Pt‐Loaded Nb─W Metal Composite Oxide for Selective Cleavage of Secondary C─O Bonds

Abstract

Selective hydrogenolysis of glycerol to 1,3‐propanediol (1,3‐PDO) is recognized as one of the most promising reactions for the valorization of biomass. Precise activation of C─O bonds of glycerol molecule is the key step to realize the high yield of catalytic conversion. Here, a Pt‐loaded Nb–W composite oxides with crystallographic shear phase for the precise activation and cleavage of secondary C─O (C(2)─O) bonds are first reported. The developed Nb14W3O44 with uniform structure possesses arrays of W–O–Nb active sites that totally distinct from individual WOx or NbOx species, which is superior to the adsorption and activation of C(2)─O bonds. The Nb14W3O44 support with rich reversible redox couples also promotes the electron feedback ability of Pt and enhances its interaction with Pt nanoparticles, resulting in high activity for H2 dissociation and hydrogenation. All these favorable factors confer the Pt/Nb14W3O44 excellent performance for selective hydrogenolysis of glycerol to 1,3‐PDO with the yield of 75.2% exceeding the record of 66%, paying the way for the commercial development of biomass conversion. The reported catalysts or approach can also be adopted to create a family of Nb–W metal composite oxides for other catalytic reactions requiring selective C─O bond activation and cleavage.

Synchronizing Deoxygenation and Hydrogenation to Effect Glycerol Hydrogenolysis over Pt/Nb2W15O50 at Low H2 Pressure

“…In addition, the Nb-rich catalysts in the previous work are similar to most catalysts in that their catalytic activity shows a strong dependence on high H 2 pressure. 10 Under the same conditions, only a 17.2% yield of 1,3-PDO was obtained on the Nb-rich catalyst (Table S4). This contrast further highlights the stronger H 2 activation capacity on Pt/ Nb 2 W 15 O 50 .…”

“…In the 1980s, Che et al pioneered the formation of 1,3-PDO in glycerol hydrogenolysis, to provide a 21% yield . In recent years, the steady progression of catalyst design has allowed the yield to increase to 76% . Based on such research, the most promising candidate for an optimal catalyst appears to be the loading of noble metals on an oxyphilic metal oxide, as these correspond to hydrogenation- and deoxygenation-active centers, respectively.…”

MOF‐Derived In2O3/CuO p‐n Heterojunction Photoanode Incorporating Graphene Nanoribbons for Solar Hydrogen Generation

“…[25] UPS with He I radiation (21.21 eV) was used to estimate the Fermi level (E F ) and valence band maximum (VBM) energy level. [26] Figure S7, Supporting Information shows the UPS spectra of CuO, In 2 O 3 , and In 2 O 3 /CuO, respectively. According to the linear intersection method, the E VBM of CuO is calculated to be −5.62 eV (vs vacuum).…”

Highly Efficient Iridium–Iron–Molybdenum Catalysts Condensed on Boron Nitride for Biomass-Derived Diols’ Hydrogenolysis to Secondary Monoalcohols

“…However, its catalytic performance, especially activity, still has considerable room for improvement: the reaction rate of 1,2-BuD hydrogenolysis to 2-butanol over Ir–Fe/BN was about 3 mmol g Ir –1 h –1 , while that of 1,2-propanediol to a mixture of propanol (about 1-propanol/2-propanol ratio of ∼1) over Ru–ReO x /SiO 2 reached 363 mmol g Ru –1 h –1 . For the hydrogenolysis of secondary C–O bond, the formation rate was >200 mmol g NM –1 h –1 (NM: noble metal, glycerol to 1,3-propanediol) . Achieving both high activity and selectivity is a long-standing challenge for selective reactions in the field of catalysis .…”