Abstract
We exploit the role of the remnant polarization to improve the electrocatalytic performance of ferroelectric perovskite. We report cost-effective, noble metal-free, ferroelectric electrocatalyst Bi0.5Na0.5TiO3 and the effect of remnant polarization on oxygen evolution reaction involved in alkaline fuel cells. The forward poling decreases the Tafel slope from 85 mv/decade to 39 mv/decade and also increases the mass activity by threefold. The effect of polarization on flat-band potential and the Schottky barrier between electrode and electrolyte contributes to enhanced electrochemical activity.
Similar content being viewed by others
References
Cook TR, Dogutan DK, Reece SY, Surendranath Y, Teets TS, Nocera DG (2010) Solar energy supply and storage for the legacy and nonlegacy worlds. Chem Rev 110(11):6474–6502
Service RF (2009) Transportation research. Hydrogen cars: fad or the future? Science (New York, NY) 324(5932):1257–1259
Lewis NS, Nocera DG (2006) Powering the planet: chemical challenges in solar energy utilization. Proc Natl Acad Sci 103(43):15729–15735
Turner JA (2004) Sustainable hydrogen production. Science 305(5686):972–974
Mallouk TE (2013) Water electrolysis: divide and conquer. Nat Chem 5(5):362–363
Gray HB (2009) Powering the planet with solar fuel. Nat Chem 1(1):7
Smith RD, Prévot MS, Fagan RD et al (2013) Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis. Science 340(6128):60–63
Kanan MW, Nocera DG (2008) In situ formation of an oxygen-evolving catalyst in neutral water containing phosphate and Co2+. Science 321(5892):1072–1075
Yeo BS, Bell AT (2011) Enhanced activity of gold-supported cobalt oxide for the electrochemical evolution of oxygen. J Am Chem Soc 133(14):5587–5593
Trasatti S (1980) Electrodes of conductive metallic oxides, vol 2. Elsevier Scientific Software, Amsterdam
Lee Y, Suntivich J, May KJ, Perry EE, Shao-Horn Y (2012) Synthesis and activities of rutile IrO2 and RuO2 nanoparticles for oxygen evolution in acid and alkaline solutions. J Phys Chem Lett 3(3):399–404
Davidson C, Kissel G, Srinivasan S (1982) Electrode kinetics of the oxygen evolution reaction at NiCo2O4 from 30% KOH.: dependence on temperature. J Electroanal Chem Interfacial Electrochem 132:129–135
Suntivich J, May KJ, Gasteiger HA, Goodenough JB, Shao-Horn Y (2011) A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 334(6061):1383–1385
Guo Y, Tong Y, Chen P et al (2015) Engineering the electronic state of a perovskite electrocatalyst for synergistically enhanced oxygen evolution reaction. Adv Mater 27(39):5989–5994
Guerrini E, Chen H, Trasatti S (2007) Oxygen evolution on aged IrO x/Ti electrodes in alkaline solutions. J Solid State Electr 11(7):939–945
Shao Z, Haile SM (2004) A high-performance cathode for the next generation of solid-oxide fuel cells. Nature 431(7005):170–173
Zhu Y, Sunarso J, Zhou W, Jiang S, Shao Z (2014) High-performance SrNb 0.1 Co 0.9− x Fe x O 3− δ perovskite cathodes for low-temperature solid oxide fuel cells. J Mater Chem A 2(37):15454–15462
Han X, Hu Y, Yang J, Cheng F, Chen J (2014) Porous perovskite CaMnO3 as an electrocatalyst for rechargeable Li–O2 batteries. Chem Commun 50(12):1497–1499
Xu JJ, Xu D, Wang ZL, Wang HG, Zhang LL, Zhang XB (2013) Synthesis of perovskite‐based porous La0. 75Sr0. 25MnO3 nanotubes as a highly efficient electrocatalyst for rechargeable lithium–oxygen batteries. Angew Chem Int Edit 52(14):3887–3890
Grimaud A, May KJ, Carlton CE et al (2013) Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution. Nat Commun 4:2439–2445
Zhou W, Sunarso J (2013) Enhancing bi-functional electrocatalytic activity of perovskite by temperature shock: a case study of LaNiO3− δ . J Phys Chem Lett 4(17):2982–2988
Zhao Y, Xu L, Mai L et al (2012) Hierarchical mesoporous perovskite La0. 5Sr0. 5CoO2. 91 nanowires with ultrahigh capacity for Li-air batteries. Proc Natl Acad Sci 109(48):19569–19574
Suntivich J, Gasteiger HA, Yabuuchi N, Nakanishi H, Goodenough JB, Shao-Horn Y (2011) Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries. Nat Chem 3(7):546–550
Matsumoto Y, Yoneyama H, Tamura H (1977) Catalytic activity for electrochemical reduction of oxygen of lanthanum nickel oxide and related oxides. J Electroanal Chem Interfacial Electrochem 79(2):319–326
Jung JI, Jeong HY, Kim MG, Nam G, Park J, Cho J (2015) Fabrication of Ba0. 5Sr0. 5Co0. 8Fe0. 2O3–δ catalysts with enhanced electrochemical performance by removing an inherent heterogeneous surface film layer. Adv Mater 27(2):266–271
Yang X, Su X, Shen M et al (2012) Enhancement of photocurrent in ferroelectric films via the incorporation of narrow bandgap nanoparticles. Adv Mater 24(9):1202–1208
