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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Ultra-high-performance core–shell structured Ru@Pt/C catalyst prepared by a facile pulse electrochemical deposition method

Core–shell structured catalysts, made by placing either a monolayer or a thin layer of a noble metal on relatively cheap core-metal nanoparticles, are fascinating and promising fuel cell catalysts due to their high utilization of noble metals. Here, we report our development of a core–shell structured catalyst, Ru@Pt/C, generated by a novel and facile pulse electrochemical deposition (PED) approach. We demonstrate that compared with a commercial Pt/C catalyst, this novel catalyst achieves over four times higher mass activity towards the anodic oxidation of methanol, and 3.6 times higher mass activity towards the cathodic reduction of oxygen. Importantly, we find that the intrinsic activity of Pt in this Ru@Pt/C catalyst is doubled due to the formation of the core–shell structure. The catalyst also shows superior stability: even after 2000 scans, it still retains up to 90% of the peak current. As a result, our findings demonstrate that this novel PED approach is a promising method for preparing high-performance core–shell catalysts for fuel cell applications.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2016

Design and synthesis of model and practical palladium catalysts using atomic layer deposition

Here, we investigated the “one-batch” synthesis of model and practical palladium catalysts using atomic layer deposition (ALD). Two types of model catalysts and one type of powder-based nanocatalyst were synthesized simultaneously by ALD under viscous flow conditions. In addition, Pd/TiO 2 (110) model catalysts were prepared by the identical ALD process but under ultrahigh vacuum conditions. Because of the self-limiting surface reaction that defines ALD, the local structure of all the Pd catalysts were essentially the same as confirmed by a suite of microscopic and spectroscopic characterization techniques. A comprehensive understanding of the Pd-based catalysts was achieved by applying both surface science probes and advanced synchrotron techniques, and by strategically selecting the catalyst substrate best suited for each characterization. Both X-ray absorption spectroscopy and X-ray resonant photoelectron spectroscopy suggested that Pd only weakly interacted with the TiO 2 support. The one-batch synthesis approach facilitated by ALD can potentially bridge the “synthesis gap” between model catalysts and practical catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

In situ , operando studies on the size and structure of supported Pt catalysts under supercritical conditions by simultaneous synchrotron-based X-ray techniques

To control the size and structure of supported Pt catalysts, the influence of additional metal particles and the effect of supports were elucidated during the cracking reaction of n-dodecane under supercritical reaction conditions. The dynamical changes in nanocatalysts and catalytic activity are studied under realistic reaction conditions by using a combination of simultaneous temperature-programmed heating, in situ Small Angle X-ray Scattering (SAXS) and X-ray Absorption Near Edge Structure (XANES). In situ SAXS results indicate that the stability of the catalysts increases with Sn concentration. In situ XANES analysis reveals that the degree of oxidation and the electronic states of catalysts are dependent on the amount of Sn. Carbonaceous deposits over spent catalysts were characterized by Raman spectroscopy, suggesting that the highest Sn loading inhibits the formation of disordered graphitic lattices, which leads to an increased catalytic activity. SiO 2 , γ-Al 2 O 3 and Mg(Al)Ox were employed as supports to investigate the support effect on the stability of Pt catalysts. In situ SAXS and XANES findings clearly reflect the improved stability of catalysts on γ-Al 2 O 3 and Mg(Al)Ox supports compared to Pt catalysts on SiO 2 and the electronic states of catalysts are strongly influenced by support materials.

