From CO<sub>2</sub> activation to catalytic reduction: a metal-free approach

Sreejyothi, P; Mandal, Swadhin K.

doi:10.1039/d0sc03528a

Cited by 91 publications

(11 citation statements)

References 124 publications

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“…While large-scale applications for CO 2 reduction require the use of “green” hydrogen, catalytic reductions using activated hydrides such as boranes or silanes are very useful as molecular probes to expand our knowledge in this field. − Their structures inherently enable heterolytic activation pathways to deliver hydrides for the two-electron reduction together with an oxophilic counterpart . Examples that facilitate the transformation of CO 2 with such reducing agents to control the selectivity to two different reduction levels are shown in Figure A–C.…”

Section: Introductionmentioning

confidence: 99%

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

Cramer

Neese

et al. 2021

JACS Au

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The selective hydrosilylation of carbon dioxide (CO 2 ) to either the formic acid, formaldehyde, or methanol level using a molecular cobalt(II) triazine complex can be controlled based on reaction parameters such as temperature, CO 2 pressure, and concentration. Here, we rationalize the catalytic mechanism that enables the selective arrival at each product platform. Key reactive intermediates were prepared and spectroscopically characterized, while the catalytic mechanism and the energy profile were analyzed with density functional theory (DFT) methods and microkinetic modeling. It transpired that the stepwise reduction of CO 2 involves three consecutive catalytic cycles, including the same cobalt(I) triazine hydride complex as the active species. The increasing kinetic barriers associated with each reduction step and the competing hydride transfer steps in the three cycles corroborate the strong influence of the catalyst environment on the product selectivity. The fundamental mechanistic insights provide a consistent description of the catalytic system and rationalize, in particular, the experimentally verified opportunity to steer the reaction toward the formaldehyde product as the chemically most challenging reduction level.

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Section: Introductionmentioning

confidence: 99%

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

Cramer

Neese

et al. 2021

JACS Au

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“…Carbon dioxide is one important contributor to the greenhouse effect, and its increasing emission from various sources triggers research of its capture and recycling into chemicals [1–13] . The use of CO 2 , which is non‐toxic and abundantly present in nature, as a C1 building block in chemical reaction systems is still not very common due to its high thermodynamic and kinetic stability [14] .…”

Section: Methodsmentioning

confidence: 99%

“…house effect, and its increasing emission from various sources triggers research of its capture and recycling into chemicals. [1][2][3][4][5][6][7][8][9][10][11][12][13] The use of CO 2 , which is non-toxic and abundantly present in nature, as a C1 building block in chemical reaction systems is still not very common due to its high thermodynamic and kinetic stability. [14] However, despite this, there are systems which are known to show reactivity towards CO 2 .…”

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confidence: 99%

The Reaction of CO₂ with a Borylnitrene: Formation of an 3‐Oxaziridinone

2021

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The reaction of a borylnitrene with carbon dioxide is studied under cryogenic matrix isolation conditions. Photogenerated CatBN (Cat=catecholato) reacts with CO2 under formation of the cycloaddition product CatBNCO2, a 3‐oxaziridinone derivative, after photoexcitation (>550 nm). The product shows Fermi resonances between the CO stretching and ring deformation modes that cause unusual 13C and 18O isotopic shifts. A computational analysis of the 3‐oxaziridinone shows this cyclic carbamate to be less strained than an α‐lactone or an α‐lactame.

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“…CO 2 , with respect to its use as a source of carbon in catalytic processes has received massive attention, as the world is addressing issues in climate change, in particular with respect to hydrogenation. The reduction of CO 2 into value-added chemical products is considered to have the most potential for chemical transformation of CO 2 [6][7][8] . A group at Imperial Chemical Industries (ICI) in Billingham during the 1980s has shown that CO 2 plays an important role in methanol syntheses from CO/CO 2 /H 2 gas mixtures over a Cu/ZnO/Al 2 O 3 catalyst.…”

Section: Introductionmentioning

confidence: 99%

Water and Carbon Dioxide Adsorption on CaO(001) Studied via Single Crystal Adsorption Calorimetry

et al. 2021

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A new method to analyze microcalorimetry data was employed to study the adsorption energies and sticking probabilities of D2O and CO2 on CaO(001) at several temperatures. This method deconvolutes the line shapes of the heat detector response into an instrument response function and exponential decay functions, which correspond to the desorption of distinct surface species. This allows for a thorough analysis of the adsorption, dissociation, and desorption processes that occur during our microcalorimetry experiments. Our microcalorimetry results, show that D2O adsorbs initially with an adsorption energy of 85–90 kJ/mol at temperatures ranging from 120 to 300 K, consistent with prior spectroscopic studies that indicate dissociation. This adsorption energy decreases with increasing coverage until either D2O multilayers are formed at low temperatures (120 K) or the surface is saturated (> 150 K). Artificially producing defects on the surface by sputtering prior to dosing D2O sharply increases this adsorption energy, but these defects may be healed after annealing the surface to 1300 K. CO2 adsorbs on CaO(001) with an initial adsorption energy of ~ 125 kJ/mol, and decreases until the saturation coverage is reached, which is a function of surface temperature. The results showed that pre-adsorbed water blocks adsorption sites, lowers the saturation coverage, and lowers the measured adsorption energy of CO2. The calorimetry data further adds to our understanding of D2O and CO2 adsorption on oxide surfaces.

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From CO₂ activation to catalytic reduction: a metal-free approach

Abstract: Over exploitation of natural resources and human activities are relentlessly fueling the emission of CO2 in atmosphere. To address this issue of excessive CO2 emissions and its potential effects on...

Cited by 91 publications

References 124 publications

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

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

The Reaction of CO₂ with a Borylnitrene: Formation of an 3‐Oxaziridinone

Water and Carbon Dioxide Adsorption on CaO(001) Studied via Single Crystal Adsorption Calorimetry

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From CO2 activation to catalytic reduction: a metal-free approach

Abstract: Over exploitation of natural resources and human activities are relentlessly fueling the emission of CO2 in atmosphere. To address this issue of excessive CO2 emissions and its potential effects on...

Cited by 91 publications

References 124 publications

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

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

The Reaction of CO2 with a Borylnitrene: Formation of an 3‐Oxaziridinone

Water and Carbon Dioxide Adsorption on CaO(001) Studied via Single Crystal Adsorption Calorimetry

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Product

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From CO₂ activation to catalytic reduction: a metal-free approach

The Reaction of CO₂ with a Borylnitrene: Formation of an 3‐Oxaziridinone