Aldulaijan Sarah, Ajeebi Afnan M, Jedidi Abdesslem, Messaoudi Sabri, Raouafi Noureddine, Dhouib Adnene
Chemistry Department, College of Science, Imam Abdulrahman Bin Faisal University P.O. Box 1982 Dammam 31441 Saudi Arabia
Chemistry Department, Faculty of Science, King Abdulaziz University Jeddah 21589 Saudi Arabia
RSC Adv. 2023 Jun 28;13(28):19607-19616. doi: 10.1039/d3ra02557h. eCollection 2023 Jun 22.
Graphene and other 2D materials have gained significant attention in the development of gas sensors. In this study, we employed Density Functional Theory (DFT) to investigate the adsorption properties of diazomethanes (1a-1g) with various functional groups (R = OH (a), OMe (b), OEt (c), OPr (d), CF (e), Ph (f)) on pristine graphene. Furthermore, we explored the adsorption behavior of activated carbenes (2a-2g) generated from the decomposition of diazomethanes on graphene, as well as the functionalized graphene derivatives (3a-3g) resulting from [2 + 1] cycloaddition reactions between (2a-2g) and graphene. The interaction between these functionalized derivatives (3a-3g) and toxic gases was also investigated. Our results revealed that carbenes exhibited a stronger affinity for graphene compared to diazomethanes. The adsorption energy of esters (3b, 3c, and 3d) on graphene decreased relative to compound 3a, while 3e exhibited increased adsorption energy due to the electron-withdrawing effect of fluorine atoms. Additionally, the adsorption energy of phenyl and nitrophenyl groups (3f and 3g) decreased due to their π-stacking interaction with graphene. Importantly, all functionalized derivatives (3a-3g) demonstrated favorable interactions with gases. Notably, the derivative 3a, acting as a hydrogen bonding donor, exhibited superior performance. Furthermore, modified graphene derivatives exhibited the highest adsorption energy with NO gas, highlighting their potential for selective NO sensing applications. These findings contribute to the understanding of gas-sensing mechanisms and the design of novel graphene-based sensor platforms.
石墨烯和其他二维材料在气体传感器的发展中受到了广泛关注。在本研究中，我们采用密度泛函理论（DFT）来研究具有各种官能团（R = OH (a)、OMe (b)、OEt (c)、OPr (d)、CF (e)、Ph (f)）的重氮甲烷（1a - 1g）在原始石墨烯上的吸附特性。此外，我们还探究了重氮甲烷分解产生的活性卡宾（2a - 2g）在石墨烯上的吸附行为，以及（2a - 2g）与石墨烯之间发生[2 + 1]环加成反应生成的功能化石墨烯衍生物（3a - 3g）。我们还研究了这些功能化衍生物（3a - 3g）与有毒气体之间的相互作用。我们的结果表明，与重氮甲烷相比，卡宾对石墨烯表现出更强的亲和力。酯类（3b、3c和3d）在石墨烯上的吸附能相对于化合物3a有所降低，而3e由于氟原子的吸电子效应表现出吸附能增加。此外，苯基和硝基苯基（3f和3g）由于与石墨烯的π堆积相互作用，其吸附能降低。重要的是，所有功能化衍生物（3a - 3g）都表现出与气体的良好相互作用。值得注意的是，作为氢键供体的衍生物3a表现出优异的性能。此外，修饰后的石墨烯衍生物对NO气体表现出最高的吸附能，突出了它们在选择性NO传感应用中的潜力。这些发现有助于理解气敏机制以及设计新型的基于石墨烯的传感器平台。
