Breaking molecular traffic jams with finned nanoporous materials
New porous catalyst with ultra-small fins facilitates molecular transport


Date:
August 10, 2020
Source:
University of Houston
Summary:
Researchers are reporting the invention of a new class of porous
catalysts that will speed up reactions, breaking the molecular
traffic jam that can slow them down. The discovery has immediate
relevance to industry for a host of applications, including the
production of fuels, chemicals for plastics and polymers, and
reactions that make molecules for food, medicine and personal
care products.



FULL STORY ========================================================================== Thousands of chemical processes used by the energy industry and for
other applications rely on the high speed of catalytic reactions, but
molecules frequently are hindered by molecular traffic jams that slow them down. Now an entirely new class of porous catalysts has been invented,
using unique fins to speed up the chemistry by allowing molecules to
skip the lines that limit the reaction.


==========================================================================
This discovery was published in Nature Materials.

The breakthrough focused on reducing barriers for molecules accessing
the interior pores of catalysts, called zeolites -- aluminosilicates
with pores smaller than a nanometer. Zeolites are widely used in
commercial processes as solid catalysts for the production of gasoline
and value-added chemicals and other products.

In these applications, chemistry within the zeolite pores first requires molecules to find the small number of openings on the outside surface of catalyst particles. This creates a queue of molecules that must "wait
in line" to enter the particle, diffuse to the active site involved in
the chemical reaction, and then exit the particle.

One approach to address these transport problems has been to synthesize
small nanoparticles. As zeolites become smaller, the amount of surface
area exposing the pores increases per amount of catalyst material,
which grants increased access for molecules entering the pores. Smaller particles also reduce the internal distance molecules must travel through
the particle.

However, the synthesis of these smaller zeolite particles is expensive,
and the resulting particles are often too inefficient for practical applications.



========================================================================== Researchers at the University of Houston, led by Jeffrey Rimer, Abraham E.

Dukler Professor of chemical and biomolecular engineering, developed a
way to induce larger catalyst particles to behave like nanoparticles
-- that is, to allow molecules to enter, spark a reaction and exit
quickly, by growing protrusions, or fins, on the surfaces of catalyst particles. By adding nanoscale fins that protrude from the external
surface of large particles, the roughened exterior of the particle significantly increased in surface area, granting molecules increased
access and reducing the transport limitations that frequently plague conventional zeolite materials.

"Our new synthesis approach capitalizes on work we have been doing in
our group for many years, focused on controlling zeolite crystallization
in ways that enable the growth of fins," Rimer said. "This new class
of materials bypasses the need to directly synthesize nanoparticles,
creating a new paradigm in zeolite catalyst design." Rimer worked with
a team of international experts in materials synthesis, characterization
and modeling to demonstrate the capability of finned zeolites to improve
the performance of this unique family of solid catalysts. By comparing
finned zeolites with conventional catalytic materials, they showed that zeolites with fins lasted almost eight times longer. Rimer said the incorporation of fins leads to shorter internal diffusion pathways and
ensures molecules efficiently reach the reaction sites while reducing
the propensity of carbon-based species to become immobilized. That build
up ultimately deactivates the catalyst.

Xiaodong Zou, professor of inorganic and structural chemistry at Stockholm University, and members of her laboratory conducted advanced 3D electron microscopy characterization to unravel the pore structures of the finned crystals and confirmed that the fins were extensions of the underlying
crystal and did not create impediments for internal diffusion.

"It is amazing to see how well all these hundreds of individual nanofins
are aligned with the parent crystal," Zou said.



========================================================================== Additional state-of-the-art techniques for characterizing zeolite
catalysts in real time were performed at Utrecht University by the
research group of Bert Weckhuysen, professor of catalysis, energy and sustainability. These measurements confirmed the exceptional ability
of finned zeolites to prolong catalyst activity well beyond that of
larger catalysts.

Weckhuysen said the use of operando spectroscopy clearly showed how the introduction of fins lowered the amount of external coke deposits during catalysis. "That substantially increased the lifetime of finned zeolite crystals," he said.

Jeremy Palmer, assistant professor of chemical and biomolecular
engineering at UH, used computational methods to model finned materials
and explain how the new design works to improve catalysis.

Researchers had expected the fins would perform better than a
standard-sized zeolite catalyst, he said. "But we found it was not just a
10% or 20% improvement. It was a tripling of efficiency. The magnitude
of the improvement was a real surprise to us." Additional work at
the University of Minnesota by the research group of Paul Dauenhauer,
professor of chemical engineering and materials science, and by Michael Tsapatsis, professor of chemical and biomolecular engineering at Johns
Hopkins University, confirmed the enhanced mass transport properties
of finned zeolites. Using a new method to track molecule diffusion by
infrared light, the UM researchers demonstrated that the fins enhanced
molecule transport between 100 and 1,000 times faster than conventional particles.

"The addition of fins allows molecules to get inside the channels of
zeolites where the chemistry happens, but it also lets molecules quickly
get out of the particle, which lets them operate for a much longer period
of time," Dauenhauer said.

The discovery has immediate relevance to industry for a host of
applications, including the production of fuels, chemicals for plastics
and polymers, and reactions that make molecules for food, medicine and
personal care products.

"The beauty of this new discovery is its potential generalization to
a wide range of zeolite materials, using techniques that are easy to incorporate in existing synthesis processes," Rimer said. "The ability to control the properties of fins could allow for much greater flexibility
in the rational design of zeolite catalysts." This work was supported
by and is part of a larger mission of the U.S.

Department of Energy, with additional support provided by various
international funding agencies.


========================================================================== Story Source: Materials provided by University_of_Houston. Original
written by Jeannie Kever.

Note: Content may be edited for style and length.


========================================================================== Journal Reference:
1. Dai, H., Shen, Y., Yang, T. et al. Finned zeolite
catalysts. Nat. Mater.,
2020 DOI: 10.1038/s41563-020-0753-1 ==========================================================================

Link to news story: https://www.sciencedaily.com/releases/2020/08/200810115520.htm

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