Kuterasiński Łukasz, Podobiński Jerzy, Datka Jerzy
Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, ul. Niezapominajek 8, 30-239 Kraków, Poland.
Molecules. 2021 May 2;26(9):2669. doi: 10.3390/molecules26092669.
In this study, IR studies of the coadsorption of ethanol and CO on Cu cations evidenced the transfer of electrons from ethanol to Cu, which caused the lowering of the frequency of the band attributed to CO bonded to the same Cu cation due to the more effective π back donation of d electrons of Cu to antibonding π* orbitals of CO. The reaction of ethanol with acid sites in zeolite HFAU above 370 K produced water and ethane, polymerizing to polyethylene. Ethanol adsorbed on zeolite Cu(2)HFAU containing acid sites and Cu also produced ethene, but in this case, the ethene was bonded to Cu and did not polymerize. C=C stretching, which is IR non-active in the free ethene molecule, became IR active, and a weak IR band at 1538 cm was present. The reaction of ethanol above 370 K in Cu(5)NaFAU zeolite (containing small amounts of Cu and bigger amounts of Cu, Cu and CuO) produced acetaldehyde, which was further oxidized to the acetate species (CHCOO). As oxygen was not supplied, the donors of oxygen were the Cu species present in our zeolite. The CO and NO adsorption experiments performed in Cu-zeolite before and after ethanol reaction evidenced that both Cu and Cu (Cu and CuO) were consumed by the ethanol oxidation reaction. The studies of the considered reaction of bulk CuO and CuO as well as zeolites, in which the contribution of Cu species was reduced by various treatments, suggest that ethanol was oxidized to acetaldehyde by Cu (the role of Cu could not be elucidated), but Cu was the oxygen donor in the acetate formation.
在本研究中,对乙醇和一氧化碳在铜阳离子上的共吸附进行的红外研究表明,电子从乙醇转移至铜,这导致归因于与同一铜阳离子键合的一氧化碳的谱带频率降低,这是由于铜的d电子向一氧化碳的反键π*轨道进行了更有效的π反馈捐赠。在370 K以上,乙醇与沸石HFAU中的酸性位点反应生成水和乙烷,乙烷聚合形成聚乙烯。吸附在含有酸性位点和铜的沸石Cu(2)HFAU上的乙醇也生成乙烯,但在这种情况下,乙烯与铜键合且未发生聚合。在游离乙烯分子中红外非活性的C=C伸缩振动变得具有红外活性,并且在1538 cm处出现一个弱红外谱带。在Cu(5)NaFAU沸石(含有少量铜以及大量的Cu、Cu和CuO)中,370 K以上的乙醇反应生成乙醛,乙醛进一步氧化为醋酸根物种(CHCOO)。由于未供应氧气,氧气的供体是我们沸石中存在的铜物种。在乙醇反应前后对铜沸石进行的一氧化碳和一氧化氮吸附实验表明,Cu和Cu(Cu和CuO)都被乙醇氧化反应消耗。对大量CuO和CuO以及沸石的相关反应研究表明,通过各种处理降低了铜物种的贡献,结果表明乙醇被Cu氧化为乙醛(无法阐明Cu的作用),但Cu是醋酸根形成过程中的氧供体。