Platinum–rare earth electrodes for hydrogen evolution in alkaline water electrolysis

Abstract In the new “Hydrogen Economy” concept, water electrolysis is considered one of the most promising technologies for hydrogen production. Novel electrocatalytic materials for the hydrogen electrode are being actively investigated to improve the energy efficiency of current electrolysers. Platinum (Pt) alloys are known to possess good catalytic activities towards the hydrogen evolution reaction (HER). However, virtually nothing is known about the effects of rare earth (RE) elements on the electrocatalytic behaviour of Pt towards the HER. In this study, the hydrogen discharge is evaluated in three different Pt–RE intermetallic alloy electrodes, namely Pt–Ce, Pt–Sm and Pt–Ho, all having equiatomic composition. The electrodes are tested in 8 M KOH aqueous electrolytes at temperatures ranging from 25 °C to 85 °C. Measurements of the HER by linear scan voltammetry allow the determination of several kinetic parameters, namely the Tafel coefficients, charge-transfer coefficients, and exchange current densities. Activation energies of 46, 59, 39, and 60 kJ mol −1 are calculated for Pt, Pt–Ce, Pt–Sm and Pt–Ho electrodes, respectively. Results show that the addition of REs improves the activity of the Pt electrocatalyst. Studies are in progress to correlate the microstructure of the studied alloys with their performance towards the HER.

[1]  F. Rosalbino,et al.  Hydrogen evolution reaction on Ni-Re (RE = rare earth) crystalline alloys , 2003 .

[2]  C. Sequeira,et al.  Platinum-rare earth intermetallic alloys as anode electrocatalysts for borohydride oxidation , 2011 .

[3]  H. Schilder,et al.  Structural, Mössbauer spectroscopic and magnetochemical investigations into EuPt5, TmPt5 and TmPt3 synthesized from platinum and gaseous lanthanide , 1997 .

[4]  Gvozden S. Tasic,et al.  Raising efficiency of hydrogen generation from alkaline water electrolysis – Energy saving , 2010 .

[5]  M. Jakšić Towards the reversible electrode for hydrogen evolution in industrially important electrochemical processes , 1986 .

[6]  Xiaohong Li,et al.  A comparison of cathodes for zero gap alkaline water electrolysers for hydrogen production , 2012 .

[7]  Gvozden S. Tasic,et al.  Characterization of the Ni–Mo catalyst formed in situ during hydrogen generation from alkaline water electrolysis , 2011 .

[8]  B. Conway,et al.  Temperature dependence of electrocatalytic behaviour of some glassy transition metal alloys for cathodic hydrogen evolution in water electrolysis , 1990 .

[9]  P. Ekdunge,et al.  Electrochemical Impedance Study on the Kinetics of Hydrogen Evolution at Amorphous Metals in Alkaline Solution , 1991 .

[10]  F. Rosalbino,et al.  Electrocatalytic properties of Fe–R (R = rare earth metal) crystalline alloys as hydrogen electrodes in alkaline water electrolysis , 2005 .

[11]  S. Trasatti Hydrogen Evolution on Oxide Electrodes , 1992 .

[12]  Rui Costa Neto,et al.  Polytypism of La-Ni phases in multicomponent AB5 type hydride electrode alloys , 2002 .

[13]  F. Rosalbino,et al.  Partial phase diagrams of the Dy–Pt and Ho–Pt systems and electrocatalytic behaviour of the DyPt and HoPt phases , 2005 .

[14]  C. Sequeira,et al.  Electrocatalytic activity of simple and modified Fe–P electrodeposits for hydrogen evolution from alkaline media , 2011 .

[15]  Ø. Ulleberg Modeling of advanced alkaline electrolyzers: a system simulation approach , 2003 .

[16]  S. Trasatti Electrocatalysis of Hydrogen Evolution: Progress in Cathode Activation , 1991 .

[17]  In-Hyuk Son Study of Ce-Pt/γ-Al2O3 for the selective oxidation of CO in H2 for application to PEFCs : Effect of gases , 2006 .

