Tag Archives: clean energy

Fast hydrogen separation with graphene-wrapped zeolite membranes for clean energy

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A May 18, 2022 news item on phys.org highlights the problem with using hydrogen as an energy source,

The effects of global warming are becoming more serious, and there is a strong demand for technological advances to reduce carbon dioxide emissions. Hydrogen is an ideal clean energy which produces water when burned. To promote the use of hydrogen energy, it is essential to develop safe, energy-saving technologies for hydrogen production and storage. Currently, hydrogen is made from natural gas, so it is not appropriate for decarbonization. Using a lot of energy to separate hydrogen would not make it qualify as clean energy.

Polymer separation membranes have the great advantage of enlarging the separation membrane and increasing the separation coefficient. However, the speed of permeation through the membrane is extremely low, and high pressure must be applied to increase the permeation speed. Therefore, a large amount of energy is required for separation using a polymer separation membrane. The goal is to create a new kind of separation membrane technology that can achieve separation speeds that are 50 times faster than that of conventional separation membranes.

A May 18, 2022 Shinshu University (Japan) press release on EurekAlert, which originated the news item, describes a proposed solution to the hydrogen problem,

The graphene-wrapped molecular-sieving membrane prepared in this study has a separation factor of 245 and a permeation coefficient of 5.8 x 106 barrers, which is more than 100 times better than that of conventional polymer separation membranes. If the size of the separation membrane is increased in the future, it is very probable that an energy-saving separation process will be established for the separation of important gases such as carbon dioxide and oxygen as well as hydrogen.

As seen in the transmission electron microscope image in Figure 1 [not shown], graphene is wrapped around the MFI-type zeolite crystal, being hydrophobic. The wrapping uses the principles of colloidal science to keep graphene and zeolite crystal planes close to each other due to reduction of the repulsive interaction. About 5 layers of graphene enclose zeolite crystals in this figure. Around the red arrow, there is a narrow interface space where only hydrogen can permeate. Graphene is also present on hydrophobic zeolite, so the structure of the zeolite crystal cannot be seen with this. Since a strong attractive force acts between graphene, the zeolite crystals wrapped with graphene are in close contact with each other by a simple compression treatment and does not let any gas through.

Figure 2 [not shown] shows a model in which zeolite crystals wrapped with graphene are in contact with each other. The surface of the zeolite crystal has grooves derived from the structure, and there is an interfacial channel between zeolite and graphene through which hydrogen molecules can selectively permeate. The model in which the black circles are connected is graphene, and there are nano-windows represented by blanks in some places. Any gas can freely permeate the nanowindows, but the very narrow channels between graphene and zeolite crystal faces allow hydrogen to permeate preferentially. This structure allows efficient separation of hydrogen and methane. On the other hand, the movement of hydrogen is rapid because there are many voids between the graphene-wrapped zeolite particles. For this reason, ultra-high-speed permeation is possible while maintaining the high separation factor of 200 or more.

Figure 3 [not shown] compares the hydrogen separation factor and gas permeation coefficient for methane with the previously reported separation membranes, which is called Robeson plot. Therefore, this separation membrane separates hydrogen at a speed of about 100 times while maintaining a higher separation coefficient than conventional separation membranes. The farther in the direction of the arrow, the better the performance. This newly developed separation membrane has paved the way for energy-saving separation technologies for the first time.

In addition, this separation principle is different from the conventional dissolution mechanism with polymers and the separation mechanism with pore size in zeolite separation membranes, and it depends on the separation target by selecting the surface structure of zeolite or another crystal. High-speed separation for any target gas is possible in principle. For this reason, if the industrial manufacturing method of this separation membrane and the separation membrane becomes scalable, the chemical industry, combustion industry, and other industries can be significantly improved energy consumption, leading to a significant reduction in carbon dioxide emissions. Currently, the group is conducting research toward the establishment of basic technology for rapidly producing a large amount of enriched oxygen from air. The development of enriched oxygen manufacturing technologies will revolutionize the steel and chemical industry and even medicine.

