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At least 1,531 records · Page 85
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Intermediate Sr 2 Co 1.5 Fe 0.5 O 6-δ Tetragonal Structure between Perovskite and Brownmillerite as a Model Catalyst with Layered Oxygen Deficiency for Enhanced Electrochemical Water Oxidation

The generation of hydrogen in an environmentally benign way is highly essential to meet future energy demands. However, in the process of splitting water electrochemically, sluggish kinetics of the oxygen evolution reaction (OER) curtails its applicability, as it drags energy input. Herein, we synthesized SrCo-Fe-O oxides to optimize their OER activity by varying the Co/Fe ratio. Among them, Sr 2 Co 1.5 Fe 0.5 O 6-δ exhibited the best OER catalytic activity in the series, with an overpotential of 318 mV at 10 mA cm -2 and Tafel slope of 44.8 mV dec -1 . High-resolution neutron powder diffraction analysis identified an intermediate structure between the perovskite and brownmillerite, with alternating layers of disorderly orientated oxygen-deficient tetrahedra and fully stoichiometric octahedra. The unique stacking of tetrahedral and octahedral units facilitates desired interactions between the electrode surface and electrolyte. Theoretical calculations revealed that increased covalency of Co 3d and O 2p in Sr 2 Co 1.5 Fe 0.5 O 6-δ oxide is another primary contributor to its augmented water oxidation ability. As a model for developing catalysts with such an intermediate structure, the synergetic effect of oxygen vacancy and hybridization between Co 3d and O 2p assured the Sr 2 Co 1.5 Fe 0.5 O 6-δ oxide as a better catalyst for its enhanced OER activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Conversion of CO 2 to Methanol and Ethanol on Pt/CeO x /TiO 2 (110): Enabling Role of Water in C–C Bond Formation

The surface chemistry of alcohol synthesis from CO 2 hydrogenation has been investigated using kinetic testing, ambient pressure x-ray photoelectron spectroscopy (AP-XPS) and DFT calculations over a multicomponent system where Pt and ceria nanoparticles coexisted on a titania template, Pt/CeO x /TiO 2 (110). Due to its high ability to bind and activate CO 2 , not seen for typical Cu-ZnO catalysts, the Pt-CeO x -TiO 2 interface is excellent for the hydrogenation of CO 2 to methanol with some ethanol also being produced (21% selectivity). The results of AP-XPS and DFT calculations indicate that the active state involves a mixture of Ti 4+ /Ti 3+ , Ce 3+ and Pt 0 /Pt + . A fast pathway for the formation of CH 3 O species is only plausible when Ce 3+ and Pt are present. The addition of water to the reaction feed facilitates the first hydrogenation of CO 2 and substantially enhances the surface coverage of C-containing species (CH 3 O, HCOO, CO 3 , CH x ), facilitating the formation of C-C bonds and the production of ethanol (38% selectivity).

36 MATERIALS SCIENCE↗
DOE OSTI2023

Structural and Chemical Evolution of an Inverse CeO x /Cu Catalyst under CO 2 Hydrogenation: Tunning Oxide Morphology to Improve Activity and Selectivity

Small nanoparticles of ceria deposited on a powder of CuO display a very high selectivity for the production of methanol via CO 2 hydrogenation. CeO 2 /CuO catalysts with ceria loadings of 5%, 20%, and 50% were investigated. Among these, the system with 5% CeO x showed the best catalytic performance at temperatures between 200 and 350 °C. The evolution of this system under reaction conditions was studied using a combination of environmental transmission electron microscopy (E-TEM), in situ X-ray absorption spectroscopy (XAS), and time-resolved X-ray diffraction (TR-XRD). For 5% CeO x /Cu, the in situ studies pointed to a full conversion of CuO into metallic copper, with a complete transformation of Ce 4+ into Ce 3+ . Images from E-TEM showed drastic changes in the morphology of the catalyst when it was exposed to H 2 , CO 2 , and CO 2 /H 2 mixtures. Under a CO 2 /H 2 feed, there was a redispersion of the ceria particles that was detected by E-TEM and in situ TR-XRD. Finally, these morphological changes were made possible by the inverse oxide/metal configuration and facilitate the binding and selective conversion of CO 2 to methanol.

