金属-有机框架协同硫酸亚铁一步法还原六价铬及去除的研究和机理探讨

Chromium and its compounds are widely used in industrial production such as electroplating, metallurgy, building materials, anti-corrosion, dyes and other industries, which inevitably leads to the increasingly serious chromium pollution. To solve this problem, especially the high toxic Cr(VI)，one of the most basic ideas is the reduction and subsequent precipitation of chromium. In light of the redox mechanism, reduction and precipitation method performed by ferrous sulfate has the advantages of cheap raw materials, but its essence carried out step by step and the need to add additional acid, alkali are easy to cause the waste of manpower, material resources, and lead to acid, alkali pollution, as well as fail to treat with trace levels of chromium wastewater. These consequently become the bottleneck in the widespread application and technology. Taking this into account, along with the former research in this field, this project want to use metal-organic framework materials with high surface as a carrier, through ‘phenol-Fe’ interaction between the surface of material and ferrous sulfate, to promote the reduction of Cr(VI) by ferrous sulfate, then enrichment Fe(III), Cr(III) after this reaction, and simultaneity accelerate the hydrolysis of Fe(III), Cr(III) to give one-step reduction and removal of chromium. Further, we explore the influence on the method from various materials, so as to establish a molecular mechanism for the regulation of this approach; and carry out a series of characterizations, to establish the mechanism of the method and the structure-performance relationship, and new ways and new ideas for treating chromium containing wastewater and exploring metal organic framework materials in the field of environment.

铬及其化合物广泛应用于工业生产如冶金、电镀、建材、防腐、染料等行业，由此不可避免地导致日益严峻的铬污染。针对这一问题，特别是其中的高毒物质六价铬，最基本的思路是铬还原然后沉淀。基于氧化还原机理考虑，硫酸亚铁还原沉淀法因原料便宜等优点略显优势，但是其本质需分步进行且需额外的加酸、加碱，易造成人力、物力方面的浪费，同时易导致酸、碱污染、以及无法处理痕量级铬废水，成为制约该技术广泛应用和推广的瓶颈。鉴于此，本项目在前期研究基础上，拟以高比表面的金属-有机框架材料为载体，通过其表面的‘苯酚’基团促进硫酸亚铁还原六价铬，同时富集反应后的三价铁、三价铬，并加速三价铁、三价铬的水解，达到一步法硫酸亚铁还原六价铬及去除；探索材料的不同对该方法的影响，从而建立分子水平上的调控机制；通过一系列的表征，确立该方法的机理和相关构效关系，为含铬废水的处理以及金属-有机框架材料在环境领域的应用提供新途径、新思路。

铬及其化合物广泛应用于工业生产如冶金、电镀、建材、防腐、染料等行业，由此不可避免地导致日益严峻的铬污染。针对这一问题，特别是其中的高毒物质六价铬，最基本的思路是铬还原然后沉淀。基于氧化还原机理考虑，硫酸亚铁还原沉淀法因原料便宜等优点略显优势，但是其本质需分步进行且需额外的加酸、加碱，易造成人力、物力方面的浪费，同时易导致酸、碱污染、以及无法处理痕量级铬废水，成为制约该技术广泛应用和推广的瓶颈。. 本项目首次提出金属-有机框架材料协同硫酸亚铁一步法还原六价铬及去除，也就是后面我们总结的MOF+技术，通过本项目的研究，我们详细揭示了MOF+技术的基本原理、组装原理、和相关工艺技术。通过该技术，我们可以一步法去除六价铬，实现超高铬的吸附容量。此外，发展了该技术在能源、催化、环境方面的重要应用。. 在此基础上，我们在Angew. Chem. Int. Ed.、Ionrg. Chem.、Chem. Eur. J.等期刊上发表SCI论文多篇。本项目完成了预期的研究目标，建立了金属-有机框架材料协同硫酸亚铁一步法还原六价铬及去除相关工艺技术，完全证实了本项目的调控思路切实可行。该研究成果创立了一条去除铬污染的有效策略。