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

Methanol tolerance of atomically dispersed single metal site catalysts: mechanistic understanding and high-performance direct methanol fuel cells

Proton-exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are promising power sources from portable electronic devices to vehicles. The high-cost issue of these low-temperature fuel cells can be primarily addressed by using platinum-group metal (PGM)-free oxygen reduction reaction (ORR) catalysts, in particular atomically dispersed metal–nitrogen–carbon (M–N–C, M = Fe, Co, Mn). Furthermore, a significant advantage of M–N–C catalysts is their superior methanol tolerance over Pt, which can mitigate the methanol cross-over effect and offer great potential of using a higher concentration of methanol in DMFCs. In this work, we investigated the ORR catalytic properties of M–N–C catalysts in methanol-containing acidic electrolytes via experiments and density functional theory (DFT) calculations. FeN 4 sites demonstrated the highest methanol tolerance ability when compared to metal-free pyridinic N, CoN 4 , and MnN 4 active sites. The methanol adsorption on MN 4 sites is even strengthened when electrode potentials are applied during the ORR. The negative influence of methanol adsorption becomes significant for methanol concentrations higher than 2.0 M. However, the methanol adsorption does not affect the 4e - ORR pathway or chemically destroy the FeN 4 sites. The understanding of the methanol-induced ORR activity loss guides the design of promising M–N–C cathode catalyst in DMFCs. Accordingly, we developed a dual-metal site Fe/Co–N–C catalyst through a combined chemical-doping and adsorption strategy. Instead of generating a possible synergistic effect, the introduced Co atoms in the first doping step act as “scissors” for Zn removal in metal–organic frameworks (MOFs), which is crucial for modifying the porosity of the catalyst and providing more defects for stabilizing the active FeN 4 sites generated in the second adsorption step. The Fe/Co–N–C catalyst significantly improved the ORR catalytic activity and delivered remarkably enhanced peak power densities (i.e., 502 and 135 mW cm -2 ) under H 2 –air and methanol–air conditions, respectively, representing the best performance for both types of fuel cells. Notably, the fundamental understanding of methanol tolerance, along with the encouraging DMFC performance, will open an avenue for the potential application of atomically dispersed M–N–C catalysts in other direct alcohol or ammonia fuel cells.

25 ENERGY STORAGE↗
DOE OSTI2020

Energetic decomposition yields efficient bimetallic Cu MOF-derived catalysts

Metal–organic frameworks (MOFs) have recently emerged as efficient self-sacrificial templates to fabricate porous carbon-supported metal nanoparticles (NPs). Due to observed increased activity, catalysts containing bimetallic NPs represent an active frontier for heterogeneous catalyst development. A strategy to synthesize active catalysts with highly dispersed bimetallic metal/metal oxides within a porous carbon matrix via rapid MOF decomposition using dopants is presented in this paper. A 2,4,6-trinitrotoluene (TNT) additive enhances the rapid thermolysis of the metal-doped Cu-based MOFs to minimize particle aggregation. Catalyst characterization reveals that a secondary metal increases dispersion of both metals over the carbon composite support. The catalyst preparation method influences both the metal particle size and oxidation state. Catalytic performance shows increased rates for 4-nitrophenol reduction even with <1 wt% of added secondary metal. Among the synthesized catalysts, the Ni–CuO@C bimetallic catalyst exhibits outstanding activity. This synthetic strategy is useful for creating highly efficient, robust, non-noble metal catalysts for development of sustainable chemical processes.

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

MOF-enabled confinement and related effects for chemical catalyst presentation and utilization

A defining characteristic of nearly all catalytically functional MOFs is uniform, molecular-scale porosity. MOF pores, linkers and nodes that define them, help regulate reactant and product transport, catalyst siting, catalyst accessibility, catalyst stability, catalyst activity, co-catalyst proximity, composition of the chemical environment at and beyond the catalytic active site, chemical intermediate and transition-state conformations, thermodynamic affinity of molecular guests for MOF interior sites, framework charge and density of charge-compensating ions, pore hydrophobicity/hydrophilicity, pore and channel rigidity vs. flexibility, and other features and properties. Collectively and individually, these properties help define overall catalyst functional behaviour. Here, this review focuses on how porous, catalyst-containing MOFs capitalize on molecular-scale confinement, containment, isolation, environment modulation, energy delivery, and mobility to accomplish desired chemical transformations with potentially superior selectivity or other efficacy, especially in comparison to catalysts in homogeneous solution environments.

