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Photo-/Electrocatalytic Reduction of CO2 Based on Ferroelectrics
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Rui Wei1, Shun Li2, Andy Li1, Yuan-Hua Lin1, *
Research. Vol 8 Article ID 0843
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Research. Vol 8 Article ID 0843
• Review Article •
Photo-/Electrocatalytic Reduction of CO2 Based on Ferroelectrics
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Rui Wei1, Shun Li2, Andy Li1, Yuan-Hua Lin1, *
Affiliations
  • 1State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China.
  • 2School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China.
About Author:

† These authors contributed equally to this work.

Published: 2025-08-20 doi: 10.34133/research.0843
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Converting CO2 into sustainable fuels or useful carbon-derived substances offers an effective strategy for tackling the energy crisis and combating global warming. Photo-/electrocatalytic CO2 reduction provides a simple, energy-efficient, and environmentally friendly route compared to existing technologies. Ferroelectric materials, characterized by their unique spontaneous and switchable polarization, have emerged as promising candidate catalysts due to their controllable surface physical and chemical properties. This review commences by summarizing the mechanism underlying ferroelectric polarization-modulated photo-/electrocatalytic CO2 reduction. We then highlight the recent key advancements in CO2 reduction utilizing ferroelectric materials, along with their performance promotion strategies. Finally, we explore the obstacles and future perspectives in this field. This review will provide useful guidance for systematic design and advancement of effective photo-/electrocatalysts based on ferroelectric materials.

Rui Wei, Shun Li, Andy Li, Yuan-Hua Lin. Photo-/Electrocatalytic Reduction of CO2 Based on Ferroelectrics[J]. Research, 2025 , 8 (8) : 0843 - . DOI: 10.34133/research.0843
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Introduction
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Global climate change and the energy crisis pose challenges to the modern society. Carbon dioxide (CO2), generated from industrial and other human activities, is the primary greenhouse gas in the atmosphere. Its emissions reached 41.6 Gt/year in 2024 (Global Carbon Budget, 2024), with its concentration directly correlated to rising global temperatures [1–4]. The escalating greenhouse effect threatens ecological sustainability and human development. Consequently, transforming CO2 into value-added chemicals and fuels can not only effectively mitigate greenhouse gas emissions but also provide a sustainable solution for future energy demands [5,6]. In this context, developing efficient CO2 conversion technology has emerged as a long-term solution for the circular economy and a key focus of research in materials science and chemical engineering [7–9].
In recent years, electrocatalysis and photocatalysis CO2 reduction (CO2RR) have demonstrated significant potential for transforming CO2 into valuable chemicals or fuels under mild conditions [10–15]. These approaches not only contribute to the reduction of greenhouse gas but also facilitate the realization of a sustainable carbon cycle [16]. Consequently, these straterties have garnered substantial attention from researchers across a wide range of disciplines. However, great challenges hinder their practical applications. Existing electrocatalytic technologies (e.g., those using Cu-based catalysts [17]) often exhibit a Faraday efficiency of less than 30% for C2+ products, with overpotentials typically exceeding 450 mV. Furthermore, the process generates a substantial number of by-products, thereby posing a considerable challenge to the selective production of specific target products [18]. Additionally, it is crucial to minimize the high overpotential encountered during electrocatalysis and reduce the cost of electrocatalysts, which typically contain noble metals [19]. As for the photocatalytic process, it is confronted with multiple challenges, including a narrow range of light absorption and rapid recombination of photogenerated electron–hole pairs, which significantly impair efficiency and selectivity of CO2RR [13,20,21].
Ferroelectric materials exhibit unique spontaneous polarization characteristics that can be reversed by an external electric field [22], making them promising for applications in sensors, capacitors, microdrivers, and other fields [23]. Recently, the potential of ferroelectric materials in improving the efficiency and selectivity of electrocatalytic and photocatalytic reactions has gained attention. Unlike conventional catalysts, which are constrained by static surfaces that hinder dynamic regulation of catalytic pathways, ferroelectric polarization-induced internal electric field in ferroelectric materials can modulate carrier transport and surface states, thereby enhancing electrocatalytic and photocatalytic performance [24]. Specifically, the internal electric field provides a strong driving force to promote electron–hole separation and migration toward opposite directions. Furthermore, the switching of spontaneous electric polarization can alter the reactivity of the catalyst’s surface, allowing for tunable adsorption and binding strengths of reaction intermediates [25]. These intriguing effects make ferroelectric materials increasingly attractive in the field of photo-/electrocatalysis, especially regarding CO2 activation and conversion [26,27].
Here, we provide a comprehensive review of the emerging field of photo-/electrochemical reduction of CO2 using ferroelectric materials, mainly focusing on mechanistic insights and material design strategies. We begin by outlining the fundamental principles of CO2RR and ferroelectric materials/polarization. Next, we discuss how ferroelectric polarization enhances electrocatalytic and photocatalytic CO2 conversion by modulating the electronic structure, surface characteristics of catalyst, and charge stransfer behavior. Subsequently, we present the state-of-the-art representative ferroelectric photo-/electrocatalysts for CO2RR and summarize the latest advancements in performance-enhancement strategies. This review paper aims to offer an in-depth investigation of ferroelectric polarization-driven photo-/electrocatalysis, providing a new perspective on optimizing CO2 conversion technology and advancing sustainable energy solutions.
