A ferroelectric crystal exhibits a stable and switchable electrical polarization that is manifested in the form of cooperative atomic displacements. A ferromagnetic crystal exhibits a stable and switchable magnetization that arises through the quantum mechanical phenomenon of exchange. There are very few 'multiferroic' materials that exhibit both of these properties, but the 'magnetoelectric' coupling of magnetic and electrical properties is a more general and widespread phenomenon. Although work in this area can be traced back to pioneering research in the 1950s and 1960s, there has been a recent resurgence of interest driven by long-term technological aspirations.

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Multiferroic and magnetoelectric materials

There is still an ongoing effort to search for sustainable, clean and highly efficient energy generation to satisfy the energy needs of modern society. Among various advanced technologies, electrocatalysis for the oxygen evolution reaction (OER) plays a key role and numerous new electrocatalysts have been developed to improve the efficiency of gas evolution. Along the way, enormous effort has been devoted to finding high-performance electrocatalysts, which has also stimulated the invention of new techniques to investigate the properties of materials or the fundamental mechanism of the OER. This accumulated knowledge not only establishes the foundation of the mechanism of the OER, but also points out the important criteria for a good electrocatalyst based on a variety of studies. Even though it may be difficult to include all cases, the aim of this review is to inspect the current progress and offer a comprehensive insight toward the OER. This review begins with examining the theoretical principles of electrode kinetics and some measurement criteria for achieving a fair evaluation among the catalysts. The second part of this review acquaints some materials for performing OER activity, in which the metal oxide materials build the basis of OER mechanism while non-oxide materials exhibit greatly promising performance toward overall water-splitting. Attention of this review is also paid to in situ approaches to electrocatalytic behavior during OER, and this information is crucial and can provide efficient strategies to design perfect electrocatalysts for OER. Finally, the OER mechanism from the perspective of both recent experimental and theoretical investigations is discussed, as well as probable strategies for improving OER performance with regards to future developments.

Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives

The magnetoelectric effect--the induction of magnetization by means of an electric field and induction of polarization by means of a magnetic field--was first presumed to exist by Pierre Curie, and subsequently attracted a great deal of interest in the 1960s and 1970s (refs 2-4). More recently, related studies on magnetic ferroelectrics have signalled a revival of interest in this phenomenon. From a technological point of view, the mutual control of electric and magnetic properties is an attractive possibility, but the number of candidate materials is limited and the effects are typically too small to be useful in applications. Here we report the discovery of ferroelectricity in a perovskite manganite, TbMnO3, where the effect of spin frustration causes sinusoidal antiferromagnetic ordering. The modulated magnetic structure is accompanied by a magnetoelastically induced lattice modulation, and with the emergence of a spontaneous polarization. In the magnetic ferroelectric TbMnO3, we found gigantic magnetoelectric and magnetocapacitance effects, which can be attributed to switching of the electric polarization induced by magnetic fields. Frustrated spin systems therefore provide a new area to search for magnetoelectric media.

Magnetic control of ferroelectric polarization

Magnetism and ferroelectricity are essential to many forms of current technology, and the quest for multiferroic materials, where these two phenomena are intimately coupled, is of great technological and fundamental importance. Ferroelectricity and magnetism tend to be mutually exclusive and interact weakly with each other when they coexist. The exciting new development is the discovery that even a weak magnetoelectric interaction can lead to spectacular cross-coupling effects when it induces electric polarization in a magnetically ordered state. Such magnetic ferroelectricity, showing an unprecedented sensitivity to ap plied magnetic fields, occurs in 'frustrated magnets' with competing interactions between spins and complex magnetic orders. We summarize key experimental findings and the current theoretical understanding of these phenomena, which have great potential for tuneable multifunctional devices.

