文献类型：期刊文献

英文题名：Visible-Light-Induced Catalytic Transfer Hydrogenation of Aromatic Aldehydes by Palladium Immobilized on Amine-Functionalized Iron-Based Metal-Organic Frameworks

作者：Dong, Shenghong[1,2];Liu, Zhen[1];Liu, Ruihan[3];Chen, Limin[3];Chen, Jinzhu[2];Xu, Yisheng[1]

机构：[1]East China Univ Sci & Technol, Int Joint Res Ctr Green Energy Chem Engn, State Key Lab Chem Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]Jinan Univ, Coll Chem & Mat Sci, 601 Huangpu Ave West, Guangzhou 510632, Guangdong, Peoples R China;[3]South China Univ Technol, Sch Environm & Energy, Guangdong Prov Key Lab Atmospher Environm & Pollu, Guangzhou Higher Educ Mega Ctr, 382 Zhonghuan Rd East, Guangzhou 510006, Guangdong, Peoples R China

年份：2018

卷号：1

期号：8

起止页码：4247

外文期刊名：ACS APPLIED NANO MATERIALS

收录：;EI(收录号：20193407345162);WOS:【SCI-EXPANDED(收录号:WOS:000461400900054)】；

基金：This work was supported by National Natural Science Foundation of China (21676089, 21472189 and 91645119), Shanghai Talent Development Fund (2017038), the Fundamental Research Funds for the Central Universities (21617431, 222201717013, 22221818014), and Natural Science Foundation of Guangdong Province, China (2018B030311010).

语种：英文

外文关键词：biomass; metal-organic frameworks; palladium; photocatalysis; transfer hydrogenation

摘要：Visible-light-induced selective transfer hydrogenation of aromatic aldehyde to the corresponding alcohol was achieved by using Pd nanocatalyst supported on amine-functionalized iron-based metalorganic frameworks [Pd/MIL-101(Fe)-NH2] with triethylamine (TEA) as an electron donor and HCOOH as a proton source. The Pd/MIL-101(Fe)-NH2, obtained by an in situ photodeposition method, showed homogeneously and highly dispersed Pd nanoparticles (NPs) with a uniform size throughout the MIL-101(Fe)-NH2 support due to an effective stabilization role of amine groups on the backbone linkage of MIL-101(Fe)-NH2. The resulting Pd/MIL-101(Fe)-NH2 exhibited excellent catalytic performance toward a visible-light-induced transfer hydrogenation of benzaldehyde by producing a benzyl alcohol yield of 77% with a full benzaldehyde conversion in the presence of TEA-HCOOH. In addition to benzaldehyde, biomass-based renewable platform molecules such as furfural and 5-hydroxymethylfurfural (HMF) were successively converted into the corresponding alcohols with the yields of 29% for furfuryl alcohol and 27% for 2,5-dihydroxymethylfuran (DHMF), respectively, which are the highest yields reported so far by visible-light-induced transfer hydrogenation method. Our experimental investigation reveals that a preliminary photoirradiation promotes in situ photodeposition of Pd salt [MIL-101(Fe)-NH3](+).1/2[PdCl4](2-) to form Pd catalyst Pd/MIL-101(Fe)-NH2 in the presence of TEA-HCOOH, and a further photoirradiation successively triggers Pd/MIL-101(Fe)-NH2-promoted transfer hydrogenation of aldehyde, again, with the help of TEA-HCOOH. Our theoretical research based on density functional theory (DFT) further confirms a dual function of amine group in the Pd/MIL-101(Fe)-NH2 for Pd NPs stabilization as well as for enhancement of the electron density of the Pd center upon light adsorption. The photocatalytic system of Pd nanocatalyst and TEA-HCOOH thus demonstrates an environmentally friendly and efficient strategy for aldehyde hydrogenation by using renewable solar energy as a driving force.