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At least 1,261 records · Page 70
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Assessing the Impact of the Inflation Reduction Act on Nuclear Plant Power Uprate and Hydrogen Cogeneration

On August 16, 2022, Congress passed the Inflation Reduction Act (IRA) to promote investment in new, carbon-free power generation and sustainable operation of existing carbon-free assets. Specifically, the IRA includes both a production tax credit (PTC – Section 45Y of the IRA) and an investment tax credit (ITC – Section 48E) which utilities may leverage to offset the costs of power uprate. Further, the IRA includes a provision (Section 45V) for a PTC associated with carbon-free hydrogen cogeneration. These tax credits, along with recent legislation efforts to decarbonize the country, have re-emphasized the importance of maintaining and optimizing the existing nuclear plant operating fleet. As a result, utilities are reexamining the possibility of uprating their existing nuclear assets to further maximize carbon-free electricity generation.

08 HYDROGEN↗
NASA NTRS2012

Characterizing 3D Vegetation Structure from Space: Mission Requirements

Human and natural forces are rapidly modifying the global distribution and structure of terrestrial ecosystems on which all of life depends, altering the global carbon cycle, affecting our climate now and for the foreseeable future, causing steep reductions in species diversity, and endangering Earth s sustainability. To understand changes and trends in terrestrial ecosystems and their functioning as carbon sources and sinks, and to characterize the impact of their changes on climate, habitat and biodiversity, new space assets are urgently needed to produce high spatial resolution global maps of the three-dimensional (3D) structure of vegetation, its biomass above ground, the carbon stored within and the implications for atmospheric green house gas concentrations and climate. These needs were articulated in a 2007 National Research Council (NRC) report (NRC, 2007) recommending a new satellite mission, DESDynI, carrying an L-band Polarized Synthetic Aperture Radar (Pol-SAR) and a multi-beam lidar (Light RAnging And Detection) operating at 1064 nm. The objectives of this paper are to articulate the importance of these new, multi-year, 3D vegetation structure and biomass measurements, to briefly review the feasibility of radar and lidar remote sensing technology to meet these requirements, to define the data products and measurement requirements, and to consider implications of mission durations. The paper addresses these objectives by synthesizing research results and other input from a broad community of terrestrial ecology, carbon cycle, and remote sensing scientists and working groups. We conclude that: (1) current global biomass and 3-D vegetation structure information is unsuitable for both science and management and policy. The only existing global datasets of biomass are approximations based on combining land cover type and representative carbon values, instead of measurements of actual biomass. Current measurement attempts based on radar and multispectral data have low explanatory power outside low biomass areas. There is no current capability for repeatable disturbance and regrowth estimates. (2) The science and policy needs for information on vegetation 3D structure can be successfully addressed by a mission capable of producing (i) a first global inventory of forest biomass with a spatial resolution 1km or finer and unprecedented accuracy (ii) annual global disturbance maps at a spatial resolution of 1 ha with subsequent biomass accumulation rates at resolutions of 1km or finer, and (iii) transects of vertical and horizontal forest structure with 30 m along-transect measurements globally at 25 m spatial resolution, essential for habitat characterization. We also show from the literature that lidar profile samples together with wall-to53 wall L-band quad-pol-SAR imagery and ecosystem dynamics models can work together to satisfy these vegetation 3D structure and biomass measurement requirements. Finally we argue that the technology readiness levels of combined pol-SAR and lidar instruments are adequate for space flight. Remaining to be worked out, are the particulars of a lidar/pol-SAR mission design that is feasible and at a minimum satisfies the information and measurement requirement articulated herein.

Hall, Forrest G.↗
DOE OSTI2023

Implementing and Improving CBMZ-MAM3 Chemistry and Aerosol Modules in the Regional Climate Model WRF-CAM5: An Evaluation over the Western US and Eastern North Pacific

