Exploring Pyroelectricity, Thermal and Photochemical Switching in a Hybrid Organic-Inorganic Crystal by In Situ X-Ray Diffraction.

The switching behavior of the novel hybrid material (FA)Na[Fe(CN)5(NO)].H2O (1) in response to temperature (T), light irradiation and electric field (E) is studied using in situ X-ray diffraction (XRD). Crystals of 1 display piezoelectricity, pyroelectricity, second and third harmonic generation. XRD shows that the FA+ are disordered at room-temperature, but stepwise cooling from 273-100 K induces gradual ordering, while cooling under an applied field (E=+40 kVcm-1) induces a sudden phase change at 140 K. Structural-dynamics calculations suggest the field pushes the system into a region of the structural potential-energy surface that is otherwise inaccessible, demonstrating that application of T and E offers an effective route to manipulating the crystal chemistry of these materials. Photocrystallography also reveals photoinduced linkage isomerism, which coexists with but is not correlated to other switching behaviors. These experiments highlight a new approach to in situ studies of hybrid materials, providing insight into the structure-property relationships that underpin their functionality.

Enhanced Hygrothermal Stability of In-Situ-Grown MAPbBr3 Nanocrystals in Polymer with Suppressed Desorption of Ligands.

Currently, the intrinsic instability of organic-inorganic hybrid perovskite nanocrystals (PNCs) at high temperature and high humidity still stands as a big barrier to hinder their potential applications in optoelectronic devices. Herein, we report the controllable in-situ-grown PNCs in polyvinylidene fluoride (PVDF) polymer with profoundly enhanced hygrothermal stability. It is found that the introduced tetradecylphosphonic acid (TDPA) ligand enables significantly improved binding to the surface of PNCs via a strong covalently coordinated P-O-Pb bond, as evidenced by density functional theory calculations and X-ray photoelectron spectroscopy analyses. Accordingly, such enhanced binding could not only make efficient passivation of the surface defects of PNCs but also enable the remarkably suppressed desorption of the ligand from the PNCs under high-temperature environments. Consequently, the photoluminescence quantum yield (PL QY) of the as-fabricated MAPbBr3-PNCs@PVDF film exhibits almost no decay after exposure to air at 333 K over 1800 h. Once the temperatures are increased from 293 to 353 K, their PL intensity can be kept as 88.6% of the initial value, much higher than that without the TDPA ligand (i.e., 42.4%). Moreover, their PL QY can be maintained above 50% over 1560 h (65 days) under harsh working conditions of 333 K and 90% humidity. As a proof of concept, the as-assembled white light-emitting diodes display a large color gamut of 125% National Television System Committee standard, suggesting their promising applications in backlight devices.

Recent Advances in Pyroelectric Materials and Applications.

As one important subclass of piezoelectric materials, pyroelectric materials have caused increasing attention owing to the unique pyroelectric effect induced by spontaneous polarization, showing broad promising application prospects due to various electrical responses induced by time-dependent temperature variation. This review systematically introduces the pyroelectric effect and evaluation of pyroelectric materials and follows by analyzing and concluding the novel properties corresponding to four kinds of main pyroelectric materials. The emphasis of this review focuses on several significant and practical applications of pyroelectric materials in thermal energy harvesting from the external environment, pyroelectric sensing, and imaging, even some electrochemical applications including hydrogen generation, wastewater treatment, sterilization, and disinfection. Finally, the development direction of pyroelectric materials, potential challenges and opportunities in the future are all discussed and proposed. Through systematical conclusion and analysis of the latest research progress in the recent two decades, this review may provide significant guide and inspiration in the development of pyroelectric materials.

Interface design for high energy density polymer nanocomposites.

This review provides a detailed overview on the latest developments in the design and control of the interface in polymer based composite dielectrics for energy storage applications. The methods employed for interface design in composite systems are described for a variety of filler types and morphologies, along with novel approaches employed to build hierarchical interfaces for multi-scale control of properties. Efforts to achieve a close control of interfacial properties and geometry are then described, which includes the creation of either flexible or rigid polymer interfaces, the use of liquid crystals and developing ceramic and carbon-based interfaces with tailored electrical properties. The impact of the variety of interface structures on composite polarization and energy storage capability are described, along with an overview of existing models to understand the polarization mechanisms and quantitatively assess the potential benefits of different structures for energy storage. The applications and properties of such interface-controlled materials are then explored, along with an overview of existing challenges and practical limitations. Finally, a summary and future perspectives are provided to highlight future directions of research in this growing and important area.

