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At least 199 records · Page 11

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DOE OSTI2021

Ballistic Δ S = 2 intersystem crossing in a cobalt cubane following ligand-field excitation probed by extreme ultraviolet spectroscopy

We report femtosecond M 2,3 -edge X-ray absorption near-edge structure (XANES) spectroscopy is used to probe the excited-state dynamics of the cobalt cubane [Co III 4 O 4 ](OAc) 4 (py) 4 (OAc = acetate, py = pyridine), a model for water oxidation catalysts. After ligand-field excitation, intersystem crossing (ISC) to a metal-centered quintet occurs in 38 fs. 30% of the hot quintet undergoes ballistic back-ISC directly to the singlet ground state, with the remainder relaxing to a long-lived triplet.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Photocatalytic Semi‐Hydrogenation of Acetylene to Polymer‐Grade Ethylene with Molecular and Metal–Organic Framework Cobaloximes

Abstract The semi‐hydrogenation of acetylene in ethylene‐rich gas streams is a high‐priority industrial chemical reaction for producing polymer‐grade ethylene. Traditional thermocatalytic routes for acetylene reduction to ethylene, despite progress, still require high temperatures and high H 2 consumption, possess relatively low selectivity, and use a noble metal catalyst. Light‐powered strategies are starting to emerge, given that they have the potential to use directly the abundant and sustainable solar irradiation, but are ineffective. Here an efficient, >99.9% selective, visible‐light powered, catalytic conversion of acetylene to ethylene is reported. The catalyst is a homogeneous molecular cobaloxime that operates in tandem with a photosensitizer at room temperature and bypasses the use of non‐environmentally friendly and flammable H 2 gas feed. The reaction proceeds through a cobalt‐hydride intermediate with ≈100% conversion of acetylene under competitive (ethylene co‐feed) conditions after only 50 min, and with no evolution of H 2 or over‐hydrogenation to ethane. The cobaloxime is further incorporated as a linker in a metal–organic framework; the result is a heterogeneous catalyst for the conversion of acetylene under competitive (ethylene co‐feed) conditions that can be recycled up to six times and remains catalytically active for 48 h, before significant loss of performance is observed.

Stone, Aaron E. B. S.↗

DOE OSTI2021

Switchable wetting of oxygen-evolving oxide catalysts

The surface wettability of catalysts is typically controlled via surface treatments that promote catalytic performance. Here we report on potential-regulated hydrophobicity/hydrophilicity at cobalt-based oxide interfaces with an alkaline solution. The switchable wetting of single particles, directly related to their activity and stability towards the oxygen evolution reaction, was revealed by electrochemical liquid-phase transmission electron microscopy. Analysis of the movement of the liquid in real time revealed distinctive wettability behaviour associated with specific potential ranges. At low potentials, an overall reduction of the hydrophobicity of the oxides was probed. Upon reversible reconstruction towards the surface oxyhydroxide phase, electrowetting was found to cause a change in the interfacial capacitance. At high potentials, the evolution of molecular oxygen, confirmed by operando electron energy-loss spectroscopy, was accompanied by a globally thinner liquid layer. This work directly links the physical wetting with the chemical oxygen evolution reaction of single particles, providing fundamental insights into solid–liquid interfacial interactions of oxygen-evolving oxides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Tuneable electronic coupling in linked bis(cubane) cobalt-oxo clusters

A family of cobalt-oxo bis(cubane) complexes wherein each subunit is derived from the Co 4 O 4 cubane, a known water oxidation catalyst, was synthesized. Both 4,4′-bipyrdine and pyrazine were demonstrated to serve as viable bridging ligands. Through an analysis of their half-wave splitting potentials, it was determined that pyrazine-bridged bis(cubane)s exhibit inter-cubane electronic coupling, and that this coupling may be tuned through ligand substitution. Electrostatic contributions to the half-wave splitting potentials were evaluated and found to result in “non-conformist” behavior related to the ion-pairing ability of the electrolytes.

Maddi, Vincent J. P. [University of California, Be↗

DOE OSTI2021

Acid-resistant catalyst supports and catalysts

A process for preparing a catalyst comprises coating substantial internal surfaces of porous inorganic powders with titanium oxide to form titanium oxide-coated inorganic powders. After the coating, an extrudate comprising the titanium oxide-coated inorganic powders is formed and calcined to form a catalyst support. Then, the catalyst support is impregnated with a solution containing one or more salts of metal selected from the group consisting of molybdenum, cobalt, and nickel.