03 NATURAL GAS↗
DOE OSTI2024

Operando Surface-Enhanced Infrared Spectroscopy Connects Interfacial Dynamics with Reaction Kinetics During Electrochemical CO 2 Reduction on Copper

The reaction microenvironment plays a key role in dictating the selectivity of electrochemical CO 2 reduction. However, understanding the chemical nature of this microenvironment under operating conditions remains a substantial challenge. For this study, we employed attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) in operando for simultaneous measurements of reaction kinetics and concentrations of reactants and intermediates at the reaction interface, all under controlled mass transport conditions. These operando measurements enable direct correlations between the reaction microenvironment, mass transport, and kinetics for a Cu electrocatalyst, such as higher local concentrations of CO 2 under faster mass transport corresponding to higher rates of CO 2 reduction. We observed that faster mass transport decreased the *CO coverage at less negative potentials (-0.6 V RHE ) and increased the *CO coverage at more negative potentials (-1.1 V RHE ). We developed a transport-coupled kinetic model that captures these spectroscopic observations and provides insight into the processes controlling interfacial concentrations of reactants and intermediates, aiding future efforts toward tailoring reaction microenvironments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Pnictogen-Bonding Catalysis: Copolymerization of CO 2 and Epoxides on Antimony(V) Platforms

The copolymerization of CO 2 and epoxides to access polycarbonates represents a promising strategy for CO 2 utilization and for the production of useful polymers. Aiming to explore alternative transition-metal-free approaches that support this chemistry, we have investigated a series of triaryl-catecholatostiboranes as pnictogen-bonding platforms for the copolymerization of CO 2 and cyclohexene oxide (CHO). Our survey of these antimony species has identified motifs that promote this polymerization reaction efficiently, provided that bis(triphenylphosphine)iminium chloride is administered as an activator. By coupling these polymerization studies with a careful assessment of the structure, electronic attributes and Lewis acidity of the catecholatostiboranes, this work shows that high activity is generally observed with the weakest pnictogen-bond donors or Lewis acids investigated. Mechanistic studies, which indicate that the polymerization reaction is first order in stiborane, reveal a nonlinear dependence on the CO 2 pressure. This nonlinear dependence could be satisfactorily modeled based on a pre-equilibrium process involving the reversible insertion of the gaseous monomer into the growing chain. Altogether these findings greatly expand the reach of pnictogen bond catalysis while also providing an entry for the use of heavy group 15 elements as competent platforms for CO 2 utilization.

antimony↗
DOE OSTI2026

Confinement Reconstruction Unlocks Stable Ru Single Atom-Doped IrO x Anodes for Long-Term High-Rate CO 2 Electrolysis

IrO 2 is a commonly employed anode catalyst for CO 2 electrolysis in membrane electrode assembly (MEA) systems. However, under high current densities, its structural reconstruction leads to activity loss and stability degradation, limiting the industrial viability of CO 2 electrolysis. In this work, we demonstrated a confinement reconstruction strategy to precisely regulate the structural evolution during electrolysis. Ethylene glycol serves as a structural modulator, protecting the catalyst surface, suppressing soluble species formation, and promoting ordered structural evolution. Single-atom Ru acts as a stability enhancer, forming robust Ir–O–Ru bridging structures that facilitate an ordered transformation from a 4-fold [RuO 4 ]/[IrO 4 ] to a 6-fold symmetry [RuO 6 ]/[IrO 6 ] octahedral framework, thereby enhancing structural rigidity and long-term stability. As a result, in MEA-based CO 2 electrolysis, the catalyst achieves a stable operation at 200 mA cm –2 for 480 h, maintaining a CO selectivity above 80%. Theoretical calculations further elucidate that the enhanced stability originates from the suppression of oxygen vacancy formation, making the lattice-oxygen-mediated mechanism (LOM) potentially less favorable. This work provides insights into the structural evolution of the OER catalysts under high-current-density conditions, paving the way for large-scale CO 2 electrolysis commercialization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Sub-Nanometer Nanoclusters of Copper Atop Single-Atom Copper Moieties toward Electrochemical CO 2 Hydrogenation to Methane

