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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 919 records · Page 51
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Production of H2 at Fast Rates Using a Nickel Electrocatalyst in Water/Acetonitrile Solutions

Efficient production of molecular hydrogen for storage of energy from renewable sources is crucial for the development of wind and solar power. Hydrogenase enzymes in nature catalyze H2 production using earth-abundant metals (iron and nickel) using precise delivery of protons to the metal center. Here we report a synthetic nickel complex containing proton relays, [Ni(PPh2NC6H4OH2)2](BF4)2 (PPh2NC6H4OH2 = 1,5-bis(p-hydroxyphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane), that catalyzes the production of H2 in an aqueous environment with turnover frequencies of 750-170,000 s-1 at directly measured overpotentials of 310-470 mV. The remarkable performance of this catalyst in aqueous environments exceeds the requirements necessary for molecular catalytic production of H2 by energy derived from photovoltaic solar cells. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

Hoffert, Wesley A.↗
DOE OSTI2013

Hybrid Li-air battery cathodes with sparse carbon nanotube arrays directly grown on carbon fiber papers

Sparsely populated, vertically aligned nitrogen doped carbon nanotube arrays (CNTAs) with dislocated-graphene stacking were grown directly on carbon fiber papers and investigated as hierarchical air cathodes in hybrid Li-air batteries with aqueous catholytes. The CNTAs were made with electrodeposited Ni nanocatalysts, followed by plasma-enhanced chemical vapor deposition. The thus obtained CNTAs can reach a population number density as low as similar to 10(7) per cm(2) on the carbon fibers, achieving an extremely high porosity of over 99% for the active layer in the cathode. The sparse CNTAs not only provide effective pathways for the reacting species, but also show a significantly high catalytic activity, which is found to be comparable to that of a supported Pt electrocatalyst. The high activity of the CNTAs is attributed to the rich graphene edges exposed on the CNT surface and nitrogen doping. Hybrid Li-air batteries with such cathodes have shown a consistent discharging capacity of 710 mA h g(-1) and a specific energy of 2057 W h kg(-1) at 0.5 mA cm(-2). Stable charge-discharge cycling at 0.5 mA cm(-2) showed an average potential difference of 1.35 V, indicative of a relatively small overpotential and high round trip efficiency (71%). Furthermore, the hybrid Li-air battery based on the hierarchical cathode can reach a power density as high as 10.4 mW cm(-2).

Li, YF↗
DOE OSTI2014

Discovering Ce-rich oxygen evolution catalysts, from high throughput screening to water electrolysis

In this paper, we report a new Ce-rich family of active oxygen evolution reaction (OER) catalysts composed of earth abundant elements, discovered using high-throughput methods. High resolution inkjet printing was used to produce 5456 discrete oxide compositions containing the elements nickel, iron, cobalt and cerium. The catalytic performance of each of these compositions was measured under conditions applicable to distributed solar fuels generation using a three-electrode scanning drop electrochemical cell. The catalytic activity and stability of representative compositions (Ni 0.5 Fe 0.3 Co 0.17 Ce 0.03 O x and Ni 0.3 Fe 0.07 Co 0.2 Ce 0.43 O x ) from 2 distinct regions were verified by resynthesizing these compositions on glassy carbon rods for electrochemical testing. The activity of the new Ce-rich catalysts was further verified using an unrelated synthetic method to electrodeposit a pseudo-ternary composition Ni 0.2 Co 0.3 Ce 0.5 O x , which produced a catalyst with 10 mA cm -2 oxygen evolution current at 310 mV overpotential. Finally, the unique Tafel behavior of these Ce-rich catalysts affords the opportunity for further improvement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Intrinsic thermodynamic and kinetic properties of Sb electrodes for Li-ion and Na-ion batteries: Experiment and Theory

