Molecular movie of gold nanoparticle oscillations driven by displaced electrons

Photocatalysis, sensors, solar cells: Plasmons promise a variety of applications if the processes triggered by optical excitation in the nanoparticles can be controlled. A research team from Hamburg and Berlin reports experimental observations of a so-called molecular movie that cannot be explained by established models in Nano Letters. The team including researchers from DESY provides a new theoretical model that explains the dynamics of excited gold nanoparticles observed in their experiments.

Plasmons are collective electron oscillations associated with highly localised fields. The decay of these oscillations after optical excitation is currently the subject of intense debate. Researchers assume that very energetic “hot” electrons are generated in the process which lose their energy by electron-electron scattering into a “warm” electron gas. The gas heats up the particle which eventually releases the excess energy into the environment. The efficiency of the energy transfer between the “hot electron”, “warm electron”, and “warm particle” stages is important for applications wanting to make use of these processes. In particular, the energy transfer from the warm electron gas to the nanoparticle appears to be so efficient that the particle is heated extremely quickly. In the process, it expands explosively, causing it to oscillate collectively, like a breathing sphere. However, so far direct experimental studies resolving the breathing oscillation have been missing.

For their study, researchers from the Departments of Physics and Chemistry at Universität Hamburg, the Max Planck Institute for the Structure and Dynamics of Matter (MPSD), the CFEL at DESY, and TU Berlin joined forces. Led by Holger Lange, Jochen Küpper, and Kartik Ayyer, who all conduct research in the Cluster of Excellence “CUI: Advanced Imaging of Matter”, and Andreas Knorr from Berlin, the team combined theory and experiment for an accurate description of the dynamics of excited gold nanoparticles.

Using single-particle X-ray diffractive imaging (SPI), performed at DESY’s FLASH facility, and transient absorption spectroscopy (TA), the researchers determined both the structural size and the electron temperature of the nanoparticles after optical excitation as a function of time. They observed that the particles already expanded with the optical excitation pulse, much faster than previously assumed. This observation directly proved the need for an immediate excitation source other than the temperature rise and associated expansion of the particle.

Read more on the DESY website

Image: Optical excitation of gold nanoparticles directly sets the particle into an oscillatory motion in which the particle periodically expands and contracts.

Credit: Univ. Hamburg/H. Lange

Understanding How the Structure of Boron Oxynitride Affects its Photocatalytic Properties

Synchrotron studies show that tuning the synthesis of boron oxynitride can improve its performance as a photocatalyst and semiconductor

Carbon dioxide (CO2) is often in the news these days. As a greenhouse gas, released during the combustion of fossil fuels, it is fuelling climate change, and reducing our CO2 emissions is critical to a sustainable future. CO2 is also a by-product of many industrial processes, including the production of ammonia used for fertilisers. On the other hand, many industries need a regular supply of CO2, and shortages have caused problems in recent years. It makes sense, therefore, to find ways to recycle some of the waste CO2 we produce into useful products. However, CO2 conversion reactions are energy-intensive, and new catalysts are needed to make the reactions more efficient. Photocatalysts absorb light energy, creating a charge separation that can then drive a chemical reaction. A team of researchers from Imperial College London are researching CO2 conversion using photocatalysis. In work recently published in Chemistry of Materials, they investigated how oxygen doping affects the photocatalytic and optoelectronic properties of boron nitride. Their results provide valuable insights into the photochemistry of boron oxynitride (BNO) at the fundamental level.

By clarifying the importance of paramagnetism in BNO semiconductors and providing fundamental insight into their photophysics, this study paves the way to tailoring its properties for CO2 conversion photocatalysis. The group has also recently used a similar methodology to investigate phosphorus doping of boron nitride, which they will explore in a future publication. 

Read more on the Diamond Light Source website

Image: Combined experimental (EPR, NEXAFS) + computational study (DFT)

Credit: Image via Chem. Mater. 2023, 35, 5, 1858-1867

Towards catalysts for solar hydrogen production

Thin films of molybdenum and sulfur belong to a class of materials that can be considered for use as photocatalysts. Inexpensive catalysts such as these are needed to produce hydrogen as a fuel using solar energy. However, they are still not very efficient as catalysts. A new instrument at the Helmholtz-Berlin Zentrum’s BESSY II now shows how a light pulse alters the surface properties of the thin film and activates the material as a catalyst.

MoS2 thin films of superposed alternating layers of molybdenum and sulfur atoms form a two-dimensional semiconducting surface. However, even a surprisingly low-intensity blue light pulse is enough to alter the properties of the surface and make it metallic. This has now been demonstrated by a team at BESSY II.

Read more on the HZB website

Image: A new instrument at BESSY II can be used to study molybdenum-sulfide thin films that are of interest as catalysts for solar hydrogen production. A light pulse triggers a phase transition from the semiconducting to the metallic phase and thus enhances the catalytic activity.

Credit: © Martin Künsting /HZB