文献类型：期刊文献

英文题名：Computation-guided surface functionalization of carbonaceous membranes for enhanced alcohol dehydration

作者：Li, Feng[1];Zhou, Yueqian[1];Lian, Cheng[1];Guo, Yaohao[2];Lei, Linfeng[1,2];Xu, Zhi[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, 130 Meilong Rd, Shanghai, Peoples R China;[2]Suzhou Lab, Suzhou 215125, Peoples R China

年份：2026

卷号：748

外文期刊名：JOURNAL OF MEMBRANE SCIENCE

收录：;EI(收录号：20261120286315);WOS:【SCI-EXPANDED(收录号:WOS:001721840600001)】；

基金：The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (22208096) , Jiangsu Funding Program for Excellent Postdoctoral Talent (2025ZB435) .

语种：英文

外文关键词：Carbon molecular sieve membranes; Alcohol dehydration; Surface functionalization; Density functional theory; Pervaporation

摘要：Carbonaceous membranes offer excellent thermal stability and molecular sieving capabilities for dehydration processes, yet their performance is often hindered by low water flux, which is critically dependent on surface chemistry. Despite extensive empirical surface functionalization efforts, the molecular-level role of specific functional groups in regulating water-selective adsorption remains unclear. Herein, density functional theory (DFT), a first-principles computational approach, was employed to systematically elucidate the role of surface functionalization in regulating water-selective adsorption and transport. A comparative investigation of oxygencontaining (-COOH, -OH, -C=O) and nitrogen-containing (graphitic, pyridinic, pyrrolic N) groups across diverse carbon environments reveals that hydroxyl (-OH) groups consistently yield the most selective enhancement of water adsorption. Specifically, hydroxyl functionalization increases water binding energies by 0.29 eV on graphitic surfaces, 0.36 eV at carbon edges, and 0.70 eV on amorphous carbon, exceeding the corresponding enhancements for methanol and ethanol. Charge-density difference analysis reveals localized electron accumulation at hydroxyl sites, consistent with the calculated increase in water binding energy and supporting strengthened hydrogen-bonding interactions. Guided by these theoretical insights, we fabricated carbon molecular sieve (CMS) hollow fiber membranes and conducted a surface modification via air plasma treatment to introduce oxygen-rich functionalities. Pervaporation experiments at 70 degrees C (90 wt% ethanol feed) demonstrated a 102% increase in permeation flux while maintaining a high water/ethanol separation factor of similar to 750 +/- 40. These results establish a quantitative structure-property relationship linking surface electronic structure, functional group and water-selective transport in carbon membranes, identifying hydroxyl functionalization as a highly effective strategy for energy-efficient ethanol dehydration.