Tag Archives: nanocatalysts

Water-based gold rush

It seems water can play an important role when using nanocatalysts made of gold nanoparticles combined with metal oxides. From a July 27, 2020 news item on ScienceDaily,

Nanocatalysts made of gold nanoparticles dispersed on metal oxides are very promising for the industrial, selective oxidation of compounds, including alcohols, into valuable chemicals. They show high catalytic activity, particularly in aqueous solution. A team of researchers from Ruhr-Universität Bochum (RUB) has been able to explain why: Water molecules play an active role in facilitating the oxygen dissociation needed for the oxidation reaction. The team of Professor Dominik Marx, Chair of Theoretical Chemistry, reports in the high-impact journal ACS Catalysis on 14 July 2020.

A July 27, 2020 Ruhr-University Bochum (RUB) press release (also on EurekAlert), which originated the news item, offers more detail,

Rushing for gold

Most industrial oxidation processes involve the use of agents, such as chlorine or organic peroxides, that produce toxic or useless by-products. Instead, using molecular oxygen, O2, and splitting it to obtain the oxygen atoms needed to produce specific products would be a greener and more attractive solution. A promising medium for this approach is the gold/metal oxide (Au/TiO2) system, where the metal oxide titania (TiO2) supports nanoparticles of gold. These nanocatalysts can catalyse the selective oxidation of molecular hydrogen, carbon monoxide and especially alcohols, among others. A crucial step behind all reactions is the dissociation of O2, which comprises a usually high energy barrier. And a crucial unknown in the process is the role of water, since the reactions take place in aqueous solutions.

In a 2018 study, the RUB group of Dominik Marx, Chair of Theoretical Chemistry and Research Area coordinator in the Cluster of Excellence Ruhr Explores Solvation (Resolv), already hinted that water molecules actively participate in the oxidative reaction: They enable a stepwise charge-transfer process that leads to oxygen dissociation in the aqueous phase. Now, the same team reveals that solvation facilitates the activation of molecular oxygen (O2) at the gold/metal oxide (Au/TiO2) nanocatalyst: In fact, water molecules help to decrease the energy barrier for the O2 dissociation. The researchers quantified that the solvent curbs the energy costs by 25 per cent compared to the gas phase. “For the first time, it has been possible to gain insights into the quantitative impact of water on the critical O2 activation reaction for this nanocatalyst – and we also understood why,” says Dominik Marx.

Mind the water molecules

The RUB researchers applied computer simulations, the so-called ab initio molecular dynamics simulations, which explicitly included not only the catalyst but also as many as 80 surrounding water molecules. This was key to gain deep insights into the liquid-phase scenario, which contains water, in direct comparison to the gas phase conditions, where water is absent. “Previous computational work employed significant simplifications or approximations that didn’t account for the true complexity of such a difficult solvent, water,” adds Dr. Niklas Siemer who recently earned his PhD at RUB based on this research.

Scientists simulated the experimental conditions with high temperature and pressure to obtain the free energy profile of O2 in both liquid and gas phase. Finally, they could trace back the mechanistic reason for the solvation effect: Water molecules induce an increase of local electron charge towards oxygen that is anchored at the nanocatalyst perimeter; this in turn leads to the less energetic costs for the dissociation. In the end, say the researchers, it’s all about the unique properties of water: “We found that the polarizability of water and its ability to donate hydrogen bonds are behind oxygen activation,” says Dr. Munoz-Santiburcio. According to the authors, the new computational strategy will help to understand and improve direct oxidation catalysis in water and alcohols.

Here’s a link to and a citation for the paper,

Solvation-Enhanced Oxygen Activation at Gold/Titania Nanocatalysts by Niklas Siemer, Daniel Muñoz-Santiburcio, and Dominik Marx. ACS Catal. 2020, 10, 15, 8530–8534 DOI: https://doi.org/10.1021/acscatal.0c01326 Publication Date: July 14, 2020 Copyright © 2020 American Chemical Society

This paper is behind a paywall.

When an atom more or less makes a big difference

As scientists continue exploring the nanoscale, it seems that finding the number of atoms in your particle makes a difference is no longer so surprising. From a Jan. 28, 2016 news item on ScienceDaily,

Combining experimental investigations and theoretical simulations, researchers have explained why platinum nanoclusters of a specific size range facilitate the hydrogenation reaction used to produce ethane from ethylene. The research offers new insights into the role of cluster shapes in catalyzing reactions at the nanoscale, and could help materials scientists optimize nanocatalysts for a broad class of other reactions.

A Jan. 28, 2016 Georgia Institute of Technology (Georgia Tech) news release (*also on EurekAlert*), which originated the news item, expands on the theme,

At the macro-scale, the conversion of ethylene has long been considered among the reactions insensitive to the structure of the catalyst used. However, by examining reactions catalyzed by platinum clusters containing between 9 and 15 atoms, researchers in Germany and the United States found that at the nanoscale, that’s no longer true. The shape of nanoscale clusters, they found, can dramatically affect reaction efficiency.

