Tag Archives: molybdenum

Jiggly jell-o as a new hydrogen fuel catalyst

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Jello [uploaded from https://www.organicauthority.com/eco-chic-table/new-jell-o-mold-jiggle-chic-holidays]

I’m quite intrigued by this ‘jell-o’ story. It’s hard to believe a childhood dessert might prove to have an application as a catalyst for producing hydrogen fuel. From a December 14, 2018 news item on Nanowerk,

A cheap and effective new catalyst developed by researchers at the University of California, Berkeley, can generate hydrogen fuel from water just as efficiently as platinum, currently the best — but also most expensive — water-splitting catalyst out there.

The catalyst, which is composed of nanometer-thin sheets of metal carbide, is manufactured using a self-assembly process that relies on a surprising ingredient: gelatin, the material that gives Jell-O its jiggle.

Two-dimensional metal carbides spark a reaction that splits water into oxygen and valuable hydrogen gas. Berkeley researchers have discovered an easy new recipe for cooking up these nanometer-thin sheets that is nearly as simple as making Jell-O from a box. (Xining Zang graphic, copyright Wiley)

A December 13, 2018 University of California at Berkeley (UC Berkeley) news release by Kara Manke (also on EurekAlert but published on Dec. 14, 2018), which originated the news item, provides more technical detail,

“Platinum is expensive, so it would be desirable to find other alternative materials to replace it,” said senior author Liwei Lin, professor of mechanical engineering at UC Berkeley. “We are actually using something similar to the Jell-O that you can eat as the foundation, and mixing it with some of the abundant earth elements to create an inexpensive new material for important catalytic reactions.”

The work appears in the Dec. 13 [2018] print edition of the journal Advanced Materials.

A zap of electricity can break apart the strong bonds that tie water molecules together, creating oxygen and hydrogen gas, the latter of which is an extremely valuable source of energy for powering hydrogen fuel cells. Hydrogen gas can also be used to help store energy from renewable yet intermittent energy sources like solar and wind power, which produce excess electricity when the sun shines or when the wind blows, but which go dormant on rainy or calm days.

A black and white image of metal carbide under high magnification.

When magnified, the two-dimensional metal carbides resemble sheets of cell[o]phane. (Xining Zang photo, copyright Wiley)

But simply sticking an electrode in a glass of water is an extremely inefficient method of generating hydrogen gas. For the past 20 years, scientists have been searching for catalysts that can speed up this reaction, making it practical for large-scale use.

“The traditional way of using water gas to generate hydrogen still dominates in industry. However, this method produces carbon dioxide as byproduct,” said first author Xining Zang, who conducted the research as a graduate student in mechanical engineering at UC Berkeley. “Electrocatalytic hydrogen generation is growing in the past decade, following the global demand to lower emissions. Developing a highly efficient and low-cost catalyst for electrohydrolysis will bring profound technical, economical and societal benefit.”

To create the catalyst, the researchers followed a recipe nearly as simple as making Jell-O from a box. They mixed gelatin and a metal ion — either molybdenum, tungsten or cobalt — with water, and then let the mixture dry.

“We believe that as gelatin dries, it self-assembles layer by layer,” Lin said. “The metal ion is carried by the gelatin, so when the gelatin self-assembles, your metal ion is also arranged into these flat layers, and these flat sheets are what give Jell-O its characteristic mirror-like surface.”

Heating the mixture to 600 degrees Celsius triggers the metal ion to react with the carbon atoms in the gelatin, forming large, nanometer-thin sheets of metal carbide. The unreacted gelatin burns away.

The researchers tested the efficiency of the catalysts by placing them in water and running an electric current through them. When stacked up against each other, molybdenum carbide split water the most efficiently, followed by tungsten carbide and then cobalt carbide, which didn’t form thin layers as well as the other two. Mixing molybdenum ions with a small amount of cobalt boosted the performance even more.

