Theoretical and Experimental Studies of Molecular Interactions between Engineered Graphene and Phosphate Ions for Graphene-Based Phosphate Sensing
Theoretical and Experimental Studies of Molecular Interactions between Engineered Graphene and Phosphate Ions for Graphene-Based Phosphate Sensing
复制标题
用于基于石墨烯的磷酸盐传感的工程石墨烯和磷酸盐离子之间的分子相互作用的理论和实验研究
DOI：
10.1021/acsanm.3c04147
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发表时间：
2023
影响因子：
5.9
通讯作者：
Martsinovich, Natalia
中科院分区：
文献类型：
--
作者：
Yong, Xue;Nagaraja, Thiba;Krishnamoorthy, Rajavel;Guanes, Ana;Das, Suprem R.;Martsinovich, Natalia
对纳米级材料与目标分子相互作用的基本了解对于传感器等电子设备的开发至关重要。特别是，尽管工程石墨烯具有用作分子传感器的巨大潜力，但工程石墨烯的结构和分子相互作用特性在很大程度上仍未得到探索。作为最终用户应用的示例，检测土壤环境中磷酸盐形式的磷对于土壤肥力和植物生长非常重要。然而，由于缺乏负担得起的技术，目前很难直接测量土壤中的磷酸盐含量；因此，需要为磷酸盐传感器开发合适的传感器技术。在这项工作中，利用密度泛函理论（DFT）计算，研究了原始石墨烯和几种改性石墨烯材料（氧化石墨烯、带空位的石墨烯和弯曲石墨烯）作为磷酸盐传感器材料的候选材料。我们的计算表明，原始石墨烯和功能化石墨烯都能够强烈吸附磷酸盐物质。此外，这些石墨烯纳米材料表现出相对于硝酸盐的磷酸盐吸附选择性，对磷酸盐具有更强的吸附能。此外，我们的计算表明，原始石墨烯和功能化石墨烯在磷酸盐吸附后电导率发生显着变化，特别是具有氧（羟基和环氧化物）官能团的石墨烯。石墨烯吸附磷酸二氢前后电阻率的实验测量表明，吸附磷酸盐后电阻率增加，与理论预测一致。我们的结果表明石墨烯和功能化石墨烯基纳米材料是开发磷酸盐传感器的良好候选材料。
Fundamental understanding of the interactions of nanoscale materials with molecules of interest is essential for the development of electronic devices, such as sensors. In particular, structures and molecular interaction properties of engineered graphenes are still largely unexplored, despite these materials’ great potential to be used as molecular sensors. As an example of end user application, the detection of phosphorus in the form of phosphate in a soil environment is important for soil fertility and plant growth. However, due to the lack of an affordable technology, it is currently hard to measure the amount of phosphate directly in the soil; therefore, suitable sensor technologies need to be developed for phosphate sensors. In this work, pristine graphene and several modified graphene materials (oxygenated graphene, graphene with vacancies, and curved graphene) were studied as candidates for phosphate sensor materials using density functional theory (DFT) calculations. Our calculations showed that both pristine graphene and functionalized graphene were able to adsorb phosphate species strongly. In addition, these graphene nanomaterials showed selectivity of adsorption of phosphate with respect to nitrate, with stronger adsorption energies for phosphate. Furthermore, our calculations showed significant changes in electrical conductivities of pristine graphene and functionalized graphenes after phosphate species adsorption, in particular, on graphene with oxygen (hydroxyl and epoxide) functional groups. Experimental measurements of electrical resistivity of graphene before and after adsorption of dihydrogen phosphate showed an increase in resistivity upon adsorption of phosphate, consistent with the theoretical predictions. Our results recommend graphene and functionalized graphene-based nanomaterials as good candidates for the development of phosphate sensors.