Catalytic Transfer Hydrogenation of the C═O Bond in Unsaturated Aldehydes over Pt Nanoparticles Embedded in Porous UiO-66 Nanoparticles

Abstract

Selective preparation of unsaturated alcohols via the hydrogenation of CO in α,β-unsaturated aldehydes is a challenging reaction. In this work, a nanoscale material Pt/UiO-66 catalyst with homogenously dispersed Pt nanoparticles encapsulated in UiO-66 was prepared. Its performance for the selective formation of unsaturated alcohols from unsaturated aldehydes with molecular H2 and via the catalytic transfer hydrogenation (CTH) was compared. It was found that Pt/UiO-66 was more selective and efficient for the hydrogenation of the CO bond to alcohol when isopropanol was utilized as hydrogen donors instead of molecular H2. The selectivity of unsaturated alcohols reached 94.6% at a 90.5% conversion of unsaturated aldehydes at 150 °C. At the same time, the utilization of isopropanol as hydrogen donors reached 92.6%, and a turnover frequency of 4071 h–1 was achieved. The CTH reaction mechanism over Pt/UiO-66 was suggested based on the results of several control experiments.

Structure–Activity Relationship for the Catalytic Hydrogenation of Nitrobenzene by Single Platinum Atoms Supported on Nitrogen-Doped Carbon

“…Peaks at around 71.1 and 74.4 eV were attributed to Pt 4f 7/2 and Pt 4f 5/2 , respectively. 60,61 Compared with Pt/ben-C (72.0 eV), the level of Pt 4f 7/2 in Pt/g-C 3 N 4 (71.1 eV), Pt/pyrrol-N x C (71.5 eV), and Pt/ani-N x C (71.7 eV) shifted negatively, whereas it shifted positively in Pt/ pyridine-N x C (72.1 eV). These shifts in the binding energy of Pt 4f were consistent with the varied level of N 1s before and after Pt loading, which could be attributed to the electronic interaction between Pt and N species.…”

Metal Organic Frameworks Derived Catalysts for the Upgrading of Platform Chemicals

“…Uniformly distributed Pt nanoparticles that embedded in porous UiO-66 (Pt/UiO-66) was also prepared through a straightforward one-pot method using DMF as a reducing agent by Ye and coworkers. [49] Liu et al further employed acetic acid as a growth regulator for UiO-66 to reduce its growth rate and H 2 as an auxiliary reducing agent to increase the reduction rate of Pt nanoparticles and avoid the incomplete embedding of Pt nanoparticles within UiO-66 (see Figure 4D). [50,51]…”

Pd–Ni–Fe Nanoparticles Supported on UiO-66 for Selective Hydrogenation of Fatty Acid Methyl Esters to Alcohols

“…Investigating methods to maximize the number of active sites with limited metal loading is of great importance for developing high-performance catalytic platforms. , Metal organic frameworks (MOFs) serve as ideal support candidates due to their periodic porous structure. , Among the MOFs, the structure of UiO-66 exhibits a high elastic modulus similar to that of zeolites and can withstand temperatures close to 500 °C. , Furthermore, UiO-66 has a higher specific surface area of over 1000 m 2 /g compared to conventional supports for carboxylate hydrogenation catalysts, such as SiO 2 , , TiO 2 , − and Al 2 O 3 . , Given its unique structural properties, UiO-66 has been used as promising support for the dispersion of MNPs in the hydrogenation of olefin and aldehyde, − ethylene oligomerization, and other reactions. To the best of our knowledge, UiO-66 has not been used alone as a support for the selective hydrogenation of fatty acid methyl esters.…”