静电辅助氢键对环境中PPCPs吸附行为的影响及作用机制

Pharmaceuticals and personal care products (PPCPs), a class of emerging ionizable organic contaminants，continuously appeared in the natural environment have caused global concerns due to their potential risks to the public health and environment. Previous researches have indicated that PPCPs could be effectively adsorbed by carbon-based adsorbents and controlled their risk. But researchers generally ignored the key problem that how negatively charged PPCPs could be efficiently adsorbed on the negatively charged sorbent surfaces. Our previous work pioneering pointed out that adsorption of weak organic acids to O-enriched carbon nanotubes is enhanced by formation of exceptionally strong hydrogen bonds at the surface, known as negative charge-assisted hydrogen bonds (CAHB), a subset of the low-barrier H-bond. But for homonuclear/heteronuclear properties of CAHB, compared the strength with ordinary hydrogen bonds and its contribution in the environmental behaviors of PPCPs are all unknown. Therefore, in this study, several different kinds of PPCPs will be selected to comparative research the role and contribution of CAHB in the adsorption of PPCPs by typical carbon-based adsorbents (carbon nanotubes and biochar) and mineral oxides. Model compounds will be selected to establish homonuclear/heteronuclear CAHB adsorption system, and the strength of homonuclear hydrogen bond, heteronuclear hydrogen bond and ordinary hydrogen bond will be compared by different experiments, such as competitive adsorption experiments, pH condition experiments. Especially, on the basis of the D2O isotope tracer experiment, using ATR-FTIR and NMR to provide molecular level evidence for CAHB. This work will get new insight into the environmental fate of PPCPs and their risk, and also provide theoretical support for development of efficient and selective removal materials and technology for PPCPs control in the environment.

药品及个人护理品（PPCPs）因被广泛使用而不断进入环境，对人类健康和生态安全的潜在危害日趋明显。碳基吸附剂可以很有效吸附PPCPs从而控制其风险，不过带负电有机分子如何在表面带负电吸附剂上高效吸附，目前仍缺乏深入认识。申请人前期研究指出，静电辅助氢键（charge-assisted H-bond, CAHB）在碳纳米管吸附有机弱酸中的显著作用，但对CAHB的同核/异核属性、作用强度及其在PPCPs吸附中的贡献均未知。本研究将对比CAHB在两种典型碳基吸附剂和矿物吸附PPCPs中的作用及贡献，利用模型化合物，构建同核/异核CAHB作用体系；通过竞争吸附、pH条件试验等，识别不同类型氢键的强弱；特别是在D2O同位素示踪试验的基础上，用ATR-FTIR和NMR获取CAHB在分子层面的成键证据，为PPCPs的环境风险评价提供新视角，也为开发高效选择性去除PPCPs的控制材料和技术提供理论支持。

药品及个人护理品（PPCPs）因被广泛使用而不断进入环境，对人类健康和生态安全的潜在危害日趋明显。碳基吸附剂可以很有效吸附PPCPs从而控制其风险，不过带负电有机分子如何在表面带负电吸附剂上高效吸附，还缺乏深入认识。申请人前期研究指出，静电辅助氢键（charge-assisted H-bond, CAHB）在碳纳米管吸附有机弱酸中的显著作用，但对CAHB的同核/异核属性、作用强度及其在PPCPs吸附中的贡献均未知。本研究对比了CAHB在两种典型碳基吸附剂和矿物吸附PPCPs中的作用及贡献，利用模型化合物，构建同核/异核CAHB作用体系；通过竞争吸附、pH条件试验等，识别了不同类型氢键的强弱；特别是在D2O同位素示踪试验的基础上，用ATR-FTIR和NMR获取CAHB在分子层面的成键直观证据。通过本项目，项目负责人共发表学术论文3篇，其中在Journal of Hazardous Materials和Science of the Total Environment环境类TOP期刊SCI论文两篇，在《中国环境科学》发表EI论文一篇，这些研究结果为PPCPs的环境风险评价提供新视角，也为开发高效选择性去除PPCPs的控制材料和技术提供理论支持。