Splitting Water Inexpensively
September 12, 2014
Since the 
product of 
hydrogen combustion is just 
water, it should make an excellent 
motor vehicle fuel.  Hydrogen has an 
energy density for combustion of 142 
kJ/
gram, which is quite a bit more than that for 
gasoline, 46.9 kJ/gram.  One reason why hydrogen-fueled vehicles have not 
caught fire (wrong choice of words!) is that there are many problems with a "
hydrogen economy."  The first problem is 
production of hydrogen.  Sure, you can make hydrogen simply by the 
electrolysis of water, but that 
electricity needs to be 
generated, somehow.
If electricity for such electrolysis was generated by a 
coal-fired power plant, that would be 
environmentally unacceptable.  However, 
photovoltaics could be used, and the direct use of 
sunlight for 
water-splitting, 
photolysis, permits the direct production of hydrogen using 
solar energy.  I wrote about photolysis in several previous articles (
Titania Photocatalysis, February 16, 2011, 
Manganese Photolysis of Water, June 1, 2011, and 
Water Photolysis by Antimony-Doped Gallium Nitride, September 1, 2011).
Once you have the hydrogen, further problems arise.  You need to 
store the hydrogen as it's produced, either by 
gas compression, 
liquefaction, or 
chemically, move it to where vehicles will fuel, and store it in those vehicles.  
Metal hydrides are one proposed method of chemical storage, but 
metals are heavy.  However, as I told one of my 
professors many years ago, if it wasn't for little problems like this, we 
scientists would be out of a job.
The problems of the hydrogen economy notwithstanding, research on more 
efficient methods of photolysis proceeds apace.  Recently, an international team of scientists from 
Stanford University (Stanford, California), 
Oak Ridge National Laboratory (Oak Ridge, Tennessee) the 
National Taiwan University of Science and Technology (Taipei, Taiwan), 
Canadian Light Source Inc. (Saskatoon, Saskatchewan, Canada), and the 
University of Tennessee (Knoxville, Tennessee), have advanced the state of the electrolysis art by 
inventing non-
precious metal electrodes that are suitable for 
low voltage water-splitting.[1-3]
The key to an efficient electrolysis cell is a good electrode 
material.  The best electrode for electrolysis is 
platinum, since it will produce hydrogen at a low voltage.  Platinum, however, is too expensive, so other 
electrocatalyst materials must be used, often with disappointing results.  The new electrode material of the present work is a 
nanoscale nickel oxide/
nickel heterostructure formed on the sidewalls of 
carbon nanotubes.  The nanotubes are grown on 
iron.  This electrode was found to function nearly as well as platinum.[1]
The electrolysis cell will operate at 1.5 volts at a 
current density of about 20 
mA/
cm2, which means that a 
laboratory beaker cell will operate from an 
AAA alkaline battery, which can deliver that voltage at a few hundred mA.[1-2]  The electrode material is robust, since the interaction of nickel metal 
ions with the carbon nanotubes impede 
reduction of the nickel.[1]  Says 
Hongjie Dai, a professor of 
chemistry at Stanford and an 
author of the study,
"Using nickel and iron, which are cheap materials, we were able to make the electrocatalysts active enough to split water at room temperature with a single 1.5-volt battery... This is the first time anyone has used non-precious metal catalysts to split water at a voltage that low. It's quite remarkable, because normally you need expensive metals, like platinum or iridium, to achieve that voltage... When we found out that a nickel-based catalyst is as effective as platinum, it came as a complete surprise."[2]
This electrode was discovered by 
Ming Gong, a 
graduate student at Stanford.  As often happens in science, the precise 
mechanism for its excellent electrolysis properties is not yet known.  Says Dai, "...we still don't fully understand the science behind it."[2]  The low operating voltage is important, since it reduces the amount of 
power needed to effect the water-splitting.  This translates to billions of 
dollars in savings in a full hydrogen economy and a huge 
environmental benefit.[2]
The material still needs to be optimized to enhance its durability.[2]  Says Dai, ""The current device would probably run for days, but weeks or months would be preferable. That goal is achievable based on my most recent results."[2]  In addition to its use in electrolysis, this electrode material might also be used in the production of 
chlorine gas and 
sodium hydroxide.[2]
Funding for this 
research was through the 
Global Climate and Energy Project, the 
Precourt Institute for Energy at Stanford, and the 
U.S. Department of Energy.[2]  Although there have been great advances in battery 
technology for 
electric vehicles, the hydrogen economy might still come to pass.  
Toyota and 
Honda expect to sell hydrogen fuel cell cars in the US in 2015, and 
Hyundai is already 
leasing fuel cell vehicles in 
Southern California.[2]
Dai and his team have previously worked on nickel-coated 
silicon for photolysis of water.  They found that a 2 
nanometer layer of nickel on silicon would split water with no degradation in a solution of water and 
potassium borate, albeit with an applied 
bias voltage.[4-6]
References:
-   Ming Gong, Wu Zhou, Mon-Che Tsai, Jigang Zhou, Mingyun Guan, Meng-Chang Lin, Bo Zhang, Yongfeng Hu, Di-Yan Wang, Jiang Yang, Stephen J. Pennycook, Bing-Joe Hwang, and Hongjie Dai, "Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis," Nature Communications, vol. 5, article no. 4695, August 22, 2014, doi:10.1038/ncomms5695.
 -   Mark Shwartz, "Stanford scientists develop water splitter that runs on ordinary AAA battery," Stanford Report, August 22, 2014.
 -   Mark Shwartz, "Stanford scientists develop low-cost water splitter," Stanford University/Precourt Institute for Energy YouTube video, August 19, 2014.  Available, also, at the Stanford University Web Site.
 -   Michael J. Kenney, Ming Gong, Yanguang Li, Justin Z. Wu, Ju Feng, Mario Lanza, and Hongjie Dai, "High-Performance Silicon Photoanodes Passivated with Ultrathin Nickel Films for Water Oxidation," Science, vol. 342, no. 6160 (November 15, 2013), pp. 836-840.
 -   John A. Turner, "Perspective - A Nickel Finish Protects Silicon Photoanodes for Water Splitting," Science, vol. 342, no. 6160 (November 15, 2013), pp. 811-812.
 -   Mark Shwartz, "Stanford scientists create a low-cost, long-lasting water splitter made of silicon and nickel," Stanford Report, November 14, 2013.