化学场驱动催化重整含氧生物质小分子制氢及串联协同降解高盐废水

With rapid development of economics in China during the past three decades, energy shortage and water pollution are becoming two major issues that we need to face today. To solve these problems, alternative techniques may depend on low temperature catalytic reforming of biomass into hydrogen and low-cost, efficient degradation of wastewater into nontoxic products. On the basis of previous study, in this project we propose a new tandem catalysis system by coupling H2 production and organic degradation in a “one-pot” reaction. First, we employ flexible fibers as the support and inorganic nanomaterials as the catalytically active sites to fabricate environmental catalytic fibers (ECF) in a unique organic/inorganic hybridization form. The recyclable ECF is then used for oxygen-promoted catalytic reforming of biomass derivatives (e.g., formaldehyde, formic acid, methanol and glycerinum) into H2 at low temperatures, as well as for simultaneous degradation of high salinity organics (e.g., dyes, phenols and pharmaceutical intermediates in sodium chloride solution) without the aid of external energy, such as photonic, thermal and electrical energy. Subsequently, we will investigate the surface/interface nature of ECF to confirm their catalytically active sites, determine the positive effect of fibers on inorganic catalyst, identify the reaction intermediates, and ultimately elucidate the reaction pathways, kinetics and mechanisms. The present tandem catalysis is believed to pave a new way to the future development of high performance, low cost, and energy saving materials for hydrogen production as well as harmful organic contaminants treatment.

能源危机和水污染是当今中国社会面临的两大难题，而利用生物质低温重整制氢以及低成本降解高盐有机废水是解决上述难题的有效途径之一。本项目采用柔性纤维作为载体，无机纳米催化剂为活性中心，设计构建有机/无机复合柔性环境催化纤维，在不依赖光、电、热等能量的作用下，利用氧气作为特殊的“催化剂”，对不同种类生物质有机小分子进行低温重整制氢（化学场驱动催化重整制氢），前期结果显示该体系制氢效率相比文献报道提高了两个数量级。同时，该制氢体系中产生的活性氧物种还能用于高盐有机污染物的高效净化处理（串联协同降解高盐废水）。本项目拟重点研究催化剂表界面化学场的形成作用机理、微观催化反应动力学和反应路径等一系列基础理论问题，阐明柔性环境催化纤维“组成−结构−催化性能”构效关系，揭示富氧条件下含氧有机小分子催化重整制氢和高盐有机废水氧化降解的串联协同反应增效机制，为开发新一代能源与环境材料提供新思路，开辟新途径。

本项目取得下述创新成果：. 一、我们利用氧气（O2）和低碳分子间的可逆氧化反应取代了OER过程，创新性地引入O2作为助催化剂，替代了贵金属Pt，从根本上改变了催化分解水制氢的反应路径，大幅提高了多场驱动低碳分子水溶液解耦催化制氢的反应速率，提出了解耦催化制氢反应新机理。研究成果在《ACS Catalysis》《J. Mater. Chem. A》《Appl. Catal. B-Environ》等期刊上发表论文10篇，授权发明专利4项。. 二、我们基于金属-载体强相互作用（SMSI效应）制备了具有核壳结构的新型Mbene催化剂，构建了微观形貌和电子状态可控的催化反应表界面，获得了兼具高活性和高稳定性的解耦催化分解水制氢材料；SMSI效应的引入不仅有效降低了催化反应能垒，还避免了催化剂在反应过程中的中毒失活现象，最终实现了高效、稳定催化低碳分子水溶液解耦制氢的目标。研究成果在《Advanced Materials》《Small》《J. Mater. Chem. A》等期刊上发表论文7篇，授权发明专利2项。. 三、我们采用先进纺织技术在聚氨酯等有机纤维上复合解耦催化制氢材料，设计制备了有机/无机耦合的能源催化纤维，用于串联降解有机污染物，现已成功应用于35000吨/天的规模化污水提标改造示范工程，3年实现经济效益15246.67万元，累计减排氨氮640吨，COD 3200吨。研究成果入选2020年“科创中国”先导技术榜单，在《Appl. Catal. B-Environ》等期刊上发表论文5篇，授权发明专利2项，成功转化1项（金额：100万元）。围绕这一研究方向，申请人参与了国家重点研发计划项目，获中国纺织工业联合会教育成果奖一等奖，“品字标浙江制造”团体标准以及2021年度浙江省生态环境科学技术三等奖各1项。