A detailed comparative study between electrochemical lithiation and sodiation of pure antimony (Sb), relating changes in structural, thermodynamic, kinetic and electrochemical properties has been carried out. For this purpose, a wide range of measurements using electrochemical (galvanostatic cycling, GITT, PITT), x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) methods as well as density functional theory (DFT) based investigations have been undertaken. Assessment of the thermodynamics reveals that the reaction proceeds identically during the first and second cycles for Li whereas it differs between the first and subsequent cycles for Na. For Li the difference between the first and subsequent cycles is rooted in an improvement of the kinetics likely due to the decrease of Sb particle size whereas the reaction with Na proceeds through a different pathway from the first to subsequent cycles and is associated with the formation of amorphous NaxSb phases. For the first time we rationalize the amorphization of NaxSb phases by the long ranged strain propagation due to Na-vacancy compared to Li-Sb. At full discharge, our XRD results show for the first time that a minor fraction of hexagonal Li3Sb forms concomitantly with cubic Li3Sb. The XRD results confirm that Sb crystallizes into hexagonal Na3Sb at full sodiation. The kinetics of the reaction is assessed by rate performance tests which highlight that both Li and Na can diffuse rapidly throughout micron thick films at room temperature. However, it is found that the (de)insertion of Li provides lower overpotentials and larger storage capacities compared to Na. The difference in rate performance is complemented by diffusion coefficient determinations near the 0 V region where both materials are crystallized into M3Sb (M=Li, Na), and the results show that the apparent diffusion coefficients for Li are equivalent or one order of magnitude higher than those for Na. Interestingly, calculations show that the energy barrier for near-neighbor vacancy motion, predominant in these close-packed phases is about twice for Na than for Li. Our analysis tries to relate the lower intrinsic diffusivity of Na compared to Li with the long-range strain propagation induced by the former, thereby leading to an intrinsic origin of differences in rates, mechanical properties and amorphization. Finally, the surface chemistry of Sb electrodes cycled in NaClO4 dissolved in pure PC with(out) the addition of 5wt% EC or FEC shows presence of ethers and NaF for the EC- and FEC-based electrolytes, respectively, and SEI films rich in Na-based carbonates.

Baggetto, Loic↗
DOE OSTI2014

A sensitivity analysis to assess the relative importance of improvements in electrocatalysts, light absorbers, and system geometry on the efficiency of solar-fuels generators

A sensitivity analysis has been performed for a variety of generic designs for solar-fuels generators. Here, the analysis has revealed the relative importance of reductions in the overpotentials of electrocatalysts, of improvements in the materials properties of light absorbers, and of optimization in the system geometry for various different types of solar-fuels generators, while considering operation at a range of temperatures as well as under a variety of illumination intensities including up to 10-fold optical concentration.

Chen, Yikai↗
DOE OSTI2014

Nuclear resonance vibrational spectroscopy reveals the FeS cluster composition and active site vibrational properties of an O 2 -tolerant NAD + -reducing [NiFe] hydrogenase

Hydrogenases are complex metalloenzymes that catalyze the reversible splitting of molecular hydrogen into protons and electrons essentially without overpotential. The NAD+-reducing soluble hydrogenase (SH) from Ralstonia eutropha is capable of H 2 conversion even in the presence of usually toxic dioxygen. The molecular details of the underlying reactions are largely unknown, mainly because of limited knowledge of the structure and function of the various metal cofactors present in the enzyme. Here, all iron-containing cofactors of the SH were investigated by 57 Fe specific nuclear resonance vibrational spectroscopy (NRVS). Our data provide experimental evidence for one [2Fe2S] center and four [4Fe4S] clusters, which is consistent with the amino acid sequence composition. Only the [2Fe2S] cluster and one of the four [4Fe4S] clusters were reduced upon incubation of the SH with NADH. This finding explains the discrepancy between the large number of FeS clusters and the small amount of FeS cluster-related signals as detected by electron paramagnetic resonance spectroscopic analysis of several NAD+-reducing hydrogenases. For the first time, Fe–CO and Fe–CN modes derived from the [NiFe] active site could be distinguished by NRVS through selective 13 C labeling of the CO ligand. This strategy also revealed the molecular coordinates that dominate the individual Fe–CO modes. The present approach explores the complex vibrational signature of the Fe–S clusters and the hydrogenase active site, thereby showing that NRVS represents a powerful tool for the elucidation of complex biocatalysts containing multiple cofactors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Highly branched cobalt phosphide nanostructures for hydrogen-evolution electrocatalysis

