Twin Boundaries-Induced Centrosymmetric Breaking of Hollow CaTiO3 Nanocuboids for Piezocatalytic Hydrogen Evolution.

Piezocatalysis, a transformative mechanochemical energy conversion technique, has received considerable attention over the past decade for its role in processes such as hydrogen evolution from water. Despite notable progress in the field, challenges remain, particularly in the areas of limited piezocatalysis efficiency and limited availability of materials requiring a non-centrosymmetric structure. Here, a pioneering contribution is presented by elucidating the piezocatalytic properties of hollow CaTiO3 nanocuboids, a centrosymmetric material with a nominally nonpolar state. Remarkably, CaTiO3 nanocuboids exhibit an impressive hydrogen production rate of 3.44 mmol g-1 h-1 under ultrasonic vibrations, surpassing the performance of the well-established piezocatalyst BaTiO3 (2.23 mmol g-1 h-1). In contrast, commercial CaTiO3 nanoparticles do not exhibit piezocatalytic performance. The exceptional performance of hollow CaTiO3 nanocuboids is attributed to the abundance presence of twin boundaries on the {110} facet within its crystal structure, which can impart significant polarization strength to CaTiO3. Extending the investigation to other centrosymmetric materials, such as SrZrO3 and BaZrO3, the experimental results also demonstrate their commendable properties for piezocatalytic hydrogen production from water. This research underscores the significant potential of centrosymmetric materials in piezocatalysis.

Oxygen Vacancy-Enhanced Centrosymmetric Breaking of SrFeO3- x for Piezoelectric-Catalyzed Synthesis of H2O2.

Normally, only noncentrosymmetric structure of the materials can potentially be piezoelectric. Thus, it is limited in the field of piezoelectricity for the centrosymmetric structure of the material. In this work, the performance of piezoelectricity is successfully achieved from centrosymmetric SrFeO3- x by modulating oxygen vacancies, which have a surface piezoelectric potential up to 93 mV by using Kelvin-probe force microscopy (KPFM). Moreover, the piezoelectric effects of SrFeO3- x are also evaluated by piezoelectric catalytic effect and density functional theory calculations (DFT). The results show that the piezo-catalytic degradation of tetracycline reaches 96% after 75 min by ultrasonic mechanical vibration and the production of H2O2 by SrFeO3- x piezoelectric synthesis could reach 1821 µmol L-1. In addition, the DFT results indicate that the intrinsic effect of oxygen vacancies effectively promotes the adsorption and activation of O2 and H2O as well as intermediates and improves the piezoelectric catalytic activity. This work provides an effective basis for realizing the piezoelectricity of centrosymmetric materials and regulating the development of piezoelectric catalytic properties.

Piezo-catalysis in BiFeO3@In2Se3 Heterojunction for High-Efficiency Uranium Removal.

Piezo-catalysis emerges as an efficient, safe, and affordable strategy for removing hazardous substances from aquatic environments. Here, the BiFeO3@In2Se3 heterojunction demonstrates remarkable prowess as a piezo-catalyst, enabling the high-efficiency removal of uranium (U) from U(VI)-containing water. A total U(VI) removal efficiency of 94.6% can be achieved under ultrasonic vibration without any sacrificial agents. During the entire catalytic process, piezo-induced electrons, hydroxyl radicals, and superoxide radicals play important roles in U(VI) removal, while the generated H2O2 is responsive to the transformation of soluble U(VI) into insoluble (UO2)O2•2H2O and UO3. Furthermore, auxiliary illumination can accelerate the increase of free charges, enabling the piezo-catalyst to retain more charges. This leads to an improved U(VI) removal efficiency of 98.8% and a significantly increased reaction rate constant. This study offers a comprehensive analysis of the fabrication of high-efficiency piezo-catalysts in the removal or extraction of U(VI) from U(VI)-containing water.

Pioneering Piezoelectric-Driven Atomic Hydrogen for Efficient Dehalogenation of Halogenated Organic Pollutants.

