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All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Cleaner Energy for Cars

Representing the Center for Catalytic Hydrocarbon Functionalization (CCHF), this document is one of the entries in the Ten Hundred and One Word Challenge. As part of the challenge, the 46 Energy Frontier Research Centers were invited to represent their science in images, cartoons, photos, words and original paintings, but any descriptions or words could only use the 1000 most commonly used words in the English language, with the addition of one word important to each of the EFRCs and the mission of DOE: energy. The mission of CCHF is to develop, validate, and optimize new methods to rearrange the bonds of hydrocarbons, implement enzymatic strategies into synthetic systems, and design optimal environments for catalysts that can be used to reversibly functionalize hydrocarbons, especially for more efficient use of natural gas including low temperature conversion to liquid fuels.

08 HYDROGEN↗
DOE OSTI2014

Effects of External EGR Loop on Cycle-to-Cycle Dynamics of Dilute SI Combustion

Operation of spark-ignition (SI) engines with high levels of charge dilution through exhaust gas recirculation (EGR) achieves significant efficiency gains while maintaining stoichiometric operation for compatibility with three-way catalysts. Dilution levels, however, are limited by cyclic variability including significant numbers of misfires that becomes significant with increasing dilution. This variability has been shown to have both stochastic and deterministic components. Stochastic effects include turbulence, mixing variations, and the like, while the deterministic effect is primarily due to the nonlinear dependence of flame propagation rates and ignition characteristics on the charge composition, which is influenced by the composition of residual gases from prior cycles. The dynamics of operation with an external EGR loop differ substantially from those of dilute operation without external recirculation, both in time-scale and cylinder synchronization effects, especially when misfires are encountered. This paper examines these differences and the implications for prior-cycle-based control strategies.

Kaul, Brian C↗
DOE OSTI2018

In-situ evaluation for upgrading of biomass over noble metal catalysts by isotopic tracing and NMR monitoring

One of the key challenges in studying the upgrading processes for the conversion of biomass is developing an understanding of the underlying conversion mechanism at the atomic scale. This study proposed an innovative high pressure in situ NMR monitoring approach for an isotopic traced upgrading process, which demonstrated a powerful capability to identify key products and provide insights into the reaction structure. The investigations for ring opening of two basic model compounds – methylcyclopentane (MCP) and cyclohexane (CH) on Ir, Pt, Ru and Pd/γ-Al 2 O 3 at 55 and 110 °C have been accomplished. For the study performed at 110 °C on Ir, Pt and Ru catalysts, the trend of H/D exchange rates were clearly dependent on the position on the ring with the highest exchange rate for the unhindered (or open side) and the lowest rate with the methyl group. However, Pd could perform almost equally efficient H/D exchanges for all sides, which may indicate that the “turnover” reactions could also occur on Pd. For both MCP and CH, Ru performed the most efficient H/D exchanges (C–H bond activation), and ring opened products were only observed with the Ru catalyst at 110 °C suggesting it is the most promising ring opening catalyst.

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 OSTI2018

Exploring the Effect of Gold Support on the Oxygen Reduction Reaction Activity of Metal Porphycenes

It has been a long-standing goal to find alternative, cost effective catalysts for oxygen reduction reaction (ORR) in fuel cells. Molecular complexes capable of efficiently catalyzing ORR, when supported on a conducting solid surface could provide interesting hybrid materials combining the best of homogeneous and heterogeneous catalysis. Here, we utilize density functional theory to study the ORR activity of molecular (unsupported) and gold supported 3d metal (II)-porphycenes (MPc). All the 3d metal-porphycenes adsorb strongly on the Au(111) support with negative free energy of formation ranging from 1.0–3.0 eV while solvation lowers the energy of molecular MPc by only 0.5 eV compared to the gas phase. These indicate that the 3d MPc are stable and anchored firmly to the gold surface under ORR conditions. Based on our analysis, the gold support enhances the ORR activity in some of the examined MPc systems. We find that the molecular MnPc and FePc are the best ORR electrocatalysts with theoretical overpotentials of 0.44 V and 0.36 V. Thus, this work highlights the important role of the support in preserving/increasing the activity of molecular catalyst.

