Ferroelectric materials have a variety of technological applications, as transducers, capacitors, sensors, etc. Great interest in molecular ferroelectrics has emerged because of their structural flexibility, tunability, and homochirality. However, the discoveries of molecular ferroelectrics are not abundant. The lack of chemical design is the main challenge in realizing new molecular ferroelectrics. Consequently, chemical design approaches, including the ideas of introducing quasi-spherical theory, homochirality, and H/F substitution, have been developed recently. Through these advanced methodologies, a wide range of ferroelectrics were successfully synthesized, changing the blind search into a targeted chemical design. In this Perspective, we aim to provide insight into the fundamental chemistry and physics of molecular ferroelectrics and propose the concept of "ferroelectrochemistry", concerned with the targeted design and performance optimization of molecular ferroelectrics from the chemical point of view. We start with the basic theories used in the modification of chemical structures for new molecular ferroelectrics, such as the quasi-spherical theory. After that, we focus on the fundamentals of homochirality from the perspective of chemistry and advantages of introducing a homochiral molecule within the scope of ferroelectrics. Further, we explore another design strategy, H/F substitution, as an analogue of the H/D isotope effect. The introduction of a F atom usually does not change the polar point group but may induce a minor structural disruption that enhances physical properties such as Curie temperature and spontaneous polarization. We hope our comprehensive studies on the targeted design and performance optimization strategies for molecular ferroelectrics may build up and enrich the content of ferroelectrochemistry.

Molecular Design Principles for Ferroelectrics: Ferroelectrochemistry

Hydrogen (H2) production is a latent feasibility of renewable clean energy. The industrial H2 production is obtained from reforming of natural gas, which consumes a large amount of nonrenewable energy and simultaneously produces greenhouse gas carbon dioxide. Electrochemical water splitting is a promising approach for the H2 production, which is sustainable and pollution-free. Therefore, developing efficient and economic technologies for electrochemical water splitting has been an important goal for researchers around the world. The utilization of green energy systems to reduce overall energy consumption is more important for H2 production. Harvesting and converting energy from the environment by different green energy systems for water splitting can efficiently decrease the external power consumption. A variety of green energy systems for efficient producing H2, such as two-electrode electrolysis of water, water splitting driven by photoelectrode devices, solar cells, thermoelectric devices, triboelectric nanogenerator, pyroelectric device or electrochemical water-gas shift device, have been developed recently. In this review, some notable progress made in the different green energy cells for water splitting is discussed in detail. We hoped this review can guide people to pay more attention to the development of green energy system to generate pollution-free H2 energy, which will realize the whole process of H2 production with low cost, pollution-free and energy sustainability conversion.

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Water Splitting: From Electrode to Green Energy System

As a major branch of hybrid perovskites, two-dimensional (2D) hybrid double perovskites are expected to be ideal systems for exploring novel ferroelectric properties, because they can accommodate a...

Two-Dimensional Organic-Inorganic Hybrid Rare-Earth Double Perovskite Ferroelectrics.

Plastic crystals (PCs), formed by certain types of molecules or ions with reorientational freedom, offer both exceptional mechanical plasticity and long range order, hence they are attractive for many mechano-adaptable technologies. While most classic PCs belong to simple globular molecular systems, a vast number of examples in the literature with diverse geometrical (cylindrical, bent, disk, etc.) and chemical (neutral, ionic, etc.) natures have proven their wide scope and opportunities. All the recent reviews on PCs aim to provide insights into a particular application, for instance, organic plastic crystal electrolytes or ferroelectrics. This tutorial review presents a holistic view of PCs by unifying the recent excellent progress in fundamental concepts from diverse areas as well as comparing them with liquid crystals, amphidynamic crystals, ordered crystals, etc. We cover the molecular and structural origins of the unique characteristics of PCs, such as exceptional plasticity, facile reversible switching of order-to-disorder states and associated colossal heat changes, and diffusion of ions/molecules, and their attractive applications in solid electrolytes, opto-electronics, ferroeletrics, piezoelectrics, pyroelectrics, barocalorics, magnetics, nonlinear optics, and so on. The recent progress not only demonstrates the diversity of scientific areas in which PCs are gaining attention but also the opportunities one can exploit using a crystal engineering approach, for example, the design of novel dynamic functional soft materials for future use in flexible devices or soft-robotic machines.