The electrocatalytic hydrodehalogenation (EHDH) process mediated by atomic hydrogen (H*) is recognized as an efficient method for degrading halogenated organic pollutants (HOPs). However, a significant challenge is the excessive energy consumption resulting from the recombination of H* to H2 production in the EHDH process. In this study, a promising strategy was proposed to generate piezo-induced atomic H*, without external energy input or chemical consumption, for the degradation and dehalogenation of HOPs. Specifically, sub-5 nm Ni nanoparticles were subtly dotted on an N-doped carbon layer coating on BaTiO3 cube, and the resulted hybrid nanocomposite (Ni-NC@BTO) can effectively break C-X (X = Cl and F) bonds under ultrasonic vibration or mechanical stirring, demonstrating high piezoelectric driven dehalogenation efficiencies toward various HOPs. Mechanistic studies revealed that the dotted Ni nanoparticles can efficiently capture H* to form Ni-H* (Habs) and drive the dehalogenation process to lower the toxicity of intermediates. COMSOL simulations confirmed a "chimney effect" on the interface of Ni nanoparticle, which facilitated the accumulation of H+ and enhanced electron transfer for H* formation by improving the surface charge of the piezocatalyst and strengthening the interfacial electric field. Our work introduces an environmentally friendly dehalogenation method for HOPs using the piezoelectric process independent of the external energy input and chemical consumption.

Enhanced remediation of PFAS-metal co-contaminated soil by ceramsite supported Fe3O4-MoS2 heterojunction as a high-performance piezocatalyst.

In this study, a novel piezoremediation system was developed to remediate an actual soil co-polluted by high contents of per- and polyfluoroalkyl substances (PFAS, 5725 µg/kg soil) and heavy metals (6455 mg/kg soil). Two piezocatalysts, MoS2/ceramsite (MC) and Fe3O4-MoS2/ceramsite (FMC), were synthesized using a facile hydrothermal-coprecipitation method. These two materials were employed to treat the co-contaminated soil in soil slurry environment under sonication. FMC exhibited significantly higher piezoremediation performance than MC, wherein 91.6% of PFAS, 97.8% of Cr6+ ions and 81% of total metals (Cr, Cu, Zn and Ni) were removed from the soil after 50 min of the FMC piezoremediation process. FMC also exhibited the advantages of easy separation from the slurry phase and excellent reusability. In comparison with MC, the Fe3O4-MoS2 heterojunction in FMC can stabilize MoS2 particles on the surface of ceramsite granules, promote the separation of electron/hole pairs, accelerate charge transfer, therefore enhancing piezocatalytic performance. The electron spin resonance analysis and free radical quenching tests show that •OH was the dominant oxidative radical responsible for PFAS degradation. The count of bacteria and the bacterial community structure in the treated soil can be basically restored to the initial states after 30 days of incubation under nutrient stimulation. Overall, this study not only provides a deep insight on soil remediation process, but also offers an efficient and reliable technique for simultaneous decontamination of organic and metal pollutants in soil.

Promoting Piezocatalytic H2 O2 Production in Pure Water by Loading Metal-Organic Cage-Modified Gold Nanoparticles on Graphitic Carbon Nitride.

Piezocatalytic hydrogen peroxide (H2 O2 ) production is a green synthesis method, but the rapid complexation of charge carriers in piezocatalysts and the difficulty of adsorbing substrates limit its performance. Here, metal-organic cage-coated gold nanoparticles are anchored on graphitic carbon nitride (MOC-AuNP/g-C3 N4 ) via hydrogen bond to serve as the multifunctional sites for efficient H2 O2 production. Experiments and theoretical calculations prove that MOC-AuNP/g-C3 N4 simultaneously optimize three key parts of piezocatalytic H2 O2 production: i) the MOC component enhances substrate (O2 ) and product (H2 O2 ) adsorption via host-guest interaction and hinders the rapid decomposition of H2 O2 on MOC-AuNP/g-C3 N4 , ii) the AuNP component affords a strong interfacial electric field that significantly promotes the migration of electrons from g-C3 N4 for O2 reduction reaction (ORR), iii) holes are used for H2 O oxidation reaction (WOR) to produce O2 and H+ to further promote ORR. Thus, MOC-AuNP/g-C3 N4 can be used as an efficient piezocatalyst to generate H2 O2 at rates up to 120.21 µmol g-1 h-1 in air and pure water without using sacrificial agents. This work proposes a new strategy for efficient piezocatalytic H2 O2 synthesis by constructing multiple active sites in semiconductor catalysts via hydrogen bonding, by enhancing substrate adsorption, rapid separation of electron-hole pairs and preventing rapid decomposition of H2 O2 .

