scholarly journals Cobalt-Catalyzed Hydrosilylation of Carbon Dioxide to the Formic Acid, Formaldehyde, and Methanol Level—How to Control the Catalytic Network?

JACS Au ◽  
2021 ◽  
Author(s):  
Hanna H. Cramer ◽  
Shengfa Ye ◽  
Frank Neese ◽  
Christophe Werlé ◽  
Walter Leitner
2018 ◽  
Author(s):  
Chandan Dey ◽  
Ronny Neumann

<p>A manganese substituted Anderson type polyoxometalate, [MnMo<sub>6</sub>O<sub>24</sub>]<sup>9-</sup>, tethered with an anthracene photosensitizer was prepared and used as catalyst for CO<sub>2</sub> reduction. The polyoxometalate-photosensitizer hybrid complex, obtained by covalent attachment of the sensitizer to only one face of the planar polyoxometalate, was characterized by NMR, IR and mass spectroscopy. Cyclic voltammetry measurements show a catalytic response for the reduction of carbon dioxide, thereby suggesting catalysis at the manganese site on the open face of the polyoxometalate. Controlled potentiometric electrolysis showed the reduction of CO<sub>2</sub> to CO with a TOF of ~15 sec<sup>-1</sup>. Further photochemical reactions showed that the polyoxometalate-anthracene hybrid complex was active for the reduction of CO<sub>2</sub> to yield formic acid and/or CO in varying amounts dependent on the reducing agent used. Control experiments showed that the attachment of the photosensitizer to [MnMo<sub>6</sub>O<sub>24</sub>]<sup>9-</sup> is necessary for photocatalysis.</p><div><br></div>


1932 ◽  
Vol 7 (2) ◽  
pp. 149-161 ◽  
Author(s):  
W. H. Hatcher ◽  
E. W. R. Steacie ◽  
Frances Howland

The kinetics of the oxidation of gaseous acetaldehyde have been investigated from 60° to 120 °C. by observing the rate of pressure decrease in a system at constant volume. A considerable induction period exists, during which the main products of the reaction are carbon dioxide, water, and formic acid. The main reaction in the subsequent stages involves the formation of peroxides and their oxidation products. The heat of activation of the reaction is 8700 calories per gram molecule. The indications are that the reactions occurring during the induction period are heterogeneous. The subsequent reaction occurs by a chain mechanism. The chains are initiated at the walls of the reaction vessel, and are also largely broken at the walls.


2011 ◽  
Vol 13 (6) ◽  
pp. 1411 ◽  
Author(s):  
M. E. M. Berger ◽  
D. Assenbaum ◽  
N. Taccardi ◽  
E. Spiecker ◽  
P. Wasserscheid

Author(s):  
Magali Roger ◽  
Thomas C. P. Reed ◽  
Frank Sargent

Escherichia coli is gram-negative bacterium that is a workhorse for biotechnology. The organism naturally performs a mixed-acid fermentation under anaerobic conditions where it synthesises formate hydrogenlyase (FHL-1). The physiological role of the enzyme is the disproportionation of formate in to H 2 and CO 2 . However, the enzyme has been observed to catalyse hydrogenation of CO 2 given the correct conditions, and so has possibilities in bio-based carbon capture and storage if it can be harnessed as a hydrogen-dependent CO 2 -reductase (HDCR). In this study, an E. coli host strain was engineered for the continuous production of formic acid from H 2 and CO 2 during bacterial growth in a pressurised batch bioreactor. Incorporation of tungsten, in place of molybdenum, in FHL-1 helped to impose a degree of catalytic bias on the enzyme. This work demonstrates that it is possible to couple cell growth to simultaneous, unidirectional formate production from carbon dioxide and develops a process for growth under pressurised gases. IMPORTANCE Greenhouse gas emissions, including waste carbon dioxide, are contributing to global climate change. A basket of solutions is needed to steadily reduce emissions, and one approach is bio-based carbon capture and storage. Here we present out latest work on harnessing a novel biological solution for carbon capture. The Escherichia coli formate hydrogenlyase (FHL-1) was engineered to be constitutively expressed. Anaerobic growth under pressurised H 2 and CO 2 gases was established and aqueous formic acid was produced as a result. Incorporation of tungsten in to the enzyme in place of molybdenum proved useful in poising FHL-1 as a hydrogen-dependent CO 2 reductase (HDCR).


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