The electrochemical CO 2 reduction (eCO 2 R) offers a compelling route for converting CO 2 into value-added fuels and chemicals. Among CO 2 -derived products, methane (CH 4 ) occupies a distinct position, serving both as a key intermediate for emerging cascade electro-oxidation to oxygenates and as a strategically important extraterrestrial fuel that can be generated in situ from off-planet CO 2 resources. Although Cu-based catalysts capable of selectively producing CH 4 have been reported, they seldom sustain high selectivity at practically relevant current densities. Here, we created a single-step co-pyrolysis strategy toward generating and anchoring Cu sub-nanometer clusters (Cu SNC ) atop Cu-N x single-atom (SA) motifs embedded within N-doped carbon (NC), with controllable nanostructures through tuning of the synthesis parameters. Complementary spectroscopic analyses and density functional theory (DFT) calculations help reveal a structure−activity correlation that could guide the catalyst design. The Cu SNC @NC sample synthesized at 550 °C pyrolysis temperature (best described and modeled as Cu 3 -CuN 4 domains) represents the most effective combination of cluster size, metal-nitrogen coordination, and adsorption energetics needed to selectively promote CH 4 generation versus other eCO 2 R products. Incorporating pulsed electrolysis and hydrophobicity-modulated transport tuning at the triple-phase boundary (TPB) further enhanced CH 4 production achieving a partial CH 4 current density of ∼321 mA cm −2 , 53% Faradaic efficiency (FECH 4 ), and less than 4% combined FE for other eCO 2 R products, simplifying downstream CH 4 purification or upgrading. This work establishes generalizable principles for controlling Cu cluster atomicity and metal−nitrogen coordination, both of which are recognized determinants of CH 4 -efficient eCO 2 R.

CH4 production↗
DOE OSTI2026

Pore-Scale Transport Effects in Electrochemical CO 2 Reduction on Gold via Coupled Microkinetic-Transport Modeling

A pore-resolved modeling framework is developed to quantify how pore-scale transport affects the intrinsic microkinetics of CO 2 -to-CO on Au. A DFT-informed microkinetic model is coupled self-consistently to a Generalized-Modified Poisson–Nernst–Planck (GMPNP) transport description in a single, electrolyte-filled cylindrical pore, allowing local concentrations and potential to feed back into site-specific reaction rates. FIB-SEM is used to determine pore sizes within realistic electrode materials. Across pore diameters, d p = 10–6000 nm, the surface-averaged CO 2 reduction rate is systematically reduced relative to the ideal microkinetic baseline where mass transport is not accounted for; the effectiveness factor 𝜂 𝑠,CO 2 , which quantifies this ratio, decreases rapidly at more negative potentials and is about 1% near −1.0 V vs SHE due to reactant depletion. Spatial maps reveal pore-bulk alkalization that emerges at higher cathodic bias, with a small, near-wall pH dip due to electrostatic repulsion of hydroxide at the cathode interface. For a fixed aspect ratio L p /d p , narrower pores exhibit larger 𝜂 𝑠,CO 2 by shortening diffusion paths, whereas variations in the aspect ratio L p /d p play a secondary role. A dimensionless analysis (surface/bulk Damköhler numbers) delineates operating regimes. In conclusion, this work offers a concept for incorporating microkinetic models into homogenized porous-electrode models through effectiveness factors and pore-size distribution.

Au-catalyst↗
DOE OSTI2020

Effects of Surface Roughness on the Electrochemical Reduction of CO 2 over Cu

We have investigated the role of surface roughening on the CO 2 reduction reaction (CO 2 RR) over Cu. The activity and product selectivity of Cu surfaces roughened by plasma pretreatment in Ar, O 2 , or N 2 were compared with that of electrochemically polished Cu samples. Differences in total and product current densities, the ratio of current densities for HER (the hydrogen evolution reaction) to CO 2 RR, and the ratio of current densities for C 2+ to C 1 products depend on the electrochemically active surface and are nearly independent of plasma composition. Theoretical analysis of an electropolished and roughened Cu surface reveals a higher fraction of undercoordinated Cu sites on the roughened surface, sites that bind CO preferentially. Roughened surfaces also contain square sites similar to those on a Cu(100) surface but with neighboring step sites, which adsorb OC-COH, a precursor to C 2+ products. Here, these findings explain the increases in the formation of oxygenates and hydrocarbons relative to CO and the ratio of oxygenates to hydrocarbons observed with increasing surface roughness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

An Electrochemical Hydrogen-Looping System for Low-Cost CO 2 Capture from Seawater

Carbon dioxide (CO 2 ) capture from seawater is a viable, long-term solution for addressing legacy carbon pollution on the planet. However, significant challenges to widespread applicability exist in terms of efficiency, cost, and scalability. In this work, we have developed an electrochemical hydrogen-looping (EHL) system that capitalizes on the generation of proton and OH – from seawater. A CO 2 capture efficiency as high as 91% is achieved for our EHL flow cell. We have demonstrated that the electrochemical hydrogen-looping flow cell can remove CO 2 from simulated seawater at a record low electric energy consumption of 660 kWh ton –1 CO 2 , which is a significant reduction of 56% compared with the currently used bipolar membrane electrodialysis technology. In conclusion, the electrochemical hydrogen-looping flow cell with its much lower energy consumption provides an economical approach for direct removal of CO 2 from seawater at practical scale.