Ultrahigh Piezocatalytic Performance of Perovskite Ferroelectric Powder via Oxygen Vacancy Engineering.

Piezocatalysis has increasingly gained prominence due to its enormous potential for addressing energy shortages and environmental pollution issues. Nonetheless, the low piezocatalytic activity of state-of-the-art materials seriously inhibits the practical applications of piezocatalysis. Here, it is proposed to greatly enhance the piezocatalytic activity for a perovskite ferroelectric, i.e., Sm-doped 0.68Pb(Mg1/3 Nb2/3 )-0.32PbTiO3 (Sm-PMN-PT, a solid solution with ultrahigh piezoelectricity), by introducing oxygen vacancies (OVs). The results show that the presence of OVs promotes the production of reactive oxygen species while enhancing the adsorption and activation of organic pollutants to improve piezocatalytic performance. The OV-Sm-PMN-PT is found to possess a superior piezocatalytic degradation rate constant of 0.073 min-1 under ultrasonic vibration, which is ≈4.9 times higher than that of pristine Sm-PMN-PT. Furthermore, the OV-Sm-PMN-PT can efficiently remove RhB under 400 rpm stirring, making it a promising candidate for water purification using low-frequency mechanical energy from nature. This research sheds light on the design of piezocatalytic materials via defect engineering.

An Emerging Family of Piezocatalysts: 2D Piezoelectric Materials.

Piezocatalysis is an emerging technique that holds great promise for the conversion of ubiquitous mechanical energy into electrochemical energy through piezoelectric effect. However, mechanical energies in natural environment (such as wind energy, water flow energy, and noise) are typically tiny, scattered, and featured with low frequency and low power. Therefore, a high response to these tiny mechanical energies is critical to achieving high piezocatalytic performance. In comparison to nanoparticles or 1D piezoelectric materials, 2D piezoelectric materials possess characteristics such as high flexibility, easy deformation, large surface area, and rich active sites, showing more promise in future for practical applications. In this review, state-of-the-art research progresses on 2D piezoelectric materials and their applications in piezocatalysis are provided. First, a detailed description of 2D piezoelectric materials are offered. Then a comprehensive summary of the piezocatalysis technique is presented and examines the piezocatalysis applications of 2D piezoelectric materials in various fields, including environmental remediation, small-molecule catalysis, and biomedicine. Finally, the main challenges and prospects of 2D piezoelectric materials and their applications in piezocatalysis are discussed. It is expected that this review can fuel the practical application of 2D piezoelectric materials in piezocatalysis.

Defect Engineered Microcrystalline Cellulose for Enhanced Cocatalyst-Free Piezo-Catalytic H2 Production.

Mechanical energy driven piezocatalytic hydrogen (H2 ) production is a promising way to solve the energy crisis . But limited by the slow separation and transfer efficiency of piezoelectric charges generated on the surface of piezocatalysts , the piezocatalytic performance is still not satisfactory. Here, defect engineering is first used to optimize the piezocatalytic performance of microcrystalline cellulose (MCC). The piezocatalytic H2 production rate of MCC with the optimal defect concentration can reach up to 84.47 µmol g-1 h-1 under ultrasonic vibration without any co-catalyst, which is ≈3.74 times higher than that of the pure MCC (22.65 µmol g-1 h-1 ). The enhanced H2 production rate by piezoelectric catalysis is mainly due to the introduction of defect engineering on MCC, which disorders the symmetry of MCC crystal structure, improves the electrical conductivity of the material, and accelerates the separation and transfer efficiency of piezoelectric charges. Moreover, the piezocatalytic H2 production rate of MCC with the optimal defect concentration can still reach up to 93.61 µmol g-1 h-1 in natural seawater, showingits commendable practicability. This study presents a novel view for designing marvelous-performance biomass piezocatalysts through defect engineering, which can efficiently convert mechanical energy into chemical energy .

Bi4TaO8Cl as a New Class of Layered Perovskite Oxyhalide Materials for Piezopotential Driven Efficient Seawater Splitting.

