Engineered Composite Interfacial Electric Field Boosts Piezocatalysis of Perovskite Ferroelectrics.

Reducing the level of annihilation of electrons and holes is considered to be a feasible strategy to promote piezocatalytic activities. But this strategy is only achieved through cumbersome sample preparation technologies, hindering its practical applications. Herein, we introduce a simple and efficient technique, the conventional solid-state method, to engineer a composite interfacial electric field to solve this problem, and validate it in a composite piezocatalysis composed of potassium sodium niobate ((K, Na)NbO3, KNN) and multiwalled carbon nanotubes (MWCNTs). The KNN-1CNT sample, a piezocatalyst doped with 1 wt % MWCNTs, shows a degradation rate (k) of 127 × 10-3 min-1 for Rhodamine B (RhB) dye and a hydrogen peroxide (H2O2) production rate of 36 µmol/h, about 27 times more than a reported ferroelectric composite piezocatalyst. The excellent piezocatalytic activities are attributed to the good crystallinity, slightly increased oxygen vacancies, and especially the optimal composite interface electric field. Therefore, our proposed method provides a paradigm for obtaining large-scale perovskite piezocatalysts with high piezocatalytic activities.

Thermally activated growth of ternary oxyhydroxides on perovskites for efficient water oxidation.

Perovskite oxides are promising catalysts for water oxidation. Herein, we constructed a Sr3CoFeWO9 triple perovskite with Co, Fe, and W atoms sharing octahedral positions. Thermally activated growth of an amorphous FeCoW oxyhydroxide layer on this perovskite pre-catalyst greatly enhanced the oxygen evolution reaction (OER) activities, reducing overpotential at 10 mA cm-2geo by 115 mV. This highlights the benefits of compositional design and structural reconstruction for efficient electrocatalytic materials.

Enhanced Temperature Stability of Pyroelectric Sensing in Multilayer Potassium Sodium Niobate-Based Ceramics with Graded Polarization Rotation.

Pyroelectric effect which refers to electrical responses induced by time temperature-dependent fluctuations has received extensive attention, showing promising application prospects for infrared (IR) technology. Although enhanced pyroelectric performances are obtained in potassium sodium niobate-based ceramics at room temperature via multi-symmetries coexistence design, the poor pyroelectric temperature stability is still an urging desire that needs to be resolved. Herin, by constructing multilayer composite ceramics and adjusting the proportion of stacked layers, improved pyroelectric coefficient, and figures of merit (FOMs), as well as enhanced temperature stabilities can be achieved. With a remained high pyroelectric coefficient of 5.45 × 10-4 C m-2°C-1 at room temperature, the pyroelectric parameters almost keep unchanged in the temperature range of 30-100 °C, showing great properties advantages compared with previous reports. The excellent properties can be attributed to the graded polarization rotation states among each lamination induced by successive phase transitions. The novel strategy for achieving stable pyroelectric sensing can further promote the application in the IR sensors field.

Facilitating Formate Selectivity via Optimizing eg* Band Broadening in NiMn Hydroxides for Ethylene Glycol Electro-Oxidation.

Ethylene glycol electro-oxidation reaction (EGOR) on nickel-based hydroxides (Ni(OH)2) represents a promising strategy for generating value-added chemicals, i.e. formate and glycolate, and coupling water-electrolytic hydrogen production. The high product selectivity was one of the most significant area of polyols electro-oxidation process. Yet, developing Ni(OH)2-based EGOR electrocatalyst with highly selective product remains a challenge due to the unclear cognition about the EGOR mechanism. Herein, Mn-doped Ni(OH)2 catalysts were utilized to investigate the EGOR mechanism. Experimental and calculation results reveal that the electronic states of eg* band play an important role in the catalytic performance and the product selectivity for EGOR. Broadening the eg* band could effectively enhance the adsorption capacity of glyoxal intermediates. On the other hand, this enhanced adsorption could lead to reduced side reactions associated with glycolate formation, simultaneously promoting the cleavage of C-C bonds. Consequently, the selectivity for formate was notably augmented by these enhancements. This work offers new insights into the regulation of catalyst electronic states for improving polyol electrocatalytic activity and product selectivity.