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

Performance of Base and Noble Metals for Electrocatalytic Hydrogenation of Bio-Oil-Derived Oxygenated Compounds

Electrocatalytic hydrogenation is a particularly attractive approach for converting the most unstable compounds in biogenic feedstocks at ambient conditions without external hydrogen. Here, we synthesized a variety of carbon-supported transition metal catalysts and characterized their activity for the electrocatalytic hydrogenation of a series of model compounds and pyrolysis oil. Carbonyl compounds, especially aromatic aldehydes, such as furfural and benzaldehyde, are particularly inclined to hydrogenation driven by an applied current. This was verified with pure solutions of the model compounds and with pyrolysis oil, where we achieved stable and steady continuous operation on Pd. By choosing the optimal catalyst composition, the conversion of benzaldehyde shifted from alcohol production (e.g., on Pd and Cu) to dimerization (e.g., on Co, Ni, and Zn). Pd and Cu were shown to offer the best compromise between reaction rates and efficiency although, in general, base metals offer similar conversions but better efficiencies that noble metals. Thus, the present work offers foundational results and guidelines for choosing the optimal metal catalyst and the applied potential for processing organic feedstocks as a function of its composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Anolyte Enhances Catalyst Utilization and Ion Transport Inside a CO 2 Electrolyzer Cathode

Electrochemical CO 2 reduction is a promising technology to capture and convert CO 2 to valuable chemicals. High Faradaic efficiencies of CO 2 reduction products are achieved with zero-gap alkaline CO 2 electrolyzers with a supporting electrolyte at the anode (anolyte). Herein, we investigate the effect of anolyte on the electrode properties such as catalyst utilization, ionic accessibility etc. of a CO 2 reduction cathode using electrochemical techniques and cell configurations that avoid the complexities related to co-electrolysis. Using 1M KOH as the anolyte and a Cu gas-diffusion-electrode with low Nafion content as the model CO 2 reduction electrode, we find that electrode capacitance (proxy for electrochemically active surface area) and ionic conductivity inside the cathode increase approximately 4 and 447 times, respectively, in presence of KOH. Liquid anolyte wets the electrode’s pore structure more efficiently than capillary condensation of feed water vapor. The ionomer coverage is very low, and its distribution inside the electrode is highly fragmented. Surface ion conduction mechanisms inside the electrode are orders of magnitude lower than the bulk ion conduction in presence of anolyte. This study shows that when an anolyte (e.g., KOH) is used, catalyst utilization and ionic accessibility inside the electrode increase significantly.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

Controlled One‐pot Synthesis of Nickel Single Atoms Embedded in Carbon Nanotube and Graphene Supports with High Loading

Abstract Single‐atom catalysts (SACs) have attracted much attentions due to the advantages of high catalysis efficiency and selectivity. However, the controllable and efficient synthesis of SACs remains a significant challenge. Herein, we report a controlled one‐pot synthesis of nickel single atoms embedded on nitrogen‐doped carbon nanotubes (NiSA−N−CNT) and nitrogen‐doped graphene (NiSA−N−G). The formation of NiSA−N−CNT is due to the solid‐to‐solid rolling up mechanism during the high temperature pyrolysis at 800 °C from the stacked and layered Ni‐doped g‐C 3 N 4 , g‐C 3 N 4 −Ni structure to a tubular CNT structure. Addition of citric acid introduces an amorphous carbon source on the layered g‐C 3 N 4 −Ni and after annealing at the same temperature of 800 °C, instead of formation of NiSA−N−CNT, Ni single atoms embedded in planar graphene type supports, NiSA−N−G were obtained. The density functional theory (DFT) calculation indicates the introduction of amorphous carbon source substantially reduces the structure fluctuation or curvature of layered g‐C 3 N 4 ‐Ni intermediate products, thus interrupting the solid‐to‐solid rolling process and leading to the formation of planar graphene type supports for Ni single atoms. The as‐synthesized NiSA−N−G with Ni atomic loading of ∼6 wt% catalysts shows a better activity and stability for the CO 2 reduction reaction (CO 2 RR) than NiSA−N−CNT with Ni atomic loading of ∼15 wt% due to the open and exposed Ni single atom active sites in NiSA−N−G. This study demonstrates for the first time the feasibility in the control of the microstructure of carbon supports in the synthesis of SACs.