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Multiferroics: a magnetic twist for ferroelectricity

In this chapter, we will restrict our attention to the ferrites and a few other closely related materials. The great interest in ferrites stems from their unique combination of a spontaneous magnetization and a high electrical resistivity. The observed magnetization results from the difference in the magnetizations of two non-equivalent sub-lattices of the magnetic ions in the crystal structure. Materials of this type should strictly be designated as “ferrimagnetic” and in some respects are more closely related to anti-ferromagnetic substances than they are to ferromagnetics in which the magnetization results from the parallel alignment of all the magnetic moments present. We shall not adhere to this special nomenclature except to emphasize effects, which are due to the existence of the sub-lattices.

Ferromagnetic materials

We have investigated the structural, magnetic, and electric properties of ferromagnetic ${\mathrm{BiMnO}}_{3}$ with a highly distorted perovskite structure. At ${T}_{E}=750--770\mathrm{K},$ a centrosymmetric--to--non-centrosymmetric structural transition takes place, which describes of the ferroelectricity in the system. The changes in the dielectric constant were induced by the magnetic ordering ${(T}_{M}\ensuremath{\approx}100\mathrm{K})$ as well as by the application of magnetic fields near ${T}_{M}.$ These features are attributed to the inherent coupling between the ferroelectric and ferromagnetic orders in the multiferroic system.

Magnetocapacitance effect in multiferroic BiMnO 3

The oxygen evolution reaction that occurs during water oxidation is of considerable importance as an essential energy conversion reaction for rechargeable metal-air batteries and direct solar water splitting. Cost-efficient ABO3 perovskites have been studied extensively because of their high activity for the oxygen evolution reaction; however, they lack stability, and an effective solution to this problem has not yet been demonstrated. Here we report that the Fe(4+)-based quadruple perovskite CaCu3Fe4O12 has high activity, which is comparable to or exceeding those of state-of-the-art catalysts such as Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) and the gold standard RuO2. The covalent bonding network incorporating multiple Cu(2+) and Fe(4+) transition metal ions significantly enhances the structural stability of CaCu3Fe4O12, which is key to achieving highly active long-life catalysts.

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Covalency-reinforced oxygen evolution reaction catalyst.

High-transition-temperature (high-Tc) superconductivity is ubiquitous in the cuprates containing CuO2 planes, but each cuprate has its own character. The study of the material dependence of the d-wave superconducting gap (SG) should provide important insights into the mechanism of high-Tc superconductivity. However, because of the ‘pseudogap’ phenomenon, it is often unclear whether the energy gaps observed by spectroscopic techniques really represent the SG. Here, we use scanning tunnelling spectroscopy to image nearly optimally doped Ca2−xNaxCuO2Cl2(Na-CCOC) with Tc=25–28 K. It enables us to observe the quasiparticle interference effect in this material, through which we obtain unambiguous information on the SG. Our analysis of quasiparticle interference in Na-CCOC reveals that the SG dispersion near the gap node is almost identical to that of Bi2Sr2CaCu2Oy (Bi2212) at the same doping level, despite the Tc of Bi2212 being three times higher than that of Na-CCOC. We also find that the SG in Na-CCOC is confined in narrower energy and momentum ranges than Bi2212, which explains—at least in part—the remarkable material dependence of Tc.

Quasiparticle interference and superconducting gap in Ca 2− x Na x CuO 2 Cl 2

Bifunctional electrocatalysts for oxygen evolution/reduction reaction (OER/ORR) are desirable for the development of energy conversion technologies. It is discovered that the manganese quadruple perovskites CaMn7 O12 and LaMn7 O12 show bifunctional catalysis in the OER/ORR. A possible origin of the high OER activity is the unique surface structure through corner-shared planar MnO4 and octahedral MnO6 units to promote direct OO bond formations.

Ikuya Yamada

Papers

Magnetocapacitance effect in multiferroic BiMnO 3

Covalency-reinforced oxygen evolution reaction catalyst.

Quasiparticle interference and superconducting gap in Ca 2− x Na x CuO 2 Cl 2

Bifunctional Oxygen Reaction Catalysis of Quadruple Manganese Perovskites

Giant negative thermal expansion in the iron perovskite SrCu3Fe4O12.