A US perspective on closing the carbon cycle to defossilize difficult-to-electrify segments of our economy.

Electrification to reduce or eliminate greenhouse gas emissions is essential to mitigate climate change. However, a substantial portion of our manufacturing and transportation infrastructure will be difficult to electrify and/or will continue to use carbon as a key component, including areas in aviation, heavy-duty and marine transportation, and the chemical industry. In this Roadmap, we explore how multidisciplinary approaches will enable us to close the carbon cycle and create a circular economy by defossilizing these difficult-to-electrify areas and those that will continue to need carbon. We discuss two approaches for this: developing carbon alternatives and improving our ability to reuse carbon, enabled by separations. Furthermore, we posit that co-design and use-driven fundamental science are essential to reach aggressive greenhouse gas reduction targets.

Key Experimental Considerations When Evaluating Functional Ionic Liquids for Combined Capture and Electrochemical Conversion of CO2.

Ionic liquids (ILs) are considered functional electrolytes for the electrocatalytic reduction of CO2 (ECO2R) due to their role in the double-layer structure formation and increased CO2 availability at the electrode surface, which reduces the voltage requirement. However, not all ILs are the same, considering the purity and degree of the functionality of the IL. Further, there are critical experimental factors that impact the evaluation of ILs for ECO2R including the reference electrode, working electrode construction, cosolvent selection, cell geometry, and whether the electrochemical cell is a single compartment or a divided cell. Here, we describe improved synthesis methods of imidazolium cyanopyrrolide IL for electrochemical studies in consideration of precursor composition and reaction time. We explored how IL with cosolvents (i.e. acetonitrile, dimethylformamide, dimethyl sulfoxide, propylene carbonate, and n-methyl-2-pyrrolidone) affects conductivity, CO2 mass transport, and ECO2R activation overpotential together with the effects of electrode materials (Sn, Ag, Au, and glassy carbon). Acetonitrile was found to be the best solvent for lowering the onset potential and increasing the catalytic current density for the production of CO owing to the enhanced ion mobility in combination with the silver electrode. Further, the ECO2R activity of molecular catalysts Ni(cyclam)Cl2 and iron tetraphenylsulfonato porphyrin (FeTPPS) on the carbon cloth electrode maintained high Faradaic efficiencies for CO in the presence of the IL. This study presents best practices for examining nontraditional multifunctional electrolytes amenable to integrated CO2 capture and conversion technologies for homogeneous and heterogeneous ECO2R.

Modular preparation of cationic bipyridines and azaarenes via C-H activation.

Bipyridines are ubiquitous in organic and inorganic chemistry because of their redox and photochemical properties and their utility as ligands to transition metals. Cationic substituents on bipyridines and azaarenes are valuable as powerful electron-withdrawing functionalities that also enhance solubility in polar solvents, but there are no general methods for direct functionalization. A versatile method for the preparation of trimethylammonium- and triarylphosphonium-substituted bipyridines and azaheterocycles is disclosed. This methodology showcases a C-H activation of pyridine N-oxides that enables a highly modular and scalable synthesis of a diverse array of cationically charged azaarenes. The addition of trimethylammonium functionalities on bipyridine derivatives resulted in more anodic reduction potentials (up to 700 mV) and increased electrochemical reversibility compared to the neutral unfunctionalized bipyridine. Additonally, metallation of 4-triphenylphosphinated biquinoline to make the corresponding Re(CO)3Cl complex resulted in reduction potentials 400 mV more anodic than the neutral derivative.

Charge and Solvent Effects on the Redox Behavior of Vanadyl Salen-Crown Complexes.

