Common ‘oxygen sponge’ catalyst soaks up hydrogen too

Common ‘oxygen sponge’ catalyst soaks up hydrogen too

4:57 AM, 11th January 2018
Common ‘oxygen sponge’ catalyst soaks up hydrogen too
In the catalytic converter, the catalyst cerium oxide grabs oxygen from air and adds it to carbon monoxide and hydrocarbons to turn them into CO2, which is nonlethal.

Having the right tool for the job enabled scientists at the Department of Energy’s Oak Ridge National Laboratory and their collaborators to discover that a workhorse catalyst of vehicle exhaust systems—an “oxygen sponge” that can soak up oxygen from air and store it for later use in oxidation reactions—may also be a “hydrogen sponge.”

The finding, published in the Journal of the American Chemical Society, may pave the way for the design of more effective catalysts for selective hydrogenation reactions. Selective hydrogenation is the key to producing valuable chemicals, for example, turning triple-bonded hydrocarbons called alkynes selectively into double-bonded alkenes — starting materials for the synthesis of plastics, fuels and other commercial products.

“Understanding how molecular hydrogen interacts with ceria (cerium oxide, CeO2), however, is a big challenge, as no regular technique can ‘see’ the light H atom. We turned to inelastic neutron spectroscopy, a technique that is very sensitive to hydrogen,” said ORNL chemist Zili Wu. At ORNL’s Spallation Neutron Source (SNS), a DOE Office of Science User Facility, a neutron beam line called VISION probed vibrational signals of atomic interactions and generated spectra describing them. “Because neutron spectroscopy could ‘see’ hydrogen due to its large neutron scattering cross-section, it succeeded where optical spectroscopy techniques failed and enabled the first direct observations of cerium hydrides both on the surface and in the bulk of a cerium oxide catalyst,” Wu said.

In vehicle engines, oxygen is needed for hydrocarbon fuel to burn. The exhaust that is generated contains deadly carbon monoxide and unburned hydrocarbons. In the catalytic converter, the catalyst cerium oxide grabs oxygen from air and adds it to carbon monoxide and hydrocarbons to turn them into carbon dioxide, which is nonlethal. The finding that cerium oxide may grab hydrogen, as well as oxygen, is promising for efforts to engineer it to catalyze both reactions that cause electron gain (“reduction” of a reactant) and electron loss (“oxidation”).

At the Center for Nanophase Materials Sciences (CNMS), a DOE Office of Science User Facility at ORNL, the researchers made nanoscale crystalline rods of cerium oxide with well-defined surface structure to facilitate an understanding of catalytic reactions that would be difficult with commercial, normally spherical particles of cerium oxide. The nanoscale rods allowed them to differentiate hydrogen in the bulk from hydrogen on the surface, where catalysis was presumed to happen. The first observation of hydrides both on the surface and in the bulk of ceria was important because it established that the bulk of the material also can participate in chemical reactions.

Also at CNMS, Wu and Guo Shiou Foo performed in situ experiments using infrared and Raman spectroscopies, which scatter photons to create spectra that give “fingerprints” of atomic vibrations. Unfortunately, these optical techniques “see” only vibrating oxygen-hydrogen bonds (from stretching between oxygen and hydrogen bonds); they are blind to hydride species on ceria. To see the hydrogen interactions directly, the researchers had to use SNS, where Yongqiang Cheng, Luke Daemen and Anibal Ramirez-Cuesta performed inelastic neutron scattering. Meanwhile, Franklin Tao, Luan Nguyen and Xiaoyan Zhang of the University of Kansas used ambient pressure X-ray photoelectron spectroscopy to characterize the oxidation state of cerium oxide, which was critical to deriving the mechanism. Moreover, Cheng, aided by Ariana Beste of the University of Tennessee, created theory-based simulations of vibrational spectra of neutrons and compared them with experimental observations.

The current neutron study used VISION to explore the nature of hydride species in the catalyst. Further studies will also employ another beamline, NOMAD, to characterize the exact structure of both the surface and bulk hydride in the catalyst. What is more important, the researchers will take advantage of NOMAD’s ability to measure diffraction patterns at temperatures at which chemical reactions occur. Adding hydrocarbons, they will explore and reveal the catalytic role of the surface hydride versus the bulk hydride in hydrogenation reactions.

The understanding they build will facilitate the design of more effective cerium-based catalysts for diverse applications.

© Oak Ridge National Laboratory


See the News in Chemical Today magazine

View the magazine on Mobile, download the Chemical Today magazine app



Your Comments (Up to 2000 characters)
Please respect our community and the integrity of its participants. WOC reserves the right to moderate and approve your comment.

Related News

Honeywell unveils Cloud Historian as part of its connected plant

HOUSTON, US: Honeywell Process Solutions (HPS) has launched its Honeywell connected plant Uniformance Cloud Historian. This new offering is ...

Read more
Arsenic and algae: finding sustainable water purification systems

A University of New Mexico undergraduate engineering student thinks algae could solve the problem of arsenic contamination in water. Chase Stearnes s ...

Read more
New efficient catalyst for key step in artificial photosynthesis

Chemists at the US Department of Energy’s Brookhaven National Laboratory have designed a new catalyst that speeds up the rate of a key step in & ...

Read more
Green functionalisation of carbon-hydrogen bonds

National University of Singapore (NUS) chemists have developed a light enhanced, nickel catalysed method for carbon-hydrogen (C-H) bond functionalisat ...

Read more
New catalyst design to reduce nitrogen oxides in diesel exhaust

Researchers have discovered a new reaction mechanism that could be used to improve catalyst designs for pollution-control systems to further reduce em ...

Read more
Catalysing a green future for chemistry

The fight against climate change is a call-to-arms for the industry. We currently rely on fossil fuels, a major source of the greenhouse gas CO2, not ...

Read more
Copyright © 2018. Kimberlite Softwares Pvt. Ltd., India. All rights reserved.
World of Chemicals.