CoP nanostructures that exposed predominantly (111) crystal facets were synthesized and evaluated for performance as electrocatalysts for the hydrogen-evolution reaction (HER). The branched CoP nanostructures were synthesized by reacting cobalt(II) acetylacetonate with trioctylphosphine in the presence of trioctylphosphine oxide. Electrodes comprised of the branched CoP nanostructures deposited at a loading density of ~1 mg cm -2 on Ti electrodes required an overpotential of -117 mV to produce a current density of -20 mA cm -2 in 0.50 M H 2 SO 4 . Hence the branched CoP nanostructures belong to the growing family of highly active non-noble-metal HER electrocatalysts. Finally, comparisons with related CoP systems have provided insights into the impact that shape-controlled nanoparticles and nanoparticle–electrode interactions have on the activity and stability of nanostructured HER electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Bio-inspired Design of Electrocatalysts for Oxalate Oxidation: a Combined Experimental and Computational Study of Mn–N–C Catalysts

We report a novel non-platinum group metal (non-PGM) catalyst derived from Mn and amino- antipyrine (MnAAPyr) that shows electrochemical activity towards the oxidation of oxalic acid comparable to Pt with an onset potential for oxalate oxidation measured to be 0.714 * 0.002 V vs. SHE at pH = 4. The material has been synthesized using a templating Sacrificial Support Method with manganese nitrate and 4-aminoantipyrine as precursors. This catalyst is a nano-structured material in which Mn is atomically dispersed on a nitrogendoped graphene matrix. XPS studies reveal high abundance of pyridinic, Mn–Nx, and pyrrolic nitrogen pointing towards the conclusion that pyridinic nitrogen atoms coordinated to manganese constitute the active centers. Thus, the main features of the MnAAPyr catalyst are it exhibits similarity to the active sites of naturally occurring enzymes that are capable of efficient and selective oxidation of oxalic acid. Density functional theory in plane wave formalism with Perdew, Burke and Ernzerhof functional was further used to study the stability and activity of different one-metal active centers that could exist in the catalyst. The results show that the stability of the Mn–Nx sites changes in the following order: MnN4 4 MnN3C 4 MnN2C2 4 MnN3. Based on the overpotentials of 0.64 V and 0.71 V vs. SHE, calculated using the free energy diagrams for the oxalate oxidation mechanism, we could conclude that the MnN3C and MnN2C2 sites are most probable Mn–Nx sites responsible for the reported catalytic activity of the new catalyst.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2015

A quantitative analysis of the efficiency of solar-driven water-splitting device designs based on tandem photoabsorbers patterned with islands of metallic electrocatalysts

The trade-off between the optical obscuration and kinetic overpotentials of electrocatalyst films patterned onto the surface of tandem light-absorber structures in model photoelectrosynthetic water-splitting systems was investigated using a 0-dimensional load-line analysis and experimental measurements. The electrocatalytic performance of the catalyst at high current densities, normalized to the electrocatalyst surface area, is an important factor in the dependence of the optimal solar-to-hydrogen (STH) conversion efficiency, η STH,opt , on the filling fraction ( f c ) of the patterned catalysts, because even under conditions that produce minority-carrier current densities of ~10 mA cm -2 at the solid/liquid interface, the current density at catalyst-bearing sites can be >1–2 A cm -2 in low filling-fraction films. A universal current-density versus potential relationship, up to current densities of 10 A cm -2 , was obtained experimentally for the hydrogen-evolution reaction (HER) using patterned Pt ultramicroelectrode (UME) arrays with a range of filling fractions and disc diameters. The η STH,opt of system designs that utilize patterned electrocatalysts located on the illuminated side of tandem photoabsorbers was then evaluated systematically. The maximum STH conversion efficiency, η STH,max , using a hypothetical electrocatalyst that was optically transparent but which nevertheless exhibited a current-density versus potential behavior that is characteristic of the most active Pt films measured experimentally regardless of their optical obscuration, was 26.7%. By comparison, the maximum η STH,opt of 24.9% for real patterned Pt electrocatalyst films closely approached this ideal-case limit. The performance and materials utilization of the patterned electrocatalysts and of the uniformly coated electrocatalysts on tandem photoabsorbers were also compared in this research. Hence, patterned electrocatalysts with very low filling fractions can provide a potentially promising path to the realization of efficient large-scale photoelectrolysis systems while minimizing the use of scarce noble metals.

