Tailoring Defects in B, N-Codoped Carbon Nanowalls for Direct Electrochemical Oxidation of Glyphosate and its Metabolites.

Tailoring the defects in graphene and its related carbon allotropes has great potential to exploit their enhanced electrochemical properties for energy applications, environmental remediation, and sensing. Vertical graphene, also known as carbon nanowalls (CNWs), exhibits a large surface area, enhanced charge transfer capability, and high defect density, making it suitable for a wide range of emerging applications. However, precise control and tuning of the defect size, position, and density remain challenging; moreover, due to their characteristic labyrinthine morphology, conventional characterization techniques and widely accepted quality indicators fail or need to be reformulated. This study primarily focuses on examining the impact of boron heterodoping and argon plasma treatment on CNW structures, uncovering complex interplays between specific defect-induced three-dimensional nanostructures and electrochemical performance. Moreover, the study introduces the use of defect-rich CNWs as a label-free electrode for directly oxidizing glyphosate (GLY), a common herbicide, and its metabolites (sarcosine and aminomethylphosphonic acid) for the first time. Crucially, we discovered that the presence of specific boron bonds (BC and BN), coupled with the absence of Lewis-base functional groups such as pyridinic-N, is essential for the oxidation of these analytes. Notably, the D+D* second-order combinational Raman modes at ≈2570 cm-1 emerged as a reliable indicator of the analytes' affinity. Contrary to expectations, the electrochemically active surface area and the presence of oxygen-containing functional groups played a secondary role. Argon-plasma post-treatment was found to adversely affect both the morphology and surface chemistry of CNWs, leading to an increase in sp3-hybridized carbon, the introduction of oxygen, and alterations in the types of nitrogen functional groups. Simulations support that certain defects are functional for GLY rather than AMPA. Sarcosine oxidation is the least affected by defect type.

N4-Vacancy-Functionalized Carbon for High-Rate Li-Ion Storage.

Although heteroatom doping and pore management separately influence the Li+ adsorption and Li+ diffusion properties, respectively, merging their functions into a single unit is intriguing and has not been fully investigated. Herein, we have successfully incorporated both heteroatom doping and pore management within the same functional unit of N4-vacancy motifs, which is realized via acid etching of formamide-derived Zn-N4-functionalized carbon materials (Zn1NC). The N4-vacancy-rich porous carbon (V-NC) renders multiple merits: (1) a high N content of 13.94 atom % for large Li-storage capacity, (2) edged unsaturated N sites favoring highly efficient Li+ adsorption and desolvation, and (3) a shortening of the Li+ diffusion length through N4 vacancy, thereby enhancing the Li-storage kinetics and high-rate performance. This work serves as an inspiration for the creation of heteroatom-edged porous structures with controllable pore sizes for high-rate alkali-ion battery applications.