Mechanisms of Photo-/Electrocatalytic CO2RR Using Ferroelectrics
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Ferroelectrics and ferroelectric polarization
Ferroelectrics are a category of materials characterized by spontaneous polarization, first documented by Valasek in 1921 in Rhosi salt [28]. Common ferroelectrics include perovskites (e.g., BaTiO3, BiFeO3, and Na1-xKxNbO3) (Fig. 1A) [29–31], Bi-based layered structures [32], potassium dihydrogen phosphate (KH2PO4), tungsten bronze (e.g., Ca0.28Ba0.72Nb2O6), fluorate [e.g., polyvinylidene difluoride (PVDF)] [33], and ilmenite (e.g., LiNbO3 and LiTaO3) [34]. The spontaneous polarization of ferroelectrics arises from the inherent asymmetry in their crystal structure, resulting in a mismatch between positive and negative charge centers and creating an electric dipole moment [35]. When an electric field is applied, the electric dipole moments within the material are rearranged, causing the polarization direction to align with the applied electric field. This direction of polarization can be altered in response to variations in the intensity of the applied electric field.
A critical phase transition temperature exists between the polarized and nonpolarized phases of ferroelectrics, which is referred to as the Curie temperature (Tc). Below Tc, ferroelectrics exhibit spontaneous polarization and ferroelectric properties. Above Tc, ferroelectrics undergoes a phase transition into a nonpolarized phase, displaying paraelectric behavior. In contrast to conventional ferroelectrics, relaxation ferroelectrics do not possess a distinct Curie temperature. Instead, their characteristic temperature is defined as the temperature at which the maximum dielectric constant (Tm) is observed. Relaxation ferroelectrics exhibit ferroelectric phases below the freezing temperatures (Tf) and paraelectric phases above the Burns temperatures (TB) (Fig. 1C and D). On the contrary, ferroelectric materials exhibit a characteristic nonlinear response to external electric fields, manifesting as hysteresis in the polarization–electric field (P–E) relationship (Fig. 1B). Remarkably, these materials preserve residual polarization even after field removal, demonstrating stable dipole moment retention. This unique remanent polarization property renders them particularly suitable for nonvolatile memory devices and energy-harvesting systems [36].
Mechanisms of ferroelectric polarization-modulated photo-/electrocatalytic CO2RR
The mechanisms of photocatalytic and electrocatalytic CO2 reduction are complex processes involving multiple steps and reaction pathways [10,37,38]. These processes aim to efficiently convert CO2 into valuable chemicals or fuels, such as carbon monoxide (CO), methane (CH4), formic acid (HCOOH), and methanol (CH3OH), utilizing either light or electrical energy as the driving force. Understanding the reaction mechanism is key to modulating reaction selectivity and improving production yields.
In the photocatalytic process, as illustrated in Fig. 2A, semiconductor materials absorb photons, leading to the excitation of electrons from the valence band (VB) to the conduction band (CB), creating holes in the VB. These excited electrons then migrate to the catalyst’s surface to participate in the reduction of CO2, while the holes facilitate the oxidation of water to produce oxygen. Initially, CO2 molecules are adsorbed onto the catalyst’s surface, forming reactive intermediates such as HCOOH and CO. These intermediates can be further reduced through a variety of mechanisms, including coupled electron and proton transfer, to yield final products such as CH3OH and CH4 [39,40].
The electrocatalytic reaction is driven by electrical energy [41]. The mechanism can be illustrated in Fig. 2B. The reaction is typically carried out in an electrochemical cell divided into 2 parts with a Nafion film to prevent the product from being oxidized. During the electrocatalytic reaction, CO2 is adsorbed on the surface of the electrode (commonly used electrode materials include metals such as copper, cobalt, silver, and their compounds). Electrons provided by the applied voltage are transferred to the electrode surface, where they engage in the reduction reaction of CO2. At the same time, protons from the electrolyte are transferred to the electrode surface and combine with the electrons to form reactive intermediates. In electrocatalytic reactions, different electrode materials and reaction conditions can affect product selectivity. For example, copper-based catalysts typically produce C2+ products (e.g., ethanol and ethylene) [42], while silver-based catalysts primarily produce CO. Modulating the electronic structure, surface properties of the electrode materials and the reaction conditions can optimize the product selectivity and catalytic efficiency [9,43,44].
In 2004, Grosso et al. [45] first proposed the use of ferroelectrics as photocatalysts, opening up a new direction for advancing the research area of catalysis. Ferroelectric materials exhibit spontaneous polarization that generates an intrinsic electric field, which can be modulated through external thermal and electrical stimuli [46]. This built-in electric field promotes directional separation of photogenerated charge carriers (Fig. 2A), suppressing recombination losses and thereby boosting photocatalytic efficiency [24,47–49]. In the context of electrocatalysis (Fig. 2B), particularly in redox reactions involving electron gain and loss [50], the ability to absorb gases and transfer charges of the catalysts are crucial factors influencing the catalytic performance [51]. Thus, the charge-polarized surface and intrinsic electric field of ferroelectric materials critically enhance electrocatalytic performance through dual mechanisms: (i) efficient reactant activation and (ii) promoted charge carrier separation/transport, significantly boosting overall catalytic activity [52].