14 SOLAR ENERGY↗
DOE OSTI2015

An electrochemical engineering assessment of the operational conditions and constraints for solar-driven water-splitting systems at near-neutral pH

The solution transport losses in a one-dimensional solar-driven water-splitting cell that operates in either concentrated acid, dilute acid, or buffered near-neutral pH electrolytes have been evaluated using a mathematical model that accounts for diffusion, migration and convective transport, as well as for bulk electrochemical reactions in the electrolyte. The Ohmic resistance loss, the Nernstian potential loss associated with pH gradients at the surface of the electrode, and electrodialysis in different electrolytes were assessed quantitatively in a stagnant cell as well as in a bubble-convected cell, in which convective mixing occurred due to product-gas evolution. In a stagnant cell that did not have convective mixing, small limiting current densities (<3 mA cm -2 ) and significant polarization losses derived from pH gradients were present in dilute acid as well as in near-neutral pH buffered electrolytes. In contrast, bubble-convected cells exhibited a significant increase in the limiting current density, and a significant reduction of the concentration overpotentials. In a bubble-convected cell, minimal solution transport losses were present in membrane-free cells, in either buffered electrolytes or in unbuffered solutions with pH ≤ 1. However, membrane-free cells lack a mechanism for product-gas separation, presenting significant practical and engineering impediments to the deployment of such systems. To produce an intrinsically safe cell, an ion-exchange membrane was incorporated into the cell. The accompanying solution losses, especially the pH gradients at the electrode surfaces, were modeled and simulated for such a system. Hence this work describes the general conditions under which intrinsically safe, efficient solar-driven water-splitting cells can be operated.

42 ENGINEERING↗
DOE OSTI2015

Operational constraints and strategies for systems to effect the sustainable, solar-driven reduction of atmospheric CO 2

The operational constraints for a 6-electron/6-proton CO 2 reduction system that operates at the concentration of CO 2 in the current atmosphere (p CO 2 = 400 ppm) have been evaluated on a variety of scale lengths that span from laboratory scale to global scale. Due to the low concentration of CO 2 in the atmosphere, limitations due to mass transport of CO 2 from the tropopause have been evaluated through five different regions, each with different characteristic length scales: the troposphere; the atmospheric boundary layer (ABL); the canopy layer; a membrane layer; and an aqueous electrolyte layer. The resulting CO 2 conductances, and associated physical transport limitations, will set the ultimate limit on the efficiency and areal requirements of a sustainable solar-driven CO 2 reduction system regardless of the activity or selectivity of catalysts for reduction of CO 2 at the molecular level. At the electrolyte/electrode interface, the steady-state limiting current density and the concomitant voltage loss associated with the CO 2 concentration overpotential in a one-dimensional solar-driven CO 2 reduction cell have been assessed quantitatively using a mathematical model that accounts for diffusion, migration and convective transport, as well as for bulk electrochemical reactions in the electrolyte. At p CO 2 = 400 ppm, the low diffusion coefficient combined with the low solubility of CO 2 in aqueous solutions constrains the steady-state limiting current density to <0.1 mA cm -2 in a typical electrochemical cell with natural convection and employing electrolytes with a range of pH values. Hence, in such a system, the CO 2 capture area must be 100- to 1000-fold larger than the solar photon collection area to enable a >10% efficient solar-driven CO 2 reduction system (based on the solar collection area). This flux limitation is consistent with estimates of oceanic CO 2 uptake fluxes that have been developed in conjunction with carbon-cycle analyses for use in coupled atmosphere/ocean general circulation models. Two strategies to improve the feasibility of obtaining efficient and sustainable CO 2 transport to a cathode surface at p CO 2 = 400 ppm are described and modeled quantitatively. The first strategy employs yet unknown catalysts, analogous to carbonic anhydrases, that dramatically accelerate the chemically enhanced CO 2 transport in the aqueous electrolyte layer by enhancing the acid–base reactions in a bicarbonate buffer system. The rapid interconversion from bicarbonate to CO 2 in the presence of such catalysts near the cathode surface would in principle yield significant increases in the steady-state limiting current density and allow for >10% solar-fuel operation at the cell level. The second strategy employs a thin-layer cell architecture to improve the diffusive transport of CO 2 by use of an ultrathin polymeric membrane electrolyte. Rapid equilibration of CO 2 at the gas/electrolyte interface, and significantly enhanced diffusive fluxes of CO 2 in electrolytes, are required to increase the steady-state limiting current density of such a system. This latter approach however only is feasible for gaseous products, because liquid products would coat the electrode and therefore thicken the hydrodynamic boundary layer and accordingly reduce the diffusive CO 2 flux to the electrode surface. Regardless of whether the limitations due to mass transport to the electrode surface are overcome on the laboratory scale, at global scales the ultimate CO 2 flux limitations will be dictated by mass transport considerations related to transport of atmospheric CO 2 to the boundary plane of the solar-driven reactor system. The transport of CO 2 across the troposphere/ABL interface, the ABL/canopy layer interface, and the canopy layer/electrolyte interface have therefore been assessed in this work, to provide upper bounds on the ultimate limits for the solar-to-fuel (STF) conversion efficiency for systems that are intended to effect the reduction of atmospheric CO 2 in a sustainable fashion at global scale.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

