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Electrochemical Reductive N-Methylation with CO 2 Enabled by a Molecular Catalyst
The development of benign methylation reactions utilizing CO 2 as a one-carbon building block would enable a more sustainable chemical industry. Electrochemical CO 2 reduction has been extensively studied, but its application for reductive methylation reactions remains out of the scope of current electrocatalysis. Here, in this work, we report the first electrochemical reductive N-methylation reaction with CO 2 and demonstrate its compatibility with amines, hydroxylamines, and hydrazine. Catalyzed by cobalt phthalocyanine molecules supported on carbon nanotubes, the N-methylation reaction proceeds in aqueous media via the chemical condensation of an electrophilic carbon intermediate, proposed to be adsorbed or near-electrode formaldehyde formed from the four-electron reduction of CO 2 , with nucleophilic nitrogenous reactants and subsequent reduction. By comparing various amines, we discover that the nucleophilicity of the amine reactant is a descriptor for the C-N coupling efficacy. We extend the scope of the reaction to be compatible with cheap and abundant nitro-compounds by developing a cascade reduction process in which CO 2 and nitro-compounds are reduced concurrently to yield N-methyl amines with high mono-methylation selectivity via the overall transfer of 12 electrons and 12 protons.
Simultaneous Capture and Conversion of CO 2 to Methanol via a Switchable Ionic Liquid and Low-Temperature Metal Catalyst (CRADA 449)
Advance development of the Integrated (Carbon Dioxide) CO 2 Capture and Conversion to Methanol (ICCCM) process, which is based on PNNL’s proprietary Carbon Dioxide Binding Organic Liquids (CO 2 BOLs) capture solvent technology for separating the CO 2 from dilute streams. Design, fabricate, and demonstrate a bench-scale ICCCM prototype for the continuous flow combined capture and catalytic conversion of CO 2 into methanol and assess viability for commercialization.
Development of a condenser for the dual catalyst water recovery system
Conceptual evaporation/condensation systems suitable for integration with the catalytic water recovery method were evaluated. The primary requirements for each concept were its capability to operate under zero-gravity conditions, condense recovered water from a vapor-noncondensable gas mixture, and integrate with the catalytic system. Specific energy requirements were estimated for concepts meeting the primary requirements, and the concept most suitable for integration with the catalytic system was proposed. A three-man rate condenser capable of integration with the proposed system, condensing water vapor in presence of noncondensables and transferring the heat of condensation to feed urine was designed, fabricated, and tested. It was treated with steam/air mixtures at atmospheric and elevated pressures and integrated with an actual catalytic water recovery system. The condenser has a condensation efficiency exceeding 90% and heat transfer rate of approximately 85% of theoretical value at coolant temperature ranging from 7 to 80 deg C.
A single-atom library for guided monometallic and concentration-complex multimetallic designs
Atomically dispersed single-atom catalysts have the potential to bridge heterogeneous and homogeneous catalysis. Dozens of single-atom catalysts have been developed, and they exhibit notable catalytic activity and selectivity that are not achievable on metal surfaces. Although promising, there is limited knowledge about the boundaries for the monometallic single-atom phase space, not to mention multimetallic phase spaces. Here, single-atom catalysts based on 37 monometallic elements are synthesized using a dissolution-and-carbonization method, characterized and analyzed to build the largest reported library of single-atom catalysts. In conjunction with in situ studies, we uncover unified principles on the oxidation state, coordination number, bond length, coordination element and metal loading of single atoms to guide the design of single-atom catalysts with atomically dispersed atoms anchored on N-doped carbon. We utilize the library to open up complex multimetallic phase spaces for single-atom catalysts and demonstrate that there is no fundamental limit on using single-atom anchor sites as structural units to assemble concentration-complex single-atom catalyst materials with up to 12 different elements. Furthermore, our work offers a single-atom library spanning from monometallic to concentration-complex multimetallic materials for the rational design of single-atom catalysts.
