拟荷叶层设计增强13X沸石的表面疏水性和CO₂吸附性能

Pseudo Lotus Leaf Layered Design to Enhance the Surface Hydrophobicity and CO₂ Adsorption Capability of 13X Molecular Sieve

摘要

通过拟荷叶层结构设计, 在13X分子筛表面构建聚苯乙烯-甲基丙烯酸甲酯(PS-PMMA)疏水层, 制备了PS-PMMA/13X分子筛. 通过集成有机纳米表面结构拟荷叶层的方法, PS-PMMA与13X分子筛的复合过程条件温和, 不破坏分子筛晶体结构, 所得PS-PMMA/13X分子筛可耐370 ℃高温, 水接触角提升至127.6°. 本文方法赋予了13X分子筛卓越的疏水性, 同时保持了其固有的吸附性能. 静态吸附实验结果表明, PS-PMMA_0.05/13X分子筛对CO₂吸附遵循Langmuir模型并表现为物理吸附; 经6 h浸水-干燥处理后在10次循环中仍保持超过92%的吸附容量. 此外, 在15%相对湿度和15%(体积分数)CO₂的模拟湿烟气条件下, 其CO₂吸附容量达0.045 g/g, 比未改性13X分子筛提高73%, 有效抑制了水汽的竞争吸附. PS-PMMA_0.05/13X分子筛在高温、低浓度及湿润环境中均表现出优异的CO₂吸附性能, 且制备方法简单, 具有良好的工况碳捕集应用潜力.

Abstract

A polystyrene-poly(methyl methacrylate)(PS-PMMA) hydrophobic layer was constructed on the surface of 13X molecular sieve and PS-PMMA/13X molecular sieve was prepared via a biomimetic lotus-leaf-like structural design. By integrating an organic nanoscale surface architecture, the fabrication of PS-PMMA/13X molecular sieve was achieved under mild conditions without disrupting the crystalline framework of the 13X molecular sieve, while maintaining thermal stability up to 370 ℃. The water contact angle increased to 127.6°, indicating significantly enhanced hydrophobicity. The modified 13X molecular sieve exhibited excellent water resistance while preserving its intrinsic adsorption properties. Static adsorption results revealed that CO₂ adsorption on PS-PMMA_0.05/13X follows the Langmuir model and is dominated by physisorption. After 6 h of water immersion followed by drying, the material retained over 92% of its adsorption capacity after ten cycles. Furthermore, under simulated humid flue gas conditions [15% relative humity(RH) and 15%(volume fraction) CO₂], the CO₂ adsorption capacity reached 0.045 g/g, representing a 73% increase compared to pristine 13X molecular sieve, effectively suppressing competitive adsorption from water vapor. The PS-PMMA_0.05/13X molecular sieve demonstrates excellent CO₂ adsorption performance under high temperature, low concentration, and humid conditions. With a simple preparation method and robust performance, it shows strong potential for practical carbon capture applications.

关键词

13X分子筛 / 表面改性 / 二氧化碳捕集

Key words

13X molecular sieve / Surface modification / Carbon dioxide capture

参考文献

[1] Bashir A., Ali M., Patil S., Aljawad M. S., Mahmoud M., Al—Shehri D., Hoteit H., Kamal M. S., Earth—Sci. Rev., 2024, 249, 104672

[2] Mirziyoyeva Z., Salahodjaev R., Front. Energy Res., 2023, 11, 1123269

[3] Zhang X., Li K., Ma Q., Fan J. L., Chin. J. Popul. Resour., 2021, 31(9), 29-33

[4] (张贤, 李凯, 马乔, 樊静丽 . 中国人口·资源与环境, 2021, 31(9), 29-33)

[5] Zhang L. Y., Song Y. F., Shi J., Shen Q., Hu D., Gao Q., Chen W., Kow K. W., Pang C. H., Sun N. N., Adv. Atmos. Sci., 2022, 39(8), 1252-1270

[6] Hong W. Y., Carbon Capture Sci. T., 2022, 3, 100044

[7] Qi G. G., Meng X. J., Chem. J. Chinese Universities, 2023, 44(10), 9-18

[8] (戚刚刚, 孟祥举 . 高等学校化学学报, 2023, 44(10), 9-18)

[9] Najafi A. M., Soltanali S., Khorashe F., Ghassabzadeh H., Chemosphere, 2023, 324, 138275

[10] Yin Y. K., Wu J. L., Wang X. Y., Ma K., Zhai W. J., Wu Z. J., Zhang J. B., Chem. Eng. Sci., 2024, 288, 119838

