光响应型金属-有机多面体对有害有机添加剂的识别及光降解研究

Recognition and photocatalytic degradation of harmful organic additives in food are the core subjects in food safety fields and chemical frontier development. In this research field, probes with the rapid response time and high selectivety for recognition of harmful organic additives in food are very few, and inorganic oxides are the primary photocatalysts for photocatalytic degradation, whose wide application is limited by their poor ability of solar harvesting. With the inspiration from native enzyme, constructing the functionalized luminescent Metal-organic Polyhedra (MOPs) for mimic enzyme recognition and catalysis are an effective way to solve the above problem. Metal-organic Polyhedra, which have recently emerged as an interesting class of porous molecules built from organic ligands and inorganic ions, is a promising artificial system for the integration of individual functional components in a structurally controlled manner. In this project, we will choose the organic fluorescent N-Phenylcarbazole as bones, and integrate aromatic interactive sites, amide group, to produce tridentate conjugate ligands, which self-assemble with metal ions with configuration matching, further construct the MOPs with the confined cavity, fluorescent signal output, hydrogen bonding and aromatic interactive sites. They have ability to recognize and distinguish the harmful organic additives with different types sensitively and selectively through the size-, shape- and synergistic multiple weak interactions matching inner polyhedra, innovating a new identification method. At the meantime, choosing bivalent cobalt ion as metal nodes, the metal-organic polyhedra with fluorescence activity and cobalt-based catalytic centers are performed to light-driven catalyze the degradation of harmful organic additives on the basis of the supramolecular recognition. We hope this project can provide a new research idea to build rapid detection system for food safty area.

食品中有害有机添加剂的识别和光降解，是食品安全领域和化学前沿发展的核心课题之一。在该领域内，高选择性的识别体系非常有限，且光催化剂主要以无机氧化物为主，受限于材料低的太阳光利用率。受到自然界光合成的启发，通过构筑具有可见光吸收的金属-有机多面体进行模拟酶识别和催化是一条行之有效的途径。本项目选择具有荧光发射功能的N-苯基咔唑衍生配体，与合适的金属离子配位自组装得到结构稳定、多重弱作用位点明确和限域的金属-有机多面体，利用结构的空间约束性和其协同的多重弱作用位点与食品中有害有机添加剂之间弱作用的匹配，达到对其选择性的识别；同时通过配体可见光区吸收的调节和选择钴离子为金属节点，作为催化中心，构筑出集可见光吸收和钴催化中心于一体的金属-有机多面体，借助于绿色的太阳光，在超分子识别的基础上进行模拟酶光催化相关添加剂降解的研究。希望该研究为建立快速食品安全检测体系提供新的研究思路。

面对全球环境污染和能源危机的巨大挑战，制备污染物检测、去除和清洁能源产生为导向的的多功能材料，是发展可持续发生和原子经济的有效途径之一，具有重要的社会意义和学术价值。本项目重点研究了光功能金属-有机配合物的组装、基于弱作用协同对有害污染物的检测、光催化污染物的降解/去除和清洁能源的产生四个方面的研究内容。发展了多例首次基于MOFs材料对有害污染物检测的方法：其中汞离子的比率荧光检测方法，检测速度快、操作简便、无需复杂前处理、成本较低；对pH可逆检测的传感材料，作用机理明确，将在离子分析领域有较大的应用可行性及广阔前景；提出了基于多重弱作用协同机制对苦味酸爆炸物检测的方法，为发展和构建安全、和谐的安全检测、保护体系具有重要的指导意义；制备了对挥发性有机醇类同系物选择性检测的材料，发展其对于铁离子的皮克“裸眼”可视化检测，将会推进多功能材料在实验室甚至是日常生活中的潜在应用；报道了高效、高活性的光催化材料，潜在的推动了光解水制氢材料向实际应用的迈进，包括纯水体系应用、高效率和高的稳定性。发表IF＞3的SCI论文10篇，申请中国专利1项。具体为：J. Mater. Chem. A（2篇）、Chem. Commun.（1篇）、Inorg. Chem.（2篇）、Chem. Eur. J.（1篇）、Dyes Pigments（1篇）、New J. Chem.（1篇）和RSC Adv.（2篇）。多篇研究成果被Chem. Soc. Rev.，Micropor. Mesopor. Mat.，ChemPlusChem等杂志的综述文章大篇幅评价和报道，部分成果也在X-MOL平台及MOFs在线予以推荐介绍。