“It is possible that other forms of carbide may provide even better performance,” Lin said.

On the left, an illustration of blue spheres, representing gelatin molecules, arranged in a lattice shape. On the right, an illustration of thin sheets of metal carbide.

Molecules in gelatin naturally self-assemble in flat sheets, carrying the metal ions with them (left). Heating the mixture to 600 degrees Celsius burns off the gelatin, leaving nanometer-thin sheets of metal carbide. (Xining Zang illustration, copyright Wiley)

The two-dimensional shape of the catalyst is one of the reasons why it is so successful. That is because the water has to be in contact with the surface of the catalyst in order to do its job, and the large surface area of the sheets mean that the metal carbides are extremely efficient for their weight.

Because the recipe is so simple, it could easily be scaled up to produce large quantities of the catalyst, the researchers say.

“We found that the performance is very close to the best catalyst made of platinum and carbon, which is the gold standard in this area,” Lin said. “This means that we can replace the very expensive platinum with our material, which is made in a very scalable manufacturing process.”

Co-authors on the study are Lujie Yang, Buxuan Li and Minsong Wei of UC Berkeley, J. Nathan Hohman and Chenhui Zhu of Lawrence Berkeley National Lab; Wenshu Chen and Jiajun Gu of Shanghai Jiao Tong University; Xiaolong Zou and Jiaming Liang of the Shenzhen Institute; and Mohan Sanghasadasa of the U.S. Army RDECOM AMRDEC.

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

Self‐Assembly of Large‐Area 2D Polycrystalline Transition Metal Carbides for Hydrogen Electrocatalysis by Xining Zang, Wenshu Chen, Xiaolong Zou, J. Nathan Hohman, Lujie Yang
Buxuan Li, Minsong Wei, Chenhui Zhu, Jiaming Liang, Mohan Sanghadasa, Jiajun Gu, Liwei Lin. Advanced Materials Volume30, Issue 50 December 13, 2018 1805188 DOI: https://doi.org/10.1002/adma.201805188 First published [online]: 09 October 2018

This paper is behind a paywall.

Cannibalisitic nanostructures

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I think this form of ‘cannibalism’ could also be described as a form of ‘self-assembly’. That said, here is an August 31, 2018 news item on ScienceDaily announcing ‘cannibalistic’ materials,

Scientists at the [US] Department of Energy’s [DOE] Oak Ridge National Laboratory [ORNL] induced a two-dimensional material to cannibalize itself for atomic “building blocks” from which stable structures formed.

The findings, reported in Nature Communications, provide insights that may improve design of 2D materials for fast-charging energy-storage and electronic devices.

An August 31, 2018 DOE/Oak Ridge National Laboratory news release (also on EurekAlert), which originated the news item, provides more detail (Note: Links have been removed),

“Under our experimental conditions, titanium and carbon atoms can spontaneously form an atomically thin layer of 2D transition-metal carbide, which was never observed before,” said Xiahan Sang of ORNL.

He and ORNL’s Raymond Unocic led a team that performed in situ experiments using state-of-the-art scanning transmission electron microscopy (STEM), combined with theory-based simulations, to reveal the mechanism’s atomistic details.

“This study is about determining the atomic-level mechanisms and kinetics that are responsible for forming new structures of a 2D transition-metal carbide such that new synthesis methods can be realized for this class of materials,” Unocic added.

The starting material was a 2D ceramic called a MXene (pronounced “max een”). Unlike most ceramics, MXenes are good electrical conductors because they are made from alternating atomic layers of carbon or nitrogen sandwiched within transition metals like titanium.

The research was a project of the Fluid Interface Reactions, Structures and Transport (FIRST) Center, a DOE Energy Frontier Research Center that explores fluid–solid interface reactions that have consequences for energy transport in everyday applications. Scientists conducted experiments to synthesize and characterize advanced materials and performed theory and simulation work to explain observed structural and functional properties of the materials. New knowledge from FIRST projects provides guideposts for future studies.