[11] Wang Z. P., Yu J. H., Xu R. R., Chem. Soc. Rev., 2012, 41(5), 1729-1741

[12] Huang W. W., Ren J. W., Fang Q. R., Valtchev V., Chem. J. Chinese Universities, 2018, 39(6), 1127-1131

[13] (黄薇薇, 任家旺, 方千荣, Valtchev V. 高等学校化学学报, 2018, 39(6), 1127-1131)

[14] Yang X. D., Wang Q. S., Chen J., Liu H. B., Xu L. P., Rao M. J., Processes, 2024, 12(8), 1547

[15] Lu J. H., Tang J. J., Li J. M., Wang S. L., Appl. Therm. Eng., 2022, 213, 118746

[16] Mi Z. R., Lu T. T., Zhang J. N., Xu R. R., Yan W. F., Chem. Res. Chinese Universities, 2022, 38(1), 9-17

[17] Wang B. H., Zhu Y., Qin Q. Y., Liu H. X., Zhu J., Appl. Catal. A: Gen., 2021, 611, 117952

[18] Cao B. N., Jia Q., Li G. Q., Cui H. T., Li F., Peng B., Li L., Chem. Commun., 2025, 61(83), 16274-16277

[19] Lu X. X., Hu H. L., Lv X. J., Zhang Y. X., Zhang J., Mod. Chem. Ind., 2023, 43(10), 105-110

[20] (卢欣欣, 胡华雷, 吕晓静, 张业新, 张建 . 现代化工, 2023, 43(10), 105-110)

[21] Babić V., Koneti S., Moldovan S., Debost M., Gilson J. P., Valtchev V., Micropor. Mesopor. Mat., 2022, 329, 111513

[22] Pliekhov O., Pliekhova O., Arčon I., Bondino F., Magnano E., Mali G., Logar N. Z., Micropor. Mesopor. Mat., 2020, 302, 110208

[23] Yin T., Meng X., Jin L. P., Yang C., Liu N. W., Shi L., Micropor. Mesopor. Mat., 2020, 305, 110327

[24] He X. R., Xue B., Wei R. X., Liao K. L, Li G. Y., Zhao T. B., Energ. Convers. Manage., 2024, 313, 118612

[25] Jovellana J. A. K. P., Pajarito B. B., Key Eng. Mater., 2019, 801, 179-184

[26] Li Y. X., Shen J. X., Peng S. S., Zhang J. K., Wu J., Liu X. Q., Sun L. B., Nat. Commun., 2020, 11(1), 3206

[27] Liu M., Jiang L., Adv. Funct. Mater., 2010, 20(21), 3753-3764

[28] Dumbre D., Ayoub E., Dawaymeh F., Abbas Y., Elmhamdi A., Matouk Z., Alazzam A., Khaleel M., Alamoodi N., Eur. Polym. J., 2024, 218, 113365

[29] Nalawade S. P., Picchioni F., Marsman J. H., Janssen L. P. B. M., J. Supercrit. Fluids, 2006, 36(3), 236-244

[30] Zhang K., He G. Y., Wang N., Dong Z. Y., Ma Y. H., Xu J., Mei D. H., Sun Q. M., Yu J. H., J. Am. Chem. Soc., 2025, 147(30), 26277-26285

[31] Liu J. B., Sun X. Z., Li N., Tan T. T., Zhang F., Sun M., Liu Q., Env. Pollut. Bioavail., 2024, 36(1), 2387683

[32] Xu Q., Lu J. Y., Zhou Z. Y., Jin Y. J., Sep. Purif. Technol., 2025, 369, 133147

[33] Sun Y. B., Tang J. F., Li G. Y., Hua Y. H., Li H., Hu S. Y., ACS Omega, 2022, 7(22), 18542-18551

[34] He W. Y., Wang J., Li Y. X., Ye W. H., Jing C., Lv M. H., Huang H. M., Fu M. L., Wu J. L., Hu Y., Ye D. Q., Acta Sci. Circ., 2022, 42(3), 373-383

[35] (何文宇, 王婧, 李艳霞, 叶文桦, 井察, 吕明慧, 黄皓旻, 付名利, 吴军良, 胡芸, 叶代启 . 环境科学学报, 2022, 42(3), 373-383)

[36] Yan X. H., Li P., Yuan H., Huang W., Hu Z., Yang R. T., Sep Purif. Technol., 2025, 354, 129304

[37] Krishnan M. R., Aldawsari Y. F., Alsharaeh E. H., J. Appl. Polym. Sci., 2021, 138(9), 49942