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

Ethylene polymerization with a crystallographically well-defined metal–organic framework supported catalyst

The inherent crystallinity of metal–organic framework (MOF) catalysts offers the possibility to understand the structure of the active site at the molecular level. This property is often lacking in traditional amorphous supports. Cr-SIM-NU-1000, a MOF-supported Cr 3+ heterogeneous catalyst, is shown to be competent for ethylene polymerization after activation with AlEt 2 Cl (DEAC), producing crystalline linear polyethylene (PE). The polymer produced has a low polydispersity (D = 2.0), in marked contrast to the Phillips supported chromium catalyst, Cr@SiO 2 (D ~ 8–65). Cr-SIM-NU-1000 achieves a turnover frequency of 2.6 × 10 3 h –1 under 40 bar ethylene pressure at room temperature, with corresponding PE productivity of 1.3 × 10 5 g PE mol –1 Cr per h. Single crystal X-ray diffraction (SC-XRD) of the pre-catalyst was conducted by collecting a structure of alkyl aluminum (DEAC) co-catalyst treated Cr-SIM-NU-1000. This crystal structure provides insight into the interactions between DEAC co-catalyst and Cr active site, revealing a Cr–C bond after treatment with DEAC. Furthermore, DEAC is crystallographically resolved at the terminal oxy-ligands of the node and likely also exists within the window pores of the framework between nodes, based on electron density mapping. Cr-SIM-NU-1000 offers the opportunity to study a structurally well-defined olefin polymerization system, with atomically precise characterization of the pre-catalyst structure. Furthermore, this allows the proposal of a mechanism and feeds into future development of next-generation heterogeneous catalyst systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Stabilized open metal sites in bimetallic metal–organic framework catalysts for hydrogen production from alcohols

Liquid organic hydrogen carriers such as alcohols and polyols are a high-capacity means of transporting and reversibly storing hydrogen that demands effective catalysts to drive the (de)hydrogenation reactions under mild conditions. We employed a combined theory/experiment approach to develop MOF-74 catalysts for alcohol dehydrogenation and examine the performance of the open metal sites (OMS), which have properties analogous to the active sites in high-performance single-site catalysts and homogeneous catalysts. Methanol dehydrogenation was used as a model reaction system for assessing the performance of five monometallic M-MOF-74 variants (M = Co, Cu, Mg, Mn, Ni). Co-MOF-74 and Ni-MOF-74 give the highest H 2 productivity. However, Ni-MOF-74 is unstable under reaction conditions and forms metallic nickel particles. To improve catalyst activity and stability, bimetallic (NixMg 1-x )-MOF-74 catalysts were developed that stabilize the Ni OMS and promote the dehydrogenation reaction. An optimal composition exists at (Ni 0.32 Mg 0.68 )-MOF-74 that gives the greatest H2 productivity, up to 203 mL gcat -1 min -1 at 300 °C, and maintains 100% selectivity to CO and H 2 between 225–275 °C. The optimized catalyst is also active for the dehydrogenation of other alcohols. DFT calculations reveal that synergistic interactions between the open metal site and the organic linker lead to lower reaction barriers in the MOF catalysts compared to the open metal site alone. This work expands the suite of hydrogen-related reactions catalyzed by MOF-74 which includes recent work on hydroformulation and our earlier reports of aryl-ether hydrogenolysis. Moreover, it highlights the use of bimetallic frameworks as an effective strategy for stabilizing a high density of catalytically active open metal sites.

08 HYDROGEN↗
DOE OSTI2024

Demystifying group-4 polyolefin hydrogenolysis catalysis: Gaseous propane hydrogenolysis mechanism over the same catalysts