Schmidt, Stephen R.↗

DOE OSTI2023

Acid-resistant catalyst supports and catalysts

Schmidt, Stephen R.↗

DOE OSTI2022

Reflection Optical Imaging to Study Oxygen Evolution Reactions

Discovery of high-efficiency water-splitting catalysts is critical for clean hydrogen fuel generation. Quantitative and reliable chemical imaging methods can play a crucial role in providing critical catalyst efficiency information for materials development and screening. Here, we developed a reflection optical imaging method to map the performance of transition metal oxide catalysts for oxygen evolution reaction (OER). The generated high concentration of oxygen in the electrolyte will decrease the refractive index of the solutions near the electrode and change the reflectivity of optical images. We successfully imaged and measured the OER on cobalt oxide, and the localized current density and overpotential distribution maps have been extracted. The oxidation and reduction of cobalt oxide can be imaged with our reflection optical imaging method as well. These maps showed that the catalytic activities are quite different at different locations, and some regions showed much higher activities. This is due to the non-uniformity created by the catalyst synthesis process and demonstrates the importance of using the optical imaging method to map the localized catalytic efficiency. In addition, the NiFe alloy’s OER catalytic activities have been studied as well. The proposed reflection optical imaging method could find many applications in catalyst activity measurement and screening.

Electrochemistry↗

DOE OSTI2020

In Situ Phosphatizing of Triphenylphosphine Encapsulated within Metal–Organic Frameworks to Design Atomic Co 1 –P 1 N 3 Interfacial Structure for Promoting Catalytic Performance

The engineering coordination environment offers great opportunity in performance tunability of isolated metal single-atom catalysts. For the most popular metal–N x (MN x ) structure, the replacement of N atoms by some other atoms with relatively weak electronegativity has been regarded as a promising strategy for optimizing the coordination environment of an active metal center and promoting its catalytic performance, which is still a challenge. Herein, we proposed a new synthetic strategy of an in situ phosphatizing of triphenylphosphine encapsulated within metal–organic frameworks for designing atomic Co 1 –P 1 N 3 interfacial structure, where a cobalt single atom is costabilized by one P atom and three N atoms (denoted as Co-SA/P-in situ). In the acidic media, the Co-SA/P-in situ catalyst with Co 1 –P 1 N 3 interfacial structure exhibits excellent activity and durability for the hydrogen evolution reaction (HER) with a low overpotential of 98 mV at 10 mA cm –2 and a small Tafel slope of 47 mV dec –1 , which are greatly superior to those of catalyst with Co 1 –N 4 interfacial structure. We discover that the bond-length-extended high-valence Co 1 –P 1 N 3 atomic interface structure plays a crucial role in boosting the HER performance, which is supported by in situ X-ray absorption fine structure (XAFS) measurements and density functional theory (DFT) calculation. With this work, we hope to promote the development of high performance metal single-atom catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

X-ray Transient Absorption Spectroscopy Reveals Light Responses of Cobalt Centers in Co-Pi OER Catalytical Devices under Electrochemical Biases

Here, operando X-ray transient absorption measurements were successfully performed for the first time on the Co-Pi catalyst, confirming a photoreduction in Co-Pi under 400 nm blue light excitation. This provides key insights into spectroelectrochemical mechanistic studies of relevant oxygen evolution catalysts and guidance for photocatalysis using these metal oxides. Limiting blue-light exposure of these films should allow for better self-healing and higher turnover in photon-driven water oxidation. These results also demonstrate the importance of performing XTA measurements under operating conditions. Further development of this technique will allow for analysis of complex materials such as tethered molecules on surfaces and in complex device architectures to yield beneficial data for applied materials.

electrochemical cells↗

DOE OSTI2024

Circumventing Kinetic Barriers to Metal Hydride Formation with Metal–Ligand Cooperativity