The representation of aerosols in climate-chemistry models is important for air quality and climate change research, but it can require significant computational resources. The objective of this study was to improve the representation of aerosols in climate–chemistry models, specifically in the carbon bond mechanism, version Z (CBMZ), and modal aerosol modules with three lognormal modes (MAM3) in the WRF-CAM5 model. The study aimed to enhance the model’s chemistry capabilities by incorporating biomass burning emissions, establishing a conversion mechanism between volatile organic compounds (VOCs) and secondary organic carbons (SOCs), and evaluating its performance against observational benchmarks. The results of the study demonstrated the effectiveness of the enhanced chemistry capabilities in the WRF-CAM5 model. Six simulations were conducted over the western U.S. and northeastern Pacific region, comparing the model’s performance with observational benchmarks such as reanalysis, ground-based, and satellite data. The findings revealed a significant reduction in root-mean-square errors (RMSE) for surface concentrations of black carbon (BC) and organic carbon (OC). Specifically, the model exhibited a 31% reduction in RMSE for BC concentrations and a 58% reduction in RMSE for OC concentrations. These outcomes underscored the importance of accurate aerosol representation in climate-chemistry models and emphasized the potential for improving simulation accuracy and reducing errors through the incorporation of enhanced chemistry modules in such models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Regulating Catalytic Properties and Thermal Stability of Pt and PtCo Intermetallic Fuel-Cell Catalysts via Strong Coupling Effects between Single-Metal Site-Rich Carbon and Pt

Developing low platinum-group-metal (PGM) catalysts for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs) for heavy-duty vehicles (HDVs) remains a great challenge due to the highly demanded power density and long-term durability. Here, this work explores the possible synergistic effect between single Mn site-rich carbon (Mn SA -NC) and Pt nanoparticles, aiming to improve intrinsic activity and stability of PGM catalysts. Density functional theory (DFT) calculations predicted a strong coupling effect between Pt and MnN 4 sites in the carbon support, strengthening their interactions to immobilize Pt nanoparticles during the ORR. The adjacent MnN 4 sites weaken oxygen adsorption at Pt to enhance intrinsic activity. Well-dispersed Pt (2.1 nm) and ordered L1 2 -Pt 3 Co nanoparticles (3.3 nm) were retained on the Mn SA -NC support after indispensable high-temperature annealing up to 800 °C, suggesting enhanced thermal stability. Both PGM catalysts were thoroughly studied in membrane electrode assemblies (MEAs), showing compelling performance and durability. The Pt@Mn SA -NC catalyst achieved a mass activity (MA) of 0.63 A mg Pt –1 at 0.9 V iR-free and maintained 78% of its initial performance after a 30,000-cycle accelerated stress test (AST). The L1 2 -Pt 3 Co@Mn SA -NC catalyst accomplished a much higher MA of 0.91 A mg Pt –1 and a current density of 1.63 A cm –2 at 0.7 V under traditional light-duty vehicle (LDV) H 2 –air conditions (150 kPa abs and 0.10 mg Pt cm –2 ). Furthermore, the same catalyst in an HDV MEA (250 kPa abs and 0.20 mg Pt cm –2 ) delivered 1.75 A cm –2 at 0.7 V, only losing 18% performance after 90,000 cycles of the AST, demonstrating great potential to meet the DOE targets.

25 ENERGY STORAGE↗
DOE OSTI2021

Characterization of zirconium carbide microspheres synthesized via internal gelation

Microspheres of zirconium carbide with grain size 40-320 nm were synthesized using internal gelation techniques and characterized by scanning electron microscopy, synchrotron X-ray diffraction, and neutron total scattering. Compared with a polycrystalline benchmark ZrC sample prepared by plasma vapor phase deposition, the microspheres display lower variance in grain size and considerably lower microstrain representative of a more homogenous internal microstructure. However, excess carbon was present in the microspheres, evident in both the X-ray and neutron diffraction data as well as a corresponding hypostoichiometric ZrC phase. Furthermore, the excess carbon phase is assumed to be pockets of carbon that remained unreacted through the combined internal gelation and subsequent carbothermic reduction synthesis process. Atomic-scale structural characterization with neutron PDF analysis confirmed the presence of localized nano-sized domains of graphite-like carbon material.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Wake Effects in Lower Carbon Future Scenarios

In August 2022, the U.S. Congress passed the Inflation Reduction Act (IRA), which intended to accelerate U.S. decarbonization, clean energy manufacturing, and deployment of new power and end-use technologies. The National Renewable Energy Laboratory has examined possible scenarios for growth by 2050 resulting from the IRA and other emissions reduction drivers and defined several possible scenarios for large-scale wind deployment. These scenarios incorporate large clusters of turbines operating as wind farms grouped around existing or likely transmission lines which will result in wind farm wakes. Using a numerical weather prediction (NWP) model, we assess these wake effects in a domain in the U. S. Southern Great Plains for a representative year with four scenarios in order to validate the simulations, estimate the internal wake impact, and quantify the cluster wake effect. Herein, we present a validation of the ”no wind farm” scenario and quantify the internal waking effect for the ”ONE” wind farm scenario. Future work will use the “MID” scenario (more than 8000 turbines) and the “HI” scenario (more than 16,000 turbines) to quantify the effect of cluster wakes or inter-farm wakes on power production.