The unique spontaneous polarization and polarization reversal characteristics of ferroelectric materials provide a novel strategy to enhance the photo-/electrocatalytic performance of CO2RR. The tunable catalytic activity of ferroelectric catalysts mainly results from the built-in electric field and polarization effects inherent to the materials [53]. As illustrated in Fig. 3, these effects significantly affect the surface electron density/electronic structure, adsorption states of reactants and products, generation and separation of electron–hole pairs, and the transport behavior of charges, leading to changes in the catalytic reaction pathways and promoted selectivity and efficiency. The individual or synergistic effects of various factors collectively determine the product distribution and selectivity of CO2RR. The following sections will discuss how these mechanisms influence the CO2RR catalytic activity of ferroelectrics in detail [54].
Modulating the surface adsorption/reaction properties
Ferroelectric materials are characterized by spontaneous polarization, allowing the formation of a permanent electric dipole within the material. This creates a stable charge on the material’s surface. The built-in electric field influences the distribution of surface charges, leading to an increase in adsorption capacity of reactant molecules (e.g., CO2 and O2) and promotion of their activation [55]. In addition, the Sabatier principle dictates that optimal catalytic efficiency depends on appropriate interactions between the catalyst’s active site and the reactants [56]. Catalytic activity declines when reactant–catalyst interactions become either excessively strong or weak, highlighting the need for balanced material design. Ferroelectric systems address this challenge through polarization-state modulation, enabling precise tuning of surface chemical environments and adsorbate–catalyst interactions [57]. The polarization-switching ability of ferroelectric materials can reverse the electric field within the ferroelectric material to overcome the Sabatier limitation [58,59]. As a result, the reactant activation, surface reactivity, and reaction selectivity of the catalytic reaction can be regulated by controlling the polarization states of the ferroelectric material’s surface [60], offering a novel strategy for the rational design of catalysts.
Tuning the electronic structure
The electric polarization effect of ferroelectric material can significantly influence their electronic structure. The modulation of electronic states leads to the optimization of the reaction pathway and allows the catalyst to interact with the reactants in a more efficient manner, ultimately enhancing its catalytic performance. As a representative example, BiCoO3/Bi5CoTi3O15 composite catalysts illustrate how ferroelectric substrates enhance both the adsorption capacity and activation energy of the catalyst for specific molecules by providing additional electronic states [61].
In addition, it is well known that the alteration of the d-band center energy is closely associated with the adsorption energy of the reactants, which can significantly influence both catalytic activity and selectivity [62,63]. In ferroelectric materials, the d-band center may shift to different energy states as a consequence of the electric fields, which in turn influences the interaction forces and modes between the metal and the reactants [64]. As a result, the regulation of electron density on ferroelectric catalyst surfaces can effectively promote the adsorption of specific intermediates involved in catalytic reactions.
Promoting the carrier separation efficiency
Photocatalytic processes initiate through light-induced generation of electron–hole pairs in the semiconductor material [65]. Ferroelectric polarization establishes an internal electric field that induces band bending, thereby significantly suppressing charge recombination, facilitating efficient charge separation, and increasing the population of available charge carriers for surface redox reactions [66,67]. Consequently, the inherent polarization properties of ferroelectric materials can substantially enhance the efficiency of both photocatalytic and electrocatalytic CO2 reduction processes.
Lowering the overpotential of electrocatalysis
Ferroelectric materials have been reported to effectively reduce electrocatalytic overpotentials [68], including hydrogen evolution reaction (HER) [69,70], oxygen evolution reaction (OER) [52,71], and nitrogen reduction reaction (NRR) [72]. The built-in polarization electric field significantly accelerates the adsorption and activation of reactants by intensifying the electric field at the electrode–electrolyte interface [52]. This mechanism can lower the energy barrier for electron transfer, allowing ferroelectric materials to achieve higher reaction rates at lower applied voltages, thereby enhancing the overall catalytic performance of the system. A very recent theoretical study on Mo-BN@In2Se3 demonstrated an electrocatalytic pathway that is contingent upon polarization flipping [73]. The limiting value of the electrocatalytic no-reducing potential on Mo-BN@P↑-In2Se3 is 0.09 eV, which is well below the isolated Mo-BN monolayer (0.35 V). Mo-BN@P↓-In2Se3 is 0.53 eV, which highlights the distinctive capacity of ferroelectric materials to lower the overpotential through reversible polarization transitions while impeding competing reactions such as HER through a built-in electric field.
Moreover, the formation of double layer reduces activation energy and facilitates electron transfer [74]. At the electrode surface, the rearrangement of ions under an electric field leads to the formation of a charge-rich double layer, thereby optimizing the interactions between the reactants and the electrode surface. This double-layer effect is particularly significant in multi-electron conversion reactions, such as CO2RR, as it not only optimizes the adsorption modes of the reactants but also reduces the energy consumption of the multi-step reactions [75,76].
Polarization-dependent CO₂RR pathways
The ferroelectric polarization offers precise control of the CO2RR pathways by dynamically tuning the surface charge distribution and intermediate adsorption configuration. For instance, density functional theory (DFT) calculations reveal the critical role of polarization direction on the reaction energy: The upward polarization (P↑) in 2-dimensional (2D) ferroelectric In2Se3 is more favorable for driving the CO2 activation reaction: *CO2→*OCOH, which ultimately tends to produce methane or formic acid (Ul = 0.58 eV) [77]. In contrast, downward polarization (P↓) stabilizes the intermediate formate (*OCHO) and ultimately tends to produce methanol (Ul = 0.64 eV). This catalytic mechanism is supported by both computational and experimental investigations, making ferroelectric materials a unique class of CO2RR catalysts with dynamically tunable reaction pathways.