Harnessing Plasticity in an Amine-Borane as a Piezoelectric and Pyroelectric Flexible Film.

We demonstrate that trimethylamine borane can exhibit desirable piezoelectric and pyroelectric properties. The material was shown to be able operate as a flexible film for both thermal sensing, thermal energy conversion and mechanical sensing with high open circuit voltages (>10 V). A piezoelectric coefficient of d33 ≈10-16 pC N-1 , and pyroelectric coefficient of p≈25.8 µC m-2 K-1 were achieved after poling, with high pyroelectric figure of merits for sensing and harvesting, along with a relative permittivity of ϵ 33 σ ≈ 6.3.

Ice-templated poly(vinylidene fluoride) ferroelectrets.

Ferroelectrets are piezoelectrically-active polymer foams that can convert externally applied loads into electric charge for sensor or energy harvesting applications. Existing processing routes used to create pores of the desired geometry and degree of alignment appropriate for ferroelectrets are based on complex mechanical stretching and chemical dissolution steps. In this work, we present the first demonstration of the use of freeze casting as a cost effective and environmentally friendly approach to produce polymeric ferroelectrets. The pore morphology, phase analysis, relative permittivity and direct piezoelectric charge coefficient (d33) of porous poly(vinylidene fluoride) (PVDF) based ferroelectrets with porosity volume fractions ranging from 24% to 78% were analysed. The long-range alignment of pore channels produced during directional freezing is shown to be beneficial in forming a highly polarised structure and high d33 ∼ 264 pC N-1 after breakdown of air within the pore channels during corona poling. This new approach opens a way to create tailored pore structures and voids in ferroelectret materials for transducer applications related to sensors and vibration energy harvesting.

Carbon fibre based flexible piezoresistive composites to empower inherent sensing capabilities for soft actuators.

New materials and technologies in sensing and actuation have led to the development of soft actuators and robots for biomedical systems, assistive devices, exploration and rescue. The use of integrated actuation-sensing materials in such systems is gaining interest, but there are few examples where the body of the actuator or soft robot acts as the sensing element. The development of smart soft actuators that have inherent sensing capabilities can provide advantages of high sensitivity, ease of manufacture and cost efficiency, without impairing actuator dynamics. To achieve this goal, we have prepared soft actuators using piezoresistive composites based on a silicone matrix impregnated with short conductive carbon fibres. The optimum carbon fibre volume fraction to achieve a frequency independent conductivity and piezoresistive response was determined, with in situ mechanical and electrical testing to quantify the piezoresistive properties. The frequency dependent electrical properties and sensitivity of the composites with deformation was explained on the basis of a microstructural resistor-capacitor network model. The piezoresistive composites were used to successfully manufacture a pneumatic soft finger actuator where the resistance change of the actuator body was able to monitor deformation with applied pressure. The creation of soft actuators with an inherent sensing capability is a promising approach for control and operation of future soft robots.

Self-Powered Smart Insole for Monitoring Human Gait Signals.

With the rapid development of low-power consumption wireless sensors and wearable electronics, harvesting energy from human motion to enable self-powered sensing is becoming desirable. Herein, a pair of smart insoles integrated with piezoelectric poly(vinylidene fluoride) (PVDF) nanogenerators (NGs) are fabricated to simultaneously harvest energy from human motion and monitor human gait signals. Multi-target magnetron sputtering technology is applied to form the aluminum electrode layers on the surface of the PVDF film and the self-powered insoles are fabricated through advanced 3D seamless flat-bed knitting technology. Output responses of the NGs are measured at different motion speeds and a maximum value of 41 V is obtained, corresponding to an output power of 168.1 µW. By connecting one NG with an external circuit, the influence of external resistance, capacitor, and motion speed on the charging characteristics of the system is systematically investigated. To demonstrate the potential of the smart insoles for monitoring human gait signals, two subjects were asked to walk on a treadmill at different speeds or with a limp. The results show that one can clearly distinguish walking with a limp from regular slow, normal, and fast walking states by using multiscale entropy analysis of the stride intervals.

Using a novel rigid-fluoride polymer to control the interfacial thickness of graphene and tailor the dielectric behavior of poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) nanocomposites.

