Effects of palladium thin films on the hydrogen permeability of Pd-Cu alloy membranes

The hydrogen permeability of surface modified Pd$_6$$_0$ Cu$_4$$_0$ wt% (Pd$_4$$_7$$.$$_3$Cu$_5$$_2$$_.$$_7$at%) membranes have been determined for the first time. Surface modification was accomplished through the deposition of Pd thin films of three different thicknesses (95.5 ± 0.1, 797.4 ± 0.2 and 1,409.6 ± 0.2 nm) on to one side of a range of as-received Pd$_6$$_0$ Cu$_4$$_0$ wt% membrane coated with a 1,409.6 ± 0.2 nm thick Pd thin film positioned on the feed side (445 kPa of hydrogen pressure) and cycled between 50 and 450 °C achieved the highest hydrogen permeability of 1.09 x 10$^-$$^8$ mol m$^-$$^1$ s$^-$$^1$ Pa$^-$$^0$$^.$$^5$ at 450 °C during the third cycle. This is a 58% increase on the value measured for the as-received Pd$_6$$_0$ Cu$_4$$_0$ wt% under the same conditions. This improvement can be attributed to a Pd-rich Pd-Cu face centred cubic (FCC) phase forming through interdiffusion between the Pd thin film and bulk Pd-Cu membrane as a result of the test conditions used during hydrogen permeability measurements. This introduces a larger hydrogen concentration gradient across the membrane due to the relatively high hydrogen solubility of the Pd-rich Pd-Cu FCC phase resulting in the observed increase in permeability

Effects of thin film Pd deposition on the hydrogen permeability of Pd60Cu40 wt% alloy membranes

AbstractPd60Cu40 wt% (Pd47.3Cu52.7 at%) membranes were surface modified by depositing Pd thin films of three different thicknesses (~100, 800 and 1400nm) on to one side of a range of as-received Pd60Cu40 wt% cold-rolled foils via magnetron sputtering. The hydrogen permeability of the membranes was then measured and compared to the uncoated material. The Pd60Cu40 wt% membrane coated with a 1400nm thick Pd thin film positioned on the feed side (445kPa of hydrogen pressure) during hydrogen permeability measurements and cycled between 50 and 450°C achieved the highest hydrogen permeability of 1.09×10−8molm−1s−1Pa−0.5 at 450°C in the third cycle. This is a 58% increase on the value measured for the as-received Pd60Cu40 wt% membrane under the same conditions.This improvement can be attributed to a Pd-rich Pd–Cu face centred cubic (FCC) phase forming through interdiffusion between the Pd thin film and bulk Pd–Cu membrane as a result of the test conditions used during hydrogen permeability measurements. This introduces a larger hydrogen concentration gradient across the membrane due to the relatively high hydrogen solubility of the Pd-rich Pd–Cu FCC phase resulting in the observed increase in permeability.The Pd60Cu40 wt% membranes coated with a ~1400nm and ~800nm thick Pd thin film retained an almost pure Pd surface throughout cycling between 50 and 450°C with a feed and permeate hydrogen pressure of 445 and 100kPa, respectively. For the deposition technique and test conditions used throughout this work, these surface modified Pd–Cu membranes appear to stabilise the Pd thin films upon cycling across the critical temperature of 295 °;C

Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss

[EN] Conventional production of hydrogen requires large industrial plants to minimize energy losses and capital costs associated with steam reforming, water-gas shift, product separation and compression. Here we present a protonic membrane reformer (PMR) that produces high-purity hydrogen from steam methane reforming in a single-stage process with near-zero energy loss. We use a BaZrO3-based proton-conducting electrolyte deposited as a dense film on a porous Ni composite electrode with dual function as a reforming catalyst. At 800 degrees C, we achieve full methane conversion by removing 99% of the formed hydrogen, which is simultaneously compressed electrochemically up to 50 bar. A thermally balanced operation regime is achieved by coupling several thermo-chemical processes. Modelling of a small-scale (10 kg H-2 day-1) hydrogen plant reveals an overall energy efficiency of >87%. The results suggest that future declining electricity prices could make PMRs a competitive alternative for industrial-scale hydrogen plants integrating CO2 capture.This work was supported by the Research Council of Norway (grant 256264) and the Spanish Government (SEV-2016-0683 grant).Malerød-Fjeld, H.; Clark, D.; Yuste Tirados, I.; Zanón González, R.; Catalán-Martínez, D.; Beeaff, D.; Hernández Morejudo, S.... (2017). Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss. Nature Energy. 2(12):923-931. https://doi.org/10.1038/s41560-017-0029-4S923931212Morejudo, S. H. et al. Direct conversion of methane to aromatics in a catalytic co-ionic membrane reactor. Science 353, 563–566 (2016).Chu, S. & Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 488, 294–303 (2012).Logan, B. E. & Elimelech, M. Membrane-based processes for sustainable power generation using water. Nature 488, 313–319 (2012).Rostrup-Nielsen, J. R. Catalysis and large-scale conversion of natural gas. Catal. Today 21, 257–267 (1994).Voss, C. Applications of pressure swing adsorption technology. Adsorption 11, 527–529 (2005).Gallucci, F., Fernandez, E., Corengia, P. & van Sint Annaland, M. Recent advances on membranes and membrane reactors for hydrogen production. Chem. Eng. Sci. 92, 40–66 (2013).Boeltken, T., Wunsch, A., Gietzelt, T., Pfeifer, P. & Dittmeyer, R. Ultra-compact microstructured methane steam reformer with integrated Palladium membrane for on-site production of pure hydrogen: Experimental demonstration. Int. J. Hydrogen Energy 39, 18058–18068 (2014).Al-Mufachi, N. A., Rees, N. V. & Steinberger-Wilkens, R. Hydrogen selective membranes: A review of palladium-based dense metal membranes. Renew. Sustainable Energy Rev. 47, 540–551 (2015).Sengodan, S. et al. Layered oxygen-deficient double perovskite as an efficient and stable anode for direct hydrocarbon solid oxide fuel cells. Nat. Mater. 14, 205–209 (2015).Myung, J.-h, Neagu, D., Miller, D. N. & Irvine, J. T. S. Switching on electrocatalytic activity in solid oxide cells. Nature 537, 528–531 (2016).Iwahara, H., Uchida, H., Ono, K. & Ogaki, K. Proton conduction in sintered oxides based on BaCeO3. J. Electrochem. Soc. 135, 529–533 (1988).Hamakawa, S., Hibino, T. & Iwahara, H. Electrochemical methane coupling using proton conductors. J. Electrochem. Soc. 140, 459–462 (1993).Bonanos, N., Knight, K. S. & Ellis, B. Perovskite solid electrolytes: structure, transport properties and fuel cell applications. Solid State Ion. 79, 161–170 (1995).Norby, T. Solid-state protonic conductors: principles, properties, progress and prospects. Solid State Ion. 125, 1–11 (1999).Kreuer, K. D. On the development of proton conducting materials for technological applications. Solid State Ion. 97, 1–15 (1997).Kreuer, K. D. Aspects of the formation and mobility of protonic charge carriers and the stability of perovskite-type oxides. Solid State Ion. 125, 285–302 (1999).Kreuer, K. D. Proton-conducting oxides. Annu. Rev. Mater. Res. 33, 333–359 (2003).Tao, S. W. & Irvine, J. T. S. A stable, easily sintered proton-conducting oxide electrolyte for moderate-temperature fuel cells and electrolyzers. Adv. Mater. 