The figures referenced in the press release are best seen in the context of the paper. I can show you part of Figure 1,

Caption: The black circle connection is a one-layer graphene model, and the nano window is shown as blank. Red hydrogen permeates the gap between graphene and the surface of the zeolite crystal. On the other hand, large CH4 molecules are difficult to permeate. Credit: Copyright©2022 The Authors, License 4.0 (CC BY-NC)

For the rest of Figure 1 and more figures, here’s a link to and a citation for the paper,

Ultrapermeable 2D-channeled graphene-wrapped zeolite molecular sieving membranes for hydrogen separation by Radovan Kukobat, Motomu Sakai, Hideki Tanaka, Hayato Otsuka, Fernando Vallejos-Burgos, Christian Lastoskie, Masahiko Matsukata, Yukichi Sasaki, Kaname Yoshida, Takuya Hayashi and Katsumi Kaneko. Science Advances 18 May 2022 Vol 8, Issue 20 DOI: 10.1126/sciadv.abl3521

This paper is open access.

Osmotic power: electricity generated with water, salt and a 3-atoms-thick membrane

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EPFL researchers have developed a system that generates electricity from osmosis with unparalleled efficiency. Their work, featured in “Nature”, uses seawater, fresh water, and a new type of membrane just three atoms thick.

A July 13, 2016 news item on Nanowerk highlights  research on osmotic power at École polytechnique fédérale de Lausanne (EPFL; Switzerland),

Proponents of clean energy will soon have a new source to add to their existing array of solar, wind, and hydropower: osmotic power. Or more specifically, energy generated by a natural phenomenon occurring when fresh water comes into contact with seawater through a membrane.

Researchers at EPFL’s Laboratory of Nanoscale Biology have developed an osmotic power generation system that delivers never-before-seen yields. Their innovation lies in a three atoms thick membrane used to separate the two fluids. …

A July 14, 2016 EPFL press release (also on EurekAlert but published July 13, 2016), which originated the news item, describes the research,

The concept is fairly simple. A semipermeable membrane separates two fluids with different salt concentrations. Salt ions travel through the membrane until the salt concentrations in the two fluids reach equilibrium. That phenomenon is precisely osmosis.

If the system is used with seawater and fresh water, salt ions in the seawater pass through the membrane into the fresh water until both fluids have the same salt concentration. And since an ion is simply an atom with an electrical charge, the movement of the salt ions can be harnessed to generate electricity.

A 3 atoms thick, selective membrane that does the job

EPFL’s system consists of two liquid-filled compartments separated by a thin membrane made of molybdenum disulfide. The membrane has a tiny hole, or nanopore, through which seawater ions pass into the fresh water until the two fluids’ salt concentrations are equal. As the ions pass through the nanopore, their electrons are transferred to an electrode – which is what is used to generate an electric current.

Thanks to its properties the membrane allows positively-charged ions to pass through, while pushing away most of the negatively-charged ones. That creates voltage between the two liquids as one builds up a positive charge and the other a negative charge. This voltage is what causes the current generated by the transfer of ions to flow.

“We had to first fabricate and then investigate the optimal size of the nanopore. If it’s too big, negative ions can pass through and the resulting voltage would be too low. If it’s too small, not enough ions can pass through and the current would be too weak,” said Jiandong Feng, lead author of the research.

What sets EPFL’s system apart is its membrane. In these types of systems, the current increases with a thinner membrane. And EPFL’s membrane is just a few atoms thick. The material it is made of – molybdenum disulfide – is ideal for generating an osmotic current. “This is the first time a two-dimensional material has been used for this type of application,” said Aleksandra Radenovic, head of the laboratory of Nanoscale Biology

Powering 50’000 energy-saving light bulbs with 1m2 membrane

The potential of the new system is huge. According to their calculations, a 1m2 membrane with 30% of its surface covered by nanopores should be able to produce 1MW of electricity – or enough to power 50,000 standard energy-saving light bulbs. And since molybdenum disulfide (MoS2) is easily found in nature or can be grown by chemical vapor deposition, the system could feasibly be ramped up for large-scale power generation. The major challenge in scaling-up this process is finding out how to make relatively uniform pores.

