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

Federsel, Christopher; Ziebart, Carolin; Jackstell, Ralf; Baumann, Wolfgang; Beller, Matthias

doi:10.1002/chem.201101343

Cited by 259 publications

(180 citation statements)

References 41 publications

Supporting

Mentioning

166

Contrasting

Unclassified

Order By: Relevance

“…This conjecture is indeed found in the scientific community [76,77] at present and many publications report on solutions of the CEC issue using the one or another approach indicated above. The large international activity has generated a broad base of conventional and novel solutions to these problems and one would think that CEC is not a serious problem from a purely academic viewpoint.…”

Section: The Chemical Toolbox Of Cecsupporting

confidence: 54%

Sustainable Energy Systems: The Strategic Role of Chemical Energy Conversion

Schlögl

2016

Top Catal

View full text Add to dashboard Cite

In our globalized economy a multitude of energy systems are in operation. They present quite different structures and targets despite their common goal of supplying the energy needs for all societal activities reflecting the different boundary conditions of respective societies. The common quest for sustainability has given renewable electricity and ''solar fuels'' a high attention. The paper describes some underlying systemic aspects of integrating renewable with fossil energy and makes the point that without chemical energy conversion (CEC) this target will not be possible. A non-exhaustive list of grand challenges in CEC is derived. Some aspects of chemical energy science are discussed.

show abstract

Section: The Chemical Toolbox Of Cecsupporting

confidence: 54%

Sustainable Energy Systems: The Strategic Role of Chemical Energy Conversion

Schlögl

2016

Top Catal

View full text Add to dashboard Cite

show abstract

“…The TON and TOF values are similar to or better than many other first-row transition metal catalysts 9,12-14,17 but significantly lower than the most active such catalysts. 10,11,16,18 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 3…”

mentioning

confidence: 97%

A Molecular Copper Catalyst for Hydrogenation of CO₂ to Formate

2015

View full text Add to dashboard Cite

There is widespread interest in the hydrogenation of CO2 to energy-rich products such as formate. However, first-row transition metal catalysts for the hydrogenation of CO2 to formate remain rare. Copper complexes are widely used in the reduction of organic substrates but their use in the catalytic hydrogenation of CO2 has been limited. Here we demonstrate that the copper(I) complex LCu(MeCN)PF6 is an active catalyst for CO2 hydrogenation in the presence of a suitable base. Screening of bases and studies of catalytic reactions by in operando spectroscopy revealed important and unusual roles for the base in promoting H2 activation and turnover.The development of catalysts for efficient hydrogenation of CO2 is an active area of research, with the potential to reduce our dependence on fossil resources for the production of chemical fuels and feedstocks. Catalysts that can convert the electrical energy from intermittent energy sources, such as wind and solar, into chemical fuels could provide a valuable energy storage mechanism by producing fuels during periods of excess supply that can be used during periods of excess demand. 1 When produced from the reduction of carbon dioxide, carbon-based fuels such as formic acid (usually trapped as formate) 2 and methanol 3 are attractive targets for energy storage, as these fuels have higher volumetric energy densities and can be stored and transported more efficiently and safely than hydrogen. 4 With an energy input of renewably generated H2 or electricity, the overall cycle can in principle be carbon-neutral, as equal quantities of CO2 are first taken up and then emitted over the life cycle of the fuel. 5Numerous transition-metal catalysts for CO2 hydrogenation to formate have been developed over the previous few decades, with turnover numbers (TON, or mol formate per mol catalyst) easily exceeding 10 4 and turnover frequencies (TOF, or turnovers per unit time) in some cases greater than 10 6 h -1 . 6-8 The most active catalysts are typically complexes of either ruthenium or iridium. The greater abundance and lower cost of first-row transition metals would make them better suited to the large-scale production of fuels, if they could be made sufficiently active as catalysts. Several examples of first-row catalysts for CO2 hydrogenation are now known, and, in particular, complexes of Fe 9-15 and Co [16][17][18][19] have been shown to be quite active. There are reasons to believe that copper complexes should be effective in CO2 hydrogenation. For instance, copper dispersions on ZnO/Al2O3 are widely used in the industrial conversion of syngas to methanol; 20,21 mechanistic studies have revealed that this reaction occurs primarily through hydrogenation of the CO2, rather than CO, in these CO2/CO/H2/H2O mixtures. 22,23 Moreover, homogeneous copper phosphine and carbene complexes are highly efficient catalysts for the reduction of CO2 to CO, 24,25 hydroboration of CO2 to form boryl formates, 26 and hydrosilylation of CO2 to form silyl formates. 27-29 These reactions are driven by t...

show abstract

“…With this purpose a catalytic experiment was performed A C C E P T E D M A N U S C R I P T For instance, Beller and co-workers reported the catalytic hydrogenation of sodium bicarbonate using cobalt dihydrogen complexes bearing the tetraphos ligand. [32] Heterogeneous catalysts are less common for carbonate hydrogenation and are mainly based on Pd. [33] It was therefore concluded that the CO 2 produced by WGS under basic conditions reacted with hydroxyl groups to form carbonate which is in turn reduced to formate through hydrogenation catalyzed by the cobalt, as summarized in Scheme 2.…”

Section: Accepted Manuscriptmentioning

confidence: 99%