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1. Implementation of ferroelectric materials in photocatalytic and photoelectrochemical water splitting

   https://doi.org/10.1039/d0nh00219d  

   Li, Yi ; Li, Jun ; Yang, Weiguang ; Wang, Xudong ( July 2020 , Nanoscale Horizons)

   null (Ed.)

   As a promising technology for sustainable hydrogen generation, photocatalytic (PC) and photoelectrochemical (PEC) water splitting have gathered immense attention over a half-century. While many review articles have covered extensive research achievements and technology innovations in water splitting, this article focuses on illustrating how the ferroelectric polarization influences charge separation and transportation in photocatalyst heterostructures during PC and PEC water splitting. This article first discusses the fundamentals of PC and PEC water splitting and how these electrochemical processes interact with the ferroelectric polarization-induced interfacial band bending, known as piezotronics. A few representative ferroelectric material-based heterogeneous photocatalyst systems are then discussed in detail to illustrate the effects of polarization, space charge region, and free charge concentration, which are critical factors determining the ferroelectric influences. Finally, a forward looking statement is provided to point out the research challenges and opportunities in this promising interdisciplinary research field between ferroelectrics and electrochemistry for clean energy applications. 

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2. Intrinsic Polymer Dielectrics for High Energy Density and Low Loss Electric Energy Storage

   Wei, Junji ; Zhu, Lei ( July 2020 , Progress in polymer science)

   High energy density, high temperature, and low loss polymer dielectrics are highly desirable for electric energy storage, e.g., film capacitors in the power electronics of electric vehicles and high-speed trains. Fundamentally, high polarization and low dielectric loss are two conflicting physical properties, because more polarization processes will involve more loss mechanisms. As such, we can only achieve a delicate balance between high dielectric constant and reasonably low loss. This review focuses on achieving low dielectric loss while trying to enhance dielectric constants for dielectric polymers, which can be divided into two categories: extrinsic and intrinsic. For extrinsic dielectric systems, the working mechanisms include dipolar (e.g., nanodielectrics) and space charge (e.g., ion gels) interfacial polarizations. These polarizations do not increase the intrinsic dielectric constants, but cause decreased breakdown strength and increased dielectric loss for polymers. For intrinsic dielectric polymers, the dielectric constant originates from electronic, atomic (or vibrational), and orientational polarizations, which are intrinsic to the polymers themselves. Because of the nature of molecular bonding for organic polymers, the dielectric constant from electronic and atomic polarizations is limited to 2-5 for hydrocarbon-based insulators (i.e., band gap > 4 eV). It is possible to use orientational polarization to enhance intrinsic dielectric constant while keeping reasonably low loss. However, nonlinear ferroelectric switching in ferroelectric polymers must be avoided. Meanwhile, paraelectric polymers often exhibit high electronic conduction due to large chain motion in the paraelectric phase. In this sense, dipolar glass polymers are more attractive for low loss dielectrics, because frozen chain dynamics enables deep traps to prevent electronic conduction. Both side-chain and main-chain dipolar glass polymers are promising candidates. Furthermore, it is possible to combine intrinsic and extrinsic dielectric properties synergistically in multilayer films to enhance breakdown strength and further reduce dielectric loss for high dielectric constant polar polymers. At last, future research directions are briefly discussed for the ultimate realization of next generation polymer film capacitors. 

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3. Piezotronic modulations in electro- and photochemical catalysis

   https://doi.org/10.1557/mrs.2018.264  

   Wang, Xudong ; Rohrer, Gregory S. ; Li, Hexing ( December 2018 , MRS Bulletin)

   Electrochemical catalyst design and optimization primarily relies on understanding and facilitating interfacial charge transfer. Recently, piezotronics have emerged as a promising method for tuning the interfacial energetics. The unique band-engineering capability using piezoelectric or ferroelectric polarization could lead to performance gains for electrochemical catalysis beyond what can be achieved by chemical or structural optimization. This article addresses the fundamentals of surface polarization and corresponding band modulation at solid–liquid interfaces. The most recent advances in piezotronic modulations are discussed from multiple perspectives of catalysis, including photocatalytic, photoelectrochemical, and electrochemical processes, particularly for energy-related applications. The concept of piezocatalysis, a direct conversion of mechanical energy to chemical energy, is introduced with an example of mechanically driven water splitting. While still in the early stages, piezotronics is envisioned to become a powerful tool for revolutionizing electrochemical catalysis. 