We report the two-electron, one-proton mechanism of cobalt hydride formation for the conversion of [Co III Cp(P Ph 2 N Bn 2 )(CH 3 CN)] 2+ to [HCo III Cp(P Ph 2 NBn 2 )] + . This complex catalytically converts CO 2 to formate under CO 2 reduction conditions, with hydride formation as a key elementary step. Through a combination of electrochemical measurements, digital simulations, theoretical calculations, and additional mechanistic and thermochemical studies, we outline the explicit role of the P Ph 2 N Bn 2 ligand in the proton-coupled electron transfer (PCET) reactivity that leads to hydride formation. We reveal three unique PCET mechanisms, and we show that the amine on the P Ph 2 N Bn 2 ligand serves as a kinetically accessible protonation site en route to the thermodynamically favored cobalt hydride. Cyclic voltammograms recorded with proton sources that span a wide range of pK a values show four distinct regimes where the mechanism changes as a function of acid strength, acid concentration, and timescale between electrochemical steps. Peak shift analysis was used to determine proton transfer rate constants where applicable. Furthermore, this work highlights the astute choices that must be made when designing catalytic systems, including the basicity and kinetic accessibility of protonation sites, acid strength, acid concentration, and timescale between electron transfer steps, to maximize catalyst stability and efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Supramolecular Enhancement of Electrochemical Nitrate Reduction Catalyzed by Cobalt Porphyrin Organic Cages for Ammonia Electrosynthesis in Water**

Abstract The electrochemical nitrate (NO 3 − ) reduction reaction (NO 3 RR) to ammonia (NH 3 ) represents a sustainable approach for denitrification to balance global nitrogen cycles and an alternative to traditional thermal Haber‐Bosch processes. Here, we present a supramolecular strategy for promoting NH 3 production in water from NO 3 RR by integrating two‐dimensional (2D) molecular cobalt porphyrin ( CoTPP ) units into a three‐dimensional (3D) porous organic cage architecture. The porphyrin box CoPB‐C8 enhances electrochemical active site exposure, facilitates substrate–catalyst interactions, and improves catalyst stability, leading to turnover numbers and frequencies for NH 3 production exceeding 200,000 and 56 s −1 , respectively. These values represent a 15‐fold increase in NO 3 RR activity and 200‐mV improvement in overpotential for the 3D CoPB‐C8 box structure compared to its 2D CoTPP counterpart. Synthetic tuning of peripheral alkyl substituents highlights the importance of supramolecular porosity and cavity size on electrochemical NO 3 RR activity. These findings establish the incorporation of 2D molecular units into 3D confined space microenvironments as an effective supramolecular design strategy for enhancing electrocatalysis.

An, Lun↗

DOE OSTI2023

Supramolecular Enhancement of Electrochemical Nitrate Reduction Catalyzed by Cobalt Porphyrin Organic Cages for Ammonia Electrosynthesis in Water**

An, Lun↗

DOE OSTI2020

Bisoxazoline-pincer ligated cobalt-catalyzed hydrogenation of alkenes

The efficient and atom economical hydrogenation of alkenes using a novel bisoxazoline ligated cobalt complex has been developed here. The hydrogenation of a variety of alkenes containing electron neutral and electron-donating groups proceeds in high yield, while electron-withdrawing and sterically hindered groups are not tolerated. Heterocycles and internal alkenes were further hydrogenated in moderate to high yields. While the catalyst is enantiopure, no enantioinduction was observed suggesting that other factors are involved in achieving enantiocontrol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Immobilization of “Capping Arene” Cobalt(II) Complexes on Ordered Mesoporous Carbon for Electrocatalytic Water Oxidation

We report the synthesis, characterization, and electrocatalytic water oxidation activity of two cobalt complexes, (6-FP)Co(NO 3 ) 2 (1) (6-FP = 8,8'-(1,2-phenylene)diquinoline) and (5-FP)Co(NO 3 ) 2 (2) (5-FP = 1,2-bis(N-7-azaindolyl)benzene), containing "capping arene" bidentate ligands with nitrogen atom donors. The cobalt complexes 1 and 2 were supported on ordered mesoporous carbon (OMC) by π-π stacking, resulting in heterogenized cobalt materials 6-FP-Co-OMC-1 and 5-FP-Co-OMC-2, respectively, and studied for electrocatalytic water oxidation. We find that 6-FP-Co-OMC-1 exhibits an overpotential of 355 mV for a current density of 10 mA cm -2 and a turnover frequency (TOF) of ~0.53 s -1 at an overpotential of 400 mV at pH 14. 6-FP-Co-OMC-1 exhibits activity that is ~1.6 times that of 5-FP-Co-OMC-2, which gives a TOF of 0.32 s -1 at 400 mV overpotential. The structural stability of the single-atom Co site was demonstrated for 6-FP-Co-OMC-1 using X-ray absorption spectroscopy for the molecular complex supported on OMC, but slow degradation in catalyst activity can be attributed to eventual formation of Co oxide clusters. DFT computations of electrocatalytic water oxidation using the molecular complexes as models provide a description of the catalytic mechanism. These studies reveal that the mechanism for O-O bond formation involves an intermediate Co IV oxo complex that undergoes an intramolecular reductive O-O coupling to form a Co II -OOH species. Further, the calculations predict that the molecular 6-FP-Co structure is more active for electrocatalytic water oxidation than 5-FP-Co, which is consistent with experimental studies of 6-FP-Co-OMC-1 and 5-FP-Co-OMC-2, highlighting the possibility that the ligand structure influences the catalytic activity of the supported molecular catalysts.