[18]  B. Conway,et al.  HYDRIDE FORMATION AT NI-CONTAINING GLASSY-METAL ELECTRODES DURING THE H2 EVOLUTION REACTION IN ALKALINE SOLUTIONS , 1990 .

[19]  Stanley Bruckenstein,et al.  Electrochemical Kinetics: Theoretical and Experimental Aspects , 1967 .

[20]  Gvozden S. Tasic,et al.  A study on the Co–W activated Ni electrodes for the hydrogen production from alkaline water electrolysis – Energy saving , 2011 .

[21]  Hubert A. Gasteiger,et al.  Handbook of fuel cells : fundamentals technology and applications , 2003 .

[22]  D. Stojić,et al.  Hydrogen generation from water electrolysis—possibilities of energy saving , 2003 .

[23]  N. Potkonjak,et al.  Comparison of different electrode materials—Energy requirements in the electrolytic hydrogen evolution process , 2006 .

[24]  M. Jakšić,et al.  Novel Spillover Interrelating Reversible Electrocatalysts for Oxygen and Hydrogen Electrode Reactions , 2010 .

[25]  F. Rosalbino,et al.  Fe–Mo–R (R = rare earth metal) crystalline alloys as a cathode material for hydrogen evolution reaction in alkaline solution , 2011 .

[26]  Y. Chen,et al.  Effect of Amorphous Transformation on Electrochemical Capacities of Rare Earth–Mg Based Alloys , 2006 .

[27]  M. Jakšić Electrocatalysis of hydrogen evolution in the light of the brewer—engel theory for bonding in metals and intermetallic phases , 1984 .

[28]  César A.C. Sequeira,et al.  Electrocatalytic abilities of hydrogen storage alloy as anode electrocatalyst of alkaline fuel cell , 2005 .

[29]  R. L. Phillips,et al.  Poison Tolerant Platinum Catalysed Cathodes for Membrane Cells , 1990 .

[30]  M. Mavrikakis,et al.  Alloy catalysts designed from first principles , 2004, Nature materials.

[31]  F. Rosalbino,et al.  Characterization of Fe–Zn–R (R = rare earth metal) crystalline alloys as electrocatalysts for hydrogen evolution , 2008 .

[32]  A. Torres-Huerta,et al.  Electrochemical performance of Ni–RE (RE = rare earth) as electrode material for hydrogen evolution reaction in alkaline medium , 2011 .

[33]  F. Rosalbino,et al.  Electrocatalytic behaviour of Co–Ni–R (R = Rare earth metal) crystalline alloys as electrode materials for hydrogen evolution reaction in alkaline medium , 2008 .

[34]  O. Petrii,et al.  Electrochemistry of hydride-forming intermetallic compounds and alloys , 1996 .

[35]  M. Jakšić,et al.  Extended Brewer hypo–hyper-d-interionic bonding theory — I. Theoretical considerations and examples for its experimental confirmation , 2005 .

[36]  M. Jakšić,et al.  Spillover Phenomena and Its Striking Impacts in Electrocatalysis for Hydrogen and Oxygen Electrode Reactions , 2011 .

[37]  Richard C. Alkire,et al.  Advances in electrochemical science and engineering , 1990 .

[38]  M. Jakšić Advances in electrocatalysis for hydrogen evolution in the light of the Brewer-Engel valence-bond theory☆ , 1987 .

[39]  Xiaohong Li,et al.  Prospects for alkaline zero gap water electrolysers for hydrogen production , 2011 .

[40]  A. Yüce,et al.  The stability of NiCoZn electrocatalyst for hydrogen evolution activity in alkaline solution during long-term electrolysis , 2009 .

[41]  Gang Wu,et al.  Electrochemical preparation and characteristics of Ni–Co–LaNi5 composite coatings as electrode materials for hydrogen evolution , 2004 .

[42]  M. W. Breiter Reaction mechanisms of the H2 oxidation/evolution reaction , 2010 .