Polyoxometalate-based single-atom catalysts for benzyl alcohol photooxidation  

多金属氧酸盐基单原子催化剂用于苯甲醇光氧化的研究

作　　者：REN Jing LIU Yu ZHAO Qiuqing YAO Shuang ZHANG Zhiming 任静;刘豫;赵秋平;姚爽;张志明(天津理工大学材料科学与工程学院,天津300384)

机构地区：[1]Institute for New Energy Materials and Low Carbon Technologies,School of Materials Science&Engineering,Tianjin University of Technology,Tianjin 300384,China

出　　处：《分子科学学报》2024年第5期448-455,共8页Journal of Molecular Science

基　　金：supported by National Natural Science Foundation of China(22071180)

摘　　要：Benzaldehyde(BnCHO)is a key component in dye production and a fundamental substance in the fine chemical sector,especially for making medicines and flavorings.Under ambient conditions,the synthesis of BnCHO through the photo-oxidation of benzyl alcohol(BnOH)demonstrates significant application potential in fine chemical synthesis.Herein,we anchored different metal cations(M=Fe,Co,Cu,and Zn)into monolacunary polyoxometalate(POM)[SiW_(11)O_(39)]^(8-)(SiW)to form single-metal substituted-POMs(MSiWs).Furthermore,we have successfully dispersed these POMs uniformly onto polymeric carbon nitride nanosheets(CN).For BnOH photooxidation without adding extra oxidants such as H_(2)O_(2),the FeSiW/CN-7 exhibited excellent photocatalytic performance with the conversion of BnOH nearly 69.17%and a BnCHO yield of 532.13 mmol·g^(-1)within 12 h.The photo-oxidation performance of BnOH is 76 and 5 times higher than that of single CN and FeSiW,respectively.This catalytic system can maintain a high catalytic efficiency after 5 cycles,indicating that FeSiW/CN possesses high catalytic stability.The results suggest that the designed POM-based single-atom catalyst FeSiW/CN is a promising candidate for the preparation of BnCHO through photooxidation under mild conditions.苯甲醛(BnCHO)作为制造染料的中间体,同时也是生产药品和香料等精细化工产品的重要原料,在精细化学合成中,利用光催化将苯甲醇氧化为苯甲醛具有潜在的应用前景。本研究将不同的金属离子(M=Fe,Co,Cu,Zn)固载于单缺位多金属氧酸盐[SiW_(11)O_(39)]^(8-)(SiW),得到单金属取代多金属氧酸盐(MSiW),进而制备单分散多金属氧酸盐分子簇催化剂MSiW/CN。在不添加H_(2)O_(2)等额外氧化剂的情况下,利用MSiW/CN进行苯甲醇光氧化以制备苯甲醛。催化实验表明在12 h内,苯甲醇的转化率近乎达到69.17%,产率为532.13 mmol·g^(-1)。与单纯的CN和FeSiW相比,苯甲醛的产量分别提高了76倍和5倍,充分说明了光催化剂FeSiW/CN-7的优越性。5次循环后,FeSiW/CN-7仍保持较高的催化效率,表明其具有良好的催化稳定性。实验表明,所设计的FeSiW/CN-7能够在温和条件下利用光氧化制备苯甲醛,是一种极具前景的光催化剂。

关 键 词：single-atom catalyst POLYOXOMETALATE PHOTOOXIDATION benzyl alcohol 

分 类 号：TQ244.1[化学工程—有机化工] O643.36[理学—物理化学]