The incorporation of charged groups proximal to a redox active transition metal center can impact the local electric field, altering redox behavior and enhancing catalysis. Vanadyl salen (salen = N,N'-ethylenebis(salicylideneaminato)) complexes functionalized with a crown ether containing a nonredox active metal cation (V-Na, V-K, V-Ba, V-La, V-Ce, and V-Nd) were synthesized. The electrochemical behavior of this series of complexes was investigated by cyclic voltammetry in solvents with varying polarity and dielectric constant (ε) (acetonitrile, ε = 37.5; N,N-dimethylformamide, ε = 36.7; and dichloromethane, ε = 8.93). The vanadium(V/IV) reduction potential shifted anodically with increasing cation charge compared to a complex lacking a proximal cation (ΔE1/2 > 900 mV in acetonitrile and >700 mV in dichloromethane). In contrast, the reduction potential for all vanadyl salen-crown complexes measured in N,N-dimethylformamide was insensitive to the magnitude of the cationic charge, regardless of the electrolyte or counteranion used. Titration studies of N,N-dimethylformamide into acetonitrile resulted in cathodic shifting of the vanadium(V/IV) reduction potential with increasing concentration of N,N-dimethylformamide. Binding constants of N,N-dimethylformamide (log(KDMF)) for the series of crown complexes show increased binding affinity in the order of V-La > V-Ba > V-K > (salen)V(O), indicating an enhancement of Lewis acid/base interaction with increasing cationic charge. The redox behavior of (salen)V(O) and (salen-OMe)V(O) (salen-OMe = N,N'-ethylenebis(3-methoxysalicylideneamine) was also investigated and compared to the crown-containing complexes. For (salen-OMe)V(O), a weak association of triflate salt at the vanadium(IV) oxidation state was observed through cyclic voltammetry titration experiments, and cation dissociation upon oxidation to vanadium(V) was identified. These studies demonstrate the noninnocent role of solvent coordination and cation/anion effects on redox behavior and, by extension, the local electric field.

Electrochemical Carbon Dioxide Capture and Concentration.

Electrochemical carbon capture and concentration (eCCC) offers a promising alternative to thermochemical processes as it circumvents the limitations of temperature-driven capture and release. This review will discuss a wide range of eCCC approaches, starting with the first examples reported in the 1960s and 1970s, then transitioning into more recent approaches and future outlooks. For each approach, the achievements in the field, current challenges, and opportunities for improvement will be described. This review is a comprehensive survey of the eCCC field and evaluates the chemical, theoretical, and electrochemical engineering aspects of different methods to aid in the development of modern economical eCCC technologies that can be utilized in large-scale carbon capture and sequestration (CCS) processes.

Translating aqueous CO2 hydrogenation activity to electrocatalytic reduction with a homogeneous cobalt catalyst.

A molecular cobalt CO2 hydrogenation catalyst was explored for electrocatalytic CO2 reduction under aqueous conditions. The resulting pH-dependent selectivity between H2 and HCO2- is rationalized with thermodynamic analysis and stoichiometric experiments.

Molecular design of redox carriers for electrochemical CO2 capture and concentration.

Developing improved methods for CO2 capture and concentration (CCC) is essential to mitigating the impact of our current emissions and can lead to carbon net negative technologies. Electrochemical approaches for CCC can achieve much higher theoretical efficiencies compared to the thermal methods that have been more commonly pursued. The use of redox carriers, or molecular species that can bind and release CO2 depending on their oxidation state, is an increasingly popular approach as carrier properties can be tailored for different applications. The key requirements for stable and efficient redox carriers are discussed in the context of chemical scaling relationships and operational conditions. Computational and experimental approaches towards developing redox carriers with optimal properties are also described.

Oxygen-Stable Electrochemical CO2 Capture and Concentration with Quinones Using Alcohol Additives.

Current methods for CO2 capture and concentration (CCC) are energy intensive due to their reliance on thermal cycles, which are intrinsically Carnot limited in efficiency. In contrast, electrochemically driven CCC (eCCC) can operate with much higher theoretical efficiencies. However, most reported systems are sensitive to O2, precluding their practical use. In order to achieve O2-stable eCCC, we pursued the development of molecular redox carriers with reduction potentials positive of the O2/O2- redox couple. Prior efforts to chemically modify redox carriers to operate at milder potentials resulted in diminished CO2 binding. To overcome these limitations, we used common alcohol additives to anodically shift the reduction potential of a quinone redox carrier, 2,3,5,6-tetrachloro-p-benzoquinone (TCQ), by up to 350 mV, conferring O2 stability. Intermolecular hydrogen-bonding interactions with the dianion and CO2-bound forms of TCQ were correlated to alcohol pKa to identify ethanol as the optimal additive, as it imparts beneficial changes to both the reduction potential and CO2-binding constant, the two key properties of eCCC redox carriers. We demonstrated a full cycle of eCCC in aerobic simulated flue gas using TCQ and ethanol, two commercially available compounds. Based on the system properties, an estimated minimum of 21 kJ/mol is required to concentrate CO2 from 10 to 100% or twice as efficient as state-of-the-art thermal amine capture systems and other reported redox carrier-based systems. Furthermore, this approach of using hydrogen-bond donor additives is general and can be used to tailor the redox properties of other quinone/alcohol combinations for specific CO2-capture applications.