Piezocatalytic water splitting is an emerging approach to generate "green hydrogen" that can address several drawbacks of photocatalytic and electrocatalytic approaches. However, existing piezocatalysts are few and with minimal structural flexibility for engineering properties. Moreover, the scope of utilizing unprocessed water is yet unknown and may widely differ from competing techniques due to the constantly varying nature of surface potential. Herein, we present Bi4TaO8Cl as a representative of a class of layered perovskite oxyhalide piezocatalysts with high hydrogen production efficiency and exciting tailorable features including the layer number, multiple cation-anion combination options, etc. In the absence of any cocatalyst and scavenger, an ultrahigh production rate is achievable (1.5 mmol g-1 h-1), along with simultaneous generation of value-added H2O2. The production rate using seawater is somewhat less yet appreciably superior to photocatalytic H2 production by most oxides as well as piezocatalysts and has been illustrated using a double-layer model for further development.

Combination NIPS/TIPS Synthesis of α-Fe2O3 and α/γ-Fe2O3 Doped PVDF Composite for Efficient Piezocatalytic Degradation of Rhodamine B.

Highly porous membranes based on polyvinylidene fluoride (PVDF) with the addition of nanoscale particles of non-magnetic and magnetic iron oxides were synthesized using a combined method of non-solvent induced phase separation (NIPS) and thermo-induced phase separation (TIPS) based on the technique developed by Dr. Blade. The obtained membranes were characterized using SEM, EDS, XRD, IR, diffuse reflectance spectroscopy, and fluorescent microscopy. It was shown that the membranes possessed a high fraction of electroactive phase, which increased up to a maximum of 96% with the addition of 2 wt% of α-Fe2O3 and α/γ-Fe2O3 nanoparticles. It was demonstrated that doping PVDF with nanoparticles contributed to the reduction of pore size in the membrane. All membranes exhibited piezocatalytic activity in the degradation of Rhodamine B. The degree of degradation increased from 69% when using pure PVDF membrane to 90% when using the composite membrane. The nature of the additive did not affect the piezocatalytic activity. It was determined that the main reactive species responsible for the degradation of Rhodamine B were •OH and •O2-. It was also shown that under piezocatalytic conditions, composite membranes generated a piezopotential of approximately 2.5 V.

Selective Production of CO from Organic Pollutants by Coupling Piezocatalysis and Advanced Oxidation Processes.

To date, the chemical conversion of organic pollutants into value-added chemical feedstocks rather than CO2 remains a major challenge. Herein, we successfully developed a coupled piezocatalytic and advanced oxidation processes (AOPs) system for achieving the conversion of various organic pollutants to CO. The CO product stems from the specific process in which organics are first oxidized to carbonate through peroxymonosulfate (PMS)-based AOPs, and then the as-obtained carbonate is converted into CO by piezoelectric reduction under ultrasonic (US) vibration by using a Co3 S4 /MoS2 catalyst. Experiments and DFT calculations show that the introduction of Co3 S4 not only effectively promotes the transfer and utilization of piezoelectric electrons but also realizes highly selective conversion from carbonate to CO. The Co3 S4 /MoS2 /PMS system has achieved selective generation of CO in actual complex wastewater treatment for the first time, indicating its potential practical applicability.

Mechanically Activated Solid-State Radical Polymerization and Cross-Linking via Piezocatalysis.

Piezocatalysis offers a means to transduce mechanical energy into chemical potential, harnessing physical force to drive redox reactions. Working in the solid state, we show here that piezoelectric BaTiO3 nanoparticles can transduce mechanical load into a flux of reactive radical species capable of initiating solid state free radical polymerization. Activation of a BaTiO3 powder by ball milling, striking with a hammer, or repeated compressive loading generates highly reactive hydroxyl radicals (⋅OH), which readily initiate radical chain growth and crosslinking of solid acrylamide, acrylate, methacrylate and styrenic monomers. Control experiments indicate a critical role for chemisorbed water on the BaTiO3 nanoparticle surface, which is oxidized to ⋅OH via mechanoredox catalysis. The force-induced production of radicals by compressing dry piezoelectric materials represents a promising new route to harness mechanical energy for solid state radical synthesis.

Piezocatalytic Techniques in Environmental Remediation.

