Tag Archives: photocatalyst

Golden nanoglue

This starts out as a graphene story before taking an abrupt turn. From a June 5, 2018 news item on Nanowerk,

Graphene has undoubtedly been the most popular research subject of nanotechnology during recent years. Made of pure carbon, this material is in principle easy to manufacture: take ordinary graphite and peel one layer off with Scotch tape. The material thus obtained is two-dimensional, yielding unique properties, different from those in three-dimensional materials.

Graphene, however, lacks one important property, semiconductivity, which complicates its usage in electronics applications. Scientists have therefore started the quest of other two-dimensional materials with this desired property.

Molybdenum disulfide, MoS2 is among the most promising candidates. Like graphene, MoS2 consists of layers, interacting weakly with one another. In addition to being a semiconductor, the semiconducting properties of MoS2 change depending on the number of atomic layers.

A June 5, 2018 University of Oulu press release, which originated the news item,  gives more detail about the work,

For the one or few layer MoS2 to be useful in applications, one must be able to join it to other components. What is thus needed is such a metallic conductor that electric current can easily flow between the conductor and the semiconductor. In the case of MoS2, a promising conductor is provided by nickel, which also has other desired properties from the applications point of view.

However, an international collaboration, led by the Nano and molecular systems research unit at the University of Oulu has recently discovered that nanoparticles made of nickel do not attach to MoS2. One needs gold, which ‘glues’ the conductor and the component together. Says docent Wei Cao of NANOMO: “The synthesis is performed through a sonochemical method.” Sonochemistry is a method where chemical reactions are established using ultrasound. NANOMO scientist Xinying Shi adds: “The semiconductor and metal can be bridged either by the crystallized gold nanoparticles, or by the newly formed MoS2-Au-Ni ternary alloy.”

The nanojunction so established has a very small electrical resistivity. It also preserves the semiconducting and magnetic properties of MoS2. In addition, the new material has desirable properties beyond those of the original constituents. For example, it acts as a photocatalyst, which works much more efficiently than pure MoS2. Manufacturing the golden nanojunction is easy and cheap, which makes the new material attractive from the applications point of view.

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

Metallic Contact between MoS2 and Ni via Au Nanoglue by Xinying Shi, Sergei Posysaev, Marko Huttula, Vladimir Pankratov, Joanna Hoszowska, Jean‐Claude Dousse, Faisal Zeeshan, Yuran Niu, Alexei Zakharov, Taohai Li. Small Volume 14, Issue22 May 29, 2018 1704526 First published online: 24 April 2018 https://doi.org/10.1002/smll.201704526

This paper is behind a paywall.

There is a pretty illustration of the ‘golden nanojunctions’,

Golden nanoglue (Courtesy of the University of Oulu)

Gold nanoparticles as catalysts for clear water and hydrogen production

The research was published online May 2014 and in a July 2014 print version,  which seems a long time ago now but there’s a renewed interest in attracting attention for this work. A Dec. 17, 2014 news item on phys.org describes this proposed water purification technology from Singapore’s A*STAR (Agency for Science Technology and Research), Note: Links have been removed,

A new catalyst could have dramatic environmental benefits if it can live up to its potential, suggests research from Singapore. A*STAR researchers have produced a catalyst with gold-nanoparticle antennas that can improve water quality in daylight and also generate hydrogen as a green energy source.

This water purification technology was developed by He-Kuan Luo, Andy Hor and colleagues from the A*STAR Institute of Materials Research and Engineering (IMRE). “Any innovative and benign technology that can remove or destroy organic pollutants from water under ambient conditions is highly welcome,” explains Hor, who is executive director of the IMRE and also affiliated with the National University of Singapore.

A Dec. 17, 2014 A*STAR research highlight, which originated the news item, describes the photocatalytic process the research team developed and tested,

Photocatalytic materials harness sunlight to create electrical charges, which provide the energy needed to drive chemical reactions in molecules attached to the catalyst’s surface. In addition to decomposing harmful molecules in water, photocatalysts are used to split water into its components of oxygen and hydrogen; hydrogen can then be employed as a green energy source.

Hor and his team set out to improve an existing catalyst. Oxygen-based compounds such as strontium titanate (SrTiO3) look promising, as they are robust and stable materials and are suitable for use in water. One of the team’s innovations was to enhance its catalytic activity by adding small quantities of the metal lanthanum, which provides additional usable electrical charges.

Catalysts also need to capture a sufficient amount of sunlight to catalyze chemical reactions. So to enable the photocatalyst to harvest more light, the scientists attached gold nanoparticles to the lanthanum-doped SrTiO3 microspheres (see image). These gold nanoparticles are enriched with electrons and hence act as antennas, concentrating light to accelerate the catalytic reaction.

The porous structure of the microspheres results in a large surface area, as it provides more binding space for organic molecules to dock to. A single gram of the material has a surface area of about 100 square meters. “The large surface area plays a critical role in achieving a good photocatalytic activity,” comments Luo.

To demonstrate the efficiency of these catalysts, the researchers studied how they decomposed the dye rhodamine B in water. Within four hours of exposure to visible light 92 per cent of the dye was gone, which is much faster than conventional catalysts that lack gold nanoparticles.

These microparticles can also be used for water splitting, says Luo. The team showed that the microparticles with gold nanoparticles performed better in water-splitting experiments than those without, further highlighting the versatility and effectiveness of these microspheres.

The researchers have provided an illustration of the process,

Improved photocatalyst microparticles containing gold nanoparticles can be used to purify water. © 2014 A*STAR Institute of Materials Research and Engineering

Improved photocatalyst microparticles containing gold nanoparticles can be used to purify water.
© 2014 A*STAR Institute of Materials Research and Engineering

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

Novel Au/La-SrTiO3 microspheres: Superimposed Effect of Gold Nanoparticles and Lanthanum Doping in Photocatalysis by Guannan Wang, Pei Wang, Dr. He-Kuan Luo, and Prof. T. S. Andy Hor. Chemistry – An Asian Journal Volume 9, Issue 7, pages 1854–1859, July 2014. Article first published online: 9 MAY 2014 DOI: 10.1002/asia.201402007

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This article is behind a paywall.

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

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).