Harnessing molecular rotations in plastic crystals: a holistic view for crystal engineering of adaptive soft materials

This article provides a comprehensive overview of piezo‐ and ferro‐electric materials based on organic molecules and organic–inorganic hybrids for mechanical energy harvesting. Molecular (organic and organic–inorganic hybrid) piezo‐ and ferroelectric materials exhibit significant advantages over traditional materials due to their simple solution‐phase synthesis, light‐weight nature, thermal stability, mechanical flexibility, high Curie temperature, and attractive piezo‐ and ferroelectric properties. However, the design and understanding of piezo‐ and ferroelectricity in organic and organic–inorganic hybrid materials for piezoelectric energy harvesting applications is less well developed. This review describes the fundamental characterization of piezo‐ and ferroelectricity for a range of recently reported organic and organic–inorganic hybrid materials. The limits of traditional piezoelectric harvesting materials are outlined, followed by an overview of the piezo‐ and ferroelectric properties of organic and organic–inorganic hybrid materials, and their composites, for mechanical energy harvesting. An extensive description of peptide‐based and other biomolecular piezo‐ and ferroelectric materials as a biofriendly alternative to current materials is also provided. Finally, current limitations and future perspectives in this emerging area of research are highlighted. This perspective aims to guide chemists, materials scientists, and engineers in the design of practically useful organic and organic–inorganic hybrid piezo‐ and ferroelectric materials and composites for mechanical energy harvesting.

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Recent Advances in Organic and Organic–Inorganic Hybrid Materials for Piezoelectric Mechanical Energy Harvesting

Molecular ferroelectric crystals have attracted growing interest as potential alternatives to conventional lead-based ceramic ferroelectrics. We have recently discovered that a class of compounds known as plastic crystals can show multiaxial ferroelectricity, which allows ferroelectric performance even in polycrystalline forms. Here, we report new plastic/ferroelectric ionic molecular crystals that exhibit remarkably small coercive electric fields at room temperature. The easily switchable ferroelectric polarization enables low-voltage switching operations and high-frequency performance. Such ferroelectric crystals can be readily processed into bulk polycrystalline forms with desired shapes that are characterized by unprecedentedly high pyroelectric figures of merit and large piezoelectricity. These multifunctional molecular crystals represent highly attractive prospects for device elements with a diverse range of applications, which will significantly boost the development of molecular ferroelectric crystals.

Plastic/Ferroelectric Crystals with Easily Switchable Polarization: Low-Voltage Operation, Unprecedentedly High Pyroelectric Performance, and Large Piezoelectric Effect in Polycrystalline Forms

The aluminum-sodalite-type oxide, Ca8[AlO2]12(MoO4)2, shows an improper ferroelectricity below a ferroelectric phase transition temperature around 630 ​K. Here we present effects of a Ga-substitution for Al on ferroelectric properties of Ca8[AlO2]12(MoO4)2. Systematic investigations with synchrotron x-ray powder diffractions and dielectric/pyroelectric measurements have clarified that the Ga-substitution suppresses the ferroelectricity and markedly enhances a thermal hysteresis of the ferroelectric phase transition. In contrast to the case of Sr-substitution for Ca, with which the ground state results in a relaxor-like state, the polar ordering of macroscopic scale has been found to survive under the Ga-substitution. The present results shed light on intuitive designing of ferroelectricity and the phase transition properties in the aluminum-sodalite-type oxide.

Koji Maruyama

Papers

Plastic/Ferroelectric Crystals with Easily Switchable Polarization: Low-Voltage Operation, Unprecedentedly High Pyroelectric Performance, and Large Piezoelectric Effect in Polycrystalline Forms

Ga-substitution effects on the improper ferroelectric phase transition of Ca8[AlO2]12(MoO4)2