As a consequence of rapid industrialization throughout the world, various environmental pollutants have begun to accumulate in water, air, and soil. This endangers the ecological environment of the earth, and environmental remediation has become an immediate priority. Among various environmental remediation techniques, piezocatalytic techniques, which uniquely take advantage of the piezoelectric effect, have attracted much attention. Piezoelectric effects allow pollutant degradation directly, while also enhancing photocatalysis by reducing the recombination of photogenerated carriers. In this Review, we provide a comprehensive summary of recent developments in piezocatalytic techniques for environmental remediation. The origin of the piezoelectric effect as well as classification of piezoelectric materials and their application in environmental remediation are systematically summarized. We also analyze the potential underlying mechanisms. Finally, urgent problems and the future development of piezocatalytic techniques are discussed.

Vibration-driven Reduction of CO2 to Acetate with 100 % Selectivity by SnS Nanobelt Piezocatalysts.

Converting CO2 into high-value C2 chemicals such as acetate with high selectivity and efficiency is a critical issue in renewable energy storage. Herein, for the first time we present a vibration-driven piezocatalysis with tin(II) monosulfide (SnS) nanobelts for conversion of CO2 to acetate with 100 % selectivity, and the highest production rate (2.21 mM h-1 ) compared with reported catalysts. Mechanism analysis reveal that the polarized charges triggered by periodic mechanical vibration promote the adsorption and activation of CO2 . The electron transfer can be facilitated due to built-in electric field, decreased band gap and work function of SnS under stress. Remarkably, reduced distance between active sites leads to charge enrichment on Sn sites, promoting the C-C coupling, reducing the energy barriers of the rate determining step. It puts forward a bran-new strategy for converting CO2 into high-value C2 products with efficient, low-cost and environment-friendly piezocatalysis utilizing mechanical energy.

Synergetic Piezo-Photocatalytic Hydrogen Evolution on Cdx Zn1-x S Solid-Solution 1D Nanorods.

Conversion of solar and mechanical vibration energies for catalytic water splitting into H2 has gained substantial attention recently. However, the sluggish charge separation and inefficient energy utilization in photocatalytic and piezocatalytic processes severely restrict the catalytic activity. In this paper, efficient piezo-photocatalytic H2 evolution from water splitting is realized via simultaneously converting solar and vibration energy over one-dimensional (1D) nanorod-structured Cdx Zn1-x S (x = 0, 0.2, 0.4, 0.6, 0.8, 1) solid solutions. Under combined visible light and ultrasound irradiation, Cd0.4 Zn0.6 S 1D nanorods deliver a prominently synergetic piezo-photocatalytic H2 yield rate of 4.45 mmol g-1  h-1 , far exceeding that under sole ultrasound or illumination. The consumedly promoted catalytic activity of Cd0.4 Zn0.6 S is attributed to strengthened charge separation by piezo-potential as disclosed by light-assisted scanning Kelvin probe force microscopy (SKPFM), increased strain sensitivity, and desirable optimization between piezoelectricity and visible-light response due to the formation of 1D configuration and solid solution. Metal and metal oxide depositions disclose that reduction and oxidation reactions separately occur at the tips and lateral edges of the Cd0.4 Zn0.6 S nanorods, in which the spatially separated reactive sites also contribute to super catalytic activity. This work is expected to inspire a new design strategy of coupled catalysis reactions for efficient renewable fuel production.

Mechanically Induced Highly Efficient Hydrogen Evolution from Water over Piezoelectric SnSe nanosheets.

Piezoelectric nanomaterials open new avenues in driving green catalysis processes (e.g., H2 evolution from water) through harvesting mechanical energy, but their catalytic efficiency is still limited. The predicted enormous piezoelectricity for 2D SnSe, together with its high charge mobility and excellent flexibility, renders it an ideal candidate for stimulating piezocatalysis redox reactions. In this work, few-layer piezoelectric SnSe nanosheets (NSs) are utilized for mechanically induced H2 evolution from water. The finite elemental method simulation demonstrates an unprecedent maximal piezoelectric potential of 44.1 V for a single SnSe NS under a pressure of 100 MPa. A record-breaking piezocurrent density of 0.3 mA cm-2 is obtained for SnSe NSs-based electrode under ultrasonic excitation (100 W, 45 kHz), which is about three orders of magnitude greater than that of reported piezocatalysts. Moreover, an exceptional H2 production rate of 948.4 µmol g-1 h-1 is achieved over the SnSe NSs without any cocatalyst, far exceeding most of the reported piezocatalysts and competitive with the current photocatalysis technology. The findings not only enrich the potential piezocatalysis materials, but also provide useful guidance toward high-efficiency mechanically driven chemical reactions such as H2 evolution from water.