While the study investigated only platinum nanoclusters and the ethylene reaction, the fundamental principles may apply to other catalysts and reactions, demonstrating how materials at the very smallest size scales can provide different properties than the same material in bulk quantities. …

“We have re-examined the validity of a very fundamental concept on a very fundamental reaction,” said Uzi Landman, a Regents’ Professor and F.E. Callaway Chair in the School of Physics at the Georgia Institute of Technology. “We found that in the ultra-small catalyst range, on the order of a nanometer in size, old concepts don’t hold. New types of reactivity can occur because of changes in one or two atoms of a cluster at the nanoscale.”

The widely-used conversion process actually involves two separate reactions: (1) dissociation of H2 molecules into single hydrogen atoms, and (2) their addition to the ethylene, which involves conversion of a double bond into a single bond. In addition to producing ethane, the reaction can also take an alternative route that leads to the production of ethylidyne, which poisons the catalyst and prevents further reaction.

The project began with Professor Ueli Heiz and researchers in his group at the Technical University of Munich experimentally examining reaction rates for clusters containing 9, 10, 11, 12 or 13 platinum atoms that had been placed atop a magnesium oxide substrate. The 9-atom nanoclusters failed to produce a significant reaction, while larger clusters catalyzed the ethylene hydrogenation reaction with increasingly better efficiency. The best reaction occurred with 13-atom clusters.

Bokwon Yoon, a research scientist in Georgia Tech’s Center for Computational Materials Science, and Landman, the center’s director, then used large-scale first-principles quantum mechanical simulations to understand how the size of the clusters – and their shape – affected the reactivity. Using their simulations, they discovered that the 9-atom cluster resembled a symmetrical “hut,” while the larger clusters had bulges that served to concentrate electrical charges from the substrate.

“That one atom changes the whole activity of the catalyst,” Landman said. “We found that the extra atom operates like a lightning rod. The distribution of the excess charge from the substrate helps facilitate the reaction. Platinum 9 has a compact shape that doesn’t facilitate the reaction, but adding just one atom changes everything.”

Here’s an illustration featuring the difference between a 9 atom cluster and a 10 atom cluster,

A single atom makes a difference in the catalytic properties of platinum nanoclusters. Shown are platinum 9 (top) and platinum 10 (bottom). (Credit: Uzi Landman, Georgia Tech)

A single atom makes a difference in the catalytic properties of platinum nanoclusters. Shown are platinum 9 (top) and platinum 10 (bottom). (Credit: Uzi Landman, Georgia Tech)

The news release explains why the larger clusters function as catalysts,

Nanoclusters with 13 atoms provided the maximum reactivity because the additional atoms shift the structure in a phenomena Landman calls “fluxionality.” This structural adjustment has also been noted in earlier work of these two research groups, in studies of clusters of gold [emphasis mine] which are used in other catalytic reactions.

“Dynamic fluxionality is the ability of the cluster to distort its structure to accommodate the reactants to actually enhance reactivity,” he explained. “Only very small aggregates of metal can show such behavior, which mimics a biochemical enzyme.”

The simulations showed that catalyst poisoning also varies with cluster size – and temperature. The 10-atom clusters can be poisoned at room temperature, while the 13-atom clusters are poisoned only at higher temperatures, helping to account for their improved reactivity.

“Small really is different,” said Landman. “Once you get into this size regime, the old rules of structure sensitivity and structure insensitivity must be assessed for their continued validity. It’s not a question anymore of surface-to-volume ratio because everything is on the surface in these very small clusters.”

While the project examined only one reaction and one type of catalyst, the principles governing nanoscale catalysis – and the importance of re-examining traditional expectations – likely apply to a broad range of reactions catalyzed by nanoclusters at the smallest size scale. Such nanocatalysts are becoming more attractive as a means of conserving supplies of costly platinum.

“It’s a much richer world at the nanoscale than at the macroscopic scale,” added Landman. “These are very important messages for materials scientists and chemists who wish to design catalysts for new purposes, because the capabilities can be very different.”

Along with the experimental surface characterization and reactivity measurements, the first-principles theoretical simulations provide a unique practical means for examining these structural and electronic issues because the clusters are too small to be seen with sufficient resolution using most electron microscopy techniques or traditional crystallography.

“We have looked at how the number of atoms dictates the geometrical structure of the cluster catalysts on the surface and how this geometrical structure is associated with electronic properties that bring about chemical bonding characteristics that enhance the reactions,” Landman added.

I highlighted the news release’s reference to gold nanoclusters as I have noted the number issue in two April 14, 2015 postings, neither of which featured Georgia Tech, Gold atoms: sometimes they’re a metal and sometimes they’re a molecule and Nature’s patterns reflected in gold nanoparticles.

Here’s a link to and a citation for the ‘platinum catalyst’ paper,

Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters by Andrew S. Crampton, Marian D. Rötzer, Claron J. Ridge, Florian F. Schweinberger, Ueli Heiz, Bokwon Yoon, & Uzi Landman.  Nature Communications 7, Article number: 10389  doi:10.1038/ncomms10389 Published 28 January 2016

This paper is open access.

*’also on EurekAlert’ added Jan. 29, 2016.