A kinetic/mechanistic investigation of gaseous propane hydrogenolysis over the single-site heterogeneous polyolefin depolymerization catalysts AlS/ZrNp 2 and AlS/HfNp 2 (AlS = sulfated alumina, Np = neopentyl), is use to probe intrinsic catalyst properties without the complexities introduced by time- and viscosity-dependent polymer medium effects. In a polymer-free automated plug-flow catalytic reactor, propane hydrogenolysis turnover frequencies approach 3,000 h −1 at 150 °C. Both catalysts exhibit approximately linear relationships between rate and [H 2 ] at substoichiometric [H 2 ] with rate law orders of 0.66 ± 0.09 and 0.48 ± 0.07 for Hf and Zr, respectively; at higher [H 2 ], the rates approach zero-order in [H 2 ]. Reaction orders in [C 3 H 8 ] and [catalyst] are essentially zero-order under all conditions, with the former implying rapid, irreversible alkane binding/activation. This rate law, activation parameter, and DFT energy span analysis support a scenario in which [H 2 ] is pivotal in one of two plausible and competing rate-determining transition states—bimolecular metal-alkyl bond hydrogenolysis vs. unimolecular β-alkyl elimination. The Zr and Hf catalyst activation parameters, ΔH ‡ = 16.8 ± 0.2 kcal mol −1 and 18.2 ± 0.6 kcal mol −1 , respectively, track the relative turnover frequencies, while ΔS ‡ = −19.1 ± 0.8 and −16.7 ± 1.4 cal mol −1 K −1 , respectively, imply highly organized transition states. These catalysts maintain activity up to 200 °C, while time-on-stream data indicate multiday activities with an extrapolated turnover number ~92,000 at 150 °C for the Zr catalyst. This methodology is attractive for depolymerization catalyst discovery and process optimization.

03 NATURAL GAS↗
DOE OSTI2023

Ultra-thin ZrO 2 overcoating on CuO-ZnO-Al 2 O 3 catalyst by atomic layer deposition for improved catalytic performance of CO 2 hydrogenation to dimethyl ether

Abstract An ultra-thin overcoating of zirconium oxide (ZrO 2 ) film on CuO-ZnO-Al 2 O 3 (CZA) catalysts by atomic layer deposition (ALD) was proved to enhance the catalytic performance of CZA/HZSM-5 (H form of Zeolite Socony Mobil-5) bifunctional catalysts for hydrogenation of CO 2 to dimethyl ether (DME). Under optimal reaction conditions (i.e. 240 °C and 2.8 MPa), the yield of product DME increased from 17.22% for the bare CZA/HZSM-5 catalysts, to 18.40% for the CZA catalyst after 5 cycles of ZrO 2 ALD with HZSM-5 catalyst. All the catalysts modified by ZrO 2 ALD displayed significantly improved catalytic stability of hydrogenation of CO 2 to DME reaction, compared to that of CZA/HZSM-5 bifunctional catalysts. The loss of DME yield in 100 h of reaction was greatly mitigated from 6.20% (loss of absolute value) to 3.01% for the CZA catalyst with 20 cycles of ZrO 2 ALD overcoating. Characterizations including hydrogen temperature programmed reduction, x-ray powder diffraction, and x-ray photoelectron spectroscopy revealed that there was strong interaction between Cu active centers and ZrO 2 .

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

Catalyst Ammonia Storage Measurements Using Radio Frequency Sensing1

Motivated by increasingly strict nitrogen oxides (NOx) limits, engine manufacturers have adopted selective catalytic reduction (SCR) technology to reduce engine-out NOx. In the SCR process, NOx react with ammonia (NH3) to form nitrogen and water vapor. The reaction is influenced by several variables, including stored ammonia on the catalyst, exhaust gas composition, and catalyst temperature. Currently, measurements from NOx and/or NH3 sensors upstream and downstream of the SCR are used with predictive models to estimate ammonia storage levels on the catalyst and control urea dosing. This study investigated a radio frequency (RF)-based method to directly monitor the ammonia storage state of the SCR. This approach utilizes the catalyst as a cavity resonator, in which an RF antenna excites electromagnetic waves within the cavity to monitor changes in the catalyst state. Ammonia storage causes changes in the dielectric properties of the catalyst, which directly impacts the RF signal. Changes in the RF signal relative to stored ammonia (NH3) were evaluated over a wide range of frequencies, temperatures, and exhaust conditions. The RF response to NH3 storage, desorption, and oxidation on the SCR was well correlated with changes in the catalyst state. Calibrated RF measurements demonstrate the ability to monitor the adsorption state of the SCR to within 10% of the sensor full scale. The results indicate direct measurement of SCR ammonia storage levels, and resulting catalyst feedback control, via RF sensing to have significant potential for optimizing the SCR system to improve NOx conversion and decrease urea consumption.

