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锐钛矿 TiO 纳米棒/还原氧化石墨烯复合材料中电子-空穴的分离和迁移得到改善及其对光催化性能的影响。

Improved electron-hole separation and migration in anatase TiO nanorod/reduced graphene oxide composites and their influence on photocatalytic performance.

机构信息

Department for Environmental Sciences and Engineering, National Institute of Chemistry, Hajdrihova 19, SI-1001 Ljubljana, Slovenia.

Department of Surface Engineering and Optoelectronics, Jožef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia.

出版信息

Nanoscale. 2017 Mar 30;9(13):4578-4592. doi: 10.1039/c7nr00704c.

Abstract

The as-synthesized TiO nanorods a-TNR (amorphous TiO layer covering the crystalline anatase TiO core) and TNR (fully crystalline anatase TiO) were decorated with reduced graphene oxide (rGO) to synthesize two series of TiO + rGO composites with different nominal loadings of GO (from 4 to 20 wt%). The structural, surface and electronic properties of the obtained TiO + rGO composites were analyzed and correlated to their performance in the photocatalytic oxidation of aqueous bisphenol A solution. X-ray photoelectron spectroscopy (XPS) analyses revealed that charge separation in TiO + rGO composites is improved due to the perfect matching of TiO and rGO valence band maxima (VBM). Cyclic voltammetry (CV) experiments revealed that the peak-to-peak separations (ΔE) are the lowest and the oxidation current densities are the highest for composites with a nominal 10 wt% GO content, meaning that it is much easier for the charge carriers to percolate through the solid, resulting in improved charge migration. Due to the high charge carrier mobility in rGO and perfect VBM matching between TiO and rGO, the electron-hole recombination in composites was suppressed, resulting in more electrons and holes being able to participate in the photocatalytic reaction. rGO amounts above 10 wt% decreased the photocatalytic activity; thus, it is critical to optimize its amount in the TiO + rGO composites for achieving the highest photocatalytic activity. BPA degradation rates correlated completely with the results of the CV measurements, which directly evidenced improved charge separation and migration as the crucial parameters governing photocatalysis.

摘要

合成的 TiO 纳米棒 a-TNR(覆盖在结晶锐钛矿 TiO 核上的非晶 TiO 层)和 TNR(完全结晶的锐钛矿 TiO)用还原氧化石墨烯(rGO)进行了修饰,以合成具有不同 GO 名义负载量(4 至 20wt%)的两个系列 TiO + rGO 复合材料。对所得 TiO + rGO 复合材料的结构、表面和电子性能进行了分析,并将其与在光催化氧化水相双酚 A 溶液中的性能相关联。X 射线光电子能谱(XPS)分析表明,由于 TiO 和 rGO 价带最大值(VBM)的完美匹配,TiO + rGO 复合材料中的电荷分离得到了改善。循环伏安(CV)实验表明,对于具有 10wt%名义 GO 含量的复合材料,其峰峰分离(ΔE)最低,氧化电流密度最高,这意味着载流子更容易在固体中渗滤,从而提高了电荷迁移率。由于 rGO 中载流子迁移率高,以及 TiO 和 rGO 之间 VBM 的完美匹配,复合材料中的电子-空穴复合被抑制,从而使更多的电子和空穴能够参与光催化反应。rGO 含量高于 10wt%会降低光催化活性;因此,优化 TiO + rGO 复合材料中 rGO 的含量对于获得最高光催化活性至关重要。BPA 降解率与 CV 测量结果完全相关,这直接证明了电荷分离和迁移的改善是光催化的关键控制参数。

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