光催化二氧化碳还原反应（carbon dioxide reduction reaction，CO₂RR）被视为解决能源与环境困境的关键技术，开发高效高选择性的光催化剂是其核心挑战。然而，体相载流子快速复合与界面反应动力学迟缓进一步限制了其实际应用。铁酸铋（BiFeO₃，BFO）铁电体大的自发极化，可以优化载流子动力学，及其窄带隙特征，具有宽的光吸收范围，而被认为是最有前途的铁电半导体催化剂之一。因此本论文以BFO为基体，通过异质结构筑、调节表面电荷传输和活性位点优化策略，系统提升其催化性能并阐明作用机制。

传统异质结因其两相固有和不灵活的电子结构以及弱内建电场，限制了光催化CO₂还原效率和产物选择性。本研究通过水热法与热沉积法构建基于极化铁酸铋纳米片（BFO(P)）和硫化镉（CdS）的铁电S型异质结催化剂，以增强界面相互作用和催化性能。本征极化场的定向有效提升了静电电位差和能带弯曲，克服了传统催化机制氧化还原电位的局限性。异质结构的协同效应使载流子寿命延长至20 ns以上，表面光电压提升至BFO的1002倍。得益于优化的载流子动力学，该催化剂在不使用牺牲剂、光敏剂、贵金属或机械能的条件下，CO产率101.25 μmol g⁻¹ h⁻¹（选择性100%），分别为原始CdS和BFO的85.46和23.47倍，显著高于已报到铁电及无机半导体光催化剂，同时有效抑制了CdS的光腐蚀并表现出高量子效率。该工作不仅阐明了强极性与铁电态调控对异质结光催化性能的促进作用，还为高效CO₂光还原催化剂的设计提供了新策略。

针对BiFeO₃的导带位置不足导致的热力学限制和动力学迟缓问题，本研究系统地探讨了过渡金属M（M=Fe、Co、Ni、Cu）修饰及极化效应对BiFeO₃催化活性的影响。采用共沉淀法批量合成BFO纳米颗粒（_npBFO），并通过两步退火和电晕极化构建_npBFO-M铁电催化剂。研究发现，过渡金属d轨道的特殊性不仅能调节_npBFO表面电荷转移，还可以优化其能带结构。其中，电子受体型的Co和Fe，不仅可以捕获电子，还促进氧空位（O_V）形成，提供更多活性位点；电子桥接型的Ni和Cu，构建界面电荷转移通道，提高体相-表面电荷传输效率，且Cu可抑制O_V生成但增强羟基吸附能力。金属M均引起了平带电位负移，尤其_npBFO-10Co平带电位负移0.5 V，显著突破_npBFO的热力学限制，使CO产率达58.9 μmol g^-1 h^-1（较_npBFO提升8.3倍）。然而，极化处理可能因极化场与晶面取向失配而降低催化活性。这项工作不仅揭示了过渡金属对_npBFO能带结构及界面电荷转移机制的调控规律，还明确了晶面取向与极化场匹配对催化性能的关键作用。

为进一步实现高活性光催化CO₂还原，本研究通过水热法制备了BiFeO₃纳米片（_nsBFO）以增加活性位点暴露，并采用二步退火策略构筑了Co-Ag双金属位点修饰的_nsBFO10C3A催化剂。实验结果表明，Co-Ag双金属的负载，形成梯度电子传输通道，这不仅优化了催化剂表面的电荷转移，同时显著抑制了载流子复合。在无光敏剂、牺牲剂及机械能条件下，_nsBFO10C3A表现出显著的CO活性（80.13 μmol g^-1 h^-1），约为_nsBFO的7倍，选择性近100%。同时，双金属界面引起_nsBFO平带电位负移至-0.77 eV，同时满足了CO₂RR的热力学要求并提供充足电子供给。这项工作揭示了双金属位点的协同机制，为多金属-铁电复合催化体系的设计提供了新参考。

The photocatalytic carbon dioxide reduction reaction (carbon dioxide reduction reaction, CO₂RR) is regarded as a pivotal technology for addressing energy and environmental challenges. The development of highly efficient and selective photocatalysts is a central challenge in this field. However, the rapid complexation of bulk-phase carriers with sluggish interfacial reaction kinetics further limits its practical application. Bismuth ferrite (BiFeO₃, BFO) ferroelectrics are regarded as the most promising ferroelectric semiconductor catalysts due to their substantial spontaneous polarization, which can enhance carrier dynamics, and their narrow bandgap feature with a broad light absorption range. Consequently, this thesis utilizes BFO as a substrate to methodically enhance its catalytic performance and elucidate the mechanism of action through heterostructure construction, modulated surface charge transport, and active site optimization strategies.