Research Progress of Ferro-Catalytic Materials for CO2RR
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Ferroelectric photocatalysts
The persistent challenge of rapid charge carrier recombination in photocatalysis has motivated innovative material design strategies. Recent advances demonstrate that ferroelectric semiconductors offer a promising solution through their intrinsic polarization-induced internal electric fields, which enable anisotropic charge separation [47–49]. This section critically examines progress in photocatalytic CO2RR over both traditional ferroelectric systems and emerging 2D materials (Table).
Traditional ferroelectric photocatalysts
Initially, investigations on ferroelectric material-based photocatalysts were mainly focused on conventional ferroelectrics, such as perovskite and Bi-based layered structures. Jia et al. [78] synthesized ferroelectric Bi4Ti3O12 nanosheets via molten salt method. Photocatalytic tests revealed impressive CO2-to-fuel conversion efficiencies, yielding CH3OH (39.10 μmol g−1 h−1) and CH3CH2OH (18.96 μmol g−1 h−1) as primary products. The energetically favorable CB position (−1.2 V versus normal hydrogen electrode) of Bi4Ti3O12 provides substantial thermodynamic impetus for CO2RR. Photogenerated holes predominantly migrate to the [Bi2O2] layer, while electrons primarily travel to the [TiO6] octahedral layer, facilitating the overall transformation process. In 2019, Tu et al. [79] developed a layered perovskite SrBi4Ti4O15 (SBTO) nanosheets, which exhibited ferroelectric-enhanced photocatalytic CO2 conversion performance. The maximum CH4 production rates reached 19.8 μmol h−1 g−1 (apparent quantum yield: 1.33% at 365 nm) for SBTO nanosheets with optimized ferroelectric properties, representing superior performance relative to benchmark photocatalysts. Complementary characterizations established a direct correlation between [100]-oriented spontaneous polarization and enhanced charge separation efficiency, accounting for the superior photocatalytic activity. Moreover, DFT calculations revealed that both electrons and holes show the smallest effective mass along the a axis, indicating high charge mobility facilitated by ferroelectric polarization. Additionally, Li et al. [80] reported that Bi2MoO6 ferroelectric nanosheets, treated by corona poling, exhibited excellent CO2 reduction activity for CO production, achieving a rate of 14.38 μmol g−1 h−1 in a gas–solid system without the need for sacrificial agents or co-catalysts. This efficiency represents an enhancement of more than one order of magnitude compared to bulk Bi2MoO6. The combined approach of corona poling and layered structure significantly improves the separation of photogenerated electrons and holes while increasing the reactive sites for CO2 adsorption, resulting in markedly enhanced photocatalytic CO2RR activity. These findings collectively demonstrated the emerging application of ferroelectric materials for photocatalytic CO2 conversion.
2D ferroelectric photocatalysts
Over recent decades, 2D materials have garnered significant interest in catalytic applications, particularly as electrocatalysts and photocatalysts [81–85], due to their advantageous structural and electronic characteristics. These include high surface-to-volume ratios, abundant catalytic sites, minimized charge migration distances, and adjustable electronic band structures. Among these, piezo-/ferroelectric 2D materials (e.g., SnSe, GeS, MXenes, BiOCl, AgBiP2Se6, and In2Se3) have been extensively studied through both experimental and computational approaches for various catalytic processes [30,54,86–90], including HER, oxygen reduction reaction (ORR), NRR, and CO2RR. Notably, recent computational studies suggest that 2D ferroelectric heterostructures, especially those with van der Waals (vdW) interfaces, may demonstrate exceptional photocatalytic CO2 conversion efficiency [91], which is attributed to efficient charge carrier separation and transfer enabled by robust interlayer electronic coupling.
Recent work by Chiang et al. [65] has revealed that simultaneous control of ferroelectric and spin polarizations in 2D CuInP2S6 (CIPS) can significantly enhance photocatalytic CO2 reduction performance (Fig. 4A and B). Controlling the ferroelectric–paraelectric phase transition and applying electrical poling treatments lead to increased CO and CH4 production with extended polarization time. Optimal product yields of 20.34 μmol g−1 (CO) and 39.88 μmol g−1 (CH4) were achieved after 60 min of polarization during 6-h catalytic tests (Fig. 4C and D). Further performance enhancement was realized through synergistic sulfur vacancy (VS) engineering and magnetic field application, where the spin-polarized VS-CIPS system demonstrated substantially improved activity relative to pristine CIPS. The modified VS-CIPS system exhibited a photocatalytic CH4 yield of 54.9 μmol g−1, which increased by 35% to 74.29 μmol g−1 under magnetic field (Fig. 4E and F). These findings establish a new strategy for enhancing CO2 photoreduction in 2D ferroelectric materials through combined defect engineering and external field control. Similarly, intrinsic polarization-induced surface band edge modifications and efficient photocatalytic CO2RR were also observed in other 2D ferroelectric systems like CuBiP2Se6 [92].
