Hydrogenolysis of Glycerol to 1,3‐Propanediol: Are Spatial and Electronic Configuration of “Metal‐Solid Acid” Interface Key for Active and Durable Catalysts?

Abstract

Therefore, in this review article, we have conducted a comprehensive and critical discussion on how steric hindrance and electronic coupling at metal-acid interfaces affect catalytic activation of internal À OH group in glycerol molecule. Selected highlights on the mechanistic investigation for ex-situ and insitu formed Brønsted acidity over Pt-WO x and IrÀ ReO x catalysts, have been discussed with experimental and computational details. The outcome of this review will provide important insights on controllable manipulation of spatial and electronic structures for selective hydrogenation reactions with broader industrial applications.[a] D.

Dynamic Formation of Brønsted Acid Sites over Supported WOx/Pt on SiO2 Inverse Catalysts─Spectroscopy, Probe Chemistry, and Calculations

“…Rigorous attempts have been made to understand the structure and chemical properties of supported Pt-WO x catalysts; see review articles. − Yet, many fundamental questions are still unanswered: (i) since only ex situ techniques were implemented for structural characterization, the WO x structure, domain size, and dynamics in controlled environments are still unknown; (ii) the effect of Pt on the distribution of WO x domains and especially its dynamics in different controlled environments are yet to be understood; (iii) direct spectroscopic evidence regarding the effect of Pt-WO x proximity on dynamic site formation is missing; and more importantly (iv) the state of inverse WO x /Pt structure is almost unexplored in the literature. These gaps hamper understanding of the supported Pt-WO x catalyst system.…”

Insight into the Influence of WOx‐Support Interaction over Pt/W/SiZr Catalysts on 1,3‐Propanediol Synthesis from Glycerol

“…[11][12][13][14] Among the reported catalysts, the Pt-WO x -based and Ir-ReO x -based catalysts are the most widely studied for the hydrogenolysis of glycerol to 1,3-PDO. [15][16][17][18][19][20][21][22] The Ir-ReO x -based catalysts are very effective for glycerol hydrogenolysis to 1,3-PDO. [23][24] However, the high solubility of ReO x in water leads to poor catalyst stability.…”

“…According to literature, the high‐efficiency catalyst for synthesis of 1,3‐PDO from glycerol hydrogenolysis requires both metal sites and Brønsted acid sites [11–14] . Among the reported catalysts, the Pt‐WO x ‐based and Ir‐ReO x ‐based catalysts are the most widely studied for the hydrogenolysis of glycerol to 1,3‐PDO [15–22] . The Ir‐ReO x ‐based catalysts are very effective for glycerol hydrogenolysis to 1,3‐PDO [23–24] .…”