Engineering↗
DOE OSTI2022

High-Platinum-Content Catalysts on Atomically Dispersed and Nitrogen Coordinated Single Manganese Site Carbons for Heavy-Duty Fuel Cells

Fuel cells for heavy-duty vehicles (HDVs) have attracted considerable attention because of their unique scalability, better fuel economy, the less demand for hydrogen refilling infrastructure. However, the potential application requires more stringent fuel cell durability up to 25,000 h. Membrane electrode assemblies (MEAs) made from platinum group metal (PGM) catalyst with relatively high loading 0.3 mgPt cm –2 play a crucial role in ensuring high-power and long-term durability. Integrating fine PGM nanoparticles and robust carbon support with strengthened interactions is critical for improving MEA performance and durability. Herein, a unique atomically dispersed and nitrogen coordinated single Mn site-rich carbon (M–N–C) support was developed for high content (40 wt%) platinum catalysts for the oxygen reduction reaction (ORR) cathode with reduced thickness. Compared with two controls studied in this work (e.g., a porous graphitic carbon-supported Pt and a commercial TKK Pt/C catalysts), the Pt (40 wt%)/Mn–N–C catalyst exhibited much enhanced catalytic activity and stability for the ORR in both aqueous acidic electrolyte and polymer electrolyte-based MEA. Here, we carefully elucidated the—role of the Mn–N–C support in promoting Pt catalyst concerning its high surface area, partially graphitic structure, and nitrogen dopants, providing better Pt nanoparticle dispersion, and strengthened interactions between Pt and carbon. Consequently, the MEA from the Pt (40 wt%)/Mn–N–C catalyst generated a 1.61 A cm –2 at 0.7 V based on HDV conditions (0.2 mgPt cm –2 and 250 kPa air). More importantly, the MEA is highly durable and can retain 1.31 A cm –2 at 0.7 V after 30,000 voltage cycles (~19% loss), surpassing the commercial Pt/C catalyst (loss of ~56%). Therefore, the Mn–N–C carbon-supported Pt catalyst holds a great promise to meet the challenging DOE target (1.07 A cm –2 at 0.7 V after 150,000 cycles) for HDVs.

25 ENERGY STORAGE↗
DOE OSTI2024

Simulated Start-Stop and the Impact of Catalyst Layer Redox on Degradation and Performance Loss in Low-Temperature Electrolysis

Stress tests are developed that focus on anode catalyst layer degradation in proton exchange membrane electrolysis due to simulated start-stop operation. Ex situ testing indicates that repeated redox cycling accelerates catalyst dissolution, due to near-surface reduction and the higher dissolution kinetics of metals when cycling to high potentials. Similar results occur in situ, where a large decrease in cell kinetics (>70%) is found along with iridium migrating from the anode catalyst layer into the membrane. Additional processes are observed, however, including changes in iridium oxidation, the formation of thinner and denser catalyst layers, and platinum migration from the transport layer. Increased interfacial weakening is also found, adding to both ohmic and kinetic loss by adding contact resistances and isolating portions of the catalyst layer. Repeated shutoffs of the water flow further accelerate performance loss and increase the frequency of tearing and delamination at interfaces and within catalyst layers. These tests were applied to several commercial catalysts, where higher loss rates were observed for catalysts that contained ruthenium or high metal content. These results demonstrate the need to understand how operational stops occur, to identify how loss mechanisms are accelerated, and to develop strategies to limit performance loss.

