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构建用于高效光催化降解盐酸土霉素和水氧化反应的双电荷转移动力学InS/BiVO n-n同型异质结:揭示物理化学、电化学和光催化性能之间的关联

Architecting a Double Charge-Transfer Dynamics InS/BiVO n-n Isotype Heterojunction for Superior Photocatalytic Oxytetracycline Hydrochloride Degradation and Water Oxidation Reaction: Unveiling the Association of Physicochemical, Electrochemical, and Photocatalytic Properties.

作者信息

Baral Basudev, Mansingh Sriram, Reddy K Hemalata, Bariki Ranjit, Parida Kulamani

机构信息

Centre for Nanoscience and Nanotechnology, ITER, SOA (Deemed to be University), Bhubaneswar 751030, Odisha, India.

Department of Chemistry, National Institute of Technology Rourkela, Rourkela 759008, Odisha, India.

出版信息

ACS Omega. 2020 Mar 9;5(10):5270-5284. doi: 10.1021/acsomega.9b04323. eCollection 2020 Mar 17.

Abstract

To surmount incompatibility provoked efficiency suppression of an anisotype heterojunction and to pursue an improved intrinsic photocatalytic activity by manipulating oriented transfer of photoinduced charge carriers, an InS/BiVO (1:1) n-n isotype heterojunction was fabricated successfully through a simple two-step calcination method, followed by a wet-chemical deposition method. The formation of an n-n isotype heterojunction was confirmed by X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and UV-visible diffuse reflectance spectroscopy. The photocatalytic efficiency of the InS/BiVO catalyst was examined over degradation of oxytetracycline hydrochloride (O-TCH) and oxygen (O) evolution reaction. Consequently, an n-n InS/BiVO isotype heterojunction exhibits a superior O-TCH degradation efficiency (94.6%, 120 min) and O evolution (695.76 μmol, 120 min) of multiple folds as compared to the pure BiVO and InS solely. This is attributed to the proper band alignment and intimate interfacial interaction promoted charge carrier separation over the n-n isotype heterojunction. The intimate interfacial contact was confirmed by transmission electron microscopy (TEM), high-resolution TEM, and field emission scanning electron microscopy analysis. The proper band alignment was confirmed by Mott-Schottky analysis. The photoelectrochemical linear sweep voltammetric study shows a superior photocurrent density (269 μA/cm) for InS/BiVO as compared to those for pristine BiVO and InS, which is in good agreement with the photocatalytic results. Furthermore, the superior charge antirecombination efficiency of the n-n isotype heterojunction was established by photoluminescence, electrochemical impedance spectroscopy, Bode analysis, transient photocurrent, and carrier density analysis. The improved photostability of the heterojunction was confirmed by chronoamperometry analysis. An orderly corelationship among physicochemical, electrochemical, and photocatalytic properties was established, and a possible mechanistic pathway was presented to better understand the outcome of the n-n isotype heterojunction. This study presents an effective way to develop new n-n isotype heterojunction-based efficient photocatalysts and could enrich wide applications in other areas.

摘要

为了克服异型异质结引发的效率抑制问题,并通过控制光生电荷载流子的定向转移来追求更高的本征光催化活性,采用简单的两步煅烧法,随后采用湿化学沉积法,成功制备了InS/BiVO(1:1)n-n同型异质结。通过X射线衍射、傅里叶变换红外光谱、X射线光电子能谱和紫外可见漫反射光谱证实了n-n同型异质结的形成。在盐酸土霉素(O-TCH)降解和析氧(O)反应中考察了InS/BiVO催化剂的光催化效率。结果表明,与纯BiVO和InS相比,n-n InS/BiVO同型异质结的O-TCH降解效率(94.6%,120分钟)和析氧(695.76μmol,120分钟)提高了数倍。这归因于合适的能带排列和紧密的界面相互作用促进了n-n同型异质结上电荷载流子的分离。通过透射电子显微镜(TEM)、高分辨率TEM和场发射扫描电子显微镜分析证实了紧密的界面接触。通过莫特-肖特基分析证实了合适的能带排列。光电化学线性扫描伏安研究表明,与原始BiVO和InS相比,InS/BiVO具有更高的光电流密度(269μA/cm),这与光催化结果吻合良好。此外,通过光致发光、电化学阻抗谱、博德分析、瞬态光电流和载流子密度分析确定了n-n同型异质结具有优异的电荷抗复合效率。通过计时电流分析证实了异质结光稳定性的提高。建立了物理化学、电化学和光催化性能之间的有序相关性,并提出了可能的机理途径,以更好地理解n-n同型异质结的结果。本研究提出了一种开发新型n-n同型异质结基高效光催化剂的有效方法,并可丰富其在其他领域的广泛应用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/48e9/7081410/5f81dfba8fb2/ao9b04323_0015.jpg

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