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Hydrogenation and Related Reductions of Carbon Dioxide with Molecular Catalysts

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Transformation and Utilization of Carbon Dioxide

Part of the book series: Green Chemistry and Sustainable Technology ((GCST))

Abstract

The use of carbon dioxide as C1 source to produce chemicals and fuels can be the basis of green and sustainable chemical industries. In this regard in the last decade, significant progress has been achieved in the hydrogenation of carbon dioxide and bicarbonate using homogeneous catalysis. For example, new catalyst systems have been reported, therefore showing high activity even under mild conditions. Furthermore, for the first time catalysts based on iron and cobalt were shown to yield TON being in the same range as many noble-metal-based complexes. In addition, interesting concepts for the catalyst recycling and the formic acid product separation have been presented as well as systems capable of hydrogen storage. Very recently, promising systems for the converting of CO2 to methanol with H2 have been developed opening new ways to a future methanol economy. Further reduction to CH4 with molecular hydrogen is still not known, but related reductions of carbon dioxide using boranes or hydrosilylation reagents can gain an interesting insight into the mechanism of such processes.

This chapter summarizes the recent developments in the reduction of carbon dioxide with molecular hydrogen and other hydride reagents starting from 2005.

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Abbreviations

Bcat:

catecholborane

Bpin:

pinacolborane

bpy:

bipyridine

cat.:

catalyst

Cp*:

pentamethylcyclopentadienyl

Cy:

cyclohexyl group

DBU:

1,8-diazabicycloundec-7-ene

DFT:

density functional theory

DHBP:

4,4′-dihydroxy-2,2′-bipyridine

DHPT:

4,7-dihydroxy-1,10-phenanthroline

DMFC:

direct methanol fuel cells

dmpe:

1,3-bis(dimethylphophino)ethane

dppm:

1,2-bis(diphenylphosphino)methane

dppp:

1,3-bis(diphenylphosphino)propane

EMIMCl:

1-ethyl-3-methylimidazolium chloride

FLP:

frustrated Lewis pairs

hex:

hexyl group

IL:

ionic liquid

iPr:

isopropyl group

IR:

infrared spectroscopy

KIE:

kinetic isotope effect

MD:

molecular dynamics

Me:

methyl group

Mes:

mesityl groups

MTA:

methanol-to-aromatics

MTD:

metadynamics

MTG:

methanol-to-gasoline

MTO:

methanol-to-olefins

mtppms:

sodium diphenylphosphinobenzene-3-sulfonate

NHC:

N-heterocyclic carbene

NMR:

nuclear magnetic resonance spectroscopy

OAc:

acetoxy group

OTf:

triflate group

Ph:

phenyl group

PNP:

pincer ligand (P donor atoms on the side arms N ~ in the middle); analogue PNN PCP

RT:

room temperature

SDQ:

single doubles quadruples

tBu:

tert-butyl group

TOF:

turnover frequency

TON:

turnover number

TMP:

tetramethylpiperidine

TS:

transition state

Verkade’s base:

2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo-[3, 3, 3]undecane

X:

halide anions such as Cl− Br−

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  1. Leibniz-Institute für Katalyse Eingetragener Verein an der Universität Rostock, Albert-Einstein Straße 29a, Rostock, 18059, Germany

    Carolin Ziebart & Matthias Beller

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  1. Carolin Ziebart
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  2. Matthias Beller
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    Bhalchandra M. Bhanage

  2. Division of Chemical Process Engineering, Hokkaido University Faculty of Engineering, Sapporo, Japan

    Masahiko Arai

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Ziebart, C., Beller, M. (2014). Hydrogenation and Related Reductions of Carbon Dioxide with Molecular Catalysts. In: Bhanage, B., Arai, M. (eds) Transformation and Utilization of Carbon Dioxide. Green Chemistry and Sustainable Technology. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-44988-8_4

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