A Flexible Composite Mechanical Energy Harvester from a Ferroelectric Organoamino Phosphonium Salt

A new binary organic salt diphenyl diisopropylamino phosphonium hexaflurophosphate (DPDP?PF₆) was shown to exhibit a good ferroelectric response and employed for mechanical energy harvesting application. The phosphonium salt crystallizes in the monoclinic noncentrosymmetric space group Cc and exhibits an H‐bonded 1D chain structure due to N?H???F interactions. Ferroelectric measurements on the single crystals of DPDP?PF₆ gave a well‐saturated rectangular hysteresis loop with a remnant (P_r) polarization value of 6 μC cm^?2. Further, composite devices based on polydimethylsiloxane (PDMS) films for various weight percentages (3, 5, 7, 10 and 20 wt %) of DPDP?PF₆ were prepared and examined for power generation by using an impact test setup. A maximum output peak‐to‐peak voltage (V_PP) of 8.5 V and an output peak‐to‐peak current (I_PP) of 0.5 μA was obtained for the non‐poled composite film with 10 wt % of DPDP?PF₆. These results show the efficacy of organic ferroelectric substances as potential micropower generators.     

Ferroelectric Polymer Nanotubes with Large Dielectric Constants for Potential All‐Organic Electronic Devices

To fabricate ferroelectric ultrathin polymer films with large dielectric constants for potential all‐organic electronic devices, ferroelectric polymer nanotubes and a composite of the nanotubes with a dispersed organic semiconductor have been fabricated by template‐assisted methods. The ferroelectricity drops markedly in spin‐coated ultrathin films less than 100 nm thick, whereas P(VDF‐TrFE) nanotubes with a wall thickness of a few ten nm sustain ferroelectricity. The composite nanotubes exhibit a giant dielectric constant as a result of significantly enhanced interface polarization between the nanosized fillers and the polymer matrix. They could be of practical use in supercapacitors, optoelectronic devices, and sensors.

     

Efficient Piezoelectric Energy Harvesting from a Discrete Hybrid Bismuth Bromide Ferroelectric Templated by Phosphonium Cation

Bismuth containing hybrid molecular ferroelectrics are receiving tremendous attention in recent years owing to their stable and non-toxic composition. However, these perovskite-like structures are primarily limited to ammonium cations. Herein, we report a new phosphonium based discrete perovskite-like hybrid ferroelectric with a formula [Me(Ph)₃P]₃[Bi₂Br₉] ( MTPBB ) and its mechanical energy harvesting capability. The Polarization-Electric field (P-E) measurements resulted in a well-defined ferroelectric hysteresis loop with a remnant polarization value of 2.1 μC cm⁻². Piezoresponse force microscopy experiments enabled visualization of the ferroelectric domain structure and evaluation of the piezoelectric strain coefficient (d₃₃) for an MTPBB single crystal and thin film sample. Furthermore, flexible devices incorporating MTPBB in polydimethylsiloxane (PDMS) matrix at various concentrations were fabricated and explored for their mechanical energy harvesting properties. The champion device with 20 wt % of MTPBB in PDMS rendered a maximum peak-to-peak open-circuit voltage of 22.9 V and a maximum power density of 7 μW cm⁻² at an optimal load of 4 MΩ. Moreover, the potential of MTPBB -based devices in low power electronics was demonstrated by storing the harvested energy in various electrolytic capacitors.     

A Multifunctional 3D Chiral Porous Ferroelectric Metal–Organic Framework for Sensing Small Organic Molecules and Dye Uptake

A flexible aromatic multicarboxylate ligand and Cd^II ions assemble into a chiral multihelical porous metal–organic framework with second‐order nonlinear optical and ferroelectric properties. The obtained guest‐free form highly selectively senses small organic molecules and adsorbs large dye molecules.     

Electrostrictive polymers for mechanical energy harvesting

This article reviews the developments in electrostrictive polymers for energy harvesting. Electrostrictive polymers are a variety of electroactive polymers that deform due to the electrostatic and polarization interaction between two electrodes with opposite electric charge. Electrostrictive polymers have been the subject of much interest and research over the past decade. In earlier years, much of the focus was placed on actuator configurations, and in more recent years, the focus has turned to investigating material properties that may enhance electromechanical activities. Since the last 5 years and with the development of low‐power electronics, the possibility of using these materials for energy harvesting has been investigated. This review outlines the operating principle in energy scavenging mode and conversion mechanisms behind this generator technology, highlights some of its advantages over existing actuator technologies, identifies some of the challenges associated with its development, and examines the main focus of research within this field, including some of the potential applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Ag Nanoparticle-Incorporated Natural Rubber for Mechanical Energy Harvesting Application

The energy conversion performance of the triboelectric nanogenerator (TENG) is a function of triboelectric charges which depend on the intrinsic properties of materials to hold charges or the dielectric properties of triboelectric materials. In this work, Ag nanoparticles were synthesized and used to incorporate into natural rubber (NR) in order to enhance the dielectric constant for enhancing the electrical output of TENG. It was found that the size of Ag nanoparticles was reduced with the increasing CTAB concentration. Furthermore, the CTAB surfactant helped the dispersion of metallic Ag nanoparticles in the NR-insulating matrix, which promoted interfacial polarization that affected the dielectric properties of the NR composite. Ag nanoparticle-incorporated NR films exhibited an improved dielectric constant of up to almost 40% and an enhanced TENG performance that generated the highest power density of 262.4 mW/m².     

