CO2 conversion covers a wide range of possible application areas from fuels to bulk and commodity chemicals and even to specialty products with biological activity such as pharmaceuticals. In the present review, we discuss selected examples in these areas in a combined analysis of the state-of-the-art of synthetic methodologies and processes with their life cycle assessment. Thereby, we attempted to assess the potential to reduce the environmental footprint in these application fields relative to the current petrochemical value chain. This analysis and discussion differs significantly from a viewpoint on CO2 utilization as a measure for global CO2 mitigation. Whereas the latter focuses on reducing the end-of-pipe problem “CO2 emissions” from todays’ industries, the approach taken here tries to identify opportunities by exploiting a novel feedstock that avoids the utilization of fossil resource in transition toward more sustainable future production. Thus, the motivation to develop CO2-based chemistry does...

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

https://purehost.bath.ac.uk/ws/files/10904963/Kember_etal_manuscript_rev_5.pdf

Catalysts for CO2/epoxide copolymerisation

While experts in various fields discuss the potential of carbon capture and storage (CCS) technologies, the utilization of carbon dioxide as chemical feedstock is also attracting renewed and rapidly growing interest. These approaches do not compete; rather, they are complementary: CCS aims to capture and store huge quantities of carbon dioxide, while the chemical exploitation of carbon dioxide aims to generate value and develop better and more-efficient processes from a limited part of the waste stream. Provided that the overall carbon footprint for the carbon dioxide-based process chain is competitive with conventional chemical production and that the reaction with the carbon dioxide molecule is enabled by the use of appropriate catalysts, carbon dioxide can be a promising carbon source with practically unlimited availability for a range of industrially relevant products. In addition, it can be used as a versatile processing fluid based on its remarkable physicochemical properties.

Chemical Technologies for Exploiting and Recycling Carbon Dioxide into the Value Chain

Recent developments in carbon dioxide utilization for the production of organic chemicals

Natural molecular biomass plays an important role in the field of renewable polymers, as they can be directly used or derivatized as monomers for controlled polymerization, in a way similar to many petroleum-derived monomers. We deliver this perspective primarily based on a monomer approach. Biomass-derived monomers are separated into four major categories according to their natural resource origins: (1) oxygen-rich monomers including carboxylic acids (lactic acid, succinic acid, itaconic acid, and levulinic acid) and furan; (2) hydrocarbon-rich monomers including vegetable oils, fatty acids, terpenes, terpenoids and resin acids; (3) hydrocarbon monomers (bio-olefins); and (4) non-hydrocarbon monomers (carbon dioxide). A variety of emerging synthetic tools (controlled polymerization and click chemistry) are particularly summarized. An overview on future opportunities and challenges, which are critical to promote biorefinery in the production of renewable chemicals and polymers, is given.

Controlled Polymerization of Next-Generation Renewable Monomers and Beyond

Copolymerization of a series of cyclic acid anhydrides with several epoxides using (salen)CrCl/onium salt catalysts has afforded polyesters with high molecular weights and narrow molecular weight distributions. The (salen)CrCl catalyst in the presence of the onium salts with formula PPNX (X = Cl–, N3–) for the copolymerization of the anhydrides, maleic (MA), succinic (SA), phthalic (PA), cyclohexene (CHE), and cyclohexane (CHA) with the epoxides, cyclohexene oxide (CHO), propylene oxide (PO), and styrene oxide (SO) resulted in completely alternating enchainment of monomers to provide pure polyesters. Temperature dependent studies of the ring-opening copolymerization of phthalic anhydride and cyclohexene oxide monomers in toluene solution have yielded activation parameters of ΔH‡ = 67.5 kJ mol–1 and ΔS‡ = −95.3 J mol–1, where the rate limiting step was ring-opening of the epoxide by the enchained anhydride. For the cyclic acid anhydride (CHA), the relative order of reactivity with epoxides decreased PO > C...