Promoting Surface Reconstruction in Spinel Oxides via Tetrahedral-Octahedral Phase Boundary Construction for Efficient Oxygen Evolution.

Understanding the origin of surface reconstruction is crucial for developing highly efficient lattice oxygen oxidation mechanism (LOM) based spinel oxides. Traditionally, the reconstruction has been achieved through electrochemical procedures, such as cyclic voltammetry (CV), linear sweep voltammetry (LSV). In this work, we found that the surface reconstruction in LOM-based CoFe0.25Al1.75O4 catalyst was an irreversible oxygen redox chemical reaction. And a lower oxygen vacancy formation energy (EO-V) could benefit the combination of the activated lattice oxygen atoms with adsorbed water molecular. Motivated by this finding, a strategy of phase boundary construction from Co tetrahedral to octahedral was employed to decrease EO-V in CoFe0.25Al1.75O4. The results showed that as the Co octahedral occupancy ratio rose to 64%, a 3.5 nm-thick reconstructed layer formed on the catalyst surface with a 158 mV decrease in overpotential. Further experiments indicated that the coexistence of tetrahedral-octahedral (O-T) phase would result in lattice mismatch, promoting non-bonding oxygen states and lowering EO-V. Then more active lattice oxygen combined with H2O molecules to generate hydroxide ions (OH-), followed by soluble cation leaching, which enhanced the reconstruction process. This work provided new insights into the relationship between the intrinsic structure of pre-catalysts and surface reconstruction in LOM-based spinel electrocatalysts.

Flexible, Wearable Wireless-Charging Power System Incorporating Piezo-Ultrasonic Arrays and MXene-Based Solid-State Supercapacitors.

With the continuous development of wearable electronics, higher requirements are put forward for flexible, detachable, stable output, and long service life power modules. Given the limited capacity of energy storage devices, the integration of energy capture and storage is a viable approach. Here, we present a flexible, wearable, wireless-charging power system that integrates a piezoelectric ultrasonic array harvester (PUAH) with MXene-based solid-state supercapacitors (MSSSs) in a soft wristband format for sustainable applications. The MSSS as the energy storage module is developed by using Ti3C2Tx nanosheet-loaded inserted finger-like carbon cloth skeletons as electrodes and poly(vinyl alcohol)/H3PO4 gel as electrolytes, with high energy density (58.74 Wh kg-1) and long cycle life (99.37%, 10,000 cycles). A two-dimensional stretchable piezoelectric array as a wireless-charging module hybridizes high-performance 1-3 composite units with serpentine electrodes, which allows wireless power via ultrasonic waves, with a maximum power density of 1.56 W cm-2 and an output voltage of 20.75 V. The overall PUAH-MSSS wireless energy supply system is 2 mm thick and offers excellent energy conversion/storage performance, cyclic stability, and mechanical flexibility. The results of this project will lay the foundation for the development of next-generation wearable electronics.

Flexible, biodegradable ultrasonic wireless electrotherapy device based on highly self-aligned piezoelectric biofilms.

Biodegradable piezoelectric devices hold great promise in on-demand transient bioelectronics. Existing piezoelectric biomaterials, however, remain obstacles to the development of such devices due to difficulties in large-scale crystal orientation alignment and weak piezoelectricity. Here, we present a strategy for the synthesis of optimally orientated, self-aligned piezoelectric γ-glycine/polyvinyl alcohol (γ-glycine/PVA) films via an ultrasound-assisted process, guided by density functional theory. The first-principles calculations reveal that the negative piezoelectric effect of γ-glycine originates from the stretching and compression of glycine molecules induced by hydrogen bonding interactions. The synthetic γ-glycine/PVA films exhibit a piezoelectricity of 10.4 picocoulombs per newton and an ultrahigh piezoelectric voltage coefficient of 324 × 10-3 volt meters per newton. The biofilms are further developed into flexible, bioresorbable, wireless piezo-ultrasound electrotherapy devices, which are demonstrated to shorten wound healing by ~40% and self-degrade in preclinical wound models. These encouraging results offer reliable approaches for engineering piezoelectric biofilms and developing transient bioelectronics.