08 HYDROGEN↗
DOE OSTI2017

Enhanced MEA Performance for PEMFCs under Low Relative Humidity and Low Oxygen Content Conditions via Catalyst Functionalization

This work demonstrates that functionalizing annealed-Pt/Ketjen black EC300j (a-Pt/KB) and dealloyed-PtNi/Ketjen black EC300j (d-PtNi/KB) catalysts using p-phenyl sulfonic acid can effectively enhance performance in the membrane electrode assemblies (MEAs) of proton exchange membrane fuel cells (PEMFCs). The functionalization increased the size of both Pt and PtNi catalyst particles and resulted in the further leaching of Ni from the PtNi catalyst while promoting the formation of nanoporous PtNi nanoparticles. The size of the SO3H-Pt/KB and SO3H-PtNi/KB carbon-based aggregates decreased dramatically, leading to the formation of catalyst layers with narrower pore size distributions.MEA tests highlighted the benefits of the surface functionalization, in which the cells with SO3H-Pt/KB and SO3H-PtNi/KB cathode catalysts showed superior high current density performance under reduced RH conditions, in comparison with cells containing annealed Pt/KB (a-Pt/KB) and de-alloyed PtNi/KB (d-PtNi/KB) catalysts. The performance improvement was particularly evident when using reactant gases with low relative humidity, indicating that the hydrophilic functional groups on the carbon improved the water retention in the cathode catalyst layer. These results show a new avenue for enhancing catalyst performance for the next generation of catalytic materials for PEMFCs.

Xin, Le↗
DOE OSTI2014

Bio-inspired MOF-based Catalysts for Lignin Valorization.

Lignin is a potentially plentiful source of renewable organics, with %7E50Mtons/yr produced by the pulp/paper industry and 200-300 Mtons/yr projected production by a US biofuels industry. This industry must process approximately 1 billion tons of biomass to meet the US Renewable Fuel goals. However, there are currently no efficient processes for converting lignin to value-added chemicals and drop-in fuels. Lignin is therefore an opportunity for production of valuable renewable chemicals, but presents staggering technical and economic challenges due to the quantities of material involved and the strong chemical bonds comprising this polymer. Aggressive chemistries and high temperatures are required to degrade lignin without catalysts. Moreover, chemical non-uniformity among lignins leads to complex product mixtures that tend to repolymerize. Conventional petrochemical approaches (pyrolysis, catalytic cracking, gasification) are energy intensive (400-800 degC), require complicated separations, and remove valuable chemical functionality. Low-temperature (25-200 degC) alternatives are clearly desirable, but enzymes are thermally fragile and incompatible with liquid organic compounds, making them impractical for large-scale biorefining. Alternatively, homogeneous catalysts, such as recently developed vanadium complexes, must be separated from product mixtures, while many heterogenous catalysts involve costly noble metals. The objective of this project is to demonstrate proof of concept that an entirely new class of biomimetic, efficient, and industrially robust synthetic catalysts based on nanoporous Metal- Organic Frameworks (MOFs) can be developed. Although catalytic MOFs are known, catalysis of bond cleavage reactions needed for lignin degradation is completely unexplored. Thus, fundamental research is required that industry and most sponsoring agencies are currently unwilling to undertake. We introduce MOFs infiltrated with titanium and nickel species as catalysts for the C-O bond hydrogenolysis in model compounds, which mimic the b-O-4, a-O-4, and 4-O-5 linkages of natural lignin. The versatile IRMOF-74(n) series is proposed as a platform for creating efficient hydrogenolysis catalysts as it not only displays tunable pore sizes, but also has the required thermal and chemical stability. The catalytic C-O bond cleavage occurs at 10 bar hydrogen pressure and temperatures as low as 120 degC. The conversion efficiency of the aromatic ether substrates into the corresponding hydrocarbons and phenols varies as PhCH 2 CH 2 OPh > PhCH 2 OPh > PhOPh (Ph = phenyl), while the catalytic activity generally follows the following trend Ni@IRMOF-74>Ti@IRMOF-74>IRMOF-74. Conversions as high as 80%, coupled with good selectivity for hydrogenolysis vs. hydrogenation, highlight the potential of MOF-based catalysts for the selective cleavage of recalcitrant aryl-ether bonds found in lignin and other biopolymers. This project supports the DOE Integrated Biorefinery Program goals, the objective of which is to convert biomass to fuels and high-value chemicals, by addressing an important technology gap: the lack of low-temperature catalysts suitable for industrial lignin degradation. Biomass, which is %7E30 wt% lignin, constitutes a potentially major source of platform chemicals that could improve overall profitability and productivity of all energy-related products, thereby benefiting consumers and reducing national dependence on imported oil. Additionally, DoD has a strong interest in low-cost drop-in fuels (Navy Biofuel Initiative) and has signed a Memorandum of Understanding with DOE and USDA to develop a sustainable biofuels industry.

