Fabrication of hierarchical ZnIn2S4@CNO nanosheets for photocatalytic hydrogen production and CO2 photoreduction  

ZnIn2S4@CNO多级纳米片用于光催化分解水制氢和还原CO2（英文）

作　　者：Kai Zhu Jie Ou-Yang Qian Zeng Sugang Meng Wei Teng Yanhua Song Sheng Tang Yanjuan Cui 祝凯;欧阳杰;曾黔;孟苏刚;滕伟;宋艳华;唐盛;崔言娟(江苏科技大学环境与化学工程学院,江苏镇江212003;淮北师范大学化学与材料科学学院,安徽淮北235000)

机构地区：[1]School of Environmental and Chemical Engineering,Jiangsu University of Science and Technology,Zhenjiang 212003,Jiangsu,China [2]College of Chemistry and Materials Science,Huaibei Normal University,Huaibei 235000,Anhui,China

出　　处：《Chinese Journal of Catalysis》2020年第3期454-463,共10页催化学报（英文）

基　　金：supported by the National Natural Science Foundation of China(21503096,21407067);the Natural Science Foundation of Educational Committee of Anhui Province(KJ2018A0387),China;Project of Anhui Province for Excellent Young Talents in Universities(gxyq2019029),China

摘　　要：Photocatalytic H2 production and CO2 reduction have attracted considerable attention for clean energy development.In this work,we designed an efficient photocatalyst by integrating lamellar oxygen-doped carbon nitride(CNO)nanosheets into ZnIn2S4(ZIS)microflowers by a one-step hydrothermal method.A well-fitted 2D hierarchical hybrid heterostructure was fabricated.Under visible light irradiation,the ZIS@CNO composite with 40 wt%CNO(ZC 40%)showed the highest hydrogen evolution rate from water(188.4μmol·h-1),which was approximately 2.1 times higher than those of CNO and ZIS(88.6 and 90.2μmol·h-1,respectively).Furthermore,the selective CO production rates of ZC 40%(12.69μmol·h-1)were 2.2 and 14.0 times higher than those of ZIS(5.85μmol·h-1)and CNO(0.91μmol·h-1),respectively,and the CH4 production rate of ZC 40%was 1.18μmol·h-1.This enhanced photocatalytic activity of CNO@ZIS is due mainly to the formation of a heterostructure that can promote the transfer of photoinduced electrons and holes between CNO and ZIS,thereby efficiently avoiding recombination of electron-hole pairs.光催化分解水制氢和还原CO2是太阳能利用领域的研究热点,对清洁能源的转化具有重要意义.石墨相氮化碳(CN)作为一种非金属半导体,是一种非常有开发潜力的光催化材料.然而限于其聚合物本质,光催化效率仍有待进一步提高.原位非金属掺杂可以利用元素电子结构调控电荷分布,优化光生电荷传输性能.同时,半导体复合,尤其是2D层状复合结构的构筑,可充分发挥2D半导体的优势,合适的能带交错有利于光生电荷的传输,可在一定程度上加速催化反应的进行.本文首先以草酸为氧掺杂源,采用二步煅烧法合成氧掺杂氮化碳纳米片催化剂(CNO).在二次煅烧和氧掺杂共同作用下,增大了CN层间距和多孔性,颗粒尺寸减小,同时增强了对光的吸光性,拓展了可见光吸收范围.接下来采用一步水热合成法得到ZnIn2S4@CNO(ZC)复合材料,在可见光照射下通过分解水制氢和CO2还原反应对复合材料进行光催化还原性能评价.采用X射线衍射(XRD)、透射电镜(TEM)、X射线光电子能谱(XPS)、荧光光谱(PL)、光电化学测试等方法对ZC进行详细的结构表征和分析.XRD和XPS结果表明,经过一步直接水热可得到层状ZC复合材料,高倍TEM进一步证实二者形成均一的2D异质复合材料.N2-吸附-脱附曲线表明,复合材料具有较大的比表面积和均一的孔结构分布,主要得益于O掺杂CNO纳米片的多孔性结构.光电性质测试结果表明,相比于CNO,复合材料具有降低的荧光发射强度和延长的荧光寿命,表明复合产物显著抑制了光生电荷的复合.电化学测试进一步表明,复合异质结的构筑有利于光生载流子的产生,同时降低了界面电荷转移电阻,提高了电荷迁移速率.因此,多孔2D异质结构的构筑对促进CN基半导体光催化还原具有重要作用.在可见光照射下(λ>400 nm),复合材料表现出优异的光催化还原性能,且随着CNO含量的增加催化活性不断提高

关 键 词：ZnIn2S4 Oxygen doped carbon nitride PHOTOCATALYSIS H2 production CO2 reduction 

分 类 号：TB3[一般工业技术—材料科学与工程]