School of Chemistry, Xi'an Jiaotong University, Xi'an 710049, People's Republic of China.
Anal Chem. 2022 Dec 13;94(49):17272-17278. doi: 10.1021/acs.analchem.2c04239. Epub 2022 Dec 1.
We demonstrate the preparation of a dual-site carbon nanozyme, boron-doped and ketonic carbonyl (-C=O) group-enriched graphdiyne (B-GDY), with an enhanced peroxidase-like activity. Taking advantage of acidic oxidation treatment, GDY oxide (GDYO) with abundant surface oxygen-containing groups is obtained from pristine bulk GDY. Upon further thermal annealing of GDYO with HBO under an inert atmosphere, B is introduced into GDY, while the loading of -C=O groups is increased onto B-GDY. We discover that boron-doped and ketonic carbonyl group-enriched graphdiyne as a dual-site carbon nanozyme endows it with an enhanced peroxidase-like activity, which is nearly 4.2-fold higher than that of GDY without B atoms and 6.6-fold higher than that of GDYO without B atoms and with low loading of -C=O groups. The high peroxidase-like activity of B-GDY is ascribed to the dual active sites (-C=O group and B atom) within it, which facilitates the adsorption and decomposition of HO into hydroxyl radicals revealed by experimental and theoretical studies. Moreover, B-GDY is successfully employed to develop a colorimetric method for the detection of glucose with good sensitivity and selectivity. This work probes into the intrinsic peroxidase activity and structure-reactivity correlation, creating effective strategies for the preparation of GDY-based nanozymes.
我们展示了一种双位点碳纳米酶的制备方法，即硼掺杂和富含酮羰基（-C=O）基团的石墨炔（B-GDY），具有增强的过氧化物酶样活性。利用酸性氧化处理，从原始块状 GDY 中获得了富含表面含氧基团的 GDY 氧化物（GDYO）。在惰性气氛下，进一步将 GDYO 与 HBO 进行热退火，将 B 引入 GDY，同时将 -C=O 基团的负载量增加到 B-GDY 上。我们发现，硼掺杂和富含酮羰基基团的石墨炔作为双位点碳纳米酶，赋予其增强的过氧化物酶样活性，比没有 B 原子的 GDY 高近 4.2 倍，比没有 B 原子且 -C=O 基团负载量低的 GDYO 高 6.6 倍。B-GDY 具有高过氧化物酶样活性，归因于其内部的双活性位点（-C=O 基团和 B 原子），这有利于实验和理论研究中 HO 的吸附和分解为羟基自由基。此外，B-GDY 成功地用于开发一种用于检测葡萄糖的比色方法，具有良好的灵敏度和选择性。这项工作探讨了内在的过氧化物酶活性和结构-反应性关系，为基于 GDY 的纳米酶的制备创造了有效的策略。
