ACS Sens. 2019 Mar 22;4(3):756-763. doi: 10.1021/acssensors.9b00137. Epub 2019 Mar 6.
A hybrid sp-sp electrochemical sensor comprising patterned regions of nondiamond-carbon (sp) in a boron doped diamond (sp) matrix is described for the simultaneous voltammetric detection of dissolved oxygen (DO) and pH in buffered aqueous solutions. Using a laser micropatterning process it is possible to write mechanically robust regions of sp carbon into a BDD electrode. These regions both promote the electrocatalytic reduction of oxygen and facilitate the proton coupled electron transfer of quinone groups, integrated into the surface of the sp carbon. In this way, in one voltammetric sweep (time of measurement ∼4 s) it is possible to determine both the DO concentration and solution pH. By varying the sp pattern the response can be optimized toward both analytes. Using a closely spaced sp microspot array, a linear response toward DO, across the range 0.0 to 8.0 mg L (0.0 to 0.25 mM; sensitivity = -8.77 × 10 A L mg, R = 0.9991) and pH range 4-10 (sensitivity = 59.7 mV pH, R = 0.9983) is demonstrated. The electrode is also capable of measuring both DO concentration and pH in the more complex buffered environment of blood. Finally, we show how the peak position for ORR is independent of pH, and thus via measurement of the difference in ORR and pH peak position, internal referencing is possible. Such electrodes show great promise for use in applications ranging from biomedical sensing to water analysis.
一种混合 sp-sp 电化学传感器,由掺硼金刚石(sp)中的非金刚石碳(sp)图案区域组成,用于同时在缓冲水溶液中检测溶解氧(DO)和 pH。使用激光微图案化工艺,可以将 sp 碳机械稳定的区域写入 BDD 电极中。这些区域都促进了氧的电催化还原,并促进了醌基团的质子偶联电子转移,这些基团整合到 sp 碳的表面。通过这种方式,在一次伏安扫描(测量时间约为 4 秒)中,可以同时确定 DO 浓度和溶液 pH。通过改变 sp 图案,可以针对两种分析物优化响应。使用紧密间隔的 sp 微点阵列,可以在 DO 的 0.0 至 8.0 mg L(0.0 至 0.25 mM;灵敏度=-8.77×10 A L mg,R=0.9991)和 pH 范围 4-10(灵敏度=59.7 mV pH,R=0.9983)之间实现线性响应。该电极还能够测量血液中更复杂缓冲环境中的 DO 浓度和 pH。最后,我们展示了 ORR 的峰位置如何与 pH 无关,因此通过测量 ORR 和 pH 峰位置的差异,可以实现内部参考。这种电极在从生物医学传感到水分析的各种应用中具有广阔的应用前景。