CAS: Collaborative Research: Ambient Polyvinyl Chloride (PVC) Upgrading Using Earth-Abundant Molecular Electrocatalysts

在化学系化学结构、动力学和机理B(CSDM-B)计划的支持下，辛辛那提大学化学系的蒋建兵和宾厄姆顿大学化学系的Julien Panetier正在开发新的催化剂，以促进小分子转化和聚氯乙烯升级。本研究的目的是利用过渡金属络合物的特性来开发新型催化剂，并从实验和计算的角度研究它们与聚氯乙烯的活性。该项目位于有机金属化学、材料和计算化学的结合点，因此，合作研究团队处于有利地位，可以为学生提供跨学科的教育和培训。涉及普通公众和代表性不足群体的外联活动也将是得到资助的项目的一部分。聚氯乙烯(PVC)是世界上产量第三大的合成塑料聚合物，广泛用于各种工业和家庭应用。然而，传统的聚氯乙烯修复和升级战略需要高能量投入，并产生对环境有害的化学物质，如HCl。本项目旨在探索富含稀土的分子催化剂，在环境条件下将聚氯乙烯转化为环境友好的高附加值聚合物。在这个研究项目中，研究小组将(I)研究用于烷基C-Cl键加氢脱氯的配体和金属中心的合理组合，(Ii)探索以二氧化碳为原料的C-Cl羧化反应，以及(Iii)考察温度和聚氯乙烯构型对电催化C-Cl活化和聚氯乙烯升级的影响。初步结果表明，在常温下的电化学条件下，镍-钳形络合物可以高产率地将烷基氯化物转化为烷基羧酸盐。建议的设计原则将允许对分子催化剂和电化学条件进行系统研究，以促进聚氯乙烯C-氯键的活化和转化。该项目结合了分子工程、材料科学、光谱学和计算，有可能为未来有关聚氯乙烯转化的可持续化学解决方案提供信息。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With support from the Chemical Structure, Dynamics & Mechanisms-B (CSDM-B) Program of the Chemistry Division, Jianbing Jiang of the Department of Chemistry at the University of Cincinnati, and Julien Panetier of the Department of Chemistry at Binghamton University are developing new catalysts to promote small molecule conversion and polyvinyl chloride upgrading. The goal of this research is to exploit the characteristics of transition metal complexes for the development of novel catalysts and study their activity with polyvinyl chloride from both an experimental and a computational standpoint. The project lies at the nexus of organometallic chemistry, materials, and computational chemistry and the collaborative research team is, therefore, well positioned to provide students with interdisciplinary education and training. Outreach activities involving the general public and underrepresented groups will also be part of the funded project. Polyvinyl chloride (PVC), the third-most-produced synthetic plastic polymer worldwide, is widely used in various industries and household applications. However, traditional PVC remediation and upgrading strategies require high energy inputs and generate environmentally hazardous chemical species, such as HCl. This project aims to explore earth-abundant molecular catalysts for the conversion of PVC into environmentally friendly and value-added polymers under ambient conditions. In this research project, the research team will (i) examine a rational combination of ligands and metal centers for the hydrodechlorination of alkyl C–Cl bonds, (ii) explore C–Cl carboxylation using CO2 as the C1 feedstock, and (iii) investigate the effects of temperature and PVC configuration on electrocatalytic C–Cl activation and PVC upgrading. Preliminary results show that Ni-pincer complexes can convert alkyl chlorides into alkyl carboxylates in high yields under ambient electrochemical conditions. The proposed design principles will allow the methodical study of molecular catalysts and electrochemical conditions to facilitate the activation and conversion of PVC C–Cl bonds. This project combines molecular engineering, materials science, spectroscopy, and computation and has the potential to inform future sustainable chemistry solutions regarding polyvinyl chloride transformation.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.