Operando Spectroscopic and Kinetic Characterization of Aerobic Allylic C–H Acetoxylation Catalyzed by Pd(OAc) 2 /4,5-Diazafluoren-9-one
Allylic C–H acetoxylations are among the most widely studied palladium(II)-catalyzed C–H oxidation reactions. While the principal reaction steps are well established, key features of the catalytic mechanisms are poorly characterized, including the identity of the turnover-limiting step and the catalyst resting state. In this study, we report a mechanistic study of aerobic allylic acetoxylation of allylbenzene with a catalyst system composed of Pd(OAc) 2 and 4,5-diazafluoren-9-one (DAF). The DAF ligand is unique in its ability to support aerobic catalytic turnover, even in the absence of benzoquinone or other co-catalysts. Herein, we describe operando spectroscopic analysis of the catalytic reaction using X-ray absorption and NMR spectroscopic methods that allow direct observation of the formation and decay of a palladium(I) species during the reaction. Kinetic studies reveal the presence of two distinct kinetic phases: (1) a burst phase, involving rapid formation of the allylic acetoxylation product and formation of the dimeric Pd I complex [Pd I (DAF)(OAc)] 2 , followed by (2) a post-burst phase that coincides with evolution of the catalyst resting state from the Pd I dimer into a π-allyl-Pd II species. The data provide unprecedented insights into the role of ancillary ligands in supporting catalytic turnover with O 2 as the stoichiometric oxidant and establish an important foundation for the development of improved catalysts for allylic oxidation reactions.
Direct study of changes in catalyst structure-kinetic properties during redox transitions using a new time-resolved technique
Direct study of changes in catalyst structure-kinetic properties during redox transitions using a new time-resolved technique The Temporal Analysis of Products (TAP) pulse response methodology1 is a transient technique offering the time scale needed to deconvolve many reaction steps from the complex network typical to industrial catalytic processes. The traditional TAP measurement observes the gas phase dynamic response but, hereto now, has been devoid of any direct measurement of change in the catalyst itself. The development of an operando technique that couples gas phase transient kinetics to dynamic metal centers and surface species is presented. Significance Unification of the TAP methodology with time-resolved spectroscopic measurement can offer unprecedented insight into the complex kinetic phenomena regulated by the solid catalyst.
A Novel Hollow Fiber Membrane Reactor for High Purity H 2 Generation from Thermal Catalytic NH 3 Decomposition (Final Report)
Ammonia (NH 3 ), as a promising carbon neutral liquid fuel (CNLF) and an effective H 2 source, can be synthesized from air and water (N 2 extracted from air and H 2 from water) using renewable energy sources. To produce H 2 as an intermediate, it is essential to develop effective and economic NH 3 decomposition technologies. We have been developing an innovative hollow fiber membrane reactor for high purity H 2 generation from thermal catalytic NH 3 decomposition. The objective of the proposed research is to fabricate a compact and robust prototype with high energy efficiency (>80%) to deliver high purity (>99%) H2 at high rate per volume (>0.15 g H 2 /h/cm 3 ) from NH3 decomposition at low temperature (<450 °C) and high conversion (>99%). Our overall technical approach is to effectively combine an active catalyst for NH 3 decomposition with a selective H 2 membrane separation process in a novel, compact modular system to generate high purity H 2 and simultaneously achieve high NH 3 conversion and optimize the entire system energy efficiency. This novel integrated membrane reactor design, together with low-cost, highly active Ru-based catalyst, makes it most appropriate for the project objective. The proposed applied research and development work, therefore, represents an innovative and transformational solution to H 2 generation from thermal catalytic NH 3 decomposition. During the course of our research we i) synthesized and characterized ruthenium(Ru)-based catalysts, evaluated their catalytic performance for NH 3 decomposition and optimized the catalyst composition and performance based on machine learning, ii) prepared SAPO-34, MFI membranes on α-alumina hollow fibers and measured their performance for H 2 /N 2 , H 2 /N 2 /NH 