25 ENERGY STORAGE↗

DOE OSTI2022

An Easily Prepared Monomeric Cobalt(II) Tetrapyrrole Complex That Efficiently Promotes the 4e – /4H + Peractivation of O 2 to Water

The selective 4e – /4H + reduction of dioxygen to water is an important reaction that takes place at the cathode of fuel cells. Monomeric aromatic tetrapyrroles (such as porphyrins, phthalocyanines, and corroles) coordinated to Co(II) or Co(III) have been considered as oxygen reduction catalysts due to their low cost and relative ease of synthesis. Furthermore, these systems have been repeatedly shown to be selective for O 2 reduction by the less desired 2e – /2H + pathway to yield hydrogen peroxide. Herein, we report the initial synthesis and study of a Co(II) tetrapyrrole complex based on a nonaromatic isocorrole scaffold that is competent for 4e – /4H + oxygen reduction reaction (ORR). This Co(II) 10,10-dimethyl isocorrole (Co[10-DMIC]) is obtained in just four simple steps and has excellent yield from a known dipyrromethane synthon. Evaluation of the steady state spectroscopic and redox properties of Co[10-DMIC] against those of Co porphyrin (cobalt 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, [Co(TPFPP)]) and corrole (cobalt 5,10,15-tris(pentafluorophenyl)corrole triphenylphosphine, Co[TPFPC](PPh 3 )) homologues demonstrated that the spectroscopic and electrochemical properties of the isocorrole are distinct from those displayed by more traditional aromatic tetrapyrroles. Further, the investigation of the ORR activity of Co[10-DMIC] using a combination of electrochemical and chemical reduction studies revealed that this simple, unadorned monomeric Co(II) tetrapyrrole is ~85% selective for the 4e – /4H + reduction of O 2 to H 2 O over the more kinetically facile 2e – /2H + process that delivers H 2 O 2 . In contrast, the same ORR evaluations conducted for the Co porphyrin and corrole homologues demonstrated that these traditional aromatic systems catalyze the 2e – /2H + conversion of O 2 to H 2 O 2 with near complete selectivity. Despite being a simple, easily prepared, monomeric tetrapyrrole platform, Co[10-DMIC] supports an ORR catalysis that has historically only been achieved using elaborate porphyrinoid-based architectures that incorporate pendant proton-transfer groups or ditopic molecular clefts or that impose cofacially oriented O 2 binding sites. Accordingly, Co[10-DMIC] represents the first simple, unadorned, monomeric metalloisocorrole complex that can be easily prepared and shows a privileged performance for the 4e – /4H + peractivation of O 2 to water as compared to other simple cobalt containing tetrapyrroles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Interplay between element-specific distortions and electrocatalytic oxygen evolution for cobalt–iron hydroxides

A microscopic understanding of how Fe-doping of Co(OH) 2 improves electrocatalytic oxygen evolution remains elusive. We study two Co 1–x Fex(OH) 2 series that differ in fabrication protocol and find composition alone poorly correlates to catalyst performance. Structural descriptors extracted using X-ray diffraction, X-ray absorption spectroscopy, and Raman spectroscopy reveal element-specific distortions in Co 1–x Fe x (OH) 2 . These structural descriptors are composition-dependent within individual sample series but inconsistent across fabrication protocols, revealing fabrication-dependence in catalyst microstructure. Correlations between structural parameters from different techniques show that Fe–O resists bond length changes, forcing distortion of Co environments. We find the difference in O–M–O bond angles between Co and Fe sites to correlate with electrocatalytic behavior across both sample series, which we attribute to asymmetric distortion of potential energy surfaces for the Co(III) to Co(IV) oxidation. A Tafel slope consistent with a rate-limiting step without electron transfer emerges as the O–Co–O angle decreases, implying a distortion-induced transition in the rate-limiting step. The fabrication dependence of electronic and bonding structure in the catalysts should be considered in theoretical and high-throughput analyses of electrocatalyst materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Supported-Single Nickel Atom Catalysts for the Methanation of Carbon Dioxide