Until now, researchers have worked on a membrane with a single nanopore, in order to understand precisely what was going on. ” From an engineering perspective, single nanopore system is ideal to further our fundamental understanding of 8=-based processes and provide useful information for industry-level commercialization”, said Jiandong Feng.

The researchers were able to run a nanotransistor from the current generated by a single nanopore and thus demonstrated a self-powered nanosystem. Low-power single-layer MoS2 transistors were fabricated in collaboration with Andras Kis’ team at at EPFL, while molecular dynamics simulations were performed by collaborators at University of Illinois at Urbana–Champaign

Harnessing the potential of estuaries

EPFL’s research is part of a growing trend. For the past several years, scientists around the world have been developing systems that leverage osmotic power to create electricity. Pilot projects have sprung up in places such as Norway, the Netherlands, Japan, and the United States to generate energy at estuaries, where rivers flow into the sea. For now, the membranes used in most systems are organic and fragile, and deliver low yields. Some systems use the movement of water, rather than ions, to power turbines that in turn produce electricity.

Once the systems become more robust, osmotic power could play a major role in the generation of renewable energy. While solar panels require adequate sunlight and wind turbines adequate wind, osmotic energy can be produced just about any time of day or night – provided there’s an estuary nearby.

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

Single-layer MoS2 nanopores as nanopower generators by Jiandong Feng, Michael Graf, Ke Liu, Dmitry Ovchinnikov, Dumitru Dumcenco, Mohammad Heiranian, Vishal Nandigana, Narayana R. Aluru, Andras Kis, & Aleksandra Radenovic. Nature (2016)  doi:10.1038/nature18593 Published online 13 July 2016

This paper is behind a paywall.

There once was a champion … it was nano-rust

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Swiss and Israeli scientists have discovered water and nano iron oxide (rust) can be used to produce solar hydrogen cheaply. From the July 7, 2013 news release on EurekAlert,

In the quest for the production of renewable and clean energy, photoelectrochemical cells (PECs) constitute a sort of a Holy Grail. PECs are devices able of splitting water molecules into hydrogen and oxygen in a single operation, thanks to solar radiation. “As a matter of fact, we’ve already discovered this precious chalice, says Michael Grätzel, Director of the Laboratory of Photonics and Interfaces (LPI) at EPFL [Ecole Polytechnique Fédérale de Lausanne] and inventor of dye-sensitized photoelectrochemical cells. Today we have just reached an important milestone on the path that will lead us forward to profitable industrial applications.”

This week, Nature Materials is indeed publishing a groundbreaking article on the subject. EPFL researchers, working with Avner Rotschild from Technion (Israel), have managed to accurately characterize the iron oxide nanostructures to be used in order to produce hydrogen at the lowest possible cost. “The whole point of our approach is to use an exceptionally abundant, stable and cheap material: rust,” adds Scott C. Warren, first author of the article.

The EFFL July 9, 2013 news release by Emmanuel Barraud about this research provides more details,

At the end of last year, Kevin Sivula, one of the collaborators at the LPI laboratory, presented a prototype electrode based on the same principle. Its efficiency was such that gas bubbles emerged as soon as it was under a light stimulus. Without a doubt, the potential of such cheap electrodes was demonstrated, even if there was still room for improvement.

By using transmission electron microscopy (TEM) techniques, researchers were able to precisely characterize the movement of the electrons through the cauliflower-looking nanostructures forming the iron oxide particles, laid on electrodes during the manufacturing process. “These measures have helped us understand the reason why we get performance differences depending on the electrodes manufacturing process”, says Grätzel.