17 WIND ENERGY↗
DOE OSTI2022

Recovering carbon losses in CO 2 electrolysis using a solid electrolyte reactor

The practical implementation of electrochemical CO 2 reduction technology is greatly challenged by notable CO 2 crossover to the anode side, where the crossed-over CO 2 is mixed with O 2 , via interfacial carbonate formation in traditional CO 2 electrolysers. Here we report a porous solid electrolyte reactor strategy to efficiently recover these carbon losses. Furthermore, by creating a permeable and ion-conducting sulfonated polymer electrolyte between cathode and anode as a buffer layer, the crossover carbonate can combine with protons generated from the anode to re-form CO 2 gas for reuse without mixing with anodic O 2 . Using a silver nanowire catalyst for CO 2 reduction to CO, we demonstrated up to 90% recovery of the crossover CO 2 in an ultrahigh gas purity form (>99%), while delivering over 90% CO Faradaic efficiency under a 200 mA cm -2 current. A high continuous CO 2 conversion efficiency of over 90% was achieved by recycling the recovered CO 2 to the CO 2 input stream.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

RAY-O-VAC BR2325 Lithium Carbon Monofluoride Cell Performance

RAY-O-VAC currently markets a 160 mAH lithium cell recommended for usage in watch and calculator products. The lithium carbon monofluoride cell offers an extended shelf life with no reduction in performance effectiveness. The BR2325 cell has aerospace applications for memory devices and telemetry systems. Over one hundred thirty (130) cells were purchased and tested for evaluation purposes. The test statistics and overall cell performance of the RAY-O-VOC BR2325 lithium carbon monofluoride cell is reviewed.

Mcdermott, J. K.↗
DOE OSTI2020

Feasibility of using reactive silicate particles with temperature-responsive coatings to enhance the security of geologic carbon storage

The large-scale deployment of geologic carbon storage will require minimizing the risk of CO 2 leakage. Here we report on a novel strategy to seal leakage pathways by injecting functionalized reactive calcium silicate (CaSiO 3 ) particles. The particles consist of a mineral silicate core within a temperature-sensitive Poly(N,N-dimethylaminoethyl methacrylate) coating that limits contact between the core and the surrounding CO 2 (aq) above a switching temperature making them relatively unreactive deep in the subsurface. If the CO 2 leaks to shallower depths and cooler temperatures, the coatings would extend and enable the silicate core to react with CO 2(aq) to form solid carbonate precipitates that reduce the permeability of the fracture or flow path. A combined laboratory- and simulation-based investigation was conducted to explore key early-stage research questions related to the feasibility of this leakage management strategy. Sand columns were injected with either coated or uncoated CaSiO 3 particles and the permeability was measured before and after exposure to CO 2 . Experiments were conducted at 35 °C and 70 °C, a range that spans the switching temperature for the coatings. Results show that at the cooler temperature the coating effectively enabled reaction and permeability reduction. At higher temperatures, the coated particles limited mineral carbonation and the permeability decrease was minimal compared to columns with uncoated particles. Here, the morphology and location of the precipitates provides insight about permeability evolution. Model simulations of 2D radial particle transport from an injection point provided insight into the effects of particle size, coating properties, and concentrations of particles in several representative rock formations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Distributed clean energy opportunities for US oil refinery operations

The oil and gas industry is increasingly seeking operational improvements to reduce costs and emissions while improving resilience. This study describes techno-economic analysis of opportunities for distributed energy resources that could be integrated to support oil and gas companies’ economic, environmental, and energy resiliency goals. Specifically, the analysis evaluates solar photovoltaics, wind turbines, battery energy storage, landfill gas, biomass, municipal solid waste-to-energy, solar steam for process heat, combined heat and power, and electrolyzers for hydrogen production at two hypothetical refineries, one located in Louisiana and the other in southern California. These technologies could reduce the sites’ consumption of grid electricity and/or natural gas and thus can help reduce emissions. This study employs the ReOPT tool and System Advisor Model to evaluate the techno-economic potential for clean energy technologies to support refineries in achieving energy goals, including energy cost savings, resiliency, and emissions reductions. Results indicate that the associated costs of emissions reductions via several distributed clean energy technologies are competitive with other emissions reduction strategies such as energy efficiency, reducing flaring, direct carbon capture and sequestration, and markets under certain conditions. There are also cost beneficial opportunities for the use of renewable energy for refining, especially for resilience, depending on local conditions such as resources and utility costs.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2024

