Solar-driven Hydrogen Economy

Hydrogen as a fuel source, rather than hydrocarbons like oil and coal, offers many benefits. Burning hydrogen produces harmless water with the potential to eliminate carbon dioxide emissions and their environmental burden. In pursuit of technologies that could lead to a breakthrough in achieving a hydrogen economy, a key issue is making hydrogen cheaply. Using catalysts to split water is the ideal way to generate hydrogen, but doing so usually requires an energy input from other chemicals, electricity, or a portion of sunlight which has high enough energy.

Now researchers at Osaka University have developed a new catalytic system for efficiently splitting water and making hydrogen with energy from normal sunlight. Their study was recently reported in Angewandte Chemie International Edition.

It has not been possible to use visible light for photocatalysis, but our approach of combining nanostructured black phosphorus for water reduction to hydrogen and bismuth vanadate for water oxidation to oxygen lets us make use of a wide range of the solar spectrum to make hydrogen and oxygen with unprecedented efficiency,” lead author Mingshan Zhu says.

Black phosphorus has a flat, two-dimensional structure similar to that of graphene and strongly absorbs light across the whole of the visible spectrum. The researchers combined the black phosphorus with bismuth vanadate, which is a well-known water oxidation catalyst.

In the same way that plants shuttle electrons between different structures in natural photosynthesis to split water and make oxygen, the two components of this new catalyst could rapidly transfer electrons excited by sunlight. The amounts of the two components was also optimized in the catalyst, leading to production of hydrogen and oxygen gases in an ideal 2:1 ratio.


Nano-based Material Is 60 Times More Efficient To Produce Hydrogen

Global climate change and the energy crisis mean that alternatives to fossil fuels are urgently needed. Among the cleanest low-carbon fuels is hydrogen, which can react with oxygen to release energy, emitting nothing more harmful than water (H2O) as the product. However, most hydrogen on earth is already locked into H2O (or other molecules), and cannot be used for power.

Hydrogen can be generated by splitting H2O, but this uses more energy than the produced hydrogen can give back. Water splitting is often driven by solar power, so-called “solar-to-hydrogenconversion. Materials like titanium oxide, known as semiconductors with the wide band-gap, are traditionally used to convert sunlight to chemical energy for the photocatalytic reaction. However, these materials are inefficient because only the ultraviolet (UV) part of light is absorbed—the rest spectrum of sunlight is wasted.

Now, a team in Osaka University has developed a material to harvest a broader spectrum of sunlight. The three-part composites of this material maximize both absorbing light and its efficiency for water splitting. The core is a traditional semiconductor, lanthanum titanium oxide (LTO). The LTO surface is partly coated with tiny specks of gold, known as nanoparticles. Finally, the gold-covered LTO is mixed with ultrathin sheets of the element black phosphorus (BP), which acts as a light absorber.

BP is a wonderful material for solar applications, because we can tune the frequency of light just by varying its thickness, from ultrathin to bulk,” the team leader Tetsuro Majima says. “This allows our new material to absorb visible and even near infrared light, which we could never achieve with LTO alone.”

By absorbing this broad sweep of energy, BP is stimulated to release electrons, which are then conducted to the gold nanoparticles coating the LTO. Gold nanoparticles also absorb visible light, causing some of its own electrons to be jolted out. The free electrons in both BP and gold nanoparticles are then transferred into the LTO semiconductor, where they act as an electric current for water splitting.

Hydrogen production using this material is enhanced not only by the broader spectrum of light absorption, but by the more efficient electron conduction, caused by the unique interface between two dimensional materials of BP and LTO. As a result, the material is 60 times more active than pure LTO.


Super-Efficient Production Of Hydrogen From Solar Energy

Hydrogen is an alternative source of energy that can be produced from renewable sources of sunlight and water. A group of Japanese researchers has developed a photocatalyst that increases hydrogen production tenfold.

When light is applied to photocatalysts, electrons and holes are produced on the surface of the catalyst, and hydrogen is obtained when these electrons reduce the hydrogen ions in water. However, in traditional photocatalysts the holes that are produced at the same time as the electrons mostly recombine on the surface of the catalyst and disappear, making it difficult to increase conversion efficiency.

Professor Tachikawa’s research group from the Kobe University developed a photocatalyst made of mesocrystal, deliberately creating a lack of uniformity in size and arrangement of the crystals. This new photocatalyst is able to spatially separate the electrons and electron holes to prevent them recombining. As a result, it has a far more efficient conversion rate for producing hydrogen than conventional nanoparticulate photocatalysts (approximately 7%).

The team developed a new method called “Topotactic Epitaxial Growth” that uses the nanometer-sized spaces in mesocrystals.
Using these findings, the research group plans to apply mesocrystal technology to realizing the super-efficient production of hydrogen from solar energy. The perovskite metal oxides, including strontium titanate, the target of this study, are the fundamental materials of electronic elements, so their results could be applied to a wide range of fields.

The discovery was made by a joint research team led by Associate Professor Tachikawa Takashi (Molecular Photoscience Research Center, Kobe University) and Professor Majima Tetsuro (Institute of Scientific and Industrial Research, Osaka University). Their findings were published  in the online version of Angewandte Chemie International Edition.


Japan Bets On Hydrogen As A Green Energy Source

Hydrogen gas is a promising alternative energy source to overcome our reliance on carbon-based fuels, and has the benefit of producing only water when it is reacted with oxygen. However, hydrogen is highly reactive and flammable, so it requires careful handling and storage. Typical hydrogen storage materials are limited by factors like water sensitivity, risk of explosion, difficulty of control of hydrogen-generation.

alstom-hydrogen-electric-train Hydrogen gas can be produced efficiently from organosilanes, some of which are suitably air-stable, non-toxic, and cheap. Catalysts that can efficiently produce hydrogen from organosilanes are therefore desired with the ultimate goal of realizing safe, inexpensive hydrogen production in high yield. Ideally, the catalyst should also operate at room temperature under aerobic conditions without the need for additional energy input. A research team led by Kiyotomi Kaneda and Takato Mitsudome at Osaka University have now developed a catalyst that realizes efficient environmentally friendly hydrogen production from organosilanes. The catalyst is composed of gold nanoparticles with a diameter of around 2 nm supported on hydroxyapatite.

The team then added the nanoparticle catalyst to solutions of different organosilanes to measure its ability to induce hydrogen production. The nanoparticle catalyst displayed the highest turnover frequency and number attained to date for hydrogen production catalysts from organosilanes. For example, the  converted 99% of dimethylphenylsilane to the corresponding silanol in just 9 min at room temperature, releasing an equimolar amount of hydrogen gas at the same time. Importantly, the catalyst was recyclable without loss of activity. On/off switching of hydrogen production was achieved using the nanoparticle catalyst because it could be easily separated from its organosilane substrate by filtration. The activity of the catalyst increased as the nanoparticle size decreased.

A prototype portable hydrogen fuel cell containing the nanoparticle catalyst and an organosilane substrate was fabricated. The fuel cell generated power in air at room temperature and could be switched on and off as desired.

Generation of hydrogen from inexpensive organosilane substrates under ambient conditions without additional energy input represents an exciting advance towards the goal of using hydrogen as a green energy source.