Polymer nanocomposites based on conductive fillers for high performance dielectrics have attracted increasing attention in recent years. However, a number of physical issues are unclear, such as the effect of interfacial thickness on the dielectric properties of the polymer nanocomposites, which limits the enhancement of permittivity. In this research, two core-shell structured reduced graphene oxide (rGO)@rigid-fluoro-polymer conducting fillers with different shell thicknesses are prepared using a surface-initiated reversible-addition-fragmentation chain transfer polymerization method, which are denoted as rGO@PTFMS-1 with a thin shell and rGO@PTFMS-2 with a thick shell. A rigid liquid crystalline fluoride-polymer poly{5-bis[(4-trifluoro-methoxyphenyl)oxycarbonyl]styrene} (PTFMS) is chosen for the first time to tailor the shell thicknesses of rGO via tailoring the degree of polymerization. The effect of interfacial thickness on the dielectric behavior of the P(VDF-TrFE-CTFE) nanocomposites with rGO and modified rGO is studied in detail. The results demonstrate that the percolation threshold of the nanocomposites increased from 0.68 vol% to 1.69 vol% with an increase in shell thickness. Compared to the rGO@PTFMS-1/P(VDF-TrFE-CTFE) composites, the rGO@PTFMS-2/P(VDF-TrFE-CTFE) composites exhibited a higher breakdown strength and a lower dielectric constant, which can be interpreted by interfacial polarization and the micro-capacitor model, resulting from the insulating nature of the rigid-polymer shell and the change of rGO's morphology. The findings provide an innovative approach to tailor dielectric composites, and promote a deeper understanding of the influence of interfacial region thickness on the dielectric performance.

Control of electro-chemical processes using energy harvesting materials and devices.

Energy harvesting is a topic of intense interest that aims to convert ambient forms of energy such as mechanical motion, light and heat, which are otherwise wasted, into useful energy. In many cases the energy harvester or nanogenerator converts motion, heat or light into electrical energy, which is subsequently rectified and stored within capacitors for applications such as wireless and self-powered sensors or low-power electronics. This review covers the new and emerging area that aims to directly couple energy harvesting materials and devices with electro-chemical systems. The harvesting approaches to be covered include pyroelectric, piezoelectric, triboelectric, flexoelectric, thermoelectric and photovoltaic effects. These are used to influence a variety of electro-chemical systems such as applications related to water splitting, catalysis, corrosion protection, degradation of pollutants, disinfection of bacteria and material synthesis. Comparisons are made between the range harvesting approaches and the modes of operation are described. Future directions for the development of electro-chemical harvesting systems are highlighted and the potential for new applications and hybrid approaches are discussed.

Hybrid Synthetic Receptors on MOSFET Devices for Detection of Prostate Specific Antigen in Human Plasma.

The study reports the use of extended gate field-effect transistors (FET) for the label-free and sensitive detection of prostate cancer (PCa) biomarkers in human plasma. The approach integrates for the first time hybrid synthetic receptors comprising of highly selective aptamer-lined pockets (apta-MIP) with FETs for sensitive detection of prostate specific antigen (PSA) at clinically relevant concentrations. The hybrid synthetic receptors were constructed by immobilizing an aptamer-PSA complex on gold and subjecting it to 13 cycles of dopamine electropolymerization. The polymerization resulted in the creation of highly selective polymeric cavities that retained the ability to recognize PSA post removal of the protein. The hybrid synthetic receptors were subsequently used in an extended gate FET setup for electrochemical detection of PSA. The sensor was reported to have a limit of detection of 0.1 pg/mL with a linear detection range from 0.1 pg/mL to 1 ng/mL PSA. Detection of 1-10 pg/mL PSA was also achieved in diluted human plasma. The present apta-MIP sensor developed in conjunction with FET devices demonstrates the potential for clinical application of synthetic hybrid receptors for the detection of clinically relevant biomarkers in complex samples.

Gas sensing using porous materials for automotive applications.

