Fe对NaNbO3的晶格掺杂和同步异质结改性及其光催化性能

doi:10.6023/A16080404

摘要/Abstract

运用溶剂热法及继之的高温晶化法制备钙钛矿结构NaNbO₃，并在此基础上同步获得了NaNbO₃晶格内Fe³⁺的掺杂和NaNbO₃晶格外α-Fe₂O₃的异质结复合.观察到了同步改性NaNbO₃对水体罗丹明B（RhB）光催化降解效率的显著提升，最适Fe含量的改性NaNbO₃对罗丹明B 1 h内的降解率可达95%，表观一级动力学速率常数为改性前NaNbO₃的近7倍.运用X射线衍射（XRD）、扫描电子显微（SEM）、X光电子能谱（XPS）、光致发光（PL）光谱、低温N₂吸附-脱附（BET法），电子自旋共振光谱（ESR），紫外-可见漫反射光谱（DRS）及光致电流检测等表征和测量探明改性体系的组成及结构，并表明Fe³⁺对Nb⁵⁺的掺杂取代可通过杂质能级形成、电子和空穴捕获以及溶氧吸附的促进从而有利于对罗丹明B的光催化降解；适量α-Fe₂O₃晶格外复合改性NaNbO₃可通过NaNbO₃与α-Fe₂O₃异质结间电子的跃迁和流动提高复合催化剂的光量子效率.Fe对NaNbO₃晶格内外改性促活的实质可能在于光生载流子迁移的促进和对其复合的抑制.

关键词: 铌酸钠, 铁改性, 光催化, 罗丹明B, 促活机制

The perovskite-type NaNbO₃ were prepared through a solvothermal process under a moderate condition followed by calcinations at high temperature.The Fe³⁺-doping inside the NaNbO₃ lattice and the heterojunctions between α-Fe₂O₃ and NaNbO₃ were acquired synchronously in a similar process by treating NaNbO₃ with ferric nitrates.The photocatalytic activity of catalysts was evaluated from the photodegradation of Rhodamine B (RhB) in aqueous solution under UV light irradiation and the significant enhancement of degradation rate of aqueous RhB on modified NaNbO₃ was observed,with the degradation ratio of RhB reached as high as 95% within 1 h,and the quasi-first-grade rate constant of the RhB degradation reaction over the modified NaNbO₃ reached almost 7 times of the pristine one under the experimental conditions.Characterizations by X-ray diffraction (XRD),scanning electron microscopy (SEM),X-ray photoelectron spectroscopy (XPS),UV-vis diffuse reflectance spectrophotometry (DRS),adsorption-desorption of N₂ at low temperature (BET calculation),photoluminescence spectroscopy (PL),electron spin resonance spectroscopy (ESR) and photocurrent measurement were performed.The compositions and structures of the as-prepared raw and modified catalysts were carefully identified.It is found that the optimal mass fraction of Fe in modified catalysts is around 2.5%,with about 30% of it exists as Fe³⁺ inside the lattice of NaNbO₃ and the remainder as α-Fe₂O₃ outside the NaNbO₃ lattice.The results of characterizations or measurements suggest that a moderate Nb⁵⁺ in NaNbO₃ can be substituted by Fe³⁺ while the perovskite-type structure of NaNbO₃ remains unchanging.The moderate Fe-doping into the lattice of NaNbO₃ improved the photocatalytic performance of NaNbO₃ by the donor level of impurities,charge capturing and adsorption of dissolved oxygen.A fitting amount of α-Fe₂O₃ cooperates harmoniously with NaNbO₃ in degradation of RhB by enhancing the light quantum efficiency through the migration and jumping of electrons or holes between α-Fe₂O₃ and NaNbO₃.It is proposed that the modification (i) promotes the excitation of photocatalysts indicated by an improved light adsorption of modified catalysts on DRS,(ii) suppresses the recombination of photogenerated charge carriers revealed by PL spectra,and (iii) promotes the charge transfer founded by photocurrent measurements.

Key words: NaNbO₃, iron modification, photocatalysis, Rhodamine B, promotion mechanism

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崔素珍, 杨汉培, 孙慧华, 聂坤, 吴俊明. Fe对NaNbO₃的晶格掺杂和同步异质结改性及其光催化性能[J]. 化学学报, 2016, 74(12): 995-1002.

Cui Suzhen, Yang Hanpei, Sun Huihua, Nie Kun, Wu Junming. Doping and Heterojunctional Cooperation of NaNbO₃ by Fe and Their Photocatalytic Properties[J]. Acta Chim. Sinica, 2016, 74(12): 995-1002.

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Fe对NaNbO₃的晶格掺杂和同步异质结改性及其光催化性能

Doping and Heterojunctional Cooperation of NaNbO₃ by Fe and Their Photocatalytic Properties

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