3 separation and evaluated carbon molecular sieve (CMS) and Pd/Ag membranes for H 2 /N 2 , H 2 /N 2 /NH 3 separation at different conditions, iii) designed and evaluated several types of membrane reactors for H 2 production from NH 3 decomposition, and iv) evaluated the H 2 delivery cost base on catalysts development, membrane development and membrane reactor. For 3,1,12 RuYK catalyst, H 2 productivity of 6.35 mmol/min/gcat with NH 3 conversion of 95~98% was achieved at 5 bar and 400 °C; for SAPO-34 membrane, the best membrane showed H 2 permeance of 7.56×10 -7 mol/(m 2 ∙s∙Pa) and H 2 /N 2 selectivity of 23.1 at 20 °C; For CMS and Pd/Ag membranes, both showed superior stability for 71%H 2 /24%N 2 /5%NH 3 mixture separation at 450 °C and 7 bar for over 120 h; for the membrane reactor, high H 2 purity of >99.99% with NH 3 conversion of >99.4% were achieved in Pd/Ag membrane reactor at 450 °C, and the NH 3 concentration was always below 10 ppb in H 2 product. The H 2 generation rate was calculated to be as high as 0.47 g/h/cm 3 and the energy efficiency was calculated to be 88%. The membrane reactor showed superior stability for over 370 h and high H 2 purity, H 2 production rate and NH 3 conversion. Based on calculation, the H 2 delivery cost can be as low as $3.66/kg.
Markovnikov-Selective Hydroboration of Olefins Catalyzed by a Copper N-Heterocyclic Carbene Complex
The efficient and atom-economical hydroboration of alkenes and alkynes using an N-heterocyclic carbene (NHC) copper hydroxide catalyst has been developed here. An equimolar combination of substrate and HBpin allows for the selective Markovnikov hydroboration of alkenes and alkynes. A variety of functional groups were tolerated in good to excellent yield. This system highlights a facile reaction setup, atom economy, high selectivity, and an easily synthesized copper–NHC catalyst.
Dimethyl Carbonate: Review of Synthesis Routes and Catalysts Used
This review summarizes the performance of potential catalysts for the synthesis of dimethyl carbonate (DMC) using CO2 as a feedstock by two major processes—the direct route of carbonylation of alcohols and the indirect route of alcoholysis of urea. The reaction mechanisms and corresponding catalysts that were previously investigated are discussed. The major challenges associated with the conversion of CO2 to DMC are the low yields, low DMC selectivity, and thermodynamic limitations (alcohol carbonylation) of reversible reactions with low equilibrium constants. This occurs mainly due to the highly stable carbon dioxide molecules. The development of novel catalysts with high yields and high selectivity needs to be studied to overcome these technical challenges. In addition, to enhance the DMC yield, the use of dehydrating agents for water removal from the reaction mixture is recommended and discussed in detail in this article. This review critically examines the different catalysts used by investigators, along with their respective operating conditions and suitability in applications for the commercial synthesis of CO2-based DMC.
Acetic Acid/Propionic Acid Conversion on Metal Doped Molybdenum Carbide Catalyst Beads for Catalytic Hot Gas Filtration
Catalytic hot gas filtration (CHGF) is used to precondition biomass derived fast pyrolysis (FP) vapors by physically removing reactive char and alkali particulates and chemically converting reactive oxygenates to species that are more easily upgraded during subsequent catalytic fast pyrolysis (CFP). Carboxylic acids, such as acetic acid and propionic acid, form during biomass fast pyrolysis and are recalcitrant to downstream catalytic vapor upgrading. This work developed and evaluated catalysts that can convert these acids to more upgradeable ketones at the laboratory scale. Selective catalytic conversion of these reactive oxygenates to more easily upgraded compounds can enhance bio-refinery processing economics through catalyst preservation by reduced coking from acid cracking, by preserving carbon efficiency, and through process intensification by coupling particulate removal with partial upgrading. Two metal-doped molybdenum carbide (Mo2C) supported catalyst beads were synthesized and evaluated and their performance compared with an undoped Mo2C control catalyst beads. For laboratory scale acetic acid conversion, calcium doped Mo2C supported catalyst beads produced the highest yield of acetone at ~96% at 450 °C among undoped and Ca or Ni doped catalysts.