Moreover, Li and Young [93] conducted DFT calculations to study the photocatalytic CO2RR activity of a novel 2D MXene Y2CO2 ferroelectric material with a suitable bandgap. The material’s capability to convert CO2 into various C1 products, including CO, formic acid, methanol, and methane, was systematically investigated. The results revealed that on an oxygen-vacancy (OV) defective Y2CO2 surface, CO2 adsorption is strongly preferred over CO adsorption on the “poled up” surface (Eads = −2.27 eV for CO2 versus −2.12 eV for CO), while this preference reverses on the “poled down” surface (Eads = −1.56 eV for CO2 versus −2.87 eV for CO). This polarization-dependent adsorption behavior enables selective molecular adsorption control. Furthermore, the study found that methanol formation is more favorable on the “poled up” surface (Eads = −0.76 eV for CH3OH) compared to the “poled down” surface (Eads = −1.14 eV), while formic acid shows stronger adsorption on the “poled down” surface (Eads = −1.40 eV versus −0.93 eV on “poled up”). Notably, methane adsorption remains weak on both surfaces (Eads > −0.5 eV), making CH4 formation energetically unfavorable. This work demonstrates that 2D Y2CO2 MXene, with its tunable adsorption properties through polarization control, represents a highly promising and efficient catalyst for CO2RR, providing valuable guidance for designing advanced 2D ferroelectric photocatalysts.
Engineering strategies of ferroelectric photocatalysts
For photocatalytic process, increasing the polarization field of ferroelectric catalysts can effectively modulate the surface electronic state and enhance the separation efficiency of photogenerated electron–hole pairs, offering significant potential to greatly improve the activity and selectivity of photocatalytic reactions. Consequently, the current engineering strategies for ferroelectric photocatalysts mainly focus on enhancing the polarization field, optimizing the adsorption modes and increasing surface active sites [94,95]. These strategies include engineering oxygen vacancy, constructing heterojunction, and introducing single-atom catalysts (SACs). The following section provides a comprehensive overview of the fundamental principles underlying these promotion strategies, along with the most illustrative examples reported recently.
Engineering oxygen vacancy
Oxygen vacancies (OV) appear in oxygen-containing compounds because of the lack of oxygen atoms in the crystal lattice [96]. The OV, acting as donor-like defects, can introduce a defect band near the CB of the metal oxide photocatalyst [97]. The presence of oxygen vacancies and the resulting saturation of metal coordination contribute to CO2 capture and electron generation reactions, ultimately promoting the CO2 photocatalytic reduction process [98]. The OV in the catalyst serves as an effective adsorption site for CO2 molecules. The insertion of an oxygen atom from the CO2 molecule into the OV leads to the formation of a stable adsorption complex. During the CO2 adsorption process, the d-orbital of the coordinated unsaturated metal atom contributes additional electrons to the lowest unoccupied molecular orbital (LUMO) of the CO2 molecule [99]. This electron transfer process not only increases the electron density of the CO2 molecule but also facilitates the breaking of chemical bonds. In particular, the electron transfer induces a distortion of the CO2 molecule’s structure, thereby reducing its chemical bonding energy and increasing its susceptibility to subsequent reaction steps [100].
Incorporating oxygen vacancies into ferroelectric materials not only enhances their ability to absorb visible light (by shifting the CB downward) but also significantly alters the materials’ charge transfer characteristics [101]. As an active site, OV plays a crucial role in modulating the photocatalytic CO2 reduction processes. A represetative study by Zhang and colleagues [102] reported ferroelectric Bi3NbTiO9 (BNT) nanosheet catalysts prepared using a one-pot hydrothermal method by creating surface oxygen vacancies through corona polarization treatment. The P–E hysteresis loop reveals that corona poling treatment and OV engineering synergistically enhance the built-in electric field polarization (Fig. 5A). Subsequent calculations reveal that the carrier density values for BNT, BNT-P, BNT-OV2, and BNT-OVP are 3.46 × 1021, 4.44 × 1021, 3.89 × 1021, and 5.63 × 1021, respectively. The flat-band potential remains unaffected by corona polarization and/or the formation of OV. These results demonstrate that the improved charge separation efficiency of BNT-OVP stems from a synergistic combination of elevated ferroelectric spontaneous polarization and the presence of OV. In addition, COMSOL simulations indicate that the incorporation of OV hinders the reverse switching of domains in the BNT nanoplates, resulting in a sustained elevated residual polarization-induced electric field (Fig. 5B). The positively polarized charge facilitates the reduction reaction, while the negatively polarized charge promotes oxidation reactions (Fig. 5C). This results in an enhanced photocatalytic CO2RR activity of the BNT nanosheets. The presence of OV creates a “pin effect” on the switching of domain poles, which in turn affects the separation of electrons and holes. Additionally, the incorporation of OV increases the CO2 adsorption energy from 0.990 to 1.808 eV, supporting the idea that OV facilitates the CO2 adsorption and reduction process.
A very recent work by Liu et al. [103] demonstrated that introducing OV in ferroelectric Bi0.5Na0.5TiO3 can create a defect level, which in turn effectively modulates the band structure, reduces the barrier for carrier transport, and promotes the separation of photogenerated electron–hole pairs. Specifically, OV engineering alters the local chemical environment of Bi0.5Na0.5TiO3, enhancing the intensity of spontaneous polarization through lattice distortion. Compared to other ferroelectric photocatalysts, Bi0.5Na0.5TiO3 with OV defects significantly enhances CO yield and product selectivity. Similarly, this strategy for constructing OV can also be applied to other polar materials systems, such as BiOIO3 nanoribbon [104], allowing it to exhibit excellent CO2 photoreduction properties that surpass those of most reported gas–solid reaction catalytic systems.
