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Cyclometalation of lanthanum(iii) based MOF for catalytic hydrogenation of carbon dioxide to formate†
Banothile C. E. Makhubela,Lars Öhrström,Susan A. Bourne,Nabanita Chatterjee,Isaac N. Beas,Gift Mehlana
RSC Advances Pub Date : 01/22/2020 00:00:00 , DOI:10.1039/C9RA09938G
Abstract

The hydrogenation of carbon dioxide (CO2) to formic acid is of great importance due to its useful properties in the chemical industry. In this work, we have prepared a novel metal–organic framework (MOF), JMS-1, using bipyridyl dicarboxylate linkers, with molecular formula [La2(bpdc)3(DMF)3]n. Network analysis of JMS-1 revealed a new 7-connected topology (zaz). The MOF backbone of the activated phase (JMS-1a) was functionalized by cyclometalation using [RuCl2(p-cymene)]2 to produce Ru(II)@JMS-1a. Both JMS-1a and Ru(II)@JMS-1a were able to convert CO2 in the presence of hydrogen to formate. Ru(II)@JMS-1a displayed outstanding conversion evidenced by a yield of 98% of formate under optimized conditions of total pressure 50 bar (CO2/H2 = 1 : 4, temperature 110 °C, time 24 h, 5 mmol KOH, 8 mL ethanol). This work is significant in providing new strategies of incorporating active catalytic centres in MOFs for efficient and selective conversion of CO2 to formate.

Graphical abstract: Cyclometalation of lanthanum(iii) based MOF for catalytic hydrogenation of carbon dioxide to formate
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