Lead-free dual-frequency ultrasound implants for wireless, biphasic deep brain stimulation.

Ultrasound-driven bioelectronics could offer a wireless scheme with sustainable power supply; however, current ultrasound implantable systems present critical challenges in biocompatibility and harvesting performance related to lead/lead-free piezoelectric materials and devices. Here, we report a lead-free dual-frequency ultrasound implants for wireless, biphasic deep brain stimulation, which integrates two developed lead-free sandwich porous 1-3-type piezoelectric composite elements with enhanced harvesting performance in a flexible printed circuit board. The implant is ultrasonically powered through a portable external dual-frequency transducer and generates programmable biphasic stimulus pulses in clinically relevant frequencies. Furthermore, we demonstrate ultrasound-driven implants for long-term biosafety therapy in deep brain stimulation through an epileptic rodent model. With biocompatibility and improved electrical performance, the lead-free materials and devices presented here could provide a promising platform for developing implantable ultrasonic electronics in the future.

Unveiling the Pivotal Role of dx2-y2 Electronic States in Nickel-Based Hydroxide Electrocatalysts for Methanol Oxidation.

The anodic methanol oxidation reaction (MOR) plays a crucial role in coupling with the cathodic hydrogen evolution reaction (HER) and enables the sustainable production of the high-valued formate. Nickel-based hydroxide (Ni(OH)2) as MOR electrocatalyst has attracted enormous attention. However, the key factor determining the intrinsic catalytic activity remains unknown, which significantly hinders the further development of Ni(OH)2 electrocatalyst. Here, we found that the d x 2 - y 2 ${{d}_{{x}^{2}-{y}^{2}}}$ electronic state within antibonding bands plays a decisive role in the whole MOR process. The onset potential depends on the deprotonation ability (Ni2+ to Ni3+), which was closely related to the band center of d x 2 - y 2 ${{d}_{{x}^{2}-{y}^{2}}}$ orbital. The closer of d x 2 - y 2 ${{d}_{{x}^{2}-{y}^{2}}}$ orbital to the Fermi level showed the stronger the deprotonation ability. Meanwhile, in the high potential region, the broadening of d x 2 - y 2 ${{d}_{{x}^{2}-{y}^{2}}}$ orbital would facilitate the electron transfer from methanol to catalysts (Ni3+ to Ni2+), further enhancing the catalytic properties. Our work for the first time clarifies the intrinsic relationship between d x 2 - y 2 ${{d}_{{x}^{2}-{y}^{2}}}$ electronic state and the MOR activities, which adds a new layer of understanding to the methanol electrooxidation research scene.

Realization of the Giant Pyroelectric Response via Modulated Polar Structures.

Among pyroelectric materials, Bi0.5Na0.5TiO3 (BNT)-based relaxors are particularly noteworthy due to their significant polarization fluctuation near the depolarization temperature (Td), resulting in a large pyroelectric response. What has been overlooked is the dynamic behavior of inherent polar structures, particularly the temperature-dependent evolution of polar nanoregions (PNRs), which significantly impacts the pyroelectric behavior. Herein, based on the large pyroelectric response origination (the ferroelectric-relaxor phase transition), the mixed nonergodic and ergodic relaxor (NR+ER) critical state is constructed, which is believed to trigger the easily fluctuating polarization state with excellent pyroelectric response. Composition engineering (with Li+, Sr2+, and Ta5+) strategically controls the relaxor process and modulates the dynamic behavior of inherent polar structures by the random field effect. The pyroelectric coefficient of more than 1441 µCm-2K-1 at room temperature (RT), more than 9221 µCm-2K-1 (RT), and ≈107911 µCm-2K-1 (Td) are achieved in the Li+-doped sample, the Sr2+-doped sample, and the (Li++Ta5+) co-doped sample, respectively. This work earns the highest RT pyroelectric coefficient in BNT-based relaxors, which is suitable for pyroelectric applications. Furthermore, it provides a strategy for modulating the pyroelectric performance of BNT-based relaxors.