基于废旧锂电池资源化的钙钛矿催化剂设计及其催化氧化VOCs新方法研究

As the important precursor of PM2.5, volatile organic compounds (VOCs) are the main factors for haze in the cities in China. Catalytic oxidation is the most promising approach for oxidizing VOCs to CO2, H2O and other compounds at low temperature. However, due to the low catalytic activity and high preparation cost, traditional catalysts were limitted for industrial application. In this research, novel perovskite catalysts with high performance and low cost are developed via the purification, deployment and doping of acid leaching solution from spent lithium ion batteries. Meanwhile, The effects of the crystal structure with multiple B-site ions and the catalyst morphology on the catalytic oxidation of VOCs are discussed. The effects of Li, Na and Al impurities from the leaching solution on the catalytic activity, stability and toxicity of perovskites is also studied. By measuring the catalytic kinetic parameters and reactive oxygen species concentration, the catalytic kinetic model is established for VOCs oxidation catalyzed by the perovskite with multiple B-site ions, and the paths to reduce the apparent activation energy and improve the catalytic reaction rate are also searched. Consequently, this work is not only expected to provide an economical and feasible method for the advanced treatment of VOCs, but also to exploit a new route for the reuse of spent lithium ion batteries.

挥发性有机化合物(VOCs)作为PM2.5的重要前驱物，是造成我国城市灾害性雾霾天气的主要元凶之一。催化氧化技术可在低温条件下将有毒有害的VOCs氧化为CO2、H2O等物质而被认为是最有前景的处理方法。然而，目前的催化剂存在活性不高、价格昂贵等缺点，限制了该技术的进一步应用。本项目提出以废旧三元锂电池为原料，通过对三元锂电池酸浸液成分纯化、调配、掺杂，制备高性能、低成本的新型钙钛矿催化剂。研究基于浸出液的B位多元离子的钙钛矿晶体结构、形貌与VOCs降解的构效关系；探讨浸出液中Li、Na、Al等杂质离子对钙钛矿催化剂活性、稳定性及抗毒性的影响；通过测定催化动力学参数和活性氧浓度，建立B位多元掺杂钙钛矿催化剂催化氧化VOCs的催化动力学模型，寻找降低反应活化能、提高催化反应速率的途径。本项目的研究旨在为VOCs催化氧化提供一种经济可行的方法，同时为废旧锂电池资源化应用开辟一条新的途径。

挥发性有机化合物(VOCs)作为PM2.5的重要前驱物，是造成我国城市灾害性雾霾天气的主要元凶之一。催化氧化技术可在低温条件下将有毒有害的VOCs氧化为CO2、H2O等物质而被认为是最有前景的处理方法。然而，目前的催化剂存在活性不高、价格昂贵等缺点，限制了该技术的进一步应用。如何利用废旧锂电池为原料，开发高性能、低成本的新型过渡金属氧化物催化剂，实现VOCs催化氧化脱除是本项目的主要研究方向。通过对废旧锂电池酸浸液进行简单纯化和调配，成功研发了一系列高活性的过渡金属氧化物催化剂(LaMn1-xBxO3, MnOx-M, M-α@δ-MnO2, MnOx(MS)-Fe, MnOx(MS)-Ce, MnOx(MS)-Bi)。探讨了废旧锂电池酸浸液中杂质元素（如Li、Al等）对催化剂催化氧化VOCs性能的影响，揭示了杂质元素对催化氧化VOCs的正负作用机制。同时探究了催化剂合成方法对催化剂微观形貌结构的影响，确立了晶体结构、形貌与VOCs降解的相互关系，建立了催化剂催化氧化VOCs的催化动力学模型。为了提高催化剂的催化活性，通过酸处理、金属元素掺杂和晶型调控等方式，改善了催化剂自身的物理化学特性（如表面酸碱特性、孔隙特性），提高了催化反应速率，解决了过渡金属氧化物活性低的问题。本课题研究共发表SCI论文24篇，中文核心论文3篇，培养硕博士生共计10名。