Typical catalysts for the electrolysis of water at low pH are based on precious metals (Pt for the cathode and IrO2 or RuO2 for the anode). However, these metals are rare and expensive, and hence lower cost and more abundant catalysts are needed if electrolytically produced hydrogen is to become more widely available. Herein, we show that electrode-film formation from aqueous solutions of first row transition metal ions at pH 1.6 can be induced under the action of an appropriate cell bias and that in the case of cobalt voltages across the cell in excess of 2 V lead to the formation of a pair of catalysts that show functional stability for oxygen evolution and proton reduction for over 24 h. We show that these films are metastable and that if the circuit is opened, they redissolve into the electrolyte bath with concomitant O2 and H2 evolution, such that the overall Faradaic efficiency for charge into the system versus amounts of gases obtained approaches unity for both O2 and H2. This work highlights the ability of first row transition metals to mediate heterogeneous electrolytic water splitting in acidic media by exploiting, rather than trying to avoid, the natural propensity of the catalysts to dissolve at the low pHs used. This in turn we hope will encourage others to examine the promise of metastable electrocatalysts based on abundant elements for a range of reactions for which they have traditionally been overlooked on account of their perceived instability under the prevailing conditions.
A rapid, clean, and continuous hydrothermal route to the synthesis of ca. 14 nm indium oxide (In(2)O(3)) nanoparticles using a superheated water flow at 400 °C and 24.1 MPa as a crystallizing medium and reagent is described. Powder X-ray diffraction (XRD) of the particles revealed that they were highly crystalline despite their very short time under hydrothermal flow conditions. Gas sensing substrates were prepared from an In(2)O(3) suspension via drop-coating, and their gas sensing properties were tested for response to butane, ethanol, CO, ammonia, and NO(2) gases. The sensors showed excellent selectivity toward ethanol, giving a response of 18-20 ppm.
The electrolysis of water is considered a promising route to the production of hydrogen from renewable energy sources. Electrolysers based on proton exchange membranes (PEMs) have a number of advantages including high current density, high product gas purity and the ability to operate at high pressure. Despite these advantages the high cost of such devices is an impediment to their widespread deployment. A principal factor in this cost are the materials and machining of flow plates for distribution of the liquid reagents and gaseous products in the electrochemical cell. We demonstrate the production and operation of a PEM electrolyser constructed from silver coated 3D printed components fabricated from polypropylene. This approach allows construction of light weight, low cost electrolysers and the rapid prototyping of flow field design. Furthermore we provide data on the operation of this electrolyser wherein we show that performance is excellent for a first generation device in terms of overall efficiency, internal resistances and current-voltage response. This development opens the door to the fabrication of light weight and cheap electrolysers as well as related electrochemical devices such as flow batteries and fuel cells. Broader contextUptake of renewable energy generation, especially wind and solar power is increasing at a dramatic rate and has the potential to contribute greatly to mankind's management of climate change due to accumulation of CO 2 . Matching supply and demand of these intermittent renewable energy sources is challenging and solutions offered oen depend on the conversion of excess electrical power to chemical or potential energy for storage until required. Hydrogen is a potential storage medium in this regard and the use of polymer electrolyte membrane (PEM) electrolysers holds great promise for the generation of hydrogen from renewable sources. Successful realisation of this goal requires product development of all parts of the PEM electrolyser from the "active" components e.g. the catalysts, to the "passive" components, namely the structural parts of the electrolyser stack. 3D printing is an emerging technology which can be used in the fabrication of many different device types. Here we present the use of 3D printing to prepare components of an electrolyser cell and demonstrate its operation. This application of 3D printing enables rapid prototyping, cost reduction and a dramatic reduction in component weight. All of which may accelerate the development of new electrolyser technologies.
Solar-to-hydrogen photoelectrochemical cells (PECs) have been proposed as a means of converting sunlight into H2 fuel. However, in traditional PECs, the oxygen evolution reaction and the hydrogen evolution reaction are coupled, and so the rate of both of these is limited by the photocurrents that can be generated from the solar flux. This in turn leads to slow rates of gas evolution that favor crossover of H2 into the O2 stream and vice versa, even through ostensibly impermeable membranes such as Nafion. Herein, we show that the use of the electron-coupled-proton buffer (ECPB) H3PMo12O40 allows solar-driven O2 evolution from water to proceed at rates of over 1 mA cm–2 on WO3 photoanodes without the need for any additional electrochemical bias. No H2 is produced in the PEC, and instead H3PMo12O40 is reduced to H5PMo12O40. If the reduced ECPB is subjected to a separate electrochemical reoxidation, then H2 is produced with full overall Faradaic efficiency.
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