570 mV photovoltage, stabilized n-Si/CoO x heterojunction photoanodes fabricated using atomic layer deposition

Heterojunction photoanodes, consisting of n-type crystalline Si(100) substrates coated with a thin ~50 nm film of cobalt oxide fabricated using atomic-layer deposition (ALD), exhibited photocurrent-onset potentials of -205 ± 20 mV relative to the formal potential for the oxygen-evolution reaction (OER), ideal regenerative solar-to-O 2 (g) conversion efficiencies of 1.42 ± 0.20%, and operated continuously for over 100 days (~2500 h) in 1.0 M KOH(aq) under simulated solar illumination. The ALD CoO x thin film: (i) formed a heterojunction with the n-Si(100) that provided a photovoltage of 575 mV under 1 Sun of simulated solar illumination; (ii) stabilized Si photoanodes that are otherwise unstable when operated in aqueous alkaline electrolytes; and, (iii) catalyzed the oxidation of water, thereby reducing the kinetic overpotential required for the reaction and increasing the overall efficiency relative to electrodes that do not have an inherently electrocatalytic coating. The process provides a simple, effective method for enabling the use of planar n-Si(100) substrates as efficient and durable photoanodes in fully integrated, photovoltaic-biased solar fuels generators.

14 SOLAR ENERGY↗
DOE OSTI2015

Biomass-derived high-performance tungsten-based electrocatalysts on graphene for hydrogen evolution

We report a new class of highly active and stable tungsten-based catalysts to replace noble metal materials for the hydrogen evolution reaction (HER) in an acidic electrolyte. The catalyst is produced by heating an earth-abundant and low-cost mixture of ammonium tungstate, soybean powder and graphene nanoplatelets (WSoyGnP). The catalyst compound consists of tungsten carbide (W₂C and WC) and tungsten nitride (WN) nanoparticles decorated on graphene nanoplatelets. The catalyst demonstrates an overpotential (η₁₀, the potential at a current density of 10 mA cm⁻²) of 0.105 V, which is the smallest among tungsten-based HER catalysts in acidic media. The coupling with graphene significantly reduces the charge transfer resistance and increases the active surface area of the product, which are favorable for enhancing the HER activity. Therefore, the approach of employing biomass and other less expensive materials as precursors for the production of catalysts with high HER activity provides a new path for the design and development of efficient catalysts for the hydrogen production industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Benchmarking nanoparticulate metal oxide electrocatalysts for the alkaline water oxidation reaction

Nanoparticulate metal-oxide catalysts are among the most prevalent systems for alkaline water oxidation. However, comparisons of the electrochemical performance of these materials have been challenging due to the different methods of attachment, catalyst loadings, and electrochemical test conditions reported in the literature. Here in this paper, we have leveraged a conventional drop-casting method that allows for the successful adhesion of a wide range of nanoparticulate catalysts to glassy-carbon electrode surfaces. We have applied this adhesion method to prepare catalyst films from 16 crystalline metal-oxide nanoparticles with a constant loading of 0.8 mg cm -2 , and evaluated the resulting nanoparticulate films for the oxygen evolution reaction under conditions relevant to an integrated solar fuels device. In general, the activities of the adhered nanoparticulate films are similar to those of thin-film catalysts prepared by electrodeposition or sputtering, achieving 10 mA cm -2 current densities per geometric area at overpotentials of ~0.35–0.5 V.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Enhancement of oxygen reduction reaction activities by Pt nanoclusters decorated on ordered mesoporous porphyrinic carbons

