UiO-66-NH2/Ag2CO3复合物简易制备及其在可见光驱动下的高效光催化性能

引用本文: 周云彩, 徐雪艳, 王鹏, 付会芬, 赵晨, 王崇臣. UiO-66-NH₂/Ag₂CO₃复合物简易制备及其在可见光驱动下的高效光催化性能[J]. 催化学报, 2019, 40(12): 1912-1923. doi: S1872-2067(19)63433-9 shu

Citation: Yun-Cai Zhou, Xue-Yan Xu, Peng Wang, Huifen Fu, Chen Zhao, Chong-Chen Wang. Facile fabrication and enhanced photocatalytic performance of visible light responsive UiO-66-NH₂/Ag₂CO₃ composite[J]. Chinese Journal of Catalysis, 2019, 40(12): 1912-1923. doi: S1872-2067(19)63433-9 shu

UiO-66-NH₂/Ag₂CO₃复合物简易制备及其在可见光驱动下的高效光催化性能

北京建筑大学建筑结构与环境修复功能材料北京重点实验室, 北京 100044
基金项目:
国家自然科学基金（51878023，51578034）；北京市属高等学校长城学者培养计划（CIT&；TCD20180323）；北京市属高等学校创新团队建设与教师职业发展计划（IDHT20170508）；北京市百千万人才工程（2018A35）；北京建筑大学研究生创新项目（PG2019039）.

摘要: 近年来，金属-有机骨架（MOFs）作为一种多相光催化剂被越来越多地应用于光催化分解水制氢、还原CO₂、还原Cr （VI）和降解环境有机污染物.尽管MOFs在光催化领域表现优异，但是仍然面临一些问题，例如多数MOFs材料仅在紫外线激发下才能表现出光催化活性，多数MOFs材料导电性不高、水稳定性欠佳及光生电子和空穴容易复合等.为此，与一些窄带隙半导体光催化剂构建复合物是增强MOFs光催化性能的一个有效策略.
本文采用简单的原位离子交换沉积法，以UiO-66-NH₂和AgNO₃为前驱体在室温下快速制备了一系列具直接Z型异质结的UiO-66-NH₂/Ag₂CO₃复合物（记为UAC-X，其中X=20、50、100、150和200，代表UiO-66-NH₂在复合物中的含量）.采用傅里叶变换红外光谱（FTIR）、粉末X射线衍射（PXRD）、扫描电镜（SEM）、透射电镜（TEM）、高倍透射电镜（HRTEM）、紫外-可见漫反射（UV-Vis DRS）和X射线光电子能谱（XPS）等技术对UAC-X复合物的形貌和结构进行了表征.研究了UAC-X在可见光照射下光催化还原六价铬（Cr（VI））和UAC-100降解有机染料的性能.探究了不同pH （pH=2、3、4、6和8）、不同小分子有机酸（柠檬酸、酒石酸和草酸）及共存离子（自来水和地表水中的离子）对光催化还原Cr（VI）的影响.
结果表明，PXRD谱图显示UAC-X的衍射峰位置分别与UiO-66-NH₂和Ag₂CO₃峰位置完全吻合.SEM、TEM和HRTEM图片证明在UAC-X复合物中Ag₂CO₃附着在UiO-66-NH₂表面.光照50min后，UAC-X复合物还原Cr（VI）的效率（UAC-20和UAC-50分别为68%和86%，UAC-100、UAC-150和UAC-200为100%）均高于UiO-66-NH₂（19%）和Ag₂CO₃（8.0%）.UAC-X复合物中UiO-66-NH₂含量增加（比如UAC-20、UAC-50和UAC-100）导致其光催化Cr（VI）活性增强，其原因在于比表面积增大，且表面增强的正电荷对Cr₂O₇^2-吸附能力增强，最终提升了其光催化效率.
不同pH值下的光催化实验结果表明：酸性条件下光催化效率远优于碱性条件，这是因为在酸性条件下充足的H⁺和表面正电性有利于Cr（VI）还原为Cr（Ⅲ）；在碱性条件下，UAC-100表面呈负电性与CrO₄^2-发生排斥，且形成的Cr（OH）₃沉淀会遮盖催化剂表面活性位点，导致光催化效率下降.反应溶液中的共存离子也会影响光催化效率：自来水中的无机离子可在一定程度上抑制UAC-100对Cr（VI）的光催化效率；湖水中存在的少量有机物可消耗空穴而减弱共存无机离子对Cr（VI）还原效率的负面影响.向无共存离子存在的模拟废水体系中加入酒石酸、柠檬酸和草酸等小分子有机酸时，UAC-100作为光催化剂还原Cr（VI）的速率和效率显著提高，这是因为小分子有机物可有效捕捉空穴，加强光生电子和空穴的分离.光致发光分析、电化学分析、电子自旋共振（ESR）和活性物质捕获实验显示，UAC-100中Ag₂CO₃导带（CB）上的光生电子转移至UiO-66-NH₂最高已占轨道（HOMO），表明在UAC-100复合物中形成了直接Z型异质结，提高了光生电子和空穴的分离效率，最终加强了光催化还原Cr （VI）的活性.同时，UAC-100经过4次光催化循环实验后其还原Cr （VI）效率仍然可达99%，且PXRD谱图未见明显变化，表明UAC-100具有稳定性和重复利用性.综上，UiO-66-NH₂/Ag₂CO₃是一种具有应用前景的高效复合型光催化剂.

关键词:

English

Facile fabrication and enhanced photocatalytic performance of visible light responsive UiO-66-NH₂/Ag₂CO₃ composite

Beijing Key Laboratory of Functional Materials for Building Structure and Environment Remediation, Beijing University of Civil Engineering and Architecture, Beijing 100044, China
Received Date: 01 May 2019
Revised Date: 26 June 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (51878023, 51578034), Great Wall Scholars Training Program Project of Beijing Municipality Universities (CIT&

Abstract: A series of UiO-66-NH₂/Ag₂CO₃ Z-scheme heterojunctions were prepared by a simple ion-exchange-solution method using UiO-66-NH₂ and semiconductor Ag₂CO₃ as precursors. The photocatalytic activities of UAC-X (UAC-20, 50, 100, 150, 200) Z-scheme heterojunctions toward the hexavalent chromium (Cr(VI)) reduction and UAC-100 toward oxidative degradation of four organic dyes like rhodamine B (RhB), methyl orange (MO), congo red (CR), and methylene blue (MB) under visible light irradiation were investigated. The effects of different pH (pH=2, 3, 4, 6, 8), small organic acids (citric acid, tartaric acid, and oxalic acid), and foreign ions (ions in tap water and surface water) on Cr(VI) reduction were explored. The results revealed that the UAC-100 heterojunctions displayed more remarkable Cr(VI) reduction performance than the pristine UiO-66-NH₂ and Ag₂CO₃, resulting from the improved separation of photo-induced electrons and holes. The enhanced photocatalytic activity of UAC-100 was further confirmed by the photoluminescence measurement, electrochemical analysis, and active species trapping experiments. After four cycles' experiments, the photocatalytic Cr(VI) reduction efficiency over UAC-100 was still over 99%, which exhibited that UAC-100 had excellent reusability and stability. Finally, the corresponding photocatalytic reaction mechanism was proposed and tested.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

UiO-66-NH₂/Ag₂CO₃复合物简易制备及其在可见光驱动下的高效光催化性能

English

Facile fabrication and enhanced photocatalytic performance of visible light responsive UiO-66-NH₂/Ag₂CO₃ composite

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