Synthesis of twenty-seven bimetallic catalysts consisting of nickel and one of nine different dopants (B, Co, Cu, Fe, Mg, Mn, Sn, V, and Zn) supported on three different metal oxides (Al 2 O 3 , CeO 2 , and SiO 2 ) is carried out via organometallic grafting. The catalysts are evaluated for their activity and selectivity for the CO 2 methanation reaction at a feed ratio of H 2 /CO 2 of 4 at 300 °C in a high-throughput flow reactor system. After in situ pre-activation (500 °C in H 2 ), Ni/Co/CeO 2 exhibited high conversion (84.3%) and selectivity for methane (99.6%). Ni/Co/CeO 2 was characterized by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction, H 2 -temperature-programmed reduction (H 2 -TPR), and CO 2 -temperature-programmed desorption (CO 2 -TPD). HRTEM showed the presence of single Ni and Co atoms on ceria after pre-reduction at 500 °C and after the methanation reaction at 300 °C for 15 h. XPS determined that the strong interaction between Ni, Co, and ceria increased after the reduction, leading to a charge transfer between Ni and Ce that created oxygen vacancies in ceria. Nickel was found to be Ni 2+ in the as-prepared material and was partially reduced in the presence of cobalt and after the activation in H 2 at 500 °C. The DFT results show that both nickel and cerium exhibit lower Bader charges in the Ni/Co/CeO 2 system, confirming that the presence of cobalt enhances the reduction of both Ni and Ce through electronic interactions. This indicates that single cationic Ni atoms are highly effective for the methanation reaction. In conclusion, the organometallic grafting technique is found to be efficient for synthesizing catalysts with highly homogeneous dispersed species at low metal loadings (0.16 wt % Ni–0.15 wt % Co), which leads to high turnover frequency (up to 248.7 h –1 ) and durability for methanation.

CO2 conversion↗

DOE OSTI2021

A mathematical analysis of carbon fixing materials that grow, reinforce, and self-heal from atmospheric carbon dioxide

Carbon fixing materials are a new class of self-healing, self-reinforcing materials we have introduced that utilize ambient CO 2 to chemically add to an ever extending carbon backbone. This class of materials can utilize biological or non-biological photocatalysts and support a wide range of potential backbone chemistries. However, there is no analysis to date that describes their fundamental limits in terms of chemical kinetics and mass transfer. In this computational study, we employ a reaction engineering, and materials science analysis to answer basic questions about the maximum growth rate, photocatalytic requirements and limits of applicable materials. Our proposed mathematical framework envelops three main functions required for carbon fixing materials: (1) adsorption of CO 2 from air, (2) photocatalytic reduction of CO 2 into selected monomers, and (3) polymerization of CO 2 -derived monomers. First, by performing a Damköhler number analysis, we derive criteria for the cross over from kinetic control to mass transfer limited growth, setting upper limits on performance of a potential photocatalyst. Next, we analyze photocatalytic reduction of CO 2 to single carbon products, using known catalytic pathways and kinetic data. We identify formaldehyde as a C1 intermediate having unique potential for incorporation into the material backbone of carbon fixing materials. As an example, we find that a diamond-shaped reaction network graph for CO 2 reduction, passing through CO and HCOOH intermediates, accurately describes kinetic data for cobalt-promoted TiO 2 nanoparticles at room temperature and 1 atm CO 2 . Finally, as an applied case study, we consider and analyze the example of a carbon fixing poly(oxymethylene) system with embedded catalyst promoting the photocatalytic reduction of CO 2 to formaldehyde. The latter then trimerizes to a trioxane monomer which subsequently polymerizes to polyoxymethylene. This reaction engineering analysis introduces benchmarks for carbon fixing materials with respect to achievable rates of photocatalysis, adsorption, and polymerization. These results should prove valuable for the design, evaluation, and benchmarking of this emergent and new class of environmentally sustainable materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