Inverse molecular design of alkoxides and phenoxides for aqueous direct air capture of CO2.

Aqueous direct air capture (DAC) is a key technology toward a carbon negative infrastructure. Developing sorbent molecules with water and oxygen tolerance and high CO2 binding capacity is therefore highly desired. We analyze the CO2 absorption chemistries on amines, alkoxides, and phenoxides with density functional theory calculations, and perform inverse molecular design of the optimal sorbent. The alkoxides and phenoxides are found to be more suitable for aqueous DAC than amines thanks to their water tolerance (lower pKa prevents protonation by water) and capture stoichiometry of 1:1 (2:1 for amines). All three molecular systems are found to generally obey the same linear scaling relationship (LSR) between [Formula: see text] and [Formula: see text], since both CO2 and proton are bonded to the nucleophilic (alkoxy or amine) binding site through a majorly [Formula: see text] bonding orbital. Several high-performance alkoxides are proposed from the computational screening. Phenoxides have comparatively poorer correlation between [Formula: see text] and [Formula: see text], showing promise for optimization. We apply a genetic algorithm to search the chemical space of substituted phenoxides for the optimal sorbent. Several promising off-LSR candidates are discovered. The most promising one features bulky ortho substituents forcing the CO2 adduct into a perpendicular configuration with respect to the aromatic ring. In this configuration, the phenoxide binds CO2 and a proton using different molecular orbitals, thereby decoupling the [Formula: see text] and [Formula: see text]. The [Formula: see text] trend and off-LSR behaviors are then confirmed by experiments, validating the inverse molecular design framework. This work not only extensively studies the chemistry of the aqueous DAC, but also presents a transferrable computational workflow for understanding and optimization of other functional molecules.

Cationic Effects on the Net Hydrogen Atom Bond Dissociation Free Energy of High-Valent Manganese Imido Complexes.

Local electric fields can alter energy landscapes to impart enhanced reactivity in enzymes and at surfaces. Similar fields can be generated in molecular systems using charged functionalities. Manganese(V) salen nitrido complexes (salen = N,N'-ethylenebis(salicylideneaminato)) appended with a crown ether unit containing Na+ (1-Na), K+, (1-K), Ba2+ (1-Ba), Sr2+ (1-Sr), La3+ (1-La), or Eu3+ (1-Eu) cation were investigated to determine the effect of charge on pKa, E1/2, and the net bond dissociation free energy (BDFE) of N-H bonds. The series, which includes the manganese(V) salen nitrido without an appended crown, spans 4 units of charge. Bounds for the pKa values of the transient imido complexes were used with the Mn(VI/V) reduction potentials to calculate the N-H BDFEs of the imidos in acetonitrile. Despite a span of >700 mV and >9 pKa units across the series, the hydrogen atom BDFE only spans ∼6 kcal/mol (between 73 and 79 kcal/mol). These results suggest that the incorporation of cationic functionalities is an effective strategy for accessing wide ranges of reduction potentials and pKa values while minimally affecting the BDFE, which is essential to modulating electron, proton, or hydrogen atom transfer pathways.

Electrochemical studies of tris(cyclopentadienyl)thorium and uranium complexes in the +2, +3, and +4 oxidation states.

Electrochemical measurements on tris(cyclopentadienyl)thorium and uranium compounds in the +2, +3, and +4 oxidation states are reported with C5H3(SiMe3)2, C5H4SiMe3, and C5Me4H ligands. The reduction potentials for both U and Th complexes trend with the electron donating abilities of the cyclopentadienyl ligand. Thorium complexes have more negative An(iii)/An(ii) reduction potentials than the uranium analogs. Electrochemical measurements of isolated Th(ii) complexes indicated that the Th(iii)/Th(ii) couple was surprisingly similar to the Th(iv)/Th(iii) couple in Cp''-ligated complexes. This suggested that Th(ii) complexes could be prepared from Th(iv) precursors and this was demonstrated synthetically by isolation of directly from UV-visible spectroelectrochemical measurements and reactions of with elemental barium indicated that the thorium system undergoes sequential one electron transformations.

