Catalytic Performance of Functionalized IRMOF-3 for the Synthesis of Glycerol Carbonate from Glycerol and Urea

Abstract

A functionalized isoreticular metal organic framework material, F-IRMOF-3, having a quaternary ammonium group was prepared by fast precipitation and solvothermal method. The synthesized MOFs exhibited good catalytic performance in the synthesis of glycerol carbonate (GC) from glycerol and urea. F-IRMOF-3 having a larger alkyl chain structure and a more nucleophilic counter anion than the synthesized congeners, exhibited better reactivity in the synthesis of GC. The introduction of a ZnO defect into the F-IRMOF-3 structure by fast precipitation was more advantageous for the glycerolysis of urea than the conventional solvothermal method because of the incorporation of acid-base bifunctional active sites by the former method. The effects of reaction parameters such as temperature, reaction time, catalyst loading, and degree of vacuum on the reactivity were also investigated. The F-IRMOF-3 catalyst can be easily recovered and reused without considerable loss of its initial activity.

Metal–Organic Frameworks-Based Catalysts for Biomass Processing

“…It was found that the catalyst bifunctionality, that is, the simultaneous presence of the acid and basic sites, contributed significantly to the catalyst performance in the synthesis of cyclic carbonates from urea and diols. A bifunctional MOF catalyst having an appropriate combination of Lewis acid and Lewis basic sites was developed specifically for this process [97]. This material, that is, the IRMOF-3 framework (Zn 4 O(BDC) 3 ) with amino functions in organic linkers was modified by a post-synthesis strategy by alkyl halides resulted in the conversion of -NH 2 to a quaternary ammonium salt species.…”

Process intensification for tertiary amine catalyzed glycerol carbonate production: translating microwave irradiation to a continuous-flow process

“…Other catalysts such as gold, 21 palladium, 22,23 copper, [24][25][26] rhodium, 27 tungsten, 28,29 zinc, 10,30 lanthanum, [31][32][33] calcium, 34,35 magnesium, [36][37][38][39][40][41] zeolites, 42,43 Naon, 44 alumina, [45][46][47] have been used to produce glycerol carbonate by carbonylation of glycerol with alkyl carbonates, 19,48,49 CO 2 (ref. 30) or urea, [50][51][52][53][54][55] arriving on the desired product with poor (when CO 2 is used) to good yields and selectivity (when alkyl carbonates are used). A more convergent approach tends to arrive on the desired glycerol carbonate during the biodiesel process and good results were obtained up to now (Fig.…”