2-Butyne-1,4-diol hydrogenation over palladium supported on Zn2+-based – MOF and host–guest MOF/calix[4]arene materials

Efficient Pd@MIL-101(Cr) hetero-catalysts for 2-butyne-1,4-diol hydrogenation exhibiting high selectivity

“…6b shows the BED selectivity versus BYD conversion. 26,52 It can be seen that the conversion of BYD increased with prolonging the reaction time, and reached 93.3% aer 5 h, suggesting the high activity of small amount of Pd@MIL-101(Cr) under these mild conditions. This extremely high selectivity of about 99.0% remained constant until the BYD conversion increased to 72.5%, and the formation of BED was mainly from BYD hydrogenation without being further catalysed to yield BDO and other side products.…”

“…60 The excellent catalytic performance of high selectivity of BED can be well explained as follows: (i) the Pd nanoparticles with irregular shape were encapsulated in the cavities of MIL-101(Cr) resulting in the block of the parts of the vertex and edge sites by the framework, therefore, further hydrogenation and isomerization of BED is substantially suppressed; (ii) alkene hydrogenation may take place on terraces with the absence of starting alkyne; (iii) the rst stage of BYD hydrogenation proceeds much faster than the second stage of BED hydrogenation due to stronger adsorption of BED on the metal-organic coordination polymers than that on activated carbon. 26 To evaluate the stability of Pd@MIL-101(Cr), which is an essential requirement for industrial catalysts, XRD and N 2 adsorption experiments were conducted to examine the structural stability before and aer catalytic reactions. As shown in Fig.…”

“…25 The production of 2-butene-1,4-diol (BED) and 1,4-butanediol (BDO) with hydrogenation of 2-butyne-1,4-diol (BYD) has an important industrial use. 26 As an essential starting material with a worldwide production $5000 tons per year, BED is used for the synthesis of vitamins and insecticides. 27 BDO has also numerous applications in manufacturing polymer and chemicals such as tetrahydrofuran and g-butyrolactone.…”

Metal–Organic Framework Supported Palladium Nanoparticles: Applications and Mechanisms

“…The hydrogenation reduction of polyunsaturated compounds is achieved by the sequential addition of hydrogen atoms into these polyunsaturated compounds (i.e., alkyne, aldehydes, and alkenes) 2e,12b,c,22. These unsaturated bonds such as CC or CO obtain hydrogen atoms from the catalytic metal (Pd) and then produce saturated or sub‐saturated compounds.…”

“…The roles of Pd NPs are to 1) dissociate H 2 into hydrogen atoms and 2) facilitate the formation of saturated or sub‐saturated compounds. In the past decades, catalytic hydrogenation of 2‐butyne‐1,4‐diol (BYD) to 2‐butene‐1,4‐diol (BED) and 1,4‐butane‐diol (BDO), especially partial hydrogenation to BED is attracting industrial interest because BED are widely applied in paper, textile, and polymer manufacturing 22a,23. As shown in Figure , BYD is first hydrogenated to produce BED, and then instantaneously adsorbed on to the Pd NP surface sites to further be hydrogenated to form BDO simultaneously, and various by‐products such as 4‐hydroxybutyraldehyde, crotyl alcohol, and butanal, and butanol are inevitably generated .…”