The high-quality material used in these experiments was synthesized by Drexel University scientists, in the form of five-ply single-crystal monolayer flakes of MXene. The flakes were taken from a parent crystal called “MAX,” which contains a transition metal denoted by “M”; an element such as aluminum or silicon, denoted by “A”; and either a carbon or nitrogen atom, denoted by “X.” The researchers used an acidic solution to etch out the monoatomic aluminum layers, exfoliate the material and delaminate it into individual monolayers of a titanium carbide MXene (Ti3C2).

The ORNL scientists suspended a large MXene flake on a heating chip with holes drilled in it so no support material, or substrate, interfered with the flake. Under vacuum, the suspended flake was exposed to heat and irradiated with an electron beam to clean the MXene surface and fully expose the layer of titanium atoms.

MXenes are typically inert because their surfaces are covered with protective functional groups—oxygen, hydrogen and fluorine atoms that remain after acid exfoliation. After protective groups are removed, the remaining material activates. Atomic-scale defects—“vacancies” created when titanium atoms are removed during etching—are exposed on the outer ply of the monolayer. “These atomic vacancies are good initiation sites,” Sang said. “It’s favorable for titanium and carbon atoms to move from defective sites to the surface.” In an area with a defect, a pore may form when atoms migrate.

“Once those functional groups are gone, now you’re left with a bare titanium layer (and underneath, alternating carbon, titanium, carbon, titanium) that’s free to reconstruct and form new structures on top of existing structures,” Sang said.

High-resolution STEM imaging proved that atoms moved from one part of the material to another to build structures. Because the material feeds on itself, the growth mechanism is cannibalistic.

“The growth mechanism is completely supported by density functional theory and reactive molecular dynamics simulations, thus opening up future possibilities to use these theory tools to determine the experimental parameters required for synthesizing specific defect structures,” said Adri van Duin of Penn State [Pennsylvania State University].

Most of the time, only one additional layer [of carbon and titanium] grew on a surface. The material changed as atoms built new layers. Ti3C2 turned into Ti4C3, for example.

“These materials are efficient at ionic transport, which lends itself well to battery and supercapacitor applications,” Unocic said. “How does ionic transport change when we add more layers to nanometer-thin MXene sheets?” This question may spur future studies.

“Because MXenes containing molybdenum, niobium, vanadium, tantalum, hafnium, chromium and other metals are available, there are opportunities to make a variety of new structures containing more than three or four metal atoms in cross-section (the current limit for MXenes produced from MAX phases),” Yury Gogotsi of Drexel University added. “Those materials may show different useful properties and create an array of 2D building blocks for advancing technology.”

At ORNL’s Center for Nanophase Materials Sciences (CNMS), Yu Xie, Weiwei Sun and Paul Kent performed first-principles theory calculations to explain why these materials grew layer by layer instead of forming alternate structures, such as squares. Xufan Li and Kai Xiao helped understand the growth mechanism, which minimizes surface energy to stabilize atomic configurations. Penn State scientists conducted large-scale dynamical reactive force field simulations showing how atoms rearranged on surfaces, confirming defect structures and their evolution as observed in experiments.

The researchers hope the new knowledge will help others grow advanced materials and generate useful nanoscale structures.

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

In situ atomistic insight into the growth mechanisms of single layer 2D transition metal carbides by Xiahan Sang, Yu Xie, Dundar E. Yilmaz, Roghayyeh Lotfi, Mohamed Alhabeb, Alireza Ostadhossein, Babak Anasori, Weiwei Sun, Xufan Li, Kai Xiao, Paul R. C. Kent, Adri C. T. van Duin, Yury Gogotsi, & Raymond R. Unocic. Nature Communicationsvolume 9, Article number: 2266 (2018) DOI: https://doi.org/10.1038/s41467-018-04610-0 Published 11 June 2018

This paper is open access.