University of Idaho, Department of Chemistry, 875 Perimeter Dr., MS 2343, Moscow, ID 83844, USA.
Analyst. 2020 Nov 9;145(22):7252-7259. doi: 10.1039/d0an01405b.
A nanocrystalline graphite-like amorphous carbon (graphite from the University of Idaho thermolyzed asphalt reaction, GUITAR) shares morphological features with classical graphites, including basal and edge planes (BP, EP). However, unlike graphites and other sp2-hybridized carbons, GUITAR has fast heterogenous electron transfer (HET) across its basal planes, and resistance to corrosion similar to sp3-C and boron-doped diamond electrodes. In this contribution, quinoid modified BP-GUITAR (q-GUITAR) is examined as a sensor for pH determination. This modification is performed by applying 2.0 V (vs. Ag/AgCl) for 150 seconds followed by 15 cyclic voltammetric scans from -0.7 to 1.0 V at 50 mV s-1 in 1.0 M H2SO4. The quinoid surface coverage of q-GUITAR is 1.35 × 10-9 mol cm-2, as measured by cyclic voltammetry. X-ray photoelectron spectroscopy analysis also confirms the high surface coverage. The quinoid surface concentration ranks highest in literature when compared with other basal plane graphitic materials. This yields a sensor that responds through a square wave voltammetric reduction peak shift of 63.3 mV per pH over a pH range from 0 to 11. The response on q-GUITAR is stable for >20 measurements and no surface re-activation is required between the measurements. The common interferents, Na+, K+ and dissolved oxygen, have no effect on the response of the q-GUITAR-based pH sensor.
一种类石墨无定形纳米碳(来自爱达荷大学热解沥青反应的石墨,GUITAR)与经典石墨具有相似的形态特征,包括基面和边缘平面(BP、EP)。然而,与石墨和其他 sp2 杂化碳不同,GUITAR 具有穿过基面的快速非均相电子转移(HET),并且具有类似于 sp3-C 和掺硼金刚石电极的耐腐蚀性。在本研究中,研究了醌改性 BP-GUITAR(q-GUITAR)作为 pH 测定的传感器。通过施加 2.0 V(相对于 Ag/AgCl)150 秒,然后在 1.0 M H2SO4 中以 50 mV s-1 的速度从-0.7 到 1.0 V 进行 15 次循环伏安扫描来进行这种修饰。通过循环伏安法测量,q-GUITAR 的醌表面覆盖率为 1.35×10-9 mol cm-2。X 射线光电子能谱分析也证实了高表面覆盖率。与其他基面石墨材料相比,醌表面浓度在文献中排名最高。这使得传感器在 pH 值为 0 到 11 范围内通过方波伏安还原峰的 63.3 mV 偏移来响应。q-GUITAR 的响应在>20 次测量中稳定,并且在测量之间不需要表面再激活。常见的干扰物 Na+、K+和溶解氧对基于 q-GUITAR 的 pH 传感器的响应没有影响。