Gomis-Berenguer Alicia, García-González Raquel, Mestre Ana S, Ania Conchi O
1ADPOR Group, Instituto Nacional del Carbon (INCAR, CSIC), 33011 Oviedo, Spain.
2Centro de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa, Portugal.
Adsorption (Boston). 2017;23(2):303-312. doi: 10.1007/s10450-016-9851-4. Epub 2016 Dec 15.
Carbon xerogels with ultrahigh micro- and mesopore volumes were synthesized from the activation of polymeric resins prepared by sol-gel polycondensation of resorcinol/formaldehyde mixtures in basic medium and subcritical drying. Various activating conditions (e.g., agent, temperature, impregnation conditions) were used and it was found that the textural features of the resulting carbon xerogels are linked to the experimental procedure of the activation reaction to promote the porosity development. The shrinkage and structural collapse of the fragile resins typically obtained upon annealing at high temperatures (during carbonization and/or physical activation) is suppressed when the impregnation of the chemical activating agent is performed under controlled conditions. If the alkaline reagent (either KOH or KCO) is put in contact with the resin by wet impregnation (liquid/solid); under such conditions, the intimate contact between both compounds allows the formation of microporosity during the activation along with the enlargement and/or preservation of the mesoporosity of the pristine resin. Furthermore, the chemical activation via wet impregnation allows the combination of high surface areas and the preservation (even higher development) of the mesoporosity created during the synthesis of the resin. The effect of the impregnation method was found highly dependent of the reagent and activation temperature, highlighting the possibility to design micro-mesoporous carbon xerogels at low temperatures with a subtle control of the activation conditions.
通过在碱性介质中对间苯二酚/甲醛混合物进行溶胶 - 凝胶缩聚制备的聚合物树脂进行活化并经亚临界干燥,合成了具有超高微孔和中孔体积的炭气凝胶。使用了各种活化条件(如试剂、温度、浸渍条件),结果发现所得炭气凝胶的织构特征与促进孔隙率发展的活化反应实验过程有关。当在受控条件下进行化学活化剂的浸渍时,可抑制通常在高温退火(碳化和/或物理活化期间)时获得的易碎树脂的收缩和结构坍塌。如果通过湿浸渍(液/固)使碱性试剂(KOH或K₂CO₃)与树脂接触;在这种条件下,两种化合物之间的紧密接触会在活化过程中形成微孔,同时使原始树脂的中孔扩大和/或保留。此外,通过湿浸渍进行化学活化可实现高比表面积与树脂合成过程中形成的中孔的保留(甚至更高程度的发展)相结合。发现浸渍方法的效果高度依赖于试剂和活化温度,这突出了通过对活化条件进行精细控制在低温下设计微介孔炭气凝胶的可能性。