山东师大唐波Angew. Chem. Int. Ed. : 长余辉材料高效全天候光催化制氢
【引言】
长余辉材料可在激发后保持数分钟至数小时的余辉。在光照下,被激发的电子被捕获并储存;当受到外围热扰动时,储存的电子被释放并与空穴复合并伴随光发射。考虑到整个光致发光过程,可认为载流子具有极长的寿命,将显著提高光催化效率并且可以在黑暗中实现连续的光催化反应。尽管长余辉材料在许多领域得到应用,例如安全显示器、生物成像和光源,但尚未应用于光催化制氢。硅酸盐长余辉材料具有发光强度高、余辉时间长、化学稳定性好、成本低等优点,适合用作光催化剂。Sr2MgSi2O7:Eu2+,Dy3+是一种常用的硅酸盐长余辉材料,具有优异的发光性能。由于Eu2+(198pm)、Dy3+(192μm)和Sr2+(195pm)的半径相似,前两种离子可以完全取代Sr2+,同时在合成过程中保持其晶胞尺寸,在掺杂的稀土离子周围形成可以存储电子的氧空位。因此,Sr2MgSi2O7:Eu2+,Dy3+有望用于全天候光催化制氢。
【成果简介】
近日,山东师范大学唐波教授(通讯作者)等利用微米尺寸砖状Sr2MgSi2O7:Eu2+,Dy3+长余辉材料,首次实现全天候光催化制氢,其太阳能-氢气(STH)转换效率为5.18 %,并在Angew. Chem. Int. Ed.上发表了题为“Round-the-Clock Photocatalytic Hydrogen Production with High Efficiency by a Long-Afterglow Material”的研究论文。该材料显著的光催化活性归因于其独特的载流子迁移路径和大量的晶格缺陷。上述研究结果扩展了长余辉材料的应用范围,提供了通过构建可延长载流子寿命的缺陷能级来设计高效光催化剂的新策略,此类材料为光催化技术的实际应用提供了可能。
【图文简介】
图1 Sr2MgSi2O7:Eu2+,Dy3+的形貌和结构表征
a,b) Sr2MgSi2O7:Eu2+,Dy3+的SEM图像;
c) Sr2MgSi2O7和Sr2MgSi2O7:Eu2+,Dy3+的XRD谱图;
d-i) Sr2MgSi2O7:Eu2+,Dy3+的EDS元素分布图像。
图2 Sr2MgSi2O7:Eu2+,Dy3+的光学性质和光电响应表征
a) Sr2MgSi2O7:Eu2+,Dy3+和Sr2MgSi2O7的紫外/可见吸收光谱;
b) Sr2MgSi2O7:Eu2+,Dy3+的激发和发射光谱;
c) 在黑暗中Sr2MgSi2O7:Eu2+,Dy3+的发光和衰减曲线;
d) 300 W Xe灯照射下Sr2MgSi2O7:Eu2+,Dy3+的光电流密度。
图3 Sr2MgSi2O7:Eu2+,Dy3+的光催化制氢性能
a) 不同pH条件下的制氢性能;
b) 用500 W高压汞灯照射15 min后,Sr2MgSi2O7:Eu2+,Dy3+和Sr2MgSi2O7在黑暗条件下制氢量随时间的变化;
c) 在紫外光照下Sr2MgSi2O7:Eu2+,Dy3+的制氢稳定性测试(每5 h抽真空);
d) 紫外光照射后Sr2MgSi2O7:Eu2+,Dy3+在黑暗中不同温度下的制氢性能。
图4 光催化过程可能的机理
a) 能级和光生电子转移过程图;
b) 光催化反应前后Eu 3d的XPS光谱;
c) 光催化反应前Dy 3d和Dy 4d的XPS光谱;
d) 光催化反应后Dy 3d和Dy 4d的XPS光谱。
【小结】
综上所述,研究人员首次利用长余辉材料Sr2MgSi2O7:Eu2+,Dy3+实现全天候光催化制氢,并获得了5.18 %的较高STH转化效率。这一特殊的光催化活性归因于独特的载流子传输路径和大量的晶格缺陷。与热力学制氢相比,光催化过程具有清洁、安全和经济的优点。作者相信通过能级调控或与其他材料复合,可有效扩大上述长余辉材料的光谱利用范围,并进一步提高其光能转换效率。该研究结果扩大了长余辉材料的应用范围,并通过构建可延长载流子寿命的缺陷能级策略提高光催化剂效率。
文献链接:Round-the-Clock Photocatalytic Hydrogen Production with High Efficiency by a Long-Afterglow Material(Angew. Chem. Int. Ed., 2018, DOI: 10.1002/anie.201810544)
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【研究团队介绍】
唐波教授研究团队现主要从事分子及纳米荧光探针的合成及其在生物成像中的应用、荧光材料合成及太阳能化学转化与储存等方面研究工作。在Nat. Commun., J. Am. Chem. Soc., Angew. Chem. Int. Ed., Nano Lett.等杂志发表SCI论文400余篇,引用达12000余次,授权国家发明专利30余项,荣获国家滚球体育 进步奖二等奖2项,山东省自然科学奖一等奖2项,山东省滚球体育 进步奖一等奖2项、技术发明奖一等奖1项。目前承担国家重点基础研究发展计划(973)、国家自然科学基金重点项目、国家自然科学基金科学仪器基础研究专项等多项国家及省部级科研项目。
【团队在该领域工作汇总】
(1)Guanwei Cui, Xiuli Yang, Yujia Zhang, Yaqi Fan, Ping Chen, Hongyu Cui, Yan Liu, Xifeng Shi, Qiaoyan Shang, and Bo Tang*,Round-the-clock Photocatalytic Hydrogen Production with High Efficiency by a Long Afterglow Material.Angew. Chem. Int. Ed., Accepted, DOI: 10.1002/anie.201810544.