Kinetic Studies of the Alternating Copolymerization of Cyclic Acid Anhydrides and Epoxides, and the Terpolymerization of Cyclic Acid Anhydrides, Epoxides, and CO2 Catalyzed by (salen)CrIIICl

Chromium(III) derivatives of the tetradentate phenoxyamine ligand H2salan, where salan = the N,N′-dimethylated bis(aminophenoxide) ligand or the saturated version of the corresponding salen ligand, in the presence of 1 equiv of [PPN]N3 (PPN=Ph3P═N+═PPh3) are shown to effectively catalyze the copolymerization of cyclohexene oxide and carbon dioxide. X-ray crystallographic analysis reveals the structure of the complex to be different from that of its salen analogue, with an all cis arrangement of the nitrogen and oxygen atoms. Although these catalysts are selective for copolymerizing propylene oxide and CO2 at ambient temperature with a high degree of regioselectivity, the copolymerization of cyclohexene oxide and CO2 requires higher temperatures (e.g., 60 °C). Nevertheless, the random polymerization of cyclohexene oxide and propylene oxide with CO2 at ambient temperature provides a terpolymer with a nearly statistical distribution of monomer units. In addition, these catalysts have been shown to be efficie...

Highly Selective and Reactive (salan)CrCl Catalyst for the Copolymerization and Block Copolymerization of Epoxides with Carbon Dioxide

The selective transformation of CO2 and epoxides to afford completely alternating copolymers remains a topic of much interest for the potential utilization of carbon dioxide in chemical synthesis. The use of salicylaldimine (salen)-metal complexes and their saturated (salan)-metal versions have proven to be the most effective and robust single-site catalyst for these processes. Herein, we report on mechanistic aspects of the copolymerization of alicyclic and aliphatic epoxides with CO2 in toluene solution and in neat epoxides in the presence of a (salan)CrCl/onium salt catalyst system. The activation barriers for both cyclohexene oxide(CHO)/CO2 and propylene oxide(PO)/CO2 were shown to be significantly higher in toluene solution than those previously reported for reactions carried out under solventless conditions. Terpolymerization of CHO/vinylcyclohexene oxide/CO2 was shown via Fineman-Ross analysis at 60 °C to proceed with little monomer selectivity, for example, rCHO = 1.03 and rVCHO = 0.847. On the other hand, terpolymerization of CHO/PO/CO2 occurred at 25 °C with a propensity for incorporation of PO in the polymer. However, at 40 °C, Fineman-Ross analysis revealed rCHO and rPO values of 0.869 and 1.49, thereby affording a terpolymer with a more equal distribution of monomers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

(Salan)CrCl, an effective catalyst for the copolymerization and terpolymerization of epoxides and carbon dioxide

Ligand Displacement from TpMn(CO)2L Complexes: A Large Rate Enhancement in Comparison to the CpMn(CO)2L Analogues

The mechanism and energetics of the displacement of solvent from photolytically generated (eta(5)-DMP)Mn(CO)(2)(Solv) complexes has been studied [DMP = 2,5-dimethylpyrrole, Solv = solvent]. Rate enhancement relative to the eta(5)-cyclopentadienyl (Cp) system is not observed in the displacement of weakly bound solvents. The bond dissociation enthalpies obtained from the kinetic analysis are in good agreement with the values obtained by detailed density functional theory (DFT) calculations. The results indicate that for both the Cp and the DMP based systems the displacement of weakly bound solvents proceeds by a dissociative or I(d) mechanism. This is in sharp contrast to CO displacement from (eta(5)-DMP)Mn(CO)(3), which is known to proceed by an associative mechanism by way of an eta(3) ring slip intermediate. The associative substitution pathway only becomes competitive with the dissociative channel when the Mn-Solv bond dissociation enthalpy is more than 33 kcal/mol.

Ross R. Poland

Papers

Kinetic Studies of the Alternating Copolymerization of Cyclic Acid Anhydrides and Epoxides, and the Terpolymerization of Cyclic Acid Anhydrides, Epoxides, and CO2 Catalyzed by (salen)CrIIICl

Highly Selective and Reactive (salan)CrCl Catalyst for the Copolymerization and Block Copolymerization of Epoxides with Carbon Dioxide

(Salan)CrCl, an effective catalyst for the copolymerization and terpolymerization of epoxides and carbon dioxide

Ligand Displacement from TpMn(CO)2L Complexes: A Large Rate Enhancement in Comparison to the CpMn(CO)2L Analogues

Ligand Substitution from the (η5-DMP)Mn(CO)2(Solv) [DMP = 2,5-dimethylpyrrole, Solv = solvent] Complexes: To Ring Slip or Not to Ring Slip?