The TASAR Project: Launching Aviation on an Optimized Route Toward Aircraft Autonomy
The Traffic Aware Strategic Aircrew Request (TASAR) concept applies onboard automation for the purpose of advising the pilot of route modifications that would be beneficial to the flight. Leveraging onboard computing platforms with connectivity to avionics and diverse data sources on and off the aircraft, TASAR introduces a new, powerful capability for in-flight trajectory management to the cockpit and its flight crew that is anticipated to induce a significant culture change in airspace operations. Flight crews empowered by TASAR and its derivative technologies could transform from today’s flight plan followers to proactive trajectory managers, taking an initial critical step towards increasing autonomy in the airspace system. TASAR was developed as a catalyst for operational autonomy, a future vision where the responsibilities and authorities of trajectory management reside with the aircraft operator and are distributed among participating aircraft, thus fulfilling a vision dating back decades and enabling a fully scalable airspace system. This NASA Technical Paper maps TASAR to its foundational vision and traces its research and development from initial concept generation to an operational evaluation by a U.S. airline in revenue service, the final stage before technology transfer and commercialization.
Developing a microwave-driven reactor for ammonia synthesis: insights into the unique challenges of microwave catalysis
Rapid development of new ammonia (NH 3 ) synthesis techniques that enable modular, intermittent production is essential to actualizing NH 3 's potential as a clean energy carrier, since contemporary methods are configured to centralized, continuous production methods with high emissions and are incompatible with renewable sources. Here, in this mission, microwave-driven catalysis is promising for its ability to enhance reaction kinetics and apply targeted heating for efficient energy use. However, owing to an incomplete understanding of the interaction between microwave fields and catalyst beds, the development of such microwave-catalysis systems remains underexplored and challenging. This paper investigates the 10× scale-up of a microwave-based NH 3 synthesis reactor using numerical and experimental approaches, achieving the largest reported microwave-driven NH 3 reactor to date. Results elucidate phenomena unique to microwave processes that are only predictable through numerical modeling, including how a catalyst's dielectric properties influence microwave field distribution by affecting penetration depth and how energy utilization can be poor even with sufficient attenuation. These dynamics change with scale, constrain reactor geometry, and potentially hamper performance. Nonetheless, we demonstrate a production rate of 56.6 g NH$_3$ per day, the highest reported NH 3 synthesis rate for laboratory-scale alternative techniques; correspondingly, the benchmark energy efficiency achieved in this paper (45.6 g NH$_3$ kW h -1 ) is the highest reported for such reactors of sufficient scale. Even with this exemplary energy efficiency, energy losses were found in excess of 50%, an issue resolvable through scale and reactor design. The efficiencies imparted by microwaves were key in these achievements, warranting further investigation toward development of microwave-driven NH 3 systems.
BETO 2021 Peer Review - Catalytic Upgrading of Pyrolysis Vapors 2.3.1.314
Catalytic fast pyrolysis (CFP) is a versatile pathway for the direct liquefaction of biomass and waste carbon sources to generate a stabilized bio-oil intermediate that can be further processed into renewable fuels, chemicals, and materials. The objective of this project is advance the CFP state-of-technology through integrated catalyst and process development, expand market responsiveness by creating routes to novel co-products, and provide experimental data to inform process modelling and scale-up activities. Research advancements over the past two years include reducing analytical uncertainty by achieving 100 ± 1% carbon balances during reaction testing with woody biomass, improving process efficiency by achieving a 4x increase in catalyst cycle length, demonstrating compatibility with waste feedstocks, and confirming process durability for 100+ reaction cycles. Additionally, this project supported a comprehensive pathway review to evaluate scale-up needs. This review resulted in the early identification of technical risks and informed proactive planning for the BETO 2022 Verification. Other impacts from this project include generation of broadly enabling scientific knowledge (14 publications/18 presentations since 2019), engagement with industry partners (e.g., Johnson Matthey and ExxonMobil), and identification of a promising pathway to market that addresses emerging demands for biogenic refinery feedstocks.