Piezocatalytic and Photocatalytic Hydrogen Peroxide Evolution of Sulfide Solid Solution Nano-Branches from Pure Water and Air.

Hydrogen peroxide (H2 O2 ) as a useful chemical has a wide range of applications, and the development of efficient semiconducting materials for H2 O2 production is deemed as a promising strategy to realize the energy conversion. In this paper, Cdx Zn1-x S (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1) nano-branches are fabricated and the piezocatalytic and photocatalytic H2 O2 evolution performance are studied. Under ultrasound condition, the H2 O2 yield of as-synthesized solid solutions is all higher than those of pristine ZnS and CdS, and optimal evolution rate achieves 21.9 µmol g-1 h-1 for Cd0.5 Zn0.5 S without any sacrificial agent, while it is increased to 151.6 µmol g-1 h-1 under visible light irradiation. The piezo/photoelectrochemical tests, piezoresponse force microscopy (PFM), and computational simulation reveal that the nano-branch structure benefits the mechanical energy conversion more, favoring the H2 O2 evolution for Cd0.5 Zn0.5 S, and a higher concentration of charge carriers is generated in photocatalysis. The active radical trapping and in situ electron spin resonance (ESR) experiments demonstrate that both of the H2 O2 generation pathways are originated from oxygen reduction by the sequential two-step single-electron reaction. This work opens a door for promoting the H2 O2 production from nanostructure and solid solution design.

A Piezo-Fenton System with Rapid Iron Cycling and Hydrogen Peroxide Self-Supply Driven by Ultrasound.

The piezo-Fenton system has attracted attention not only because it can enhance the Fenton reaction activity by mechanical energy input, but also because it is expected to realize a class of stimuli-responsive advanced oxidation systems by regulating energy input and hydrogen peroxide self-supply, thus greatly enriching the application possibilities of Fenton chemistry. In this work, a series of Fe-doped g-C3 N4 (g-C3 N4 -Fe) as a piezo-Fenton system were synthesized where the iron stably immobilized through Fe-N interaction. The piezo-induced electrons generate on g-C3 N4 matrix support the conversion of Fe(III) to Fe(II) and promote rate-limiting step of Fenton reaction. With the optimal Fe loading, g-C3 N4 -0.5Fe can achieve methylene blue (MB) degradation under ultrasonic treatment with first-order kinetic rate constants of 75×10-3  min-1 . Most importantly, the g-C3 N4 -Fe can maintain good catalytic activity in a wide pH range (pH=2.0∼9.0) and be cyclic used without iron leaching to solution (<0.001 µg ⋅ L-1 ), overcoming the disadvantage of traditional Fe-based Fenton catalysts that can only be applied under acidic conditions and prone to secondary pollution. In addition, g-C3 N4 -0.5Fe also exhibits antibacterial properties of Escherichia coli and Staphylococcus aureus under ultrasound. Hydroxyl radicals mainly contribute to the degradation of MB and the sterilization process. Our work is an attempt to clarify the role of g-C3 N4 -Fe in the conversion of mechanical energy to ROS and provide inspirations for the piezo-Fenton system design.

The Mechanism of Piezocatalysis: Energy Band Theory or Screening Charge Effect?

Piezocatalysis, a newly emerging catalysis technology that relies on the piezopotential and piezoelectric properties of the catalysts, is attracting unprecedented research enthusiasm for applications in energy conversion, organic synthesis, and environmental remediation. Despite the rapid development in the past three years, the mechanism of piezocatalysis is still under debate. A fundamental understanding of the working principles of this technology should enable the future design and optimization of piezocatalysts. Herein, we provide an overview of the two popular theories used to explain the observed piezocatalysis: energy band theory and screening charge effect. A comprehensive discussion and clarification of the differences, relevance, evidence, and contradiction of the two mechanisms are provided. Finally, challenges and perspectives for future mechanistic studies are highlighted. Hopefully, this Review can help readers gain a better understanding of piezocatalysis and enable its application in their own research.