Adaptive Laboratory Evolution for Enhanced Performance of Cupriavidus Necator on Formic Acid

The threat of global warming, driven by rising carbon emissions, highlights the need to decarbonize our economy. This requires innovative solutions for managing carbon waste and its effective utilization. One promising method for CO2 capture and sequestration is the electrochemical reduction of CO2 to formic acid, a soluble C1 molecule that can be used to store carbon and energy, and as a feedstock for biological conversion. Cupriavidus necator H16, a soil bacterium capable of consuming and growing on formic acid as its sole carbon and energy source, is well positioned to upgrade CO2-derived formic acid into platform chemicals and fuel precursors. To improve the performance of C. necator on formic acid, adaptive laboratory evolution (ALE), a proven tool for improving microbial fitness, has been conducted using continuous pH-stat bioreactors. The system works on the basis that consumption of formic acid raises the pH and triggers the addition of more formic acid to maintain the pH (in this case 6.7), such that formic acid is provided at the same rate as it is consumed. This system has been coupled with level control to achieve continuous fermentation where cells acquiring mutations that improve growth on formic acid become more abundant in the population, from which they can be isolated and characterized. During developmental experiments it was discovered that formic acid accumulated to inhibitory levels. It was determined that the nitrogen source, ammonium hydroxide, must be tailored to the carbon consumption to avoid formic acid accumulation. The ALE ran in three lineages for approximately 3000 hours and more than 500 generations. Evolved isolates obtained from each lineage demonstrated an increase in growth rate in conjunction with improve formate utilization compared to the parental strain when evaluated in pH-stat bioreactors. The isolates with improved performance were then subjected to whole genome sequencing to identify potentially causative mutations. Mutations in several key genes across different lineages have been found and will be evaluated individually and in combination to identify those that improve growth on formic acid. Incorporating these mutations into production strains has the potential to greatly improve formic acid conversion and further industrial decarbonization.

adaptive laboratory evolution↗
DOE OSTI2026

Regulation of Energy and Mass Transport in a Hydrogen-Bonded Framework for Visible-Light-Driven CO2 Reduction in Water

Photoenzymatic reduction of CO2 to formate is a promising strategy for carbon valorization, yet its efficiency is still limited by inefficient energy and mass transport. Here, we design a series of isostructural hydrogen-bonded organic frameworks (HOFs) that establish confinement effects to promote photocatalytic NADH regeneration and the subsequent NADH-dependent enzymatic CO2-to-formate reduction. We demonstrate that spatial confinement within the framework channels localizes exciton migration to nanoscale domains and promotes interfacial dissociation. Additionally, Rh-induced electronic-structure modulation enables ultrafast electron transfer, while the intrinsic hydrogen-bond network furnishes directional proton conduction to NAD+. These synergistic regulations afford a photocatalytic NADH regeneration efficiency of 99.8% with a record apparent quantum efficiency of 32.8%, and drive formate production at a rate of 3020 μmol g-1 h-1 with 100% selectivity─the highest rate reported to date for all light-driven systems in water. The HOF-based catalyst retains 86.3% of its initial activity over five cycles, highlighting its robustness. This work offers mechanistic insight into how microenvironment engineering within HOF architectures regulates energy and mass transport in photoenzymatic catalysis, paving the way for the rational design of advanced hybrid catalytic systems.

Xu, Jiaxing↗
DOE OSTI2025

Evaluating the carbon capture potential of industrial waste as a feedstock for enhanced weathering