Piezoelectric Energy Harvesting from a Ferroelectric Hybrid Salt [Ph3MeP]4[Ni(NCS)6] Embedded in a Polymer Matrix

Organic–inorganic hybrid ferroelectrics are an exciting class of molecular materials with promising applications in the area of energy and electronics. The synthesis, ferroelectric and piezoelectric energy harvesting behavior of a 3d metal ion‐containing A₄BX₆ type organic–inorganic hybrid salt [Ph₃MeP]₄[Ni(NCS)₆] ( 1 ) is now presented. P‐E hysteresis loop studies on 1 show a remnant ferroelectric polarization value of 18.71 μC cm^?2, at room temperature. Composite thermoplastic polyurethane (TPU) devices with 5, 10, 15 and 20 wt % compositions of 1 were prepared and employed for piezoelectric energy harvesting studies. A maximum output voltage of 19.29 V and a calculated power density value of 2.51 mW cm^?3 were observed for the 15 wt % 1 ‐TPU device. The capacitor charging experiments on the 15 wt % 1 ‐TPU composite device shows an excellent energy storage performance with the highest stored energies and measured charges of 198.8 μJ and 600 μC, respectively.     

Metal–Organic Frameworks as a Versatile Tool To Study and Model Energy Transfer Processes

Development of materials with efficient and directional energy transfer (ET) could significantly modify the existing energy and material landscape. Metal–organic frameworks (MOFs) are a unique tool to address the upcoming challenges related to the enhancement of ET efficiency and directional energy transport. To harness MOFs as a versatile platform, mechanistic and structural aspects governing ET efficiency should be elucidated. In this context, we review ET mechanisms and structural motifs based on the recent advances achieved in MOF chemistry and also highlight the possible practical applications that are enabled by these studies.     

A Molecular Ferroelectric Showing Room‐Temperature Record‐Fast Switching of Spontaneous Polarization

Fast switching of spontaneous polarization (P_s) is one of the most essential requirements for ferroelectrics used in the field of data storage. However, in contrast to inorganic counterparts, the low operating frequency (<500 Hz) for molecular ferroelectrics severely hinders their large‐scale applications. Herein, for the first time, we achieved the room‐temperature fastest switching of the P_s in a new molecular ferroelectric, N‐methylmorpholinium trinitrophenolate ( 1 ), which displays notable ferroelectricity (P_s=3.2 μc cm^?2). Strikingly, electric polarizations of 1 have been switched under a record‐high frequency of 263 kHz, and this performance remains stable without any obvious fatigue after ca. 2×10⁵ switching cycles. To our knowledge, 1 is the first organic ferroelectric to switch polarization at such a high operating frequency, exceeding the majority of organic ferroelectrics, which opens up new possibilities for its potential in the field of non‐volatile memory.     

Organic Supercapacitors as the Next Generation Energy Storage Device: Emergence,Opportunity, and Challenges

Harnessing new materials for developing high-energy storage devices set off research in the field of organic supercapacitors. Various attractive properties like high energy density, lower device weight, excellent cycling stability, and impressive pseudocapacitive nature make organic supercapacitors suitable candidates for high-end storage device applications. This review highlights the overall progress and future of organic supercapacitors. Sustainable energy production and storage depend on low cost, large supercapacitor packs with high energy density. Organic supercapacitors with high pseudocapacitance, lightweight form factor, and higher device potential are alternatives to other energy storage devices. There are many recent ongoing research works that focus on organic electrolytes along with the material aspect of organic supercapacitors. This review summarizes the current research status and the chemistry behind the storage mechanism in organic supercapacitors to overcome the challenges and achieve superior performance for future opportunities.     

Efficient Solar‐Driven Water Harvesting from Arid Air with Metal–Organic Frameworks Modified by Hygroscopic Salt

Freshwater scarcity is a global challenge threatening human survival, especially for people living in arid regions. Sorption‐based atmospheric water harvesting (AWH) is an appealing way to solve this problem. However, the state‐of‐the‐art AWH technologies have poor water harvesting performance in arid climates owing to the low water sorption capacity of common sorbents under low humidity conditions. We report a high‐performance composite sorbent for efficient water harvesting from arid air by confining hygroscopic salt in a metal–organic framework matrix (LiCl@MIL‐101(Cr)). The composite sorbent shows 0.77 g g^?1 water sorption capacity at 1.2 kPa vapor pressure (30 % relative humidity at 30 °C) by integrating the multi‐step sorption processes of salt chemisorption, deliquescence, and solution absorption. A highly efficient AWH prototype is demonstrated with LiCl@MIL‐101(Cr) that can enable the harvesting of 0.45–0.7 kg water per kilogram of material under laboratory and outdoor ambient conditions powered by natural sunlight without optical concentration and additional energy input.     