Kakekhani A, Ismail-Beigi S (2016) Polarization-driven catalysis via ferroelectric oxide surfaces. Phys Chem Chem Phys 18(29):19676–19695
Cui Y, Briscoe J, Dunn S (2013) Effect of ferroelectricity on solar-light-driven photocatalytic activity of BaTiO3-x influence on the carrier separation and Stern layer formation. Chem Mater 25(21):4215–4223
Watanabe Y, Okano M, Masuda A (2001) Surface conduction on insulating BaTiO3 crystal suggesting an intrinsic surface electron layer. Phys Rev Lett 86(2):332–335
Yang W-C, Rodriguez BJ, Gruverman A, Nemanich R (2004) Polarization-dependent electron affinity of LiNbO3 surfaces. Appl Phys Lett 85:2316–2318
Sones CL, Mailis S, Brocklesby WS, Eason RW, Owen JR (2002) Differential etch rates in z-cut LiNbO3 for variable HF/HNO3 concentrations. J Mater Chem 12(2):295–298
Park S, Lee CW, Kang M-G et al (2014) A ferroelectric photocatalyst for enhancing hydrogen evolution: polarized particulate suspension. Phys Chem Chem Phys 16(22):10408–10413
Garra J, Vohs J, Bonnell D (2009) The effect of ferroelectric polarization on the interaction of water and methanol with the surface of LiNbO 3 (0001). Surf Sci 603(8):1106–1114
Kakekhani A, Ismail-Beigi S, Altman EI (2015) Ferroelectrics: A pathway to switchable surface chemistry and catalysis. Surf Sci 650:302–316
Yuan Y, Reece TJ, Sharma P et al (2011) Efficiency enhancement in organic solar cells with ferroelectric polymers. Nat Mater 10(4):296–302
Garcia V, Bibes M, Bocher L et al (2010) Ferroelectric control of spin polarization. Science 327(5969):1106–1110
Morris MR, Pendlebury SR, Hong J, Dunn S, Durrant JR (2016) Effect of internal electric fields on charge carrier dynamics in a ferroelectric material for solar energy conversion. Adv Mater 28:7123–7128
Parmar K, Negi N (2017) Tailoring structural and electrical properties of A-site non-stoichiometric Na0. 5Bi0. 5TiO3 ceramic at different sintering temperature. Adv Appl Ceram 116(1):8–18
Li M, Zhang H, Cook SN et al (2015) Dramatic influence of A-site nonstoichiometry on the electrical conductivity and conduction mechanisms in the perovskite oxide Bi0. 5Na0. 5TiO3. Chem Mater 27(2):629–634
Fancher CM, Blendell JE, Bowman KJ (2013) Poling effect on d 33 in textured Bi0. 5Na0. 5TiO3-based materials. Scr Mater 68(7):443–446
Sung Y, Kim J, Cho J et al (2010) Effects of Na nonstoichiometry in (Bi0.5Na0.5+ x) TiO3 ceramics. Appl Phys Lett 96(2):022901–022903
Suchanicz J, Roleder K, Kania A, Hańaderek J (1988) Electrostrictive strain and pyroeffect in the region of phase coexistence in Na0. 5Bi0. 5TiO3. Ferroelectrics 77(1):107–110
Kushwaha HS, Vaish R (2015) Enhanced visible light photocatalytic activity of curcumin-sensitized perovskite Bi0. 5Na0. 5TiO3 for rhodamine 6G Degradation. Int J Appl Ceram Tech 13:333–339
Singh L et al (2016) Comparative dielectric and ferroelectric characteristics of Bi0. 5Na0. 5TiO3, CaCu3Ti4O12, and 0.5 Bi0. 5Na0. 5TiO3–0.5 CaCu3Ti4O12 Electroceramics. J Electron Mater 45(6):2662–2672
Dawson JA, Chen H, Tanaka I (2015) Crystal structure, defect chemistry and oxygen ion transport of the ferroelectric perovskite, Na0.5 Bi0.5 TiO3: insights from first-principles calculations. J Mater Chem A 3(32):16574–16582
Jeong I-K, Sung YS, Song TK, Kim MH, Llobet A (2015) Structural evolution of bismuth sodium titanate induced by A-site non-stoichiometry: neutron powder diffraction studies. J Korean Phys Soc 67(9):1583–1587
Inoue Y, Sato K, Sato K (1989) Photovoltaic and photocatalytic behaviour of a ferroelectric semiconductor, lead strontium zirconate titanate, with a polarization axis perpendicular to the surface. J Chem Soc Faraday Trans 1 85(7):1765–1774
Ping Y, Goddard WA III, Galli GA (2015) Energetics and solvation effects at the photoanode/catalyst interface: ohmic contact versus Schottky barrier. J Am Chem Soc 137(16):5264–5267
Choi T, Lee S, Choi Y, Kiryukhin V, Cheong S-W (2009) Switchable ferroelectric diode and photovoltaic effect in BiFeO3. Science 324(5923):63–66
Burbure NV, Salvador PA, Rohrer GS (2010) Photochemical reactivity of titania films on BaTiO3 substrates: origin of spatial selectivity. Chem Mater 22(21):5823–5830
Acknowledgements
One of the authors (Rahul Vaish) acknowledges the support from the Indian National Science Academy (INSA) under Young Scientist Project Scheme (SP/YSP/102/2014/1065).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that there is no conflict of interest.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Kushwaha, H.S., Halder, A. & Vaish, R. Ferroelectric electrocatalysts: a new class of materials for oxygen evolution reaction with synergistic effect of ferroelectric polarization. J Mater Sci 53, 1414–1423 (2018). https://doi.org/10.1007/s10853-017-1611-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-017-1611-7