Abstract Limiting anthropogenic global climate warming since the start of the industrial period to less than 2 °C will very likely require both deep and rapid reductions in anthropogenic greenhouse gas emissions and a range of approaches toward carbon dioxide removal (CDR). One prominent CDR approach is enhanced weathering (EW), in which crushed silicate rock is applied on land or in the open ocean to accelerate natural weathering processes that absorb carbon dioxide from Earth’s ocean–atmosphere system. However, in addition to a range of potential environmental, socioeconomic, and ethical issues associated with this pathway, bottlenecks in feedstock sourcing represent a key barrier for deployment of EW at scale. Here, we evaluate the potential of silicate wastes produced from industrial processes—such as steel slag and cement waste—as feedstocks for the EW process. An empirical model that links industrial alkaline waste production to gross domestic product at purchase power parity is developed to forecast waste production in the alternative futures described by the shared socioeconomic pathway (SSP) framework. By incorporating these results into an intermediate-complexity Earth system model, we also explore the impacts of EW using industrial waste on changes to global temperature, ocean pH, and ocean aragonite saturation state, while also quantifying overall CDR efficiency through the end of the century. We estimate a maximum cumulative end-of-century capture potential of ∼400 GtCO 2 for industrial waste, which could represent a significant fraction of the projected CDR requirement of many mitigation scenarios in the SSP framework. However, feedstock-dependent environmental impacts and the technoeconomics of feedstock redistribution may ultimately limit deployment scope.

Xu, Pengxiao (ORCID:0009000633724293)↗
DOE OSTI2021

The unique Phe–His dyad of 2-ketopropyl coenzyme M oxidoreductase/carboxylase selectively promotes carboxylation and S–C bond cleavage

The 2-ketopropyl-coenzyme M oxidoreductase/carboxylase (2-KPCC) enzyme is the only member of the disulfide oxidoreductase (DSOR) family of enzymes, which are important for reductively cleaving S–S bonds, to have carboxylation activity. 2-KPCC catalyzes the conversion of 2-ketopropyl-coenzyme M to acetoacetate, which is used as a carbon source, in a controlled reaction to exclude protons. A conserved His–Glu motif present in DSORs is key in the protonation step; however, in 2-KPCC, the dyad is substituted by Phe–His. Here, we propose that this difference is important for coupling carboxylation with C–S bond cleavage. We substituted the Phe–His dyad in 2-KPCC to be more DSOR like, replacing the phenylalanine with histidine (F501H) and the histidine with glutamate (H506E), and solved crystal structures of F501H and the double variant F501H_H506E. We found that F501 protects the enolacetone intermediate from protons and that the F501H variant strongly promotes protonation. We also provided evidence for the involvement of the H506 residue in stabilizing the developing charge during the formation of acetoacetate, which acts as a product inhibitor in the WT but not the H506E variant enzymes. Finally, we determined that the F501H substitution promotes a DSOR-like charge transfer interaction with flavin adenine dinucleotide, eliminating the need for cysteine as an internal base. Taken together, these results indicate that the 2-KPCC dyad is responsible for selectively promoting carboxylation and inhibiting protonation in the formation of acetoacetate.

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

Resolving dynamic mineral-organic interactions in the rhizosphere by combining in-situ microsensors with plant-soil reactive transport modeling

Associations between minerals and organic matter represent one of the most important carbon storage mechanisms in soils. Plant roots are major sources of soil carbon, and resolving the dynamics and dominance of microbial consumption versus mineral sorption of root-derived carbon is critical to understanding soil carbon storage. Here we integrate in-situ rhizosphere microsensor and plant physiological measurements with a 3-D plant-soil reactive transport model to explore the fate of dissolved organic carbon (DOC) in the rhizosphere, particularly its microbial consumption and interaction with Fe oxide minerals. Over several days, a microdialysis probe sampling pore water at the root-soil interface of growing Vicia faba roots in live soil, revealed clear diel patterns of DOC concentration. Daytime DOC spikes coincided with peaks in leaf-level photosynthesis rates and were accompanied by declining redox potential and dissolved oxygen as well as increasing pH in the rhizosphere. Incorporating microsensor data into our modeling framework showed that the measured rapid loss of DOC after each mid-day spike could not be explained by consumption via aerobic respiration, nor via anaerobic respiration dominated by Fe oxide reduction. Rather, in the model, a large fraction of rhizosphere DOC was rapidly immobilized each day by adsorption to Fe oxides. Further, modeled microbial Fe reduction (fueled by DOC) did not mobilize significant organic carbon from Fe oxides during the day. Instead, the model predicted equilibrium desorption of organic carbon from Fe oxides at night. This new mechanistic modeling framework, which couples aboveground plant physiological measurements with non-destructive high-resolution monitoring of rhizosphere processes, has great potential for exploring the dynamics and balance of the various microbial reactions and mineral interactions controlling carbon transformations and storage in soils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

2D Metal/Graphene and 2D Metal/Graphene/Metal Systems for Electrocatalytic Conversion of CO 2 to Formic Acid

Abstract Efficiently transforming CO 