Electrical energy↗
DOE OSTI2022

Establishing the Role of Operating Potential and Mass Transfer in Multicarbon Product Generation for Photoelectrochemical CO 2 Reduction Cells Using a Cu Catalyst

There is increasing interest in the possibility of photoelectrochemical (PEC) reduction of CO 2 to C 2+ products; however, the criteria for maximizing PEC solar-to-C 2+ (STC 2+ ) rates are not well understood. We report here a continuum-scale model of PEC CO 2 reduction (CO 2 R) on Cu in 0.1 M CsHCO 3 and use it to optimize the design and operating conditions for generating C 2+ products. Furthermore, we demonstrate that the potential-dependent product distribution of CO 2 R on Cu requires operating near the potential that maximizes C 2+ generation rates ($V$ id ), unlike PEC water splitting, which desires operation at the maximum photocurrent density. Because of this requirement, the criterion for a high STC 2+ rate includes high-photocurrent semiconductors with photovoltages near $V$ id and low series resistance. The STC 2+ rate in these systems is enhanced by optimal CO 2 transport and exhibits low sensitivity to dirunal solar irradiance variations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Ionic Liquid Functionalizes the Metal Organic Framework for Microwave-Assisted Direct Air Capture of CO 2

Sorbents for direct air capture (DAC) of CO 2 typically employ a chemisorbing material that requires regeneration at elevated temperatures, which is an energy-intensive step. Here, we developed composites of metal organic framework (MOF) with a functional ionic liquid (IL) at 5, 20, and 35 wt % loading, capable of CO 2 chemisorption and regeneration by moisture-swing coupled microwave (MW) irradiation. In dynamic breakthrough measurements, CO 2 from synthetic air (500 ppm of CO 2 ) was selectively absorbed (0.5 mmol/g at 30 °C) and then rapidly released (2–4 min) by dielectric heating at 60 °C. The developed IL/MOF composites demonstrate (1) targeted energy transfer to the IL domains where CO 2 is released due to dielectric heating upon MW irradiation and (2) a fast desorption rate due to large surface area offered by the MOF architecture. Furthermore, this study establishes carbon capture through surface enhancement of a porous substrate with ILs for future DAC processes that can be powered by sustainable energy sources.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Atomically Dispersed Iron–Nitrogen Sites on Hierarchically Mesoporous Carbon Nanotube and Graphene Nanoribbon Networks for CO 2 Reduction

Atomically dispersed metal and nitrogen co-doped carbon (M-N/C) catalysts hold great promise for electrochemical CO 2 conversion. However, there is a lack of cost-effective synthesis approaches to meet the goal of economic mass production of single-atom M-N/C with desirable carbon support architecture for efficient CO 2 reduction. Herein, we report facile transformation of commercial carbon nanotube (CNT) into isolated Fe-N 4 sites anchored on carbon nanotube and graphene nanoribbon (GNR) networks (Fe-N/CNT@GNR). The oxidization-induced partial unzipping of CNT results in the generation of GNR nanolayers attached to the remaining fibrous CNT frameworks, which reticulates a hierarchically mesoporous complex and thus enables a high electrochemical active surface area and smooth mass transport. The Fe residues originating from CNT growth seeds serve as Fe sources to form isolated Fe-N-4 moieties located at the CNT and GNR basal plane and edges with high intrinsic capability of activating CO 2 and suppressing hydrogen evolution. The Fe-N/CNT@GNR delivers a stable CO Faradaic efficiency of 96% with a partial current density of 22.6 mA cm -2 at a low overpotential of 650 mV, making it one of the most active M-N/C catalysts reported. This work presents an effective strategy to fabricate advanced atomistic catalysts and highlights the key roles of support architecture in single-atom electrocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Computational Investigation of a CO 2 Conversion Strategy via Diels–Alder Reaction in a Carbon Capture Solvent