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4. Simultaneous Enhancement of Charge Separation and Hole Transportation in a TiO 2 –SrTiO 3 Core–Shell Nanowire Photoelectrochemical System

   https://doi.org/10.1002/adma.201701432  

   Wu, Fei ; Yu, Yanhao ; Yang, Huang ; German, Lazarus N. ; Li, Zhenquan ; Chen, Jianguo ; Yang, Weiguang ; Huang, Lu ; Shi, Weimin ; Wang, Linjun ; et al ( May 2017 , Advanced Materials)

   Efficient charge separation and transportation are key factors that determine the photoelectrochemical (PEC) water‐splitting efficiency. Here, a simultaneous enhancement of charge separation and hole transportation on the basis of ferroelectric polarization in TiO₂–SrTiO₃core–shell nanowires (NWs) is reported. The SrTiO₃shell with controllable thicknesses generates a considerable spontaneous polarization, which effectively tunes the electrical band bending of TiO₂. Combined with its intrinsically high charge mobility, the ferroelectric SrTiO₃thin shell significantly improves the charge‐separation efficiency (η_separation) with minimized influence on the hole‐migration property of TiO₂photoelectrodes, leading to a drastically increased photocurrent density (J_ph). Specifically, the 10 nm‐thick SrTiO₃shell yields the highestJ_phand η_separationof 1.43 mA cm⁻²and 87.7% at 1.23 V versus reversible hydrogen electrode, respectively, corresponding to 83% and 79% improvements compared with those of pristine TiO₂NWs. The PEC performance can be further manipulated by thermal treatment, and the control of SrTiO₃film thicknesses and electric poling directions. This work suggests a material with combined ferroelectric and semiconducting features could be a promising solution for advancing PEC systems by concurrently promoting the charge‐separation and hole‐transportation properties.

    

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5. Enhanced Piezoelectric, Ferroelectric, and Electrostrictive Properties of Lead‐Free (1‐ x )BCZT‐( x )BCST Electroceramics with Energy Harvesting Capability

   https://doi.org/10.1002/smll.202300549  

   Baraskar, Bharat G. ; Kolekar, Yesappa D. ; Thombare, Balu. R. ; James, Ajit. R. ; Kambale, Rahul C. ; Ramana, C. V. ( May 2023 , Small)

   Next‐generation electronics and energy technologies can now be developed as a result of the design, discovery, and development of novel, environmental friendly lead (Pb)‐free ferroelectric materials with improved characteristics and performance. However, there have only been a few reports of such complex materials’ design with multi‐phase interfacial chemistry, which can facilitate enhanced properties and performance. In this context, herein, novel lead‐free piezoelectric materials (1‐x)Ba_0.95Ca_0.05Ti_0.95Zr_0.05O₃‐(x)Ba_0.95Ca_0.05Ti_0.95Sn_0.05O₃, are reported, which are represented as (1‐x)BCZT‐(x)BCST, with demonstrated excellent properties and energy harvesting performance. The (1‐x)BCZT‐(x)BCST materials are synthesized by high‐temperature solid‐state ceramic reaction method by varyingxin the full range (x= 0.00–1.00). In‐depth exploration research is performed on the structural, dielectric, ferroelectric, and electro‐mechanical properties of (1‐x)BCZT‐(x)BCST ceramics. The formation of perovskite structure for all ceramics without the presence of any impurity phases is confirmed by X‐ray diffraction (XRD) analyses, which also reveals that the Ca²⁺, Zr⁴⁺, and Sn⁴⁺are well dispersed within the BaTiO₃lattice. For all (1‐x)BCZT‐(x)BCST ceramics, thorough investigation of phase formation and phase‐stability using XRD, Rietveld refinement, Raman spectroscopy, high‐resolution transmission electron microscopy (HRTEM), and temperature‐dependent dielectric measurements provide conclusive evidence for the coexistence of orthorhombic + tetragonal (Amm2+P4mm) phases at room temperature. The steady transition ofAmm2crystal symmetry toP4mmcrystal symmetry with increasingxcontent is also demonstrated by Rietveld refinement data and related analyses. The phase transition temperatures, rhombohedral‐orthorhombic (T_R‐O), orthorhombic‐ tetragonal (T_O‐T), and tetragonal‐cubic (T_C), gradually shift toward lower temperature with increasingxcontent. For (1‐x)BCZT‐(x)BCST ceramics, significantly improved dielectric and ferroelectric properties are observed, including relatively high dielectric constantε_r≈ 1900–3300 (near room temperature),ε_r≈ 8800–12 900 (near Curie temperature), dielectric loss, tanδ≈ 0.01–0.02, remanent polarizationP_r≈ 9.4–14 µC cm⁻², coercive electric fieldE_c≈ 2.5–3.6 kV cm⁻¹. Further, high electric field‐induced strainS≈ 0.12–0.175%, piezoelectric charge coefficientd₃₃≈ 296–360 pC N⁻¹, converse piezoelectric coefficient ≈ 240–340 pm V⁻¹, planar electromechanical coupling coefficientk_p≈ 0.34–0.45, and electrostrictive coefficient (Q₃₃)_avg≈ 0.026–0.038 m⁴C⁻²are attained. Output performance with respect to mechanical energy demonstrates that the (0.6)BCZT‐(0.4)BCST composition (x= 0.4) displays better efficiency for generating electrical energy and, thus, the synthesized lead‐free piezoelectric (1‐x)BCZT‐(x)BCST samples are suitable for energy harvesting applications. The results and analyses point to the outcome that the (1‐x)BCZT‐(x)BCST ceramics as a potentially strong contender within the family of Pb‐free piezoelectric materials for future electronics and energy harvesting device technologies.

    

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