18, 11581-1584 (2006).Wang, H., Peng, R., Wu, X., Hu, J. & Xia, C. Sintering behavior and conductivity study of yttrium-doped BaCeO3–BaZrO3 solid solutions using ZnO additives. J. Am. Ceram. Soc. 92, 2623–2629 (2009).Coors, W. G. in Advances in Ceramics—Synthesis and Characterization, Processing and Specific Applications (Ed. Sikalidis, C.) Ch. 22, 501–520 (InTech, UK, 2011) (2011).Manabe, R. et al. Surface protonics promotes catalysis. Sci. Rep. 6, 38007, (2016).Rohland, B., Eberle, K., Ströbel, R., Scholta, J. & Garche, J. Electrochemical hydrogen compressor. Electrochimica Acta 43, 3841–3846 (1998).Kochetova, N., Animitsa, I., Medvedev, D., Demin, A. & Tsiakaras, P. Recent activity in the development of proton-conducting oxides for high-temperature applications. RSC Adv. 6, 73222–73268 (2016).Yamazaki, Y. et al. Proton trapping in yttrium-doped barium zirconate. Nat. Mater. 12, 647–651 (2013).Kjølseth, C. et al. Space-charge theory applied to the grain boundary impedance of proton conducting BaZr0.9Y0.1O3-δ . Solid State Ion. 181, 268–275 (2010).Coors, W. G A stoichiometric titration method for measuring galvanic hydrogen flux in ceramic hydrogen separation membranes. J. Membr. Sci. 458, 245–253 (2014).Zeppieri, M., Villa, P. L., Verdone, N., Scarsella, M. & De Filippis, P. Kinetic of methane steam reforming reaction over nickel- and rhodium-based catalysts. Appl. Catal. A 387, 147–154 (2010).Wang, B., Zhu, J. & Lin, Z. A theoretical framework for multiphysics modeling of methane fueled solid oxide fuel cell and analysis of low steam methane reforming kinetics. Appl. Energy 176, 1–11 (2016).Overview of Electricity Production and Use in Europe (European Environment Agency, 2016).Edwards, R., Larive, J.-F., Rickeard, D. & Weindorf, W. Well-To-Wheels Analysis of Future Automotive Fuels and Powertrains in the European Context, Well-to-Tank Report Version 4.a, JEC Well-to-Wheels Analysis (Joint Research Centre, 2014).Cho, V. H., Hamilton, B. A. & Kuehn, N. J. Assessment of Hydrogen Production with CO 2 Capture Volume 1: Baseline State-of-the-Art Plants (National Energy Technology Laboratory, 2010).Schjølberg, I. et al. Small-Scale Reformers for On-Site Hydrogen Supply (International Energy Agency-Hydrogen Implementing Agreement, 2012).de Visser, E. et al. Dynamis CO2 quality recommendations. Int. J. Greenhouse Gas Control 2, 478–484 (2008).Bertucciolo, L. et al. Development of Water Electrolysis in the European Union (Fuel Cells and Hydrogen Joint Undertaking, 2014).Edwards, R. et al. Well-To-Wheels Analysis of Future Automotive Fuels and Powertrains in the European Context, Well-to-Wheels Report Version 4.a, JEC Well-to-Wheels Analysis (Joint Research Centre 2014).Huss, A., Maas, H. & Hass, H. Well-to-Wheels Analysis of Future Automotive Fuels and Powertrains in the European Context, Tank-to-Wheels Report Version 4.0, JEC Technical Reports (Joint Research Centre, 2013)

The role of hydrogen and fuel cell technology in providing security for the UK energy system

It is not yet well understood how hydrogen and fuel cell technology could perform in the UK energy system (ES) and what influence it may have in contributing towards its security. This article aims to discuss the potential of a hydrogen economy examining its ability to reduce dependency on fossil fuels sourced both domestically and internationally. A snapshot of the hydrogen economy is presented introducing the latest development in hydrogen production technologies and distribution infrastructure. It has been postulated that with the introduction of a CO2 tax, integrating carbon capture and sequestration (CCS) systems with commercial hydrogen production technologies such as steam methane reforming (SMR), coal gasification (CG) and biomass gasification could significantly reduce the levelised cost of hydrogen (LCOH) production. The role of hydrogen and fuel cell technology in coupling the building, transport and industrial sectors has been demonstrated. Decarbonisation of heat in the UK is expected to incur a large cost for transitioning the incumbent network and it is expected that government assistance will be necessary to lessen the burden on consumers. Deployment of fuel cell combined heat and power (CHP) systems and integration into the UK ES could make great strides towards improving its security