Conventional heterojunctions suffer from intrinsic limitations including phase incompatibility, inflexible electronic structures, and weak built-in electric fields, which severely restrict the efficiency and product selectivity in photocatalytic CO₂ reduction. Herein, we constructed a ferroelectric S-scheme heterojunction catalyst by integrating polarized bismuth ferrite nanosheets (BFO(P)) with cadmium sulfide (CdS) via hydrothermal synthesis and thermal deposition. The oriented polarization field effectively enhanced the electrostatic potential difference and band bending, overcoming the redox potential limitations of conventional catalytic mechanisms. The synergistic effects of the heterostructure prolonged charge carrier lifetimes to over 20 ns and amplified the surface photovoltage to 1002 times that of pristine BFO. Benefiting from optimized carrier dynamics, the catalyst achieved a CO evolution rate of 101.25 μmol g^-1 h^-1 (100% selectivity) without sacrificial agents, photosensitizers, noble metals, or mechanical energy, representing 85.46- and 23.47-fold enhancements over pristine CdS and BFO, respectively. This performance surpasses most reported ferroelectric and inorganic semiconductor photocatalysts, while effectively suppressing CdS photo corrosion and maintaining high quantum efficiency. This work not only elucidates the critical role of strong polarization and ferroelectric state modulation in enhancing heterojunction photocatalytic performance but also provides a novel strategy for designing efficient CO₂ photoreduction catalysts.

The inherent thermodynamic limitations of bismuth ferrite (_npBFO), stemming from its insufficient conduction band position and sluggish charge kinetics, pose critical challenges for photocatalytic applications. This study systematically investigates dual modulation strategies involving transition metals (M = Fe, Co, Ni, Cu) and polarization engineering to overcome these constraints. _npBFO nanoparticles were synthesized via co-precipitation, followed by two-step annealing and corona poling to fabricate _npBFO-M ferroelectric catalysts. Systematic characterization revealed that the d-orbital characteristics of transition metals distinctly govern charge transfer and band structure remodeling, Electron-accepting Co/Fe dopants facilitated electron trapping and oxygen vacancy (O_V) generation, while charge-bridging Ni/Cu enhanced interfacial charge transfer efficiency and modulated hydroxyl adsorption capacities despite suppressing O_V formation. All M-dopants induced negative shifts in flat-band potentials, with _npBFO-10Co exhibiting a remarkable 0.5 V shift those significantly alleviated thermodynamic limitations, achieving a CO evolution rate of 58.9 μmol g^-1 h^-1 (8.3-fold enhancement vs. _npBFO). Crucially, polarization-induced charge redistribution partially counteracted catalytic activity when polarization fields mismatched with crystal facet orientation. This work establishes design guidelines for breaking activity bottlenecks in ferroelectric photocatalysts through rational facet-polarization alignment and meticulous electronic-structure engineering.

Despite advances in ferroelectric photocatalysis, achieving high-efficiency CO₂ reduction remains hindered by insufficient active site accessibility and uncontrollable charge recombination. To address these challenges, we developed a ferroelectric catalyst featuring cobalt-silver bimetallic sites on ultrathin bismuth ferrite nanosheets (_nsBFO10C3A) through hydrothermal synthesis coupled with a two-step annealing protocol. The synergistic interplay between Co-Ag bimetallic sites establishes a gradient electronic transfer pathway that simultaneously enhances surface charge mobility and suppresses bulk recombination. The engineered catalyst achieved exceptional CO₂-to-CO conversion with a production rate of 80.13 μmol g^-1 h^-1 (near 100% selectivity) in the absence of photosensitizers, sacrificial agents, or mechanical energy input, representing a 7-fold enhancement versus pristine _nsBFO. Spectro electrochemical analyses revealed that the bimetallic interface induced a substantial negative shift of the flat-band potential to -0.77 eV (vs. RHE), which simultaneously fulfills thermodynamic requirements for CO₂ reduction and enables sustained electron supply kinetics. This work demonstrates how strategic integration of multifetal active centers with nanoengineered ferroelectrics can overcome fundamental limitations in solar fuel production, providing atomic-level insights for designing high-performance photocatalytic architectures.

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