Allendorf, Mark D.↗
DOE OSTI2016

Final Report of a CRADA Between Pacific Northwest National Laboratory and Cummins, Incorporated (CRADA No.PNNL/283): “Enhanced High and Low Temperature Performance of NO x Reduction Catalyst Materials”

The NO x Storage-Reduction (NSR, also known as lean-NO x trap – LNT), is based upon the concept of storing NO x as nitrates over storage components, typically barium species, during a lean-burn operation cycle and then reducing the stored nitrates to N 2 during fuel-rich conditions over a precious metal catalyst [1]. NO x Selective Catalytic Reduction (SCR), on the other hand, is accomplished by deliberately introducing reductant urea into the engine exhaust to reduce NO x with the aid of a Cu(Fe)/zeolite catalyst [2]. These two technologies have been recognized as the most promising approaches for meeting stringent NO x emission standards for diesel vehicles within the Environmental Protection Agency’s (EPA’s) 2007/2010 mandated limits. For NSR, problems arising from either or both thermal and SO 2 deactivation must be addressed to meet durability standards. For SCR, SO 2 deactivation is less of an issue, but hydrothermal deactivation of the zeolite catalysts must be addressed. With continuing R&D efforts in advanced powertrains, highly novel operating modes for internal combustion engines (ICEs) are being researched in order to meet the very stringent new demands for fuel efficiency (e.g., U.S. ‘‘CAFE’’ standards for average miles/gallon are scheduled to increase dramatically over the next 10–15 years). These new ICE engine operation modes, while highly fuel-efficient, result in much lower exhaust temperatures than current engines; temperatures so low that it is hard to imagine how the current catalytic emission control technologies will be able to function. For example, while steady-state operation of the NO x reduction technology at 150 °C may be required, current ‘‘light-off’’ temperatures for CHA-based zeolite catalysts are closer to 200 °C. Therefore, understanding low-temperature limitations in NO x reduction has become one of the most daunting challenges in R&D on new catalyst materials and processes that can effectively eliminate emissions at these quite low exhaust temperatures. This project has two clear focuses: (1) development of potassium-based high-temperature NSR materials, and studying their key causes of deactivation and methods of regeneration. By comparing results obtained on ‘Simple Model’ Pt-K/Al 2 O 3 with ‘Enhanced Model’ Pt-K/ MgAlO x and Pt-K/TiO 2 materials, we have developed an understanding of the role of various additives on the deactivation and regeneration processes. Studies have also been performed on the real commercial samples being used in a Dodge Ram truck with a Cummins diesel emission control system. However, the results about these ‘commercial samples’ will not be covered in this report. Following a brief description of our experimental approach, we will present a few highlights from some of the work performed in this CRADA with more details about these results provided in publications/reports/presentations lists presented at the end of the report. (2) for the Cu and Fe/Chabazite SCR catalysts, since these are so newly developed and references from open literature and industry are nearly absent, our work started from zeolite synthesis and catalyst synthesis methodology development, before research on their low- and high-temperature performance, deactivation, regeneration, etc. was conducted. Again, most work reported here is based on our “model” catalysts synthesized in-house. Work done on the ‘commercial samples’ will not be covered in this report.

