Wang Hongmei, Zhang Xiaoxu, Shen Ziqi, Ma Zichuan
Hebei Key Laboratory of Inorganic Nano-Materials, College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang 050024, China.
School of Environmental Science and Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, China.
Molecules. 2025 Jul 29;30(15):3171. doi: 10.3390/molecules30153171.
The recovery and abatement of volatile organic compounds (VOCs) have received increasing attention due to their significant environmental and health impacts. Supported sulfonic acid materials have shown great potential in converting aromatic VOCs into their non-volatile derivatives through reactive adsorption. However, the anchoring state of sulfonic acid groups, which is closely related to the properties of the support, greatly affects their performance. In this study, two supported sulfonic acid materials, SZO and SMO, were prepared by treating ZrO and MgO with chlorosulfonic acid, respectively, to investigate the influence of the support properties on the anchoring state of sulfonic acid groups and their reactive adsorption performance for -xylene. The supports, adsorbents, and adsorption products were extensively characterized, and the reactivity of SZO and SMO towards -xylene was systematically compared. The results showed that sulfonic acid groups are anchored on the ZrO surface through covalent bonding, forming positively charged sulfonic acid sites ([OZr-O]-SO3H) with a loading of 3.6 mmol/g. As a result, SZO exhibited excellent removal efficiency (≥91.3%) and high breakthrough adsorption capacity (ranging from 38.59 to 82.07 mg/g) for -xylene in the temperature range of 130 -150 °C. In contrast, sulfonic acid groups are anchored on the MgO surface via ion-paired bonding, leading to the formation of negatively charged sulfonic acid sites ([OMg]:OSOH), which prevents their participation in the electrophilic sulfonation reaction with -xylene molecules. This work provides new insights into tuning and enhancing the performance of supported sulfonic acid materials for the resource-oriented treatment of aromatic VOCs.
挥发性有机化合物（VOCs）的回收与减排因其对环境和健康的重大影响而受到越来越多的关注。负载型磺酸材料在通过反应吸附将芳香族VOCs转化为其非挥发性衍生物方面显示出巨大潜力。然而，磺酸基团的锚定状态与载体性质密切相关，极大地影响了它们的性能。在本研究中，分别用氯磺酸处理ZrO和MgO制备了两种负载型磺酸材料SZO和SMO，以研究载体性质对磺酸基团锚定状态及其对二甲苯反应吸附性能的影响。对载体、吸附剂和吸附产物进行了广泛表征，并系统比较了SZO和SMO对二甲苯的反应活性。结果表明，磺酸基团通过共价键锚定在ZrO表面，形成负载量为3.6 mmol/g的带正电磺酸位点（[OZr - O]-SO3H）。因此，SZO在130 - 150 °C温度范围内对二甲苯表现出优异的去除效率（≥91.3%）和高穿透吸附容量（38.59至82.07 mg/g）。相比之下，磺酸基团通过离子对键锚定在MgO表面，导致形成带负电的磺酸位点（[OMg]:OSOH），这阻止了它们参与与二甲苯分子的亲电磺化反应。这项工作为调整和提高负载型磺酸材料对芳香族VOCs进行资源化处理的性能提供了新的见解。
