工业化的快速发展导致有机染料废水污染问题日益突出，罗丹明B (RhB)、甲基橙 (MO) 等难降解染料对水体生态安全构成严重威胁。传统光催化技术虽具备绿色环保特性，但其实际应用受限于太阳能利用率低、光穿透性深度不足等瓶颈。因此，开发其他能量形式 (如机械能、热能和电能) 的新型的绿色催化技术势在必行。本研究以铁酸铋 (BiFeO₃，BFO) 与硫化锌镉 (Cd_xZn_1-xS，CZS) 为基体，基于缺陷工程、能带工程及异质界面设计策略，构建高效催化体系，系统探究催化剂在压电、热释电及铁电效应驱动下对RhB和MO的催化降解性能，揭示其对有机染料废水的高效降解机制。本研究的主要内容如下：

1、铁酸铋及硫化镉改性的铁酸铋催化剂制备及其催化性能研究

本研究通过尿素辅助煅烧法精准构建氧空位 (OVs) 浓度可调的BFO纳米催化剂，BFO-3样品因适中的OVs浓度展现出最优压电催化性能，对RhB和MO的降解率 (D) 分别达40.5%和25.9%。研究结果表明，催化活性增强机制源于OVs作为活性位点促进压电诱导的电子-空穴对 (e^--h⁺) 分离，加速生成超氧自由基 (O₂^-) 和羟基自由基 (∙OH)。为进一步提升催化性能，采用水热法在BFO-3表面包覆CdS纳米层，构建BFO-3@CdS复合材料。得益于CdS包覆层优化的载流子迁移效率，BFO-3@CdS-6样品在铁电、热释电及压电催化中性能显著提升：铁电催化下，经2.5 kV极化处理2 h后，7 h内RhB和MO的D分别提升至62.9%和51.1%；热释电催化中，经84次冷热循环 (25-65 °C) 后，D达52.6%和58.7%；压电催化下，超声105 min后D高达85.4%和52.4%。利用多样化的能量形式激发压电、热释电及铁电效应，促使BFO-3@CdS材料内部实现e^--h⁺的高效分离，进而将机械能、热能及电能有效地转化为化学能，使得BFO-3@CdS能够在较短时间内高效降解染料。

2、硫化锌镉及二硫化钼改性的硫化锌镉催化剂制备及其压电催化性能研究

本研究通过水热法合成Zn/Cd比例可调的CZS压电催化剂，研究结果表明CZS-9样品 (Zn/Cd=1:9) 具有最优的降解效率，在超声振动105 min后对RhB和MO的D分别达到40.5%和25.9%。能带结构分析表明，Cd含量的增加显著优化了材料能带结构，使导带位置更负、价带位置更正，从而增强e^--h⁺对的氧化还原能力。进一步构建的CZS-9/MoS₂异质结复合材料在7% MoS₂包覆量时展现出优异的压电催化性能，RhB和MO的D分别提升至90.8%和57.9%，这归因于CZS-9与MoS₂的协同效应增强了压电响应，促进载流子分离与迁移效率，实现对染料的高效降解。

综上所述，本研究通过异质界面设计策略，构建BFO-3@CdS和CZS-9/MoS₂复合催化体系，显著促进载流子的分离与迁移，实现对有机染料的高效降解，并探明了材料结构与催化性能的构效关系，揭示了压电催化材料对有机染料的高效降解机制，为开发高性能压电催化剂及推进工业废水深度处理技术提供了创新思路。

