Effect of Tungsten Modification on Zirconium Phosphate-Supported Pt Catalyst for Selective Hydrogenolysis of Glycerol to 1-Propanol

Abstract

Hydrogenolysis of glycerol to propanols is highly promising for the sustainable development of biomass refining. In this work, modified amorphous zirconium phosphate (ZrP)-supported Pt catalysts were developed and characterized thoroughly by X-ray diffraction, temperature-programmed desorption of ammonia, Fourier transform infrared spectra of adsorbed pyridine, temperature-programmed reduction, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and Brunauer–Emmett–Teller surface area. The as-obtained catalysts were employed for selective glycerol hydrogenolysis to 1-propanol (1-PO) in a fixed-bed reactor. Owing to the incorporation of WO x , both the total acidity and the dispersion of Pt nanoparticles were enhanced significantly. The Pt/7WO x -ZrP catalyst could afford 81% yield of 1-PO at full conversion of glycerol in a long-term catalytic stability test (at least 70 h reaction time) and was regenerated by calcination in air. The results of the catalytic activity test and catalyst characterization indicated that the acid sites of the catalysts promoted the selective dehydration of glycerol into acrolein, whereas the Pt sites facilitated H2 dissociation and a sequential hydrogenation of acrolein into 1-PO.

Direct Transformation of Glycerol to Propanal using Zirconium Phosphate‐Supported Bimetallic Catalysts

“…[30] The sole ZrP without metals has also been tested in H 2 flow, 74 % glycerol conversion with a 53 % selectivity of AE was observed, along with a decreased selectivity to HA ( Table 1, entries 1 and 2). Besides, a small amount of PA (selectivity: 31 %) was also formed, likely arising from the effect of the stainless-steel walls of the fixed-bed reactor, [32] which can be confirmed further by the following control experiment: a low conversion of AE (36.5 %) could be achieved even without catalyst in H 2 flow (Table S1, entry 1). Interestingly, in the presence of Ru/CoO/ZrP catalyst, AE was almost converted into PA (in 96 % selectivity) ( Table S1, entry 2).…”

“…In previous studies, our group found that zirconium phosphate (ZrP) is a water‐tolerant and thermally stable solid acid catalyst, which provided an excellent performance for gas‐phase selective dehydration of glycerol to acrolein (AE) . Thereafter, we also developed a one‐pot hydrogenolysis of glycerol to 1‐propanol over sequential two‐layer catalysts (ZrP and Ru/SiO 2 ) or a single Pt/7WO 3 ‐ZrP catalytic system in a continuous‐flow fixed‐bed reactor . As a continuation of our efforts to achieve novel applications of this easily accessible, cheap, and stable solid acid catalyst, we report herein a direct PA production from glycerol over ZrP‐supported bimetallic catalysts.…”

“…[30] Thereafter, we also developed a one-pot hydrogenolysis of glycerol to 1-propanol over sequential two-layer catalysts (ZrP and Ru/SiO 2 ) or a single Pt/7WO 3 -ZrP catalytic system in a continuous-flow fixed-bed reactor. [31,32] As a continuation of our efforts to achieve novel applications of this easily accessible, cheap, and stable solid acid catalyst, we report herein a direct PA production from glycerol over ZrP-supported bimetallic catalysts. It was found that Ru/CoO/ZrP was a highly efficient catalyst for glycerol hydrogenolysis, which can achieve full conversion of glycerol and an excellent selectivity to PA (80.2 %) by one-step route under continuous-flow conditions.…”

The Promotional Effect of Sulfates on TiO2 Supported Pt‐WOx Catalyst for Hydrogenolysis of Glycerol

“…So far, the efficient hydrogenolysis of glycerol in aqueous phase are mostly conducted over a bifunctional catalyst including a noble metal (Ir, Rh, or Pt) and a transition metal oxide (such as ReO x or WO x ). [2,3,[13][14][15][16][17][18] Among them, Ir-ReO x based catalysts were mainly studied by Tomishige's group and 38 % yield of 1,3-PDO with 81 % conversion of glycerol was achieved over IrÀ Re/SiO 2 catalyst. [17] Pt-WO x based catalysts were widely investigated and showed high industrial application potential owing to their superior selectivity to 1,3-PDO.…”

A Cationic Ru(II) Complex Intercalated into Zirconium Phosphate Layers Catalyzes Selective Hydrogenation via Heterolytic Hydrogen Activation

“…It can be envisioned that the desirable properties can be achieved from a deep understanding of the intercalation structure. [50] As a continuation of our efforts to design an easily accessible, highly active and stable ZrP catalysis, [51][52][53][54] in this work we report the design and preparation of a recyclable catalyst by the intercalation of a Ru(II) complex into ZrP layers (Ru-ZrP). The structure of catalyst was investigated in detail and active species was further identified by experimental study and DFT calculation.…”