Ferroelectric oxide surface chemistry: water splitting via pyroelectricity

Kakekhani, Arvin; Ismail‐Beigi, Sohrab

doi:10.1039/c6ta00513f

Cited by 109 publications

(97 citation statements)

References 191 publications

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“…At higher temperatures, dissociative adsorption of 18 O2 and CO helps to fill the vacant sites (ii) and leave adsorbed O* and C* (iii), permitting CO2 formation via adsorbate reaction (iv) or through direct combination of incoming O2 with C* or incoming CO with O* (v) (the Eley-Rideal mechanism) [143]. Although BaTiO3 did not demonstrate high activity in this study, recent calculations have predicted better results for other ferroelectric materials and reactions when following particular polarization/catalytic cycles [144,145]…”

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confidence: 72%

Surface-screening mechanisms in ferroelectric thin films and their effect on polarization dynamics and domain structures

et al. 2018

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For over 70 years, ferroelectric materials have been one of the central research topics for condensed matter physics and material science, an interest driven both by fundamental science and applications. However, ferroelectric surfaces, the key component of ferroelectric films and nanostructures, still present a significant theoretical and even conceptual challenge. Indeed, stability of ferroelectric phase per se necessitates screening of polarization charge. At surfaces, this can lead to coupling between ferroelectric and semiconducting properties of material, or with surface (electro) chemistry, going well beyond classical models applicable for ferroelectric interfaces. In this review, we summarize recent studies of surface-screening phenomena in ferroelectrics. We provide a brief overview of the historical understanding of the physics of ferroelectric surfaces, and existing theoretical models that both introduce screening mechanisms and explore the relationship between screening and relevant aspects of ferroelectric functionalities starting from phase stability itself. Given that the majority of ferroelectrics exist in multiple-domain states, we focus on local studies of screening phenomena using scanning probe microscopy techniques. We discuss recent studies of static and dynamic phenomena on ferroelectric surfaces, as well as phenomena observed under lateral transport, light, chemical, and pressure stimuli. We also note that the need for ionic screening renders polarization switching a coupled physical-electrochemical process and discuss the non-trivial phenomena such as chaotic behavior during domain switching that stem from this.

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confidence: 72%

Surface-screening mechanisms in ferroelectric thin films and their effect on polarization dynamics and domain structures

et al. 2018

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“…[27] Thirdly,m ore effective external polarization methods need to be developed. Similar to stress-induced piezoelectric polarization, temperature fluctuation of pyroelectrics gives rise to polarization of an electric field, [56] and may promote the separation of photoexcited e À and h + . should be exploited as an excitation source and could also advance the practical applications of photocatalysis.…”

Section: Discussionmentioning

confidence: 99%

“…are highly anticipated. Similar to stress-induced piezoelectric polarization, temperature fluctuation of pyroelectrics gives rise to polarization of an electric field, [56] and may promote the separation of photoexcited e À and h + .…”

Section: Discussionmentioning

confidence: 99%

The Role of Polarization in Photocatalysis

et al. 2019

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Semiconductor photocatalysis as a desirable technology shows great potential in environmental remediation and renewable energy generation, but its efficiency is severely restricted by the rapid recombination of charge carriers in the bulk phase and on the surface of photocatalysts. Polarization has emerged as one of the most effective strategies for addressing the above‐mentioned issues, thus effectively promoting photocatalysis. This review summarizes the recent advances on improvements of photocatalytic activity by polarization‐promoted bulk and surface charge separation. Highlighted is the recent progress in charge separation advanced by different types of polarization, such as macroscopic polarization, piezoelectric polarization, ferroelectric polarization, and surface polarization, and the related mechanisms. Finally, the strategies and challenges for polarization enhancement to further enhance charge separation and photocatalysis are discussed.

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“…Enhanced carrier separation as ar esult of the polarization is expected to enable ad rastically improved catalytic performance.I na ddition, for the normal catalytic process,a nother problem that limits the catalytic activity is the correlation among the binding energies of catalysts, reactants,i ntermediates,a nd products (described as the scaling relationship), which follows the Sabatier principle.I t is notable that the interaction between catalysts and adsorbates is neither too weak to hinder the adsorption of reactants onto the surface of catalysts nor too strong to prohibit the desorption of products from the surface of catalysts.Periodic stress applied on the catalysts favors the adsorption and desorption processes of reactants and products,r espectively, mediated by the periodic polarization. [8] Finally,other forms of clean energy,including wind, tidal, and geothermal energy,c an also be exploited as energy sources to trigger the PIEZOcatalysis.W ind and tide can be utilized to apply stress on catalysts,w hile geothermal energy can be employed as the heat source to change the temperature of catalysts.A ss uch, ag reater progress in the wide spectrum of practical utilization of PIEZOcatalysts will be facilitated.…”

Section: Discussionmentioning

confidence: 99%

“…[7] DFT calculations showed that the built-in electric field also mediates the adsorption and desorption of reactants and products on the surface of piezoelectric catalysts,which is conducive to overcoming some fundamental limitations on catalysis caused by the Sabatier principle. [8] Moreover,p iezoelectric polarization was also reported to tune the catalytic rate by effectively adjusting the barrier height of aheterogeneous semiconductor interface. [9] This Minireview highlights recent development in PIE-ZOpotential-enabled catalysis that capitalizes on piezoelectric, pyroelectric,a nd ferroelectric semiconductors.W es ummarize the recent development of PIEZOelectric semiconductors,t heir PIEZOpotential-mediated catalytic mechanism, special techniques to tailor their piezoelectric proper-…”

Section: Introductionmentioning

confidence: 99%

Enabling PIEZOpotential in PIEZOelectric Semiconductors for Enhanced Catalytic Activities

et al. 2019

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The past several decades have witnessed significant advances in the synthesis and applications of PIEZOelectric semiconductors, an important class of materials, including piezoelectric, pyroelectric, and ferroelectric semiconductors. The intriguing combination of physical and chemical phenomena in PIEZOelectric semiconductors has triggered much interest in PIEZOcatalysis, that is, catalysis enabled by PIEZOpotential (i.e., piezopotential, pyropotential, and ferropotential)‐induced built‐in electric fields, which is the focus of this Minireview. First, the PIEZOelectric materials are briefly introduced. Second, recent developments in PIEZOcatalysis are highlighted, including the introduction of representative PIEZOelectric semiconductors, their possible catalytic mechanisms, novel techniques to produce their PIEZOelectric effects during the catalytic process, and several examples of PIEZOcatalysis. Finally, the challenges in the field and exciting opportunities to further improve the PIEZOcatalytic efficiency are discussed.

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Ferroelectric oxide surface chemistry: water splitting via pyroelectricity

Abstract: We propose a cyclic catalytic system that splits water by harnessing the pyroelectric effect in ferroelectric oxides.

Cited by 109 publications

References 191 publications

Surface-screening mechanisms in ferroelectric thin films and their effect on polarization dynamics and domain structures

Surface-screening mechanisms in ferroelectric thin films and their effect on polarization dynamics and domain structures

The Role of Polarization in Photocatalysis

Enabling PIEZOpotential in PIEZOelectric Semiconductors for Enhanced Catalytic Activities

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