High-Pressure Combinatorial Screening of Homogeneous Catalysts:  Hydrogenation of Carbon Dioxide

Abstract

A simple method for high-pressure combinatorial catalyst discovery with visual (dye-based) assay is described. With this method, the first highly active catalyst, incorporating metals outside the platinum group, has been identified for CO(2) hydrogenation.

Recent advances in catalytic hydrogenation of carbon dioxide

“…Tai et al found that combinations of FeCl 3 , NiCl 2 , or MoCl 3 with dcpe yielded significant activity for CO 2 hydrogenation to formic acid. 274 Merz et al reported the remarkably distinct reactivity of hydridozinc heterobimetallic cubanes towards CO 2 hydrogenation. 286 The hydride transfer from Zn-H to CO 2 is substantially accelerated in the presence of Li ions leading to the respective metal formate hydrates.…”

A Well‐Defined Iron Catalyst for the Reduction of Bicarbonates and Carbon Dioxide to Formates, Alkyl Formates, and Formamides

“…Although formic acid was formed under optimized conditions (FeCl 3 /1,2-bisdicyclohexylphosphinoethane) with an improved catalyst turnover number of 113, the reaction proceeded only in the presence 0.5 equivalents of the expensive base 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU) at 100 bar total pressure. [14] Moreover, a large excess of carbon dioxide was used in both reports, and consequently no yields based on CO 2 or amine are given. Therefore, the need still exists to develop an efficient iron catalyst for the hydrogenation of CO 2 and carbonates.…”

Catalytic Hydrogenation of Carbon Dioxide and Bicarbonates with a Well‐Defined Cobalt Dihydrogen Complex

“…[4] So far, mainly noble metal complexes based on ruthenium, rhodium and iridium have been studied for this transformation and impressive catalyst productivities have been achieved. [5] On the other hand, non-precious-metal catalysts based on iron, manganese or zinc [6,7] have scarcely been investigated and the obtained catalytic activities are low (turnover numbers (TONs) < 120).…”