Selective loading of co-catalyst
Anchoring co-catalysts represents a promising approach to improve the performance of photocatalytic materials [105]. Ferroelectric materials can direct the selective deposition of redox co-catalysts on different polar facet. The inherent spontaneous polarization of ferroelectric materials creates strong internal electric fields that drive the spatial separation of photogenerated charge carriers, accumulating electrons on one polar facet and holes on the opposite facet [53]. This charge separation provides a powerful driving force for the selective anchoring of reduction co-catalysts (e.g., Pt or Ag) onto the electron-rich facet and oxidation co-catalysts (TiO2, MnOx, or Co3O4) onto the hole-rich facet [106,107], thereby dramatically enhancing photocatalytic efficiency by minimizing charge recombination, providing dedicated active sites for each half-reaction, spatially separating incompatible products to prevent back-reactions, and improving overall reaction kinetics and stability.
Yang et al. [108] employed photodeposition method to load AuCu and MnOx cocatalysts on oppositely poled facets of ferroelectric PbTiO3 nanoplates. A band bending occurs along with the formation of built-in electric fields near the semiconductor–cocatalyst interfaces, together with an intrinsic ferroelectric polarization field, which provide a strong driving force for the directional drift of photogenerated electrons and holes toward AuCu and MnOx, respectively, resulting in significantly enhanced photocatalytic activity.
Constructing ferroelectric–semiconductor heterojunctions
Heterojunctions represent interfacial regions formed by the junction of 2 dissimilar semiconductors exhibiting distinct electronic band configurations, thereby generating built-in electric fields that improve charge carrier separation and transport under illumination [109–113]. Utilizing the electric field generated in ferroelectric materials and heterojunctions to synergistically enhance the separation of electrons and holes is considered a highly promising approach for developing efficient photocatalysts [114,115]. Incorporating ferroelectric materials can regulate the degree of band bending through manipulation of spontaneous polarization and enhance the strength of the built-in electric field within the heterojunction [116].
Heterojunction photocatalysts are classified into 3 main categories: type II, type S, and type Z heterojunctions [59,117–119]. Type II heterostructures comprise 2 semiconductor materials with staggered band alignment. This energetically favorable configuration induces spontaneous spatial separation of photogenerated charge carriers, yielding enhanced photocatalytic activity beyond the capabilities of individual semiconductor components [98,115]. Implementation of this design principle in 2D CIPS bilayers demonstrated that the intrinsic polarization field effectively suppresses charge recombination with predominant CH4 production (Fig. 5D and E) [91]. Notably, a high solar-to-fuel efficiency of 8.40% was achieved over the CIPS bilayer heterojunctions. An in situ atom-sharing strategy has been used to prepare Cs2SnI6/SnS2 heterojunction. Compared to pure ferroelectric SnS2, the photocatalytic CO2RR performance of the heterojunction was significantly enhanced by about 5 times (Fig. 5F) [120]. This strategy can be extended to the preparation of various perovskite–metal dihalide heterostructures (Cs3M2X9/M2Y3, where M = Bi, Sb; X = Br, I; Y = S, Se). Similarly, well-constructed g-C3N4/BaTiO3 heterojunction photocatalyst also showed significantly enhanced reverse movement of photoexcited carriers due to the coupling effect of the heterojunction and ferroelectric polarization, effectively reducing the recombination and substantially improving the CO2RR performance [121]. The classical Z-scheme configuration integrates 2 semiconductor photocatalysts with staggered band alignment coupled with an oxidation–reduction mediator system. Z-type BiFeO3/CsPbBr3 heterojunction has been demonstrated and resulted in a notable enhancement in catalytic activity [122]. Type S heterostructures are constructed by combining a reducing-type semiconductor photocatalyst with a smaller work function and higher Fermi level, and an oxidizing-type semiconductor photocatalyst with a larger work function and lower Fermi level in an offset configuration [123]. Well-designed 2D/2D S-scheme heterojunction composed of ferroelectric Bi3TiNbO9 and C3N5 nanosheets was reported, achieving efficient charge transfer through the depolarization field [124]. Further studies are needed to extend their application to CO2 reduction and reveal the role of ferroelectric polarization in these composite catalysts.
Besides experimental work, theoretical simulations have also been conducted on ferroelectric–semiconductor heterostructures. For example, Alawode and Kolpak [125] introduced an innovative dynamically adjustable stoichiometric ZnO(112̅0)n/PbTiO3 catalytic system, where surface reactivity is modulated by the PbTiO3 substrate’s polarization orientation and the ZnO(112̅0) layer thickness (Fig. 6). This configuration results in a substantially reduced energy pathway for CO2 transformation. Their findings revealed pronounced variations in CO2 adsorption energy upon polarization reversal, implying that reaction thermodynamics and reaction routes for CO2 activation can be precisely regulated, as evidenced by the dynamic polarization-switching mechanism proposed for CO2 dissociation on ZnO(112̅0)/PbTiO3. Such a strategy may extend to more heterogeneous structures, offering new opportunities for manipulating reaction energetics.