[38] Cheng X. Y., Wu C. L., Wu X., Li H. X., Coal Convers., 2021, 44(3), 76-82

[39] (程晓莹, 武成利, 吴祥, 李寒旭 . 煤炭转化, 2021, 44(3), 76-82)

[40] Si Y. C., Wu T., Multipurpose Util. Miner. Resour., 2022, 43(4), 157-161

[41] (司玉成, 吴涛 . 矿产综合利用, 2022, 43(4), 157-161)

[42] Aldosari M. A., Alsaud K. B. B., Othman A., Al—Hindawi M., Faisal N. H., Ahmed R., Michael F. M., Krishnan M. R., Asharaeh E., Polymers, 2020, 12(5), 1155

[43] Dai R. J., Zhao Y. Q., Zhai Q. C., Wang S. Y., Li H., Chen X. X., Yu J. L., Dou J. X., Colloid Surface A., 2025, 716, 136716

[44] Krishnan M. R., Alshabib R. M., Alsharaeh E. H., Polymers, 2025, 17(14), 1970

[45] Madhu J., Santhanam A., Natarajan M., Velauthapillai D., RSC Adv., 2022, 12(36), 23221-23239

[46] Ren W. R., Zhou G. L., Li R. H., Jiang W. L., Wang Z. R., Li J. C., Xuan S. G., Cui Y. X., Pet. Process. Pet., 2024, 55(12), 13-21

[47] (任文瑞, 周广林, 李汝晗, 姜伟丽, 王仲戎, 李继聪, 宣守国, 崔玉鑫 . 石油炼制与化工, 2024, 55(12), 13-21)

[48] Mi Z. R., Li S. J., Liu W., Wang J., Deng D. H., Liu P. S., Tian P., Liu C., Yan W. F., Zhu K. K., J. Am. Chem. Soc., 2025, 147(20), 16922-16934

[49] Xu Z. C., Yu Z. D., Wu H. F., Wu P. W., Wu H. X., Chao Y. H., Zhu W. S., Liu Z. C., Xu C. M., CIESC J., 2025, 76(5), 2198-2208

[50] (徐智超, 俞镇东, 吴昊峰, 吴沛文, 武洪翔, 巢艳红, 朱文帅, 刘植昌, 徐春明 . 化工学报, 2025, 76(5), 2198-2208)

[51] Zhan F., Gao W. N., Zhao F., Qin P., Sun X. L., Sun C. K., Tang S. S., Wang L., Soft Matter, 2022, 18(11), 2123-2128

[52] Shen Y., Yang X. W., Zheng J. Y., Liang Y. H., Zhao X. X., Ying Z. Y., Zhao J. K., Ye J. X., Zhang S. H., Sep. Purif. Technol., 2025, 373, 133488

[53] Olushola S. B., Bocus K. M. A., Devnath B., Reza M. T., Pahinkar D. G., Surf. Interf., 2026, 83, 108554

[54] Hu M. H., Qie Z. P., Liu Z. B., Lu X. P., Bai S. Y., Lv L, Wang Z. P., Xiang H. Z., Ou X. X., Zhuang Y. Y., Micropor. Mesopor. Mat., 2025, 384, 113465

[55] Han C. H., Teng Y., Zhang K., Acta Sci. Circ., 2026, 46(1), 310-320

[56] (韩晨浩, 滕阳, 张锴 . 环境科学学报, 2026, 46(1), 310-320)

[57] Zhou A. G., Yang C. R., Xue M., Xue B., Zheng J. L., Li X. C., Nie F., Zhao X. L., Mi J. G., Sep. Purif. Technol., 2025, 355, 129689

[58] Kwon D. I., Kim J. C., Lee H., Lee W., Jo C., Chem. Eng. J., 2022, 427, 131461

[59] Zhao T., Wei Y. J., Wang J. W., Wang Q., Chen Y. L., Liu X. Z., Zhao Y. F., Sep. Purif. Technol., 2023, 317, 123762

[60] Gao F., Li Y. K., Bian Z. J., Hu J., Liu H. L., J. Mater. Chem. A., 2015, 3(15), 8091-8097

[61] Miyamoto M., Ono S., Kusukami K., Oumi Y., Uemiya S., ChemSusChem, 2018, 11(11), 1756-1760

基金资助

国家自然科学基金(31960211)

国家自然科学基金(81960651)

贵州省高层次创新型人才基金(QKHPTRC-GCC[2023]-024)

贵州省自然科学基金(QKHPTRC-CXTD[2023]005)

贵州大学引进人才科研项目([2023]33)

贵州大学基础研究项目([2023]18)

贵州省能源智能开发与高效利用实验室开放基金(GEL-KY-2025-012)