Zhao, Shiyong↗
DOE OSTI2025

Enhanced Activity in Layered Metal-Oxide-Based Oxygen Evolution Catalysts by Layer-by-Layer Modulation of Metal-Ion Identity

Few-layered potassium nickel and cobalt oxides show drastic differences in catalytic activity based on metal ion preorganization. Uniform compositions [(CoO 2 /K) 6 or (NiO 2 /K) 6 ] show limited activity, while homogeneously mixed-metal cobalt/nickel oxides [(Co n Ni (1–n) O 2 /K) 6 ] display moderate improvement. However, a layer-by-layer arrangement of alternating cobalt and nickel oxide sheets [e.g., (CoO 2 /K/NiO 2 /K)] provides superior catalytic performance, reducing the oxygen evolution overpotential by ∼200–400 mV. Density functional theory simulations provide an illustration of the electronic properties (density of states and localization of orbitals) that promote catalysis in the layer-segregated materials over those of homogeneous composition. This study reveals that atomic preorganization of metal ions within layered catalysts plays a more crucial role than the overall metal composition in enhancing catalytic efficiency for oxygen evolution.

catalysts↗
DOE OSTI2018

Atomically Dispersed Transition Metals on Carbon Nanotubes with Ultrahigh Loading for Selective Electrochemical Carbon Dioxide Reduction

Single-atom catalysts (SACs) are the smallest entities for catalytic reactions with projected high atomic efficiency, superior activity, and selectivity; however, practical applications of SACs suffer from a very low metal loading of 1–2 wt%. Here, a class of SACs based on atomically dispersed transition metals on nitrogen-doped carbon nanotubes (MSA-N-CNTs, where M = Ni, Co, NiCo, CoFe, and NiPt) is synthesized with an extraordinarily high metal loading, e.g., 20 wt% in the case of NiSA-N-CNTs, using a new multistep pyrolysis process. Among these materials, NiSA-N-CNTs show an excellent selectivity and activity for the electrochemical reduction of CO 2 to CO, achieving a turnover frequency (TOF) of 11.7 s -1 at -0.55 V (vs reversible hydrogen electrode (RHE)), two orders of magnitude higher than Ni nanoparticles supported on CNTs.

36 MATERIALS SCIENCE↗
DOE OSTI2019

One-Nanometer-Thick Pt 3 Ni Bimetallic Alloy Nanowires Advanced Oxygen Reduction Reaction: Integrating Multiple Advantages into One Catalyst

Developing highly active as well as durable oxygen reduction reaction (ORR) electrocatalysts are still imperative for clean and efficient energy conversion device, such as fuel cells and metal-air battery. For this purpose and maximize the utilization of noble Pt, we present here a facile, yet scalable strategy for the high-precise synthesis of 1-nm-thick Pt 3 Ni bimetallic alloy nanowires (Pt 3 Ni BANWs). The seed-mediated growth mechanism of Pt 3 Ni BANWs was identified subsequently. As expected, the Pt 3 Ni BANWs delivered enhanced mass activity (0.546 A mgPt –1 , exceeding the 2020 target of DOE) in comparison to Pt nanowires assembly (Pt NWA, 0.098 A mgPt –1 ) and Pt/C (Pt, 0.135 A mgPt –1 ), because of the rational integration of multiple compositional and structural advantages. Moreover, the Pt 3 Ni BANWs displayed enhanced durability (37% MA retention) than Pt NWA and Pt after 50 000 potential cycles. All these results indicate that the ultrathin Pt 3 Ni BANWs are potential candidates for catalyzing ORR with acceptable activity and durability. In conclusion, the present work could not only provide a facile strategy but also a general guidance for the design of superb performance Pt-based nanowire catalysts for ORR.

25 ENERGY STORAGE↗
DOE OSTI2026

Effect of Initiator Density, Catalyst Concentration, and Surface Curvature on the Uniformity of Polymers Grafted from Spherical Nanoparticles

Polymer-grafted nanoparticles (PGNPs) are versatile hybrid materials whose properties critically depend on brush dimensions, uniformity, and grafting density. Herein, we systematically investigated how initiator density, catalyst concentration, and nanoparticle curvature govern the growth of poly(methyl methacrylate) (PMMA) brushes grafted from spherical SiO 2 nanoparticles via surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET ATRP). By tuning the initiator density through a combination of “active” and “dummy” silane initiators anchored on the nanoparticles’ surface and controlling the catalyst concentration, we reveal that increased initiator crowding and smaller surface curvature amplify steric hindrance, leading to decreased initiation efficiency and broader molecular weight distributions. Correlation with the corresponding unattached chains by ARGET ATRP suggests the presence of permanently inaccessible (“buried”) initiation sites, which are a characteristic of surface-grafted systems. At sufficient Cu catalyst concentrations, uniform brush growth is attained across different initiator densities, whereas decreased catalyst concentrations accentuate nonconcurrent initiation and propagation. These findings provide mechanistic insights into the interplay of initiator density, catalyst concentration, and surface curvature, offering design principles for tailoring the PGNP architecture. These results can guide the structural engineering of densely grafted surfaces, including nanoparticles and flat substrates, for applications in nanocomposites, photonics, and functional coatings.