Improvements in the efficiency of combustion within a vehicle can lead to reductions in the emission of harmful pollutants and increased fuel efficiency. Gas sensors have a role to play in this process, since they can provide real time feedback to vehicular fuel and emissions management systems as well as reducing the discrepancy between emissions observed in factory tests and 'real world' scenarios. In this review we survey the current state-of-the-art in using porous materials for sensing the gases relevant to automotive emissions. Two broad classes of porous material - zeolites and metal-organic frameworks (MOFs) - are introduced, and their potential for gas sensing is discussed. The adsorptive, spectroscopic and electronic techniques for sensing gases using porous materials are summarised. Examples of the use of zeolites and MOFs in the sensing of water vapour, oxygen, NOx, carbon monoxide and carbon dioxide, hydrocarbons and volatile organic compounds, ammonia, hydrogen sulfide, sulfur dioxide and hydrogen are then detailed. Both types of porous material (zeolites and MOFs) reveal great promise for the fabrication of sensors for exhaust gases and vapours due to high selectivity and sensitivity. The size and shape selectivity of the zeolite and MOF materials are controlled by variation of pore dimensions, chemical composition (hydrophilicity/hydrophobicity), crystal size and orientation, thus enabling detection and differentiation between different gases and vapours.

Self-Powered Stretchable Sensor Arrays Exhibiting Magnetoelasticity for Real-Time Human-Machine Interaction.

Stretchable strain sensors are highly desirable for human motion monitoring, and can be used to build new forms of bionic robots. However, the current use of flexible strain gauges is hindered by the need for an external power supply, and the demand for long-term operation. Here, a new flexible self-powered strain sensor system based on an electromagnetic generator that possesses a high stretchability in excess of 150%, a short response time of 30 ms, and an excellent linearity (R2  > 0.98), is presented. Based on this new form of sensor, a human-machine interaction system is designed to achieve remote control of a robot hand and vehicle using a human hand, which provides a new scheme for real-time gesture interaction.

Intelligent Recognition Using Ultralight Multifunctional Nano-Layered Carbon Aerogel Sensors with Human-Like Tactile Perception.

Humans can perceive our complex world through multi-sensory fusion. Under limited visual conditions, people can sense a variety of tactile signals to identify objects accurately and rapidly. However, replicating this unique capability in robots remains a significant challenge. Here, we present a new form of ultralight multifunctional tactile nano-layered carbon aerogel sensor that provides pressure, temperature, material recognition and 3D location capabilities, which is combined with multimodal supervised learning algorithms for object recognition. The sensor exhibits human-like pressure (0.04-100 kPa) and temperature (21.5-66.2 °C) detection, millisecond response times (11 ms), a pressure sensitivity of 92.22 kPa-1 and triboelectric durability of over 6000 cycles. The devised algorithm has universality and can accommodate a range of application scenarios. The tactile system can identify common foods in a kitchen scene with 94.63% accuracy and explore the topographic and geomorphic features of a Mars scene with 100% accuracy. This sensing approach empowers robots with versatile tactile perception to advance future society toward heightened sensing, recognition and intelligence.

Nanophase-photocatalysis: loading, storing, and release of H2O2 using graphitic carbon nitride.

A blue light mediated photochemical process using solid graphitic carbon nitride (g-C3N4) in ambient air/isopropanol vapour is suggested to be linked to "nanophase" water inclusions and is shown to produce approx. 50 µmol H2O2 per gram of g-C3N4, which can be stored in the solid g-C3N4 for later release for applications, for example, in disinfection or anti-bacterial surfaces.

Understanding the Effects of Cross-Linking Density on the Self-Healing Performance of Epoxidized Natural Rubber and Natural Rubber.

The demand for self-healing elastomers is increasing due to the potential opportunities such materials offer in reducing down-time and cost through extended product lifetimes and reduction of waste. However, further understanding of self-healing mechanisms and processes is required in order to develop a wider range of commercially applicable materials with self-healing properties. Epoxidized natural rubber (ENR) is a derivative of polyisoprene. ENR25 and ENR50 are commercially available materials with 25 and 50 mol % epoxidation, respectively. Recently, reports of the use of ENR in self-healing materials have begun to emerge. However, to date, there has been limited analysis of the self-healing mechanism at the molecular level. The aim of this work is to gain understanding of the relevant self-healing mechanisms through systematic characterization and analysis of the effect of cross-linking on the self-healing performance of ENR and natural rubber (NR). In our study, cross-linking of ENR and NR with dicumyl peroxide and sulfur to provide realistic models of commercial rubber formulations is described, and a cross-linking density of 5 × 10-5 mol cm-3 in sulfur-cured ENR is demonstrated to achieve a healing efficiency of 143% for the tensile strength. This work provides the foundation for further modification of ENR, with the goal of understanding and controlling ENR's self-healing ability for future applications.