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

Platinum Group Metal Catalysts: Supply Chain Deep Dive Assessment

The report “America’s Strategy to Secure the Supply Chain for a Robust Clean Energy Transition” lays out the challenges and opportunities faced by the United States in the energy supply chain as well as the federal government plans to address these challenges and opportunities. It is accompanied by several issue-specific deep dive assessments, including this one, in response to Executive Order 14017 “America’s Supply Chains,” which directs the Secretary of Energy to submit a report on supply chains for the energy sector industrial base. The Executive Order is helping the federal government to build more secure and diverse U.S. supply chains, including energy supply chains. This report focuses on the supply chain for catalysts, specifically platinum group metal (PGM) catalysts, used for decarbonizing energy technologies. Catalysts are substances that increase the rate, conversion, and selectivity of chemical reactions and are used in a variety of applications such as chemical manufacturing, petroleum refining, and catalytic converters. Catalysts containing PGMs (“PGM catalysts”) are particularly useful in widespread industrial applications, including the production of high-volume chemicals such as ammonia, acetic acid, nitric acid, and the refining of crude oil into petroleum products. The PGM metals possess extraordinary properties such as being active oxidation and hydrogenation catalysts; excellent electrical conductors and electrodes; and outstanding adsorbers of oxygen and hydrogen. Within the energy industrial base, PGM catalysts improve the energy and materials efficiency of petroleum refining and chemical industry processes and reduce energy consumption in manufacturing. In addition to their use in catalytic converters, PGM catalysts are important to maximizing the efficiency of emerging decarbonization technologies, specifically in proton exchange membrane (PEM) electrolyzers for green hydrogen production from water and PEM fuel cells for transportation and stationary energy storage. Green hydrogen is expected to play a significant role in decarbonization scenarios.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2015

Catalyst-Based Nonchemical Water Treatment System Frank E. Moss US Courthouse Salt Lake City, Utah

In 2012 and 2013, the US General Services Administration (GSA) and Oak Ridge National Laboratory conducted an evaluation of a novel nonchemical water treatment (NCWT) system at the Frank E. Moss US Courthouse in Salt Lake City, Utah. This system purports to use a proprietary metallic catalyst to change the water’s chemistry such that hard calcite does not form on surfaces that are in contact with the water. The catalyst-based NCWT system was installed on an electric domestic water heater in the courthouse. 1 This water heater had been experiencing severe calcite buildup on the heating elements. The calcite buildup impeded heat transfer from the heating elements into the domestic water, leading to the thermostat being set excessively high in an attempt to maintain the water temperature. This caused excess heat to build up on the elements, resulting in their premature failure which required frequent replacement. The buildup also required the elements to stay energized constantly to produce enough heat to maintain temperature in the domestic hot water system. After installing the catalyst-based NCWT system, calcite buildup was dramatically reduced and failure of the elements ceased. Labor and material savings from not having to replace the elements ($\$$1,060/year) allow for less than a two-year simple payback when compared to the installed cost of the system ($\$$1,692) plus minimal annual maintenance ($\$$100/year). The catalyst-based NCWT system should be considered for deployment in any heating system that is subject to calcification, including hydronic heating systems and boilers, condensing boilers, gas water heaters, and electric water heaters. Had the catalyst-based NCWT technology not been installed on the water heater, a conventional salt-based calcite prevention system would have provided the same prevention of calcite buildup. The budget installed cost of such a system would have been $\$$3,200 plus $\$$350/year in chemicals and $\$$1,500/year labor to service the chemicals. Comparing the conventional to the catalyst-based system, the latter has both a lower installed cost and annual operating cost. The original test plan was to install the technology on both the domestic water heating system and on the site’s cooling tower, which had faced calcite issues in its history. This tower has had a calcite buildup problem that is currently being addressed with a salt-based treatment system. The project’s timeline did not allow for installing a system and testing it on the tower during the initial phase of this project in 2012 and 2013. A preliminary economic analysis was performed to estimate the installed cost and potential savings on the cooling tower. If installed on the site’s cooling tower, the installed cost of the catalyst-based system would be more expensive than the salt-based system ($\$$32,380 vs. $\$$2,700 for the salt-based). However, the salt-based system requires $\$$900/year in chemicals and $\$$3,900/year in labor, neither of which is needed by the catalyst based system. This would give a simple payback of less than seven years using the technology on a cooling tower.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