Single-atom ferroelectric nanohybrids
The concept of SACs was first reported by Qiao et al. [126] as a novel catalyst type consisting of dispersed single metal atoms as the active centers [127,128]. The monatomic dispersion of SACs allows each isolated metal atom to participate in catalytic reactions, significantly enhancing the efficiency of chemical processes. In the CO2RR, the highly stable molecular structure of CO2 leads to a higher dissociation energy for the C=O bond compared to other chemical bonds, such as C–C or C–H bonds [129]. This indicates that the reduction of CO2 requires a higher activation energy. Concurrently, the dissociation of the C=O bond requires the involvement of multiple electron and proton transfer processes, as well as complex multi-step reactions [130]. This makes enhancing reaction selectivity challenging. In this context, SACs utilize the unsaturated d-orbitals of transition metals (TMs) for electron transfer with CO2 molecules, facilitating the formation of a more reducible intermediate and lowering the dissociation energy of the C=O bond [92]. In this sense, ferroelectric substrates provide ideal platforms for stabilizing isolated metal atoms, creating ferroelectric-supported SACs [92,131]. Such hybrid systems synergistically integrate the switchable polarization of ferroelectrics with the exceptional reactivity of atomic metal sites, leading to enhanced performance in CO2RR with regard to both activity and product selectivity.
Jiang et al. [92] performed DFT simulations to elucidate the CO2RR mechanism in Ag@CuBiP2Se6 system, where ferroelectric polarization cooperates with single-atom catalytic sites (Fig. 7A). Computational results reveal that the ferroelectric CuBiP2Se6 matrix generates a built-in polarization field, which drives directional charge carrier separation and transport. Meanwhile, Ag SAC anchored on the substrate can serve as an electron reservoir to modify the bonding configuration of the surface through appropriate static electron transfer, effectively promoting the adsorption and activation of CO2 molecules. The complementary effects between the ferroelectric-induced bulk polarization and atomic-level charge regulation at Ag sites collectively enhance CO2 capture and conversion efficiency. Notably, switching the ferroelectric polarization can selectively produce 2 different products (CH4 or CH3OH), providing further evidence of the feasibility of regulating the reaction pathway through a ferroelectric polarization switch.
In addition, Liu et al. [132] reported the modulation of periodic 1D Au single-atom arrays by polarization electric field of ferroelectric Bi4Ti3O12 nanosheets. The Au single-atom arrays significantly reduce the Gibbs free energy for CO2RR through Au-O=C=O-Au dual-site adsorption compared to that on Au isolated single atoms. Moreover, the Au single-atom arrays hinder the depolarization of Bi4Ti3O12, maintaining a stronger driving force for separating photogenerated charges. As a result, Bi4Ti3O12 with Au single-atom arrays displays a high CO production rate of 34.15 μmol·g−1·h−1, which is 18 times higher than that of pristine Bi4Ti3O12 (Fig. 7B and C). More importantly, the polarization electric field proves to be a general tactic for the synthesis of 1D Pt, Ag, Fe, Co, and Ni single-atom arrays on the ferroelectric Bi4Ti3O12 surface. The experimental and computational evidence collectively demonstrates that engineering ferroelectric-supported SACs establishes a dual-functional platform for optimizing both reaction kinetics and product distribution of photocatalytic CO2 reduction.
Ferroelectric electrocatalysts
Besides intensively investigated photocatalysis, ferroelectric materials have also been applied to the field of electrocatalysis recently. In electrocatalysis, the switchable ferroelectric polarization effect can directly control gas adsorption strength, overpotential, and selectivities. In addition, it can also regulate the orbitals of the surface metal atoms. Consequently, this effect can not only activate the reactants effectively but also play a crucial role in enhancing the activity and selectivity of electrocatalytic CO2RR [77].
The single-atom engineering strategy has also been demonstrated to be applicable to the field of electrocatalysis [133]. The switchable electric polarization in layered In2Se3 can dynamically tune the activation barriers, intermediate stabilization, and selectivity in electrocatalytic CO2RR catalyzed by isolated TM atoms (Fig. 8A). Based on the single-atom ferroelectric nanohybrid construction strategy, 6 TMs, including Ni, Nb, Pd, Re, Rh, and Zr, were identified as potential catalysts for electrochemical CO2RR using DFT calculations [77]. These findings show that the inversion of polarization in single-layer ferroelectric In2Se3 can regulate the energies of empty and occupied d-orbitals, as well as d-electrons of adsorbed TM atoms, thereby optimizing catalytic performance in terms of CO2 activation, limiting potential, reaction pathway, and final product composition. Notably, the Re@In2Se3 and Nb@In2Se3 catalysts can selectively produce different desired products on the same catalyst through ferroelectric polarization switching (Fig. 8B). Compared to conventional nonferroelectric substrates, such as Pd@C3N4, TMs exhibit significantly lower limit potentials and unique ferroelectric-controllable CO2 catalytic properties using In2Se3. Additionally, computational investigations employing reversible hydrogen electrode (RHE) and fixed-potential methodologies were conducted on TM single atoms (M = Fe, Co, Ni, Cu) supported on monolayer α-In2Se3, systematically evaluating polarization-switching effects on CO2 electroreduction mechanisms [134]. The results indicate thermodynamic preference for *OCHO intermediate formation during CO2 protonation, establishing this pathway as the predominant initiation step across the M@In2Se3 series. The computational screening identifies Co-embedded In2Se3 with carbon coordination (Co@In2Se3-C) as the optimal candidate, exhibiting the lowest theoretical overpotential (−0.385 V versus RHE) among the evaluated systems.