Coupling Enhancement of a Flexible BiFeO3 Film-Based Nanogenerator for Simultaneously Scavenging Light and Vibration Energies.

Coupled nanogenerators have been a research hotspot due to their ability to harvest a variety of forms of energy such as light, mechanical and thermal energy and achieve a stable direct current output. Ferroelectric films are frequently investigated for photovoltaic applications due to their unique photovoltaic properties and bandgap-independent photovoltage, while the flexoelectric effect is an electromechanical property commonly found in solid dielectrics. Here, we effectively construct a new form of coupled nanogenerator based on a flexible BiFeO3 ferroelectric film that combines both flexoelectric and photovoltaic effects to successfully harvest both light and vibration energies. This device converts an alternating current into a direct current and achieves a 6.2% charge enhancement and a 19.3% energy enhancement to achieve a multi-dimensional "1 + 1 > 2" coupling enhancement in terms of current, charge and energy. This work proposes a new approach to the coupling of multiple energy harvesting mechanisms in ferroelectric nanogenerators and provides a new strategy to enhance the transduction efficiency of flexible functional devices.

High Efficiency Water Splitting using Ultrasound Coupled to a BaTiO3 Nanofluid.

To date, a number of studies have reported the use of vibrations coupled to ferroelectric materials for water splitting. However, producing a stable particle suspension for high efficiency and long-term stability remains a challenge. Here, the first report of the production of a nanofluidic BaTiO3 suspension containing a mixture of cubic and tetragonal phases that splits water under ultrasound is provided. The BaTiO3 particle size reduces from approximately 400 nm to approximately 150 nm during the application of ultrasound and the fine-scale nature of the particulates leads to the formation of a stable nanofluid consisting of BaTiO3 particles suspended as a nanofluid. Long-term testing demonstrates repeatable H2 evolution over 4 days with a continuous 24 h period of stable catalysis. A maximum rate of H2 evolution is found to be 270 mmol h-1 g-1 for a loading of 5 mg l-1 of BaTiO3 in 10% MeOH/H2 O. This work indicates the potential of harnessing vibrations for water splitting in functional materials and is the first demonstration of exploiting a ferroelectric nanofluid for stable water splitting, which leads to the highest efficiency of piezoelectrically driven water splitting reported to date.

Commercialisation of CMOS integrated circuit technology in multi-electrode arrays for neuroscience and cell-based biosensors.

The adaptation of standard integrated circuit (IC) technology as a transducer in cell-based biosensors in drug discovery pharmacology, neural interface systems and electrophysiology requires electrodes that are electrochemically stable, biocompatible and affordable. Unfortunately, the ubiquitous Complementary Metal Oxide Semiconductor (CMOS) IC technology does not meet the first of these requirements. For devices intended only for research, modification of CMOS by post-processing using cleanroom facilities has been achieved. However, to enable adoption of CMOS as a basis for commercial biosensors, the economies of scale of CMOS fabrication must be maintained by using only low-cost post-processing techniques. This review highlights the methodologies employed in cell-based biosensor design where CMOS-based integrated circuits (ICs) form an integral part of the transducer system. Particular emphasis will be placed on the application of multi-electrode arrays for in vitro neuroscience applications. Identifying suitable IC packaging methods presents further significant challenges when considering specific applications. The various challenges and difficulties are reviewed and some potential solutions are presented.

2D Nanomaterials for Effective Energy Scavenging.

The development of a nation is deeply related to its energy consumption. 2D nanomaterials have become a spotlight for energy harvesting applications from the small-scale of low-power electronics to a large-scale for industry-level applications, such as self-powered sensor devices, environmental monitoring, and large-scale power generation. Scientists from around the world are working to utilize their engrossing properties to overcome the challenges in material selection and fabrication technologies for compact energy scavenging devices to replace batteries and traditional power sources. In this review, the variety of techniques for scavenging energies from sustainable sources such as solar, air, waste heat, and surrounding mechanical forces are discussed that exploit the fascinating properties of 2D nanomaterials. In addition, practical applications of these fabricated power generating devices and their performance as an alternative to conventional power supplies are discussed with the future pertinence to solve the energy problems in various fields and applications.