A first-principles density functional theory study on the piezocatalytic activity of tetragonal perovskite PbTiO3

Piezoelectric materials have been found to possess high catalytic activity under external mechanical excitations, such as ultrasonic waves or collisions. Energy band theory (EBT) based on electronic excitation in semiconductors has been widely used to investigate piezocatalytic activity from a macro...

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Main Authors: Xinyi Sun, Xiangyu Zhu, Erjun Kan, Cheng Zhan
Format: Article
Language:English
Published: Frontiers Media S.A. 2025-03-01
Series:Frontiers in Physics
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Online Access:https://www.frontiersin.org/articles/10.3389/fphy.2025.1562239/full
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author Xinyi Sun
Xinyi Sun
Xinyi Sun
Xiangyu Zhu
Xiangyu Zhu
Xiangyu Zhu
Erjun Kan
Erjun Kan
Erjun Kan
Cheng Zhan
Cheng Zhan
Cheng Zhan
author_facet Xinyi Sun
Xinyi Sun
Xinyi Sun
Xiangyu Zhu
Xiangyu Zhu
Xiangyu Zhu
Erjun Kan
Erjun Kan
Erjun Kan
Cheng Zhan
Cheng Zhan
Cheng Zhan
author_sort Xinyi Sun
collection DOAJ
description Piezoelectric materials have been found to possess high catalytic activity under external mechanical excitations, such as ultrasonic waves or collisions. Energy band theory (EBT) based on electronic excitation in semiconductors has been widely used to investigate piezocatalytic activity from a macroscopic perspective, while the microscopic correlation between the piezoelectric feature and surface chemical reactivity was not fully understood at the current stage. In this work, to overcome the limitation of conventional finite element modeling of piezoelectric materials, we employ the first-principles density functional theory (DFT) to study the electronic properties, macroscopic electrostatic potential, surface polarization, and chemical adsorption energy of tetragonal PbTiO3 under external mechanical strains. The correlations between the band structure, piezopotential, space charge distribution, and surface adsorption energy of the *OH/H groups are discussed in our work. Our simulation shows that the bulk PTO and layered PTO exhibit opposite trends in the band gap change under external strain. In addition, a nonmonotonic correlation between the change of dipole moment piezopotential versus the applied strain was found in few-layer PTO, which could directly quantify the driving force of piezocatalysis. Finally, the enhanced surface adsorption of *OH and *H on PTO was observed under both tensile and compressive strain, which reveals how piezoelectric features affect the surface chemical process in thermodynamics. Our work provides a significant mechanistic insight into the piezocatalytic behavior of general polar perovskite, which could facilitate the development of piezoelectric materials in energy conversion and environmental applications.
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spelling doaj-art-2ed45e51087946c893cd197831ec08402025-08-20T03:42:39ZengFrontiers Media S.A.Frontiers in Physics2296-424X2025-03-011310.3389/fphy.2025.15622391562239A first-principles density functional theory study on the piezocatalytic activity of tetragonal perovskite PbTiO3Xinyi Sun0Xinyi Sun1Xinyi Sun2Xiangyu Zhu3Xiangyu Zhu4Xiangyu Zhu5Erjun Kan6Erjun Kan7Erjun Kan8Cheng Zhan9Cheng Zhan10Cheng Zhan11MIIT Key Laboratory of Semiconductor Microstructure and Quantum Sensing, Nanjing University of Science and Technology, Nanjing, ChinaSchool of Physics, Nanjing University of Science and Technology, Nanjing, ChinaEngineering Research Center of Semiconductor Device Optoelectronic Hybrid Integration in Jiangsu Province, Nanjing University of Science and Technology, Nanjing, ChinaMIIT Key Laboratory of Semiconductor Microstructure and Quantum Sensing, Nanjing University of Science and Technology, Nanjing, ChinaSchool of Physics, Nanjing University of Science and Technology, Nanjing, ChinaEngineering Research Center of Semiconductor Device Optoelectronic Hybrid Integration in Jiangsu Province, Nanjing University of Science and Technology, Nanjing, ChinaMIIT Key Laboratory of Semiconductor Microstructure and Quantum Sensing, Nanjing University of Science and Technology, Nanjing, ChinaSchool of Physics, Nanjing University of Science and Technology, Nanjing, ChinaEngineering Research Center of Semiconductor Device Optoelectronic Hybrid Integration in Jiangsu Province, Nanjing University of Science and Technology, Nanjing, ChinaMIIT Key Laboratory of Semiconductor Microstructure and Quantum Sensing, Nanjing University of Science and Technology, Nanjing, ChinaSchool of Physics, Nanjing University of Science and Technology, Nanjing, ChinaEngineering Research Center of Semiconductor Device Optoelectronic Hybrid Integration in Jiangsu Province, Nanjing University of Science and Technology, Nanjing, ChinaPiezoelectric materials have been found to possess high catalytic activity under external mechanical excitations, such as ultrasonic waves or collisions. Energy band theory (EBT) based on electronic excitation in semiconductors has been widely used to investigate piezocatalytic activity from a macroscopic perspective, while the microscopic correlation between the piezoelectric feature and surface chemical reactivity was not fully understood at the current stage. In this work, to overcome the limitation of conventional finite element modeling of piezoelectric materials, we employ the first-principles density functional theory (DFT) to study the electronic properties, macroscopic electrostatic potential, surface polarization, and chemical adsorption energy of tetragonal PbTiO3 under external mechanical strains. The correlations between the band structure, piezopotential, space charge distribution, and surface adsorption energy of the *OH/H groups are discussed in our work. Our simulation shows that the bulk PTO and layered PTO exhibit opposite trends in the band gap change under external strain. In addition, a nonmonotonic correlation between the change of dipole moment piezopotential versus the applied strain was found in few-layer PTO, which could directly quantify the driving force of piezocatalysis. Finally, the enhanced surface adsorption of *OH and *H on PTO was observed under both tensile and compressive strain, which reveals how piezoelectric features affect the surface chemical process in thermodynamics. Our work provides a significant mechanistic insight into the piezocatalytic behavior of general polar perovskite, which could facilitate the development of piezoelectric materials in energy conversion and environmental applications.https://www.frontiersin.org/articles/10.3389/fphy.2025.1562239/fullpiezocatalysisdensity functional theoryperovskitewater splittingsurface chemistry
spellingShingle Xinyi Sun
Xinyi Sun
Xinyi Sun
Xiangyu Zhu
Xiangyu Zhu
Xiangyu Zhu
Erjun Kan
Erjun Kan
Erjun Kan
Cheng Zhan
Cheng Zhan
Cheng Zhan
A first-principles density functional theory study on the piezocatalytic activity of tetragonal perovskite PbTiO3
Frontiers in Physics
piezocatalysis
density functional theory
perovskite
water splitting
surface chemistry
title A first-principles density functional theory study on the piezocatalytic activity of tetragonal perovskite PbTiO3
title_full A first-principles density functional theory study on the piezocatalytic activity of tetragonal perovskite PbTiO3
title_fullStr A first-principles density functional theory study on the piezocatalytic activity of tetragonal perovskite PbTiO3
title_full_unstemmed A first-principles density functional theory study on the piezocatalytic activity of tetragonal perovskite PbTiO3
title_short A first-principles density functional theory study on the piezocatalytic activity of tetragonal perovskite PbTiO3
title_sort first principles density functional theory study on the piezocatalytic activity of tetragonal perovskite pbtio3
topic piezocatalysis
density functional theory
perovskite
water splitting
surface chemistry
url https://www.frontiersin.org/articles/10.3389/fphy.2025.1562239/full
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