In addition, the synergistic effect between the metal cluster and ferroelectric substrate is anticipated to impact the CO2RR performance substantially. Yang et al. [135] comprehensively examined CO2 electroreduction pathways on Cu3 trimer catalysts supported by polar Janus MoSX (X = Se, Te) monolayers using DFT calculations. The broken vertical symmetry in these Janus structures induces intrinsic out-of-plane dipoles, creating asymmetric interfacial environments for Cu3 cluster stabilization on opposing polar facets. The computational results establish a strong correlation between substrate polarization vectors (both magnitude and orientation) and the CO2 reduction activity of supported Cu3 ensembles. Among all configurations, the S-terminated MoSTe-supported Cu3 catalyst [Cu3(S)@MoSTe] achieved peak performance for CH4 generation, exhibiting 3.2-fold higher activity than Se-terminated counterparts. This work elucidates the pivotal influence of Janus substrate polarization on adsorbate binding energetics, where tailored interfacial electric fields optimize intermediate stabilization and overall catalytic efficiency.
Conclusion and Perspective
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Ferroelectric materials possess spontaneous polarization and reversible switching properties that enable precise modulation of catalytic activity and selectivity in CO2 reduction for both photocatalytic and electrocatalytic pathways. These effects can significantaly tune the surface charges, electronic structure, adsorption behavior of reactants and products, and separation and migration of free charges, leading to controllable catalytic reaction pathways and enhanced photo-/electrocatalytic CO2RR selectivity and efficiency. In this short review, we comprehensively summarized the reaction mechanisms of ferroelectric polarization-modulated CO2RR, highlighted key advances in ferroelectrics-based photocatalyts/electrocatalysts for CO2RR, and discussed new strategies to enhance the catalytic efficiency of ferroelectric materials. While significant progress has been made in the field of ferroelectric catalysis for CO2RR, there are still many challenges to be addressed. Future research should focus on the design of novel high-efficient ferroelectric catalytic materials, the deeper understanding of the underlying mechanisms, and the development of synergistic strategies to achieve more efficient and selective CO2 reduction (Fig. 9).
First, future research should prioritize the rational design and well-controlled synthesis of high-efficient ferroelectric photo/electrocatalysts. Modulation strategies of ferroelectric catalysts include creating surface defects, introducing active sites, and tuning ferroelectric domain/domain walls. In particular, the emerging 2D ferroelectrics are the most promising candidates (e.g., SnSe [136,137], GaSe, Bi2O2Se [138], and CIPS [65]), which can be well controlled by modulating the strain/defects to enhance the spontaneous polarization. The key industrial challenges of 2D ferroelectric catalysts include their high production costs and stability. Therefore, high-throughput screening is required to combine with machine learning algorithms to build a database of 2D ferroelectric materials (including descriptors such as band gap, polarization strength, and adsorption energy) and screen for stable and low-cost ferroelectric materials and optimal ferroelectric–co-catalyst combinations. Moreover, polarization stability degradation due to the screening effect should also be carefully addressed, which can be improved by forming a ferroelectric–semiconductor heterojunction [139].
Second, a deeper understanding of the fundamental mechanisms underlying ferroelectric photo-/electrocatalysis is essential for material design and optimization of selectivity toward desired CO2RR products. Research should focus on identifying the key intermediates and transition states involved in these pathways and how they are influenced by the polarization field. In situ characterization techniques are desiable (e.g., electrochemical–piezoelectric force microscopy system) for directly detecting the evolution of the surface charge distribution during polarization flip in real time. Moreover, in situ spectroscopic techniques including surface-enhanced Raman spectroscopy (TR-SERS) and Fourier transform infrared (FTIR) can be used to reveal the dynamic changes of key intermediates (*COOH, *CO, etc.). Besides, multiscale simulations such as first-principles calculations and molecular dynamics simulations are required to reveal the effect of polarization direction on the energy barrier and the reaction kinetics, and finite element method (e.g., COMSOL) can be employed to simulate the electric field distributions.
Third, synergistic strategies combining multiple effects should be explored to combine ferroelectric polarization with complementary effects to improve CO2RR performance. The optimization of ferroelectric catalysts is chiefly concerned with enhancing polarization and adsorption capacity. Vacancy engineering, heterojunctions, and SACs have been identified as effective strategies for enhancing CO2RR activity. Consequently, further exploration is necessary to integrate diverse strategies to optimize the synergistic effect. For instance, for ferroelectric–photothermal synergy, the localized heating risks depolarization above Tc, and thus, alternative approaches (e.g., plasmonic heating below Tc, or strain-engineered thermally stable ferroelectrics) should be explored. Also, polyatomic active site engineering, which utilizes stabilizing complementary intermediates on the polarized surfaces (e.g., CO2-activated and C–C-coupled sites), is promising for selectively form multicarbons. Moreover, spatially graded reactors need to be developed, which can tailor polarization gradients to guide reactants through optimized adsorption, activation, and desorption zones.
Funding
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  • National Key Research and Development Program of China(2021YFB3800601)
  • Basic Science Center Project of the National Natural Science Foundation of China(52388201)
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doi: 10.34133/research.0843
  • Receive Date：2025-05-27
  • Online Date：2026-11-01
  • Published：2025-08-20
Article Data
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  • Received：2025-05-27
  • Revised：2025-07-26
  • Accepted：2025-07-26
Funding
National Key Research and Development Program of China(2021YFB3800601)
Basic Science Center Project of the National Natural Science Foundation of China(52388201)
Affiliations
    1State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China.
    2School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China.

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表12种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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