The high cost of Pt-based membrane electrode assemblies (MEAs) is a critical hurdle for the commercialization of polymer electrolyte fuel cells (PEFCs). Recently, non-precious metal-based catalysts (NPMCs) have demonstrated much enhanced activity but their oxygen reduction reaction (ORR) activity is still inferior to that of Pt-based catalysts resulting in a much thicker electrode in the MEA. For the reduction of mass transport and ohmic overpotential we adopted a new concept of catalyst that combines an ultra-low amount of Pt nanoclusters with metal–nitrogen (M–Nx) doped ordered mesoporous porphyrinic carbon (FeCo–OMPC(L)). The 5 wt% Pt/FeCo–OMPC(L) showed a 2-fold enhancement in activities compared to a higher loading of Pt. Our experimental results supported by first-principles calculations indicate that a trace amount of Pt nanoclusters on FeCo–OMPC(L) significantly enhances the ORR activity due to their electronic effect as well as geometric effect from the reduced active sites. Finally, in terms of fuel cell commercialization, this class of catalysts is a promising candidate due to the limited use of Pt in the MEA.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Evaluating the role of acidic, basic, and polar amino acids and dipeptides on a molecular electrocatalyst for H 2 oxidation

Amino acids and peptides have been shown to have a significant influence on the H2 production and oxidation reactivity of Ni(P R 2 N R’ 2 ) 2 , where P R 2 N R’ 2 = 1,5-diaza-3,7-diphosphacyclooctane, R is either phenyl (Ph) or cyclohexyl (Cy), and R’ is either an amino acid or peptide. Most recently, the Ni(P Cy 2 Naminoacid 2 ) 2 complexes (CyAA) have shown enhanced H 2 oxidation rates, water solubility, and in the case of arginine (CyArg) and phenylalanine (CyPhe), electrocatalytic reversibility. Both the backbone –COOH and side chain interactions were shown to be critical to catalytic performance. Here we further investigate the roles of the outer coordination sphere by evaluating amino acids with acidic, basic, and hydrophilic side chains, as well as dipeptides which combine multiple successful features from previous complexes. Six new complexes were prepared, three containing single amino acids: aspartic acid (CyAsp), lysine (CyLys), and serine (CySer) and three containing dipeptides: glycine-phenylalanine (Cy(GlyPhe)), phenylalanine-glycine (Cy(PheGly)), and aspartic acid-phenylananine (Cy(AspPhe)). The resulting catalytic performance demonstrates that complexes need both interactions between side chain and –COOH groups for fast, efficient catalysis. The fastest of all of the catalysts, Cy(AspPhe), had both of these features, while the other dipeptide complexes with an amide replacing the -COOH were both slower; however, the amide group was demonstrated to participate in the proton pathway when side chain interactions are present to position it. Both the hydrophilic and basic side chains, notably lacking in side chain interactions, significantly increased the overpotential, with only modest increases in TOF. Of all of the complexes, only CyAsp was reversible at room temperature, and only in water, the first of these complexes to demonstrate room temperature reversibility in water. These results continue to provide and solidify design rules for controlling reactivity and efficiency of Ni(P 2 N 2 ) 2 complexes with the outer coordination sphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Hydricity, electrochemistry, and excited-state chemistry of Ir complexes for CO 2 reduction

Here, we prepared electron-rich derivatives of [Ir(tpy)(ppy)Cl] + with modification of the bidentate (ppy) or tridentate (tpy) ligands in attempt to increase the reactivity for CO 2 reduction and the ability to transfer hydrides (hydricity). Density functional theory (DFT) calculations reveal that complexes with dimethyl-substituted ppy have similar hydricities to the non-substituted parent complex, and photocatalytic CO 2 reduction studies show selective CO formation. Substitution of tpy for bis(benzimidazole)-phenyl or -pyridine (L3 and L4, respectively) induces changes in the physical properties much more pronounced than addition of methyl groups to ppy. Theoretical data predict [Ir(L3)(ppy)(H)] is the strongest hydride donor among complexes studied in this work, but [Ir(L3)(ppy)(NCCH 3 )] + cannot be reduced photochemically because the excited state reduction potential is only 0.52 V due to the negative ground state potential of –1.91 V. The excited state [Ir(L4)(ppy)(NCCH 3 )] 2+ is the strongest oxidant among complexes studied in this work and the singly reduced species is formed readily upon photolysis in the presence of tertiary amines. Both [Ir(L3)(ppy)(NCCH 3 )] + and [Ir(L4)(ppy)(NCCH 3 )] 2+ exhibit electrocatalytic current for CO 2 reduction. While a significantly greater overpotential is needed for the L3 complex, a small amount of formate (5-10 %) generation in addition to CO was observed as predicted by the DFT calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