BETO 2021 Peer Review - Overview of the Chemical Catalysis for Bioenergy Consortium
Catalysis plays a central role in converting biomass and carbon-rich waste feedstocks into fuels and chemicals; however, critical catalysis challenges exist that are limiting commercialization of emerging bioenergy technologies. By leveraging unique U.S. Department of Energy National Laboratory capabilities and expertise, the Chemical Catalysis for Bioenergy consortium seeks to overcome these catalysis challenges and accelerate the catalyst and process development cycle. The foundation of the consortium consists of an integrated and collaborative portfolio of catalytic technologies and enabling capabilities, which positions ChemCatBio to address both technology-specific and overarching catalysis challenges across the development cycle from discovery to scale-up. The core catalysis projects target technological advancements for specific conversion processes, such as catalytic upgrading of biochemical process intermediates, catalytic fast pyrolysis, C1 and C2 upgrading, and electrochemical CO2 reduction, while the enabling technologies provide access to world-class capabilities and expertise in computational modeling, materials synthesis, advanced in situ and in operando catalyst characterization, and catalyst design tools.
Long-term durability test of highly efficient membrane electrode assemblies for anion exchange membrane seawater electrolyzers
Direct seawater electrolysis faces fundamental electrochemical challenges, such as suppression of chlorine adsorption and/or evolution reactions that poison the current state-of-the-art anode catalysts and accelerate the degradation of the anion exchange membrane (AEM). The technically favored solution path for addressing these issues includes development of novel selective catalysts and implementation of limited operating conditions. Therefore, development of highly active, selective, cost-effective, and stable seawater-splitting catalysts is required for a successful commercialization of the AEM water electrolyzers (AEMWEs). In this work, we report for the first-time an extended operation for over 1000 h of advanced AEMWEs, operating directly with seawater. To fabricate the membrane electrode assemblies (MEAs), catalyst coated electrodes (CCEs) are assembled with Sustainion® X37-50 grade T anion exchange membranes. The anode CCEs are fabricated by spraying an ink prepared from nanostructured NiFe-layered double hydroxide (LDH) catalyst that are synthesized by the solvothermal method and deposited directly onto platinized titanium porous transport layers (PTLs). The cathode CCEs are prepared by spraying an ink prepared from commercial Renay-Nickel catalyst onto a nickel fiber felt. As prepared AEM electrolyzer cells operated with seawater and demonstrated better than previously reported in the literature performance of over 1000 h of operation at a constant current density of 300 mA cm –2 .
Designing Sites in Heterogeneous Catalysis: Are We Reaching Selectivities Competitive With Those of Homogeneous Catalysts?
A critical review of different prominent nanotechnologies adapted to catalysis is provided, with focus on how they contribute to the improvement of selectivity in heterogeneous catalysis. Ways to modify catalytic sites range from the use of the reversible or irreversible adsorption of molecular modifiers to the immobilization or tethering of homogeneous catalysts and the development of well-defined catalytic sites on solid surfaces. The latter covers methods for the dispersion of single-atom sites within solid supports as well as the use of complex nanostructures, and it includes the post-modification of materials via processes such as silylation and atomic layer deposition. All these methodologies exhibit both advantages and limitations, but all offer new avenues for the design of catalysts for specific applications. Because of the high cost of most nanotechnologies and the fact that the resulting materials may exhibit limited thermal or chemical stability, they may be best aimed at improving the selective synthesis of high value-added chemicals, to be incorporated in organic synthesis schemes, but other applications are being explored as well to address problems in energy production, for instance, and to design greener chemical processes. Finally, the details of each of these approaches are discussed, and representative examples are provided. We conclude with some general remarks on the future of this field.