Jin Zhenxing, Zhang Jun, Qiu Jiyu, Hu Yuxuan, Di Tingmin, Wang Tielin
Key Laboratory of Green Chemical Process of Ministry of Education, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, PR China.
Key Laboratory of Green Chemical Process of Ministry of Education, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, PR China.
J Colloid Interface Sci. 2023 Dec 15;652(Pt A):122-131. doi: 10.1016/j.jcis.2023.08.025. Epub 2023 Aug 6.
Metalloporphyrin compounds have excellent electron transfer and visible light absorption ability, demonstrating broad application prospects in the field of photocatalysis. In this work, the nitrogen vacancies (NVs) were successfully introduced into zinc porphyrin (ZnTCPP) ultrathin nanosheets through surface N plasma treatment, which is environmentally friendly and can react in low temperatures. Furthermore, the prepared nitrogen vacancies-zinc porphyrin (NVs-ZnTCPP) materials exhibited excellent photocatalytic CO reduction activity and selectivity, specifically, the CO production rate of ZnTCPP-1 (N plasma treatment, 1 min) achieved as high as 12.5 µmol gh, which is about 2.7 times greater than that of untreated ZnTCPP. Based on the experimental and density functional theory calculation (DFT) results, it is found that the promoted photocatalytic performance of NVs-ZnTCPP could be mainly attributed to nitrogen vacancy-induced spin polarization by reducing the reaction barriers and inhibiting the recombination of photoexcited carriers. This work provides a new perspective for the construction of vacancy-based metalloporphyrin, and further explores the intrinsic mechanism between the electron spin property and the performance of the photocatalyst.
金属卟啉化合物具有优异的电子转移和可见光吸收能力，在光催化领域展现出广阔的应用前景。在本工作中，通过表面氮等离子体处理成功地将氮空位（NVs）引入到锌卟啉（ZnTCPP）超薄纳米片中，该处理方法环保且能在低温下反应。此外，制备的氮空位 - 锌卟啉（NVs - ZnTCPP）材料表现出优异的光催化CO还原活性和选择性，具体而言，ZnTCPP - 1（氮等离子体处理1分钟）的CO生成速率高达12.5 μmol g⁻¹ h⁻¹，约为未处理的ZnTCPP的2.7倍。基于实验和密度泛函理论计算（DFT）结果，发现NVs - ZnTCPP光催化性能的提升主要归因于氮空位诱导的自旋极化，其降低了反应势垒并抑制了光生载流子的复合。本工作为基于空位的金属卟啉的构建提供了新的视角，并进一步探索了电子自旋性质与光催化剂性能之间的内在机制。
