrode interface play a decisive role.

From a more general point of view, interfaces, or surfaces, are the outer boundary of any condensed matter. Due to the resulting symmetry breaking, the arrangement of atoms or molecules at the interface often varies significantly from that in the bulk. Studies of the molecular scale structural properties of liquids at interfaces are intriguing, as these give insights into the fundamental molecule–molecule and molecule–substrate interactions. Investigations have included layering of ionic liquids [1], layering of metallic [2] and non-metallic liquids [3], and the (potential-dependent) structure of water adsorbed on solid surfaces [4]. However, basic insights into how a non-aqueous electrolyte–salt solution organizes at a solid interface, in particular from experiments, is still missing [5]. In many technological applications, the atomic scale properties of interfaces govern the functionality of the system. A prominent example is the importance of the structure and molecular arrangement of the liquid at the functional solid–liquid interface in batteries. More specifi­cally, in LIBs, the arrangement of the electrolyte molecules directly at the electrode interface, and the electric double layer (EDL) formation are expected to govern the interfacial ion transport during charge/discharge, as well as affect the origin and properties of the solid electrolyte interphase (SEI).

>Read more on the Stanford Synchrotron Radiation Lightsource website

Image: (a) Fresnel-normalized XRR (symbols) of the sapphire/LiPF6:EC:DMC and corresponding model fits (lines). (b) Fit-derived electron density profiles. (c) Comparison of the XRR- and MD-derived (blue) density profiles. The MD-derived profile is smeared by the XRR-derived roughness. All curves are spaced vertically for clarity. (d) Periodicity at the solid/liquid interface vs. LiPF6 concentration. (e) Normalized correlation lengths. (f) Schematic illustration of the proposed origin induced increased layer spacing with increasing salt-concentration.

Scientists decipher key principle behind reaction of metalloenzymes

So-called pre-distorted states accelerate photochemical reactions too

What enables electrons to be transferred swiftly, for example during photosynthesis? An interdisciplinary team of researchers has worked out the details of how important bioinorganic electron transfer systems operate. Using a combination of very different, time-resolved measurement methods at DESY’s X-ray source PETRA III and other facilities, the scientists were able to show that so-called pre-distorted states can speed up photochemical reactions or make them possible in the first place. The group headed by Sonja Herres-Pawlis from the RWTH Aachen University  Michael Rübhausen from the University of Hamburg and Wolfgang Zinth from Munich’s Ludwig Maximilian University, is presenting its findings in the journal Nature Chemistry.

The scientists had studied the pre-distorted, “entatic” state using a model system. An entatic state is the term used by chemists to refer to the configuration of a molecule in which the normal arrangement of the atoms is modified by external binding partners such that the energy threshold for the desired reaction is lowered, resulting in a higher speed of reaction. One example of this is the metalloprotein plastocyanin, which has a copper atom at its centre and is responsible for important steps in the transfer of electrons during photosynthesis. Depending on its oxidation state, the copper atom either prefers a planar configuration, in which all the surrounding atoms are arranged in the same plane (planar geometry), or a tetrahedral arrangement of the neighbouring ligands. However the binding partner in the protein forces the copper atom to adopt a sort of intermediate arrangement. This highly distorted tetrahedron allows a very rapid shift between the two oxidation states of the copper atom.

>Read more on the PETRA III website

Image Caption: Entatic state model complexes optimize the energies of starting and final configuration to enable fast reaction rates (illustrated by the hilly ground). The work demonstrates that the entatic state principle can be used to tune the photochemistry of copper complexes.
Credit: RWTH Aachen, Sonja Herres-Pawlis

Scientists measure accelerated emission

Grazing light for rapid events

An international team, including scientists from DESY,  has verified a prediction about the quantum-mechanical behaviour of resonant systems made more than 50 years ago. In experiments at SACLA, the Japanese X-ray laser, and at the European Synchrotron Radiation Facility ESRF in France, the group led by Aleksandr Chumakov from ESRF could show a dramatic reduction in the time to emit the first X-ray photon from an ensemble of excited nuclei when the number of X-rays for the excitation was increased. This behaviour is in good agreement with one limit of a superradiant system, predicted by the US physicist Robert Dicke in 1954, as the scientists report in the journal Nature Physics.

One of the broad challenges of science is to understand the behaviour of groups of atoms based on the response of a single atom in isolation, which is usually much simpler. A facet of this is understanding the behaviour of a group of identical oscillators. An analogy is a collection of bells that all have the same tone: one can easily imagine the sound of a single bell struck once – a clear tone ringing out with a volume that decays away over time.

But what happens if one gently taps all the bells in a large collection? Will the tone be the same as a single one? What about the volume? What about the direction – does it matter where you are standing when you listen to the sound? Does it matter if you tap them all at the same time?

>Read more on the FLASH website