Co、Ni 和 Cu 共掺杂 BiO 纳米光催化剂的制备：能带隙修饰的 DFT 分析、罗丹明 B 和三氯吡氧乙酸的吸附和光降解分析。
Co, Ni and Cu incorporated BiO nano photocatalysts: Synthesis, DFT analysis of band gap modification, adsorption and photodegradation analysis of rhodamine B and Triclopyr.
机构信息
Department of Chemistry, Maharshi Dayanand University, Rohtak, 124001, India.
Department of Chemistry, Maharshi Dayanand University, Rohtak, 124001, India.
出版信息
Environ Res. 2023 Sep 15;233:116478. doi: 10.1016/j.envres.2023.116478. Epub 2023 Jun 20.
This study deals with the fabrication of metal ion (M = Co, Ni, and Cu) doped- BiO photocatalysts by solution combustion method. All the synthesized materials were characterized and analysed with the help of XRD, FESEM, EDX, HRTEM, UVDRS, Zeta potential, PL, and LCMS techniques for the structural, morphological, surface charge, optical and degradation pathways characteristics. Synthesized compounds were used for the decontamination (adsorption and degradation) of two organic pollutants namely Rhodamine B and Triclopyr. Adsorption aspects of the pollutants were studied in terms of different isotherm, kinetic and thermodynamic models. Adsorption phenomenon was best fitted with the Freundlich (R = 0.992) and Langmuir isotherm (R = 0.999) models along with pseudo second order model of kinetics for RhB and TC, respectively. Moreover, the thermodynamic parameters indicated exothermic and endothermic adsorption (ΔH ° (-7.19 kJ/mol) for RhB) and (ΔH ° (52.335 kJ/mol) for TC), respectively. Evaluated negative values of ΔG ° indicated spontaneous adsorption with most favourable at 298 K and 318 K for both the pollutants (RhB and TC) respectively. Modification with metal ions significantly improved the removal efficiency of pure BiO photocatalyst and followed the trend Co/BiO > Ni/BiO > Cu/BiO > BiO. DFT calculations demonstrate that amongst the doped materials, only Co/BiO is characterized by an indirect band gap; which exhibited efficacious photocatalytic activity. Besides, the highest degradation efficiency was obtained in the case of Co/BiO (2 mol %); being 99.80% for RhB in 30 min and 98.50% for TC in 60 min, respectively. The doped nanostructures lead to higher absorption of visible light and more separation of light-induced charged carriers. Effect of pH of the reaction medium and role of reactive oxygen species was also examined. Finally, a probable mechanism of charge transfer and degradation of the pollutants was also presented.
本研究通过溶液燃烧法制备了金属离子（M=Co、Ni 和 Cu）掺杂的 BiO 光催化剂。所有合成材料均通过 XRD、FESEM、EDX、HRTEM、UVDRS、Zeta 电位、PL 和 LCMS 技术进行了结构、形态、表面电荷、光学和降解途径特性的表征和分析。合成的化合物用于两种有机污染物罗丹明 B 和三氯吡的净化（吸附和降解）。研究了污染物的吸附等温线、动力学和热力学模型。吸附现象最符合 Freundlich（R=0.992）和 Langmuir 等温线（R=0.999）模型，以及罗丹明 B 和 TC 的准二级动力学模型。此外，热力学参数表明吸附是放热和吸热的（ΔH°（-7.19 kJ/mol）用于 RhB）和（ΔH°（52.335 kJ/mol）用于 TC），分别。评估的负ΔG°值表明吸附是自发的，在 298 K 和 318 K 时，两种污染物（RhB 和 TC）的吸附最有利。金属离子的修饰显著提高了纯 BiO 光催化剂的去除效率，其趋势为 Co/BiO＞Ni/BiO＞Cu/BiO＞BiO。DFT 计算表明，在所研究的掺杂材料中，只有 Co/BiO 具有间接带隙；表现出有效的光催化活性。此外，在 Co/BiO（2 mol%）的情况下，获得了最高的降解效率；在 30 分钟内 RhB 的降解效率为 99.80%，在 60 分钟内 TC 的降解效率为 98.50%。掺杂的纳米结构导致可见光的吸收更高，光诱导载流子的分离更好。还研究了反应介质 pH 的影响和活性氧物质的作用。最后，还提出了污染物的电荷转移和降解的可能机制。
Zotero 插件