RESUMO
We have measured the flexophotovoltaic effect of single crystals of halide perovskites MAPbBr_{3} and MAPbI_{3}, as well as the benchmark oxide perovskite SrTiO_{3}. For halide perovskites, the flexophotovoltaic effect is found to be orders of magnitude larger than for SrTiO_{3}, and indeed large enough to induce photovoltages bigger than the band gap. Moreover, we find that in MAPbI_{3} the flexophotovoltaic effect is additional to a native bulk photovoltaic response that is switchable and ferroelectric-like. The results suggest that strain gradient engineering can be a powerful tool to modify the photovoltaic output even in already well-established photovoltaic materials.
RESUMO
Carborane compounds, known for their exceptional thermal stability and non-toxic attributes, have garnered widespread utility in medicine, supramolecular design, coordination/organometallic chemistry, and others. Although there is considerable interest among chemists, the integration of suitable carborane molecules into ferroelectric materials remains a formidable challenge. In this study, we employ the quasi-spherical design strategy to introduce functional groups at the boron vertices of the o-carborane cage, aiming to reduce molecular symmetry. This approach led to the successful synthesis of the pioneering ferroelectric crystals composed of cage-like carboranes: 9-OH-o-carborane (1) and 9-SH-o-carborane (2), which undergo above-room ferroelectric phase transitions (Tc) at approximately 367â K and 347â K. Interestingly, 1 and 2 represent uniaxial and multiaxial ferroelectrics respectively, with 2 exhibiting six polar axes and as many as twelve equivalent polarization directions. As the pioneering instance of carborane ferroelectric crystals, this study introduces a novel structural archetype for molecular ferroelectrics, thereby providing fresh insights into the exploration of molecular ferroelectric crystals with promising applications.
RESUMO
Piezoelectric catalysis, which converts mechanical energy into chemical activity, has important applications in environmental remediation. However, the piezo-catalytic activity of various piezoelectric materials is limited by the weak piezoelectricity as well as the mismatched band-gap, leading to inefficient electron-hole pair generation and difficult carrier migration. Here, a simple strategy combining phase boundary and energy band structure modulation was innovatively proposed to enhance the piezo-catalytic activity of BaTiO3 ferroelectric by Ce ions selecting different doping sites. Thanks to the coexistence of tetragonal (P4mm) and orthorhombic (Amm2) phases effectively flattened the Gibbs free-energy and thus enhanced the piezoelectric activity, as well as suitable energy bandwidth facilitating the carrier migration were realized in the B-sites doped Ba(Ti0.95Ce0.05)O3. The degradation rate constant k of tetracycline (TC) was high to 30.56 × 10-3 min-1, which was 2.03 times higher than that of pure BaTiO3 and superior to most representative lead-free perovskite piezoelectric materials. Theoretical calculations validated that the charge density and high O2 and OH- adsorption energy on the Ba(Ti0.95Ce0.05)O3 surface promoted more efficient â¢O2- and â¢OH radicals conversion and bettered response to piezo-catalytic reaction. This work is important to design high-performance piezo-catalysts by synergistic regulation of phase boundary and energy band structure in perovskite materials for long-term antibiotic tetracycline removal.
RESUMO
The flexoelectric effect, which refers to the mechanical-electric coupling between strain gradient and charge polarization, should be considered for use in charge production for catalytically driving chemical reactions. We have previously revealed that halide perovskites can generate orders of higher magnitude flexoelectricity under the illumination of light than in the dark. In this study, we report the catalytic hydrogen production by photo-mechanical coupling involving the photoflexoelectric effect of flexible methylammonium lead iodide (MAPbI3) nanowires (NWs) in hydrogen iodide solution. Upon concurrent light illumination and mechanical vibration, large strain gradients were introduced in flexible MAPbI3 NWs, which subsequently induced significant hydrogen generation (at a rate of 756.5 µmol g-1 h-1, surpassing those values from either photo- or piezocatalysis of MAPbI3 nanoparticles). This photo-mechanical coupling strategy of mechanocatalysis, which enables the simultaneous utilization of multiple energy sources, provides a potentially new mechanism in mechanochemistry for highly efficient hydrogen production.