The rapid development of industrialization has led to prominent pollution issues from organic dye wastewater, where refractory dyes such as Rhodamine B (RhB) and Methyl Orange (MO) pose serious threats to aquatic ecological safety. Although traditional photocatalytic technology exhibits environmentally friendly characteristics, its practical application is constrained by bottlenecks such as low solar energy utilization efficiency and insufficient light penetration depth. Therefore, it is imperative to develop novel green catalytic technologies utilizing other energy forms (e.g., mechanical energy, thermal energy, and electrical energy). This study employs bismuth ferrite (BiFeO₃ BFO) and cadmium zinc sulfide (Cd_xZn_1-x CZS) as matrix materials. Through defect engineering, bandgap engineering, and heterointerface design strategies, we construct high-efficiency catalytic systems to systematically investigate the catalytic degradation performance of RhB and MO driven by piezoelectric, pyroelectric, and ferroelectric effects. The mechanisms underlying the efficient degradation of organic dyes will be elucidated. The main contents of this study are as follows:

1. Synthesis and investigation of catalytic performance of bismuth ferrite and cadmium sulfide-modified bismuth ferrite catalysts

This study precisely constructed BFO nanocatalysts with tunable oxygen vacancy (OVs) concentration via the urea-assisted calcination method. The BFO-3 sample exhibited optimal piezoelectric catalytic performance due to its appropriate OVs concentration, with the degradation rates (D) for RhB and MO reaching 40.5% and 25.9%, respectively. The enhanced catalytic activity originates from OVs acting as active sites to promote piezoelectric-induced electron-hole pairs (e^--h⁺) separation, accelerating the generation of superoxide radicals (⋅O₂^-) and hydroxyl radicals (⋅OH). To further improve catalytic performance, a CdS nanolayer was coated on BFO-3 surface via hydrothermal method to construct BFO-3@CdS composite. Benefiting from optimized carrier migration efficiency by CdS coating, BFO-3@CdS-6 exhibits significantly enhanced performance in ferroelectric, pyroelectric, and piezoelectric catalysis: Under ferroelectric catalysis after 2.5 kV polarization for 2 h, RhB and MO degradation rates increase to 62.9% and 51.1% within 7 h; In pyroelectric catalysis after 84 thermal cycles (25-65°C), degradation rates reach 52.6% and 58.7%; Under piezoelectric catalysis, 85.4% and 52.4% degradation rates are achieved after 105 min ultrasonication. The diversified energy forms (mechanical, thermal, and electrical) activate piezoelectric, pyroelectric, and ferroelectric effects to realize efficient e^--h⁺ separation in BFO-3@CdS, effectively converting these energy forms into chemical energy. This enables BFO-3@CdS to achieve rapid and efficient dye degradation within short durations

2. Preparation of zinc cadmium sulfide and molybdenum disulfide-modified zinc cadmium sulfide catalysts and study of their piezoelectric catalytic performance

This study synthesized CZS piezoelectric catalysts with tunable Zn/Cd ratios via the hydrothermal method. The results show that the CZS-9 sample (Zn/Cd=1:9) possesses the optimal degradation efficiency, with the D for RhB and MO reaching 40.5% and 25.9%, respectively, after 105 min of ultrasonic vibration. Band structure analysis reveals that increased Cd content significantly optimizes the material’s energy band structure, rendering a more negative conduction band position and a more positive valence band position, thereby enhancing the redox capability of e^--h⁺ pairs. The further-constructed CZS-9/MoS₂ heterojunction composite with 7% MoS₂ coating exhibits exceptional piezoelectric catalysts performance, elevating RhB and MO degradation rates to 90.8% and 57.9%. This enhancement is attributed to the synergistic effect between CZS-9 and MoS₂, which strengthens the piezoelectric response, promotes carrier separation and migration efficiency, and achieves efficient dye degradation.

In summary, this study employs a heterointerface design strategy to construct BFO-3@CdS and CZS-9/MoS₂ composite catalytic systems, which significantly enhance carrier separation and migration, achieving efficient degradation of organic dyes. The structure-activity relationships between material architectures and catalytic performance are systematically elucidated, and the mechanisms underlying the efficient degradation of organic dyes by piezoelectric catalytic materials are clarified. This work provides innovative insights for developing high-performance piezoelectric catalysts and advancing advanced industrial wastewater treatment technologies.

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