(2)Guanwei Cui, Wen Wang, Mingyue Ma, Junfeng Xie, Xifeng Shi, Ning Deng, Jianping Xin, and Bo Tang*,IR-Driven Photocatalytic Water Splitting with WO2-NaxWO3Hybrid Conductor Material.Nano Lett., 2015, 15, 7199-7203.
(3)Guan-wei Cui, Wei-liang Wang, Ming-yue Ma, Ming Zhang, Xin-yuan Xia, Feng-yun Han, Xi-feng Shi,Ying-qiang Zhao, Yu-Bin Dong and Bo Tang*.Rational design of carbon and TiO2assembly materials: covered or strewn, which is better for photocatalysis?Chem. Commun., 2013, 49, 6415-6417.
(4)Xi-Feng Shi, Xin-Yuan Xia, Guan-Wei Cui*, Ning Deng, Ying-Qiang Zhao, Lin-Hai Zhuo, Bo Tang*.Multiple exciton generation application of PbS quantum dots in ZnO@PbS/graphene oxide for enhanced photocatalytic activity. Appl. Catal. B: Environ., 2015, 163, 123-128.
(5)Yingqiang Zhao, Ming-Yue Ma, Guan-Wei Cui*, Xi-Feng Shi, Feng-Yun Han, Xin-Yuan Xia, Bo Tang*.A New Strategy to Realize Efficient Spacial Charge Separation on Carbonaceous Photocatalyst.Carbon, 2014, 73, 333-337.
(6)Junfeng Xie*, Jianping Xin, Ruoxing Wang, Xiaodong Zhang, Fengcai Lei, Haichao Qu, Pin Hao, Guanwei Cui, Bo Tang* and Yi Xie*.Sub-3 nm Pores in Two-Dimensional Nanomesh Promoting the Generation of Electroactive Phase for Robust Water Oxidation.Nano Energy, 2018, 53, 74-82.
(7)Junfeng Xie*, Haichao Qu, Fengcai Lei, Xu Peng, Weiwei Liu, Li Gao, Pin Hao, Guanwei Cui and Bo Tang*.Partially Amorphous Nickel-Iron Layered Double Hydroxide Nanosheet Arrays for Robust Bifunctional Electrocatalysis.J. Mater. Chem. A, 2018, 6, 16121-16129.
(8)Qian Wang*, Bohui Dong, Yingqiang Zhao, Fang Huang, Junfeng Xie, Guanwei Cui, Bo Tang*.Controllable green synthesis of crassula peforata-like TiO₂ with highphotocatalytic activity based on deep eutectic solvent (DES).Chem. Eng. J., 2018, 348, 811-819.
(9)Xifeng Shi, Jiahui Zhang, Guanwei Cui*, Ning Deng, Wen Wang, Qian Wang, and Bo Tang*.Photocatalytic H₂ evolution improvement for H free-radical stabilization by electrostatic interaction of a Cu-BTC MOF with ZnO/GO. Nano Res., 2018, 11, 979-987.
(10)Ran Wang, Gang Li*, Andong Zhang, Wen Wang, Guanwei Cui, Jian-Feng Zhao, Zhiqiang Shi* and Bo Tang*.Efficient Energy-Level Modification of Novel Pyran-annulated Perylene Diimides for Photocatalytic Water Splitting. Chem. Commun., 2017, 53, 6918-6921.
(11)Junfeng Xie, Jianping Xin, Guanwei Cui, Xinxia Zhang, Lijie Zhou, Yunlong Wang, Weiwei Liu, Caihua Wang, Mei Ning, XinyuanXia, Yingqiang Zhao and Bo Tang*.Vertically aligned oxygen-doped molybdenumdisulfide nanosheets grown on carbon cloth realizing robust hydrogen evolution reaction.Inorg. Chem. Front., 2016, 3, 1160-1166.
(12)Pin Hao, JianTian, Yuanhua Sang , Chia-Chi Tuan, Guanwei Cui, Xifeng Shi, C P Wong, Bo Tang* and Hong Liu*.1D Ni-Co Oxide and Sulfide Nanoarray/Carbon Aerogel Hybrid Nanostructures for Asymmetric Supercapacitors with High Energy Density and Excellent Cycle Stability.Nanoscale, 2016, 8, 16292-16301.
(13)Yingqiang Zhao, Fengyun Han, Qian Wang, Guan-Wei Cui*, Xi-Feng Shi, Xin-Yuan Xia, Junfeng Xie, Yong Li and Bo Tang*.Core–Shell Composites Based on Multiwalled Carbon Nanotubes and Cesium Tungsten Bronze to Realize Charge Transport Balance for Photocatalytic Water Oxidation, ChemCatChem, 2016, 8, 624-630.
(14)Xinyuan Xia, Ning Deng, Guanwei Cui, Junfeng Xie, Xifeng Shi, Yingqiang Zhao, Qian Wang, Wen Wang and Bo Tang*.NIR light induced H2evolution by a metal-free photocatalyst.Chem. Commun., 2015, 51, 10899-10902
(15)Xi-Feng Shi,Na Li, Ke Zhao, Guan-Wei Cui, Ying-Qiang Zhao, Ming-Yue Ma, Ke-Hua Xu, Ping Li, Yu-Bin Dong*, Bo Tang*.A dye-sensitized FeOOH-CNT photocatalyst with threeelectron transfer channels regulated by hydrogen bonding. Appl. Catal. B:Environ., 2013, 136-137, 334-340.
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