Electric Fields in Catalysis: From Enzymes to Molecular Catalysts.

Electric fields underlie all reactions and impact reactivity by interacting with the dipoles and net charges of transition states, products, and reactants to modify the free energy landscape. However, they are rarely given deliberate consideration in synthetic design to rationally control reactivity. This Perspective discusses the commonalities of electric field effects across multiple platforms, from enzymes to molecular catalysts, and identifies practical challenges to applying them in synthetic molecular systems to mediate reactivity.

Stabilization of U(III) to Oxidation and Hydrolysis by Encapsulation Using 2.2.2-Cryptand.

The electrochemical properties of U(III)-in-crypt (crypt = 2.2.2-cryptand) were examined in dimethylformamide (DMF) and acetonitrile (MeCN) to determine the oxidative stability offered by crypt as a ligand. Cyclic voltammetry revealed a U(III)/U(IV) irreversible oxidation at EPA= -0.49 V (vs Fe(C5H5)2+/0) in DMF and at EPA= -0.31 V (vs Fe(C5H5)2+/0) in MeCN. The electrochemistry of U(III)-in-crypt complexes in the presence of water was also examined. These studies are supported by crystallographically characterized examples of U(III)-in-crypt complexes as DMF, MeCN, and water adducts.

Reducing CO2 to HCO2- at Mild Potentials: Lessons from Formate Dehydrogenase.

The catalytic reduction of CO2 to HCO2- requires a formal transfer of a hydride (two electrons, one proton). Synthetic approaches for inorganic molecular catalysts have exclusively relied on classic metal hydrides, where the proton and electrons originate from the metal (via heterolytic cleavage of an M-H bond). An analysis of the scaling relationships that exist in classic metal hydrides reveal that hydride donors sufficiently hydridic to perform CO2 reduction are only accessible at very reducing electrochemical potentials, which is consistent with known synthetic electrocatalysts. By comparison, the formate dehydrogenase enzymes operate at relatively mild potentials. In contrast to reported synthetic catalysts, none of the major mechanistic proposals for hydride transfer in formate dehydrogenase proceed through a classic metal hydride. Instead, they invoke formal hydride transfer from an orthogonal or bidirectional mechanism, where the proton and electrons are not colocated. We discuss the thermodynamic advantages of this approach for favoring CO2 reduction at mild potentials, along with guidelines for replicating this strategy in synthetic systems.

Kinetic and mechanistic analysis of a synthetic reversible CO2/HCO2- electrocatalyst.

[Pt(depe)2](PF6)2 electrocatalyzes the reversible conversion between CO2 and HCO2- with high selectivity and low overpotential but low rates. A comprehensive kinetic analysis indicates the rate determining step for CO2 reduction is the reactivity of a Pt hydride intermediate to produce HCO2-. To accelerate catalysis, the use of cationic and hydrogen-bond donor additives are explored.

Using nature's blueprint to expand catalysis with Earth-abundant metals.

Numerous redox transformations that are essential to life are catalyzed by metalloenzymes that feature Earth-abundant metals. In contrast, platinum-group metals have been the cornerstone of many industrial catalytic reactions for decades, providing high activity, thermal stability, and tolerance to chemical poisons. We assert that nature's blueprint provides the fundamental principles for vastly expanding the use of abundant metals in catalysis. We highlight the key physical properties of abundant metals that distinguish them from precious metals, and we look to nature to understand how the inherent attributes of abundant metals can be embraced to produce highly efficient catalysts for reactions crucial to the sustainable production and transformation of fuels and chemicals.

Single molecule magnet behaviour in a square planar S = 1/2 Co(ii) complex and spin-state assignment of multiple relaxation modes.

We report the first example of field-induced single molecule magnet (SMM) behaviour in a square-planar S = 1/2 Co(ii) pincer complex [(PNNNP)CoBr]Br (2). The related five-coordinate complexes [(PCNCP)CoBr2] (1) and [(PONOP)CoBr2] (3) also exhibit SMM properties. Partial spin crossover displayed by 3 allows for assignment of distinct relaxation modes to each spin state.