By comparing several electrodes, whose manufacturing method is now mastered, scientists were able to identify the “champion” structure. A 10×10 cm prototype has been produced and its effectiveness is in line with expectations. The next step will be the development of the industrial process to large-scale manufacturing. A European funding and the Swiss federal government could provide support for this last part.

Evidently, the long-term goal is to produce hydrogen – the fuel of the future – in an environmentally friendly and especially competitive way. For Michael Grätzel, “current methods, in which a conventional photovoltaic cell is coupled to an electrolyzer for producing hydrogen, cost 15 € per kilo at their cheapest. We’re aiming at a € 5 charge per kilo”.

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

Identifying champion nanostructures for solar water-splitting by Scott C. Warren, Kislon Voïtchovsky, Hen Dotan, Celine M. Leroy, Maurin Cornuz, Francesco Stellacci, Cécile Hébert, Avner Rothschild & Michael Grätzel. Nature Materials (2013) doi:10.1038/nmat3684
Published online 07 July 2013

This paper is behind a paywall.

Disorder engineering turns ‘white’ nanoparticles to ‘black’ nanoparticles for clean energy

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Titanium dioxide crystals are white, except when they’re black. According to an Apr. 10, 2013 news item on Nanowerk, researchers at the Lawrence Berkeley National Laboratory (US) have found a way to change white titanium dioxide crystals to black thereby changing some of their properties,

A unique atomic-scale engineering technique for turning low-efficiency photocatalytic “white” nanoparticles of titanium dioxide into high-efficiency “black” nanoparticles could be the key to clean energy technologies based on hydrogen.

Samuel Mao, a scientist who holds joint appointments with Berkeley Lab’s Environmental Energy Technologies Division and the University of California at Berkeley, leads the development of a technique for engineering disorder into the nanocrystalline structure of the semiconductor titanium dioxide. This turns the naturally white crystals black in color, a sign that the crystals are now able to absorb infrared as well as visible and ultraviolet light. The expanded absorption spectrum substantially improves the efficiency with which black titanium dioxide can use sunlight to split water molecules for the production of hydrogen.

The Apr. 10, 2013 Berkeley Lab news release, which originated the news item, provides more detail about how this discovery might have an impact on clean energy efforts,

The promise of hydrogen in batteries or fuels is a clean and renewable source of energy that does not exacerbate global climate change. The challenge is cost-effectively mass-producing it. Despite being the most abundant element in the universe, pure hydrogen is scarce on Earth because hydrogen combines with just about any other type of atom. Using solar energy to split the water molecule into hydrogen and oxygen is the ideal way to produce pure hydrogen. This, however, requires an efficient photocatalyst that water won’t corrode. Titanium dioxide can stand up to water but until the work of Mao and his group was only able to absorb ultraviolet light, which accounts for barely ten percent of the energy in sunlight.In his ACS [American Chemical Society]  talk [at the 245th meeting, Apr. 7 – 11, 2013], titled “Disorder Engineering: Turning Titanium Dioxide Nanoparticles Black,” Mao described how he developed the concept of “disorder engineering,” and how the introduction of hydrogenated disorders creates mid-band gap energy states above the valence band maximum to enhance hydrogen mobility. His studies have not only yielded a promising new photocatalyst for generating hydrogen, but have also helped dispel some widely held scientific beliefs.

“Our tests have shown that a good semiconductor photocatalyst does not have to be a single crystal with minimal defects and energy levels just beneath the bottom of conduction band,” Mao said.

Characterization studies at Berkeley Lab’s Advanced Light Source also helped answer the question of how much of the hydrogen  detected in their experiments comes from the photocatalytic reaction, and how much comes from hydrogen absorbed in the titanium oxide during the hydrogenation synthesis process.

“Our measurements indicate that only a very small amount of hydrogen is absorbed in black titanium dioxide, about 0.05 milligrams, as compared to the 40 milligrams of hydrogen detected during a 100 hour solar-driven hydrogen production experiment,” Mao said.

I must say, this ‘disorder engineering’ sounds much more appealing than some of the other disorders one hears about (e.g. personality disorders).