Department of Mechanical Engineering, Iowa State University, Ames, Iowa 50011, United States.
Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States.
ACS Nano. 2022 Jan 25;16(1):15-28. doi: 10.1021/acsnano.1c04197. Epub 2021 Nov 23.
The integration of microfluidics and electrochemical cells is at the forefront of emerging sensors and energy systems; however, a fabrication scheme that can create both the microfluidics and electrochemical cells in a scalable fashion is still lacking. We present a one-step, mask-free process to create, pattern, and tune laser-induced graphene (LIG) with a ubiquitous CO laser. The laser parameters are adjusted to create LIG with different electrical conductivity, surface morphology, and surface wettability without the need for postchemical modification. Such definitive control over material properties enables the creation of LIG-based integrated open microfluidics and electrochemical sensors that are capable of dividing a single water sample along four multifurcating paths to three ion selective electrodes (ISEs) for potassium (K), nitrate (NO), and ammonium (NH) monitoring and to an enzymatic pesticide sensor for organophosphate pesticide (parathion) monitoring. The ISEs displayed near-Nernstian sensitivities and low limits of detection (LODs) (10 M, 10 M, and 10 M for the K, NO, and NH ISEs, respectively) while the pesticide sensor exhibited the lowest LOD (15.4 pM) for an electrochemical parathion sensor to date. LIG was also specifically patterned and tuned to create a high-performance electrochemical micro supercapacitor (MSC) capable of improving the power density by 2 orders of magnitude compared to a Li-based thin-film battery and the energy density by 3 orders of magnitude compared to a commercial electrolytic capacitor. Hence, this tunable fabrication approach to LIG is expected to enable a wide range of real-time, point-of-use health and environmental sensors as well as energy storage/harvesting modules.
微流控和电化学电池的集成是新兴传感器和能源系统的前沿领域;然而,仍然缺乏一种能够以可扩展的方式同时制造微流控和电化学电池的制造方案。我们提出了一种一步法、无掩模工艺,使用普遍存在的 CO 激光器来制造、图案化和调整激光诱导石墨烯 (LIG)。通过调整激光参数,可以在无需后化学修饰的情况下,制造出具有不同电导率、表面形貌和表面润湿性的 LIG。对材料特性的这种明确控制使得能够创建基于 LIG 的集成开放式微流控和电化学传感器,这些传感器能够将单个水样沿着四个分叉路径分成三个离子选择性电极 (ISE) 用于钾 (K)、硝酸盐 (NO) 和铵 (NH) 监测,以及用于有机磷农药 (对硫磷) 监测的酶农药传感器。ISE 显示出近 Nernst 灵敏度和低检测限(K、NO 和 NH ISE 的 LOD 分别为 10 M、10 M 和 10 M),而农药传感器的 LOD 最低(15.4 pM),是迄今为止电化学对硫磷传感器的最低 LOD。LIG 还经过专门的图案化和调整,以创建高性能电化学微超级电容器 (MSC),与基于 Li 的薄膜电池相比,其功率密度提高了 2 个数量级,与商用电解电容器相比,其能量密度提高了 3 个数量级。因此,这种可调谐的 LIG 制造方法有望实现各种实时、现场使用的健康和环境传感器以及储能/采集模块。