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

Bio-inspired Iron Catalysts for Hydrocarbon Oxidations

Stereoselective oxidation of C–H and C=C bonds are catalyzed by nonheme iron enzymes. Inspired by these bioinorganic systems, our group has been exploring the use of nonheme iron complexes as catalysts for the oxidation of hydrocarbons using H2O2 as an environmentally friendly and atom-efficient oxidant in order to gain mechanistic insights into these novel transformations. In particular, we have focused on clarifying the nature of the high-valent iron oxidants likely to be involved in these transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Development of a reactor with carbon catalysts for modular-scale, low-cost electrochemical generation of H 2 O 2

The development of small-scale, decentralized reactors for H 2 O 2 production that can couple to renewable energy sources would be of great benefit, particularly for water purification in the developing world. Herein, we describe our efforts to develop electrochemical reactors for H 2 O 2 generation with high Faradaic efficiencies of >90%, requiring cell voltages of only ~1.6 V. The reactor employs a carbon-based catalyst that demonstrates excellent performance for H 2 O 2 production under alkaline conditions, as demonstrated by fundamental studies involving rotating-ring disk electrode methods. Finally, the low-cost, membrane-free reactor design represents a step towards a continuous, modular-scale, de-centralized production of H 2 O 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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 OSTI2018

Layered double hydroxides with atomic-scale defects for superior electrocatalysis

Atomic composition tuning and defect engineering are effective strategies to enhance the catalytic performance of multicomponent catalysts by improving the synergetic effect; however, it remains challenging to dramatically tune the active sites on multicomponent materials through simultaneous defect engineering at the atomic scale because of the similarities of the local environment. Here in this paper, using the oxygen evolution reaction (OER) as a probe reaction, we deliberately introduced base-soluble Zn(II) or Al(III) sites into NiFe layered double hydroxides(LDHs), which are one of the best OER catalysts. Then, the Zn(II) or Al(III) siteswere selectively etched to create atomic M(II)/M(III) defects, which dramatically enhanced the OER activity. At a current density of 20 mA·cm -2 , only 200 mV overpotential was required to generate M(II) defect-rich NiFe LDHs, which is the best NiFe-based OER catalyst reported to date. Density functional theory(DFT) calculations revealed that the creation of dangling Ni–Fe sites (i.e., unsaturated coordinated Ni–Fe sites) by defect engineering of a Ni–O–Fe site at the atomic scale efficiently lowers the Gibbs free energy of the oxygen evolution process. This defect engineering strategy provides new insights into catalysts at the atomic scale and should be beneficial for the design of a variety of catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Performance of Polymer Electrolyte Membrane Water Electrolysis Systems: Configuration, Stack Materials, Turndown and Efficiency

A cell model is developed and validated to analyze the performance of polymer electrolyte membrane water electrolysis (PEMWE) stacks and systems. It is used to characterize the oxygen evolution reaction (OER) activity on a TiO2-supported IrO2 catalyst and an unsupported IrO2 powder catalyst. Electrochemical, stack, and system thermoneutral potentials are defined and determined for isothermal and non-isothermal stack operation. Conditions are determined under which the system thermoneutral potential or flammability of H2 in the O2 anode stream limits the stack turndown and operating temperature. Performance is analyzed of a complete PEMWE system with an electrolyzer stack containing an IrO2/TiO2 anode catalyst (2 mg/cm2 Ir loading) and N117-like membrane mitigated for H2 crossover, anode balance-of-plant (BOP) components, cathode BOP system with temperature swing adsorption for H2 purification, and electrical BOP system with transformer and rectifier. At the rated power condition, defined as 2 A/cm2 at 1.9 V, 80 °C, and 30 bar H2 pressure, the stack/system efficiency is 65.3%/60.3% at beginning of life (BOL), decreasing to 59.3%/53.9% at end of life (EOL). The peak stack/system efficiency is 76.3%/70.2% at BOL, decreasing to 71.2%/65.6% at EOL. Improvements in catalyst activity and membrane are identified for a 50% increase in current to 3 A/cm2 at 1.8 V.

36 MATERIALS SCIENCE↗