无铅钙钛矿纳米晶的制备及其光催化二氧化碳还原性能研究  

Study on preparation of lead-free perovskite nanocrystals and their photocatalytic performances in carbon dioxide reduction

作　　者：李银成 林介本 梁俊辉 郭震宁 LI Yincheng;LIN Jieben;LIANG Junhui;GUO Zhenning(College of General Education,Minnan Science and Technology College,Quanzhou 362000,Fujian,China;School of Materials and Chemistry,China Jiliang University,Hangzhou 300018,Zhejiang,China;College of Information Science&Engineering,Huaqiao University,Xiamen 361021,Fujian,China)

机构地区：[1]闽南科技学院通识教育学院,福建泉州362000 [2]中国计量大学材料与化学学院,浙江杭州300018 [3]华侨大学信息科学与工程学院,福建厦门361021

出　　处：《低碳化学与化工》2024年第5期21-27,43,共8页Low-Carbon Chemistry and Chemical Engineering

基　　金：国家自然科学基金青年项目(62304214);泉州芯谷半导体现代产业学院产学项目(MKCYXY-2023-01);半导体照明与光伏应用创新团队(MKKYTD202301);福建高校杰出青年科研人才培育计划(闽教科[2018]47号)。

摘　　要：具有优异光电性能的全无机铅卤钙钛矿是用于光催化二氧化碳还原的理想材料,但是铅的毒性和固有的不稳定性限制了其商业化应用。为此,采用反溶剂法分别制备了无铅钙钛矿材料Cs_(2)PtBr_(6)微晶和Cs_(2)PtBr_(6)纳米晶,利用SEM、TEM、XRD和紫外可见吸收光谱等方法对样品的形貌、组成和光电性能进行了表征。结果表明,将Cs_(2)PtBr_(6)微晶转化为Cs_(2)PtBr_(6)纳米晶后,样品的比表面积增大,可见光范围内的吸收性能增强,光生载流子平均寿命由Cs_(2)PtBr_(6)微晶的1.83 ns延长到Cs_(2)PtBr_(6)纳米晶的2.42 ns,并且Cs_(2)PtBr_(6)纳米晶中的平均光电流密度是Cs_(2)PtBr_(6)微晶相应值的6.4倍,Cs_(2)PtBr_(6)纳米晶的电荷转移电阻值小于Cs_(2)PtBr_(6)微晶的电荷转移电阻值,Cs_(2)PtBr_(6)纳米晶的光生载流子的分离效率和转移效率得到提高。其中,在搅拌温度为50℃时合成的Cs_(2)PtBr_(6)纳米晶具有最高的光催化活性,在反应气组成为V_(CO_(2)):V_(H_(2)):V_(N_(2))=21:63:16、总质量空速为20000 mL/(g·h)和可见光照射反应3 h的条件下,其一氧化碳的产量为74.8μmol/g,且一氧化碳选择性达到100%。以上结果可为开发高性能的光催化剂提供参考。All-inorganic lead halide perovskites with excellent optoelectronic properties are ideal materials for photocatalytic carbon dioxide reduction.However,the toxicity and inherent instability of Pb limit their practical commercial application.To this end,lead-free perovskite materials Cs_(2)PtBr_(6) microcrystal and Cs_(2)PtBr_(6) nanocrystal were synthesized by anti-solvent method.The morphologies,compositions and optoelectronic properties of the samples were characterized by SEM,TEM,XRD and Ultraviolet-visible absorption spectrum,et al.The results show that the specific surface area of the sample is increased and the absorption performance is enhanced after Cs_(2)PtBr_(6) microcrystal is converted into Cs_(2)PtBr_(6) nanocrystal.The average photogenerated carrier lifetime is extended from 1.83 ns in Cs_(2)PtBr_(6) microcrystal to 2.42 ns in Cs_(2)PtBr_(6) nanocrystal.Moreover,the average photocurrent density of Cs_(2)PtBr_(6) nanocrystal is 6.4 times stronger than that of Cs_(2)PtBr_(6) microcrystal,and the charge transfer resistance of Cs_(2)PtBr_(6) nanocrystal is smaller than corresponding value of Cs_(2)PtBr_(6) microcrystal,so the separation and transfer efficiency of photogenerated carriers are improved.Among them,Cs_(2)PtBr_(6) nanocrystal synthesized under 50℃of stirring temperature has the highest photocatalytic activity,and the carbon monoxide yield under the set up conditions of V_(CO_(2)):V_(H_(2)):V_(N_(2))=21:63:16,total mass empty speed is 20000 mL/(g·h)and visible light irradiation for 3 h is 74.8μmol/g,and the selectivity of carbon monoxide reaches 100%.These results can provide reference for the development of high-performance photocatalysts.

关 键 词：光催化 二氧化碳还原 无铅钙钛矿 纳米晶 

分 类 号：TQ426[化学工程] O643.36[理学—物理化学]