有机/无机杂化材料担载季铵盐催化剂的制备及其在相转移催化反应中的应用

利用溶胶-凝胶(S0l-gel)技术制备了新型的有机／无机杂化材料担载的季铵盐催化剂。优化了制备方法、反应条件等多种因素；考察了其作为相转移催化剂在1-溴代正庚烷与碘化钾的亲核取代反应中的应用，转化率最高可达到95％。     

Chlorocholine Perchlorate is an Organic Ferroelectric with Two-Step Ladder-like Dielectric,Second Harmonic Generation Effects,and Ferroelectricity

The organic salt chlorocholine perchlorate [ClCH₂CH₂N(CH₃)₃⋅ClO₄] ( CCP ) is found to be a molecular ferroelectric with a high theoretical spontaneous polarization (Ps) value up to 17.09 μC cm⁻². CCP exhibits two successive order-disorder phase transition at 332 and 365 K with space groups changing from Cc to Cmc2₁ and then P6₃/mmc, accompanied by unusual two-step ladder-like dielectric, SHG signal with obvious “on/off” contrasts. These findingings provides a further instance of exploring successive thermal-stimuli multi-responsive switching materials applied as switches and sensors.     

Phosphorescence Energy Transfer: Ambient Afterglow Fluorescence from Water-Processable and Purely Organic Dyes via Delayed Sensitization

Ambient afterglow luminescence from metal-free organic chromophores would provide a promising alternative to the well-explored inorganic phosphors. However, the realization of air-stable and solution-processable organic afterglow systems with long-lived triplet or singlet states remains a formidable challenge. In the present study, a delayed sensitization of the singlet state of organic dyes via phosphorescence energy transfer from organic phosphors is proposed as an alternative strategy to realize “afterglow fluorescence”. This concept is demonstrated with a long-lived phosphor as the energy donor and commercially available fluorescent dyes as the energy acceptor. Triplet-to-singlet Förster-resonance energy-transfer (TS-FRET) between donor and acceptor chromophores, which are co-organized in an amorphous polymer matrix, results in tuneable yellow and red afterglow from the fluorescent acceptors. Moreover, these afterglow fluorescent hybrids are highly solution-processable and show excellent air-stability with good quantum yields.     

An Environmentally Friendly and Flexible Aqueous Zinc Battery Using an Organic Cathode

Rechargeable batteries have been used to power various electric devices and store energy from renewables, but their toxic components (namely, electrode materials, electrolyte, and separator) generally cause serious environment issues when disused. Such toxicity characteristic makes them difficult to power future wearable electronic devices. Now an environmentally friendly and highly safe rechargeable battery, based on a pyrene‐4,5,9,10‐tetraone (PTO) cathode and zinc anode in mild aqueous electrolyte is presented. The PTO‐cathode shows a high specific capacity (336 mAh g^?1) for Zn²⁺ storage with fast kinetics and high reversibility. Thus, the PTO//Zn full cell exhibits a high energy density (186.7 Wh kg^?1), supercapacitor‐like power behavior and long‐term lifespan (over 1000 cycles). Moreover, a belt‐shaped PTO//Zn battery with robust mechanical durability and remarkable flexibility is first fabricated to clarify its potential application in wearable electronic devices.     

Lasing from an Organic Micro-Helix

Organic solid-state semiconductor lasers are attracting ever-increasing interest for their potential application in future photonic circuits. Despite the great progress made in recent years, an organic laser from 3D chiral structures has not been achieved. Now, the first example of an organic nano-laser from the micro-helix structure of an achiral molecule is presented. Highly regular micro-helixes with left/right-handed helicity from a distyrylbenzene derivative (HM-DSB) were fabricated and characterized under microscope spectrometers. These chiral micro-helixes exhibit unique photonic properties, including helicity-dependent circularly polarized luminescence (CPL), periodic optical waveguiding, and length-dependent amplified spontaneous emission (ASE) behavior. The successful observation of laser behavior from the organic micro-helix extends our understanding to morphology chirality of organic photonic materials and provides a new design strategy towards chiral photonic circuits.     

Emerging Light-Harvesting Materials Based on Organic Photovoltaic D/A Heterojunctions for Efficient Photocatalytic Water Splitting

Photocatalytic water splitting to hydrogen is a highly promising method to meet the surging energy consumption globally through the environmentally friendly means. As the initial step before photocatalysis, harvesting photons from sunlight is crucially important, thus making the design of photosensitizers with visible even near-infrared (NIR) absorptions get more and more attentions. In the past three years, organic donor/acceptor (D/A) heterojunctions with absorptions extending to 950 nm, have emerged as the new star light-harvesting materials for photocatalytic water splitting, demonstrating exciting advantages over inorganic materials in solar light utilization, hydrogen yielding rate, etc. This Minireview firstly gives a brief discussion about the principle processes and determining factors for photocatalytic water splitting with organic photovoltaic D/A heterojunction as photosensitizers. Thereafter, the current progress is summarized in details by introducing typical and excellent D/A heterojunction-based photocatalytic systems. Finally, not only the great prospects but also the most challenging issues confronted by organic D/A heterojunctions are indicated along with a perspective on the opportunities and new directions for future material explorations.