Molecular-level insights into reactive separations are crucial for the design of new conversion pathways of carbon dioxide (CO 2 ). This work explores a postulated pathway that directs CO 2 to undergo inverse-electron-demand Diels–Alder reactions to produce heterocycles using the CO 2 chemically fixed on water-lean solvent molecules. Density functional theory calculations are applied to evaluate the lowest unoccupied molecular orbital (LUMO) energies of three types of reactants (1,3-butadiene, 1,3-cyclohexadiene, and 1,2,4,5-tetrazine) with various functional substituents. These calculations also provide a data set (5.8k data) for developing a machine learning model to efficiently predict LUMO energies. A computational screening of LUMO energies for an additional 47k diene and tetrazine candidates is performed, and a list of candidates with lowered LUMO energies by electron-withdrawing substituents is provided. These candidates are further examined by their reaction energy barriers computed from the interatomic potential or density functional theory. Two major energy barriers are identified, one for the proton transfer within the water-lean solvent and the other for the CO 2 transfer from the solvent molecule to the reactant candidate (diene or tetrazine). The functional substituents have a more significant impact on the second barrier but a very slight one on the first barrier. This exploratory work demonstrates a new possibility for guiding experimental efforts toward the chemical conversion of fixated CO 2 to value-added compounds.

Chemical reactions↗
DOE OSTI2026

Effect of Storage Conditions on Efficacy of Poly(ethylenimine)-Alumina CO 2 Sorbents

Solid amine sorbents are one of the primary components of DAC technologies that allow for the removal of ultradilute CO 2 from the atmosphere. A main drawback in the implementation of solid amine sorbents in industrial-scale DAC applications is their instability under certain operational or storage conditions over an extended period. In this work, the effect of storage temperature and gas composition in the storage headspace on the long-term stability of a poly(ethylenimine)-alumina (PEI/γ-Al 2 O 3 ) sorbent is explored. PEI/γ-Al 2 O 3 sorbents with 70 and 100% pore filling are aged under varying gases (N 2 , O 2 , Ar, 0.04% CO 2 −N 2 , CO 2 , and ambient air) in an oven (40 °C), at common ambient indoor temperature conditions (23 °C), or in a freezer (−4 °C). The CO 2 sorption capacity, as measured by thermogravimetric analysis (TGA), along with FTIR spectra of the fresh and aged sorbents, reveal that at 23 and −4 °C, storage under ambient air or inert gas (Ar) provides reasonable long-term stability, with <13% degradation over 12 and 5 months of storage. Interestingly, with storage at 40 °C, similar levels of deactivation were observed under pure O 2 and N 2 after 4 months of storage, which suggests that nonoxidative thermal reactions can occur under prolonged storage conditions under N 2 . In contrast, with storage under CO 2 , sorbent degradation is substantially suppressed compared to storage under N 2 , ambient air, O 2 , or Ar, yielding sorbents with no observable loss in capacity after 2 months, compared to a 66, 63, and 62% loss under N 2 , ambient air, and N 2 in the same period at 40 °C, respectively. Overall, these findings provide guidance for practical amine sorbent storage in academic or industrial settings where amine sorbents are used for carbon capture.

Atmospheric chemistry↗
DOE OSTI2023

Evolution of the Cellulose Microfibril through Gamma-Valerolactone-Assisted Co-Solvent and Enzymatic Hydrolysis

Biomass recalcitrance during deconstruction remains a key bottleneck to affordable biomass processing technologies. A clear connection between the cell wall structure and biomass deconstruction is necessary to understand how lignocellulosic material is broken down to valuable monomeric components. Here, we monitor changes in the cellulose microfibril domains of poplar, sorghum, and switchgrass throughout gamma-valerolactone (GVL)–water co-solvent pretreatment and enzymatic hydrolysis using solid-state 13 C cross-polarization magic angle spinning nuclear magnetic resonance spectroscopy (CP/MAS 13 C-NMR) and wide-angle X-ray scattering (WAXS). Spectral fitting of NMR peaks corresponding to different cellulose microenvironments at the C 4 carbon center suggests that a mildly acidic GVL–water co-solvent pretreatment of poplar leads to nearly full removal of xylan–cellulose linkages, which primes the cellulose for enzymatic attack. The spectral fitting also suggests that the pretreatment causes significant depletion of the inaccessible fibril surface domains with an increase in more thermally stable crystalline resonances (I β ). WAXS confirmed a decrease in the lattice spacing between (200) crystalline planes with increasing co-solvent pretreatment severity. These results are interpreted as an opening of bound microfibril surfaces previously inaccessible to the co-solvent system, which leaves behind a more thermally stable, crystalline domain that is potentially prone to relaxation and recrystallization. Full conversion of residual GVL-pretreated biomass was achieved after the GVL co-solvent pretreatment at 140 °C using a commercial enzyme cocktail, CTec2, which contains different cellulases and other enzymes. Spectral fitting of enzymatically hydrolyzed samples by a single engineered cellulase, CelR, suggests that the residual cellulose recalcitrance is mainly due to the inability of CelR to digest the I β crystalline domain present in pretreated samples. This work helps to provide new information regarding the structure of the cell wall and recalcitrance throughout GVL–water mild acidolysis and CelR enzymatic biomass deconstruction by tracking the evolution of structural domains within the cellulose microfibril. This work further directs recommendations for improving the conversion and sugar yields in future studies. Finally, our findings inform inquiry into larger questions of cellulose recalcitrance through GVL pretreatment and CelR enzymatic hydrolysis and give insight into subsequent required steps for full cellulose conversion with attention to the most recalcitrant cellulose structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Incorporating Diurnal and Meter-Scale Variations of Ambient CO 2 Concentrations in Development of Direct Air Capture Technologies

To be implemented on climate-relevant scales, direct air capture of CO 2 (DAC) will require large capital-intensive facilities and careful attention to cost minimization. In making decisions among potential sites for DAC facilities, all of the factors that will impact process cost and efficiency should be considered. In this paper we focus on a factor that has previously received little attention in the DAC community, namely variations in atmospheric conditions on hourly time scales and length scales of meters. We present data curated from extensive previous studies of biosphere-atmosphere fluxes with observations of CO 2 concentration, temperature, and relative humidity (RH) with hourly resolution from many sites in North America. These include locations where typical diurnal variations in CO 2 concentration during summer months exceeds 150 ppm. These variations are larger than the seasonal variations that exist between averaged CO 2 concentrations in winter and summer, and they are highly correlated with diurnal variations in temperature and RH. Diurnal variations are dependent on the height above ground at which CO 2 concentrations are measured, with smaller variations existing at heights of 10 m or more than at ground level. We illustrate the potential implications of these short-term variations for the operation and optimization of a DAC process with process-level calculations for a specific adsorption-based process using amine-rich adsorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Temperature and Solvent Effects on H 2 Splitting and Hydricity: Ramifications on CO 2 Hydrogenation by a Rhenium Pincer Catalyst

The catalytic hydrogenation of carbon dioxide holds immense promise for applications in sustainable fuel synthesis and hydrogen storage. Mechanistic studies that connect thermodynamic parameters with the kinetics of catalysis can provide new understanding and guide predictive design of improved catalysts. Reported here are thermochemical and kinetic analyses of a new pincer-ligated rhenium complex ( tBu POCOP)Re(CO) 2 ( tBu POCOP = 2,6-bis(di-tert-butylphosphinito)phenyl) that catalyzes CO 2 hydrogenation to formate with faster rates at lower temperature. Because the catalyst follows the prototypical “outer sphere” hydrogenation mechanism, comprehensive studies of temperature and solvent effects on the H 2 splitting and hydride transfer steps are expected to be relevant to many other catalysts. Strikingly large entropy associated with cleavage of H2 results in a strong temperature dependence on the concentration of [( tBu POCOP)Re(CO) 2 H] – present during catalysis, which is further impacted by changing the solvent from toluene to tetrahydrofuran to acetonitrile. New methods for determining the hydricity of metal hydrides and formate at temperatures other than 298 K were developed, providing insight into how temperature can influence the favorability of hydride transfer during catalysis. These thermochemical insights guided the selection of conditions for CO 2 hydrogenation to formate with high activity (up to 364 h –1 at 1 atm or 3330 h –1 at 20 atm of 1:1 H 2 CO 2 ). In cases where hydride transfer is the highest individual kinetic barrier, entropic contributions to outer sphere H 2 splitting lead to a unique temperature dependence: catalytic activity increases as temperature decreases in tetrahydrofuran (200-fold increase upon cooling from 50 to 0 °C) and toluene (4-fold increase upon cooling from 100 to 50 °C). Furthermore, the ramifications on catalyst structure-function relationships are discussed, including comparisons between “outer sphere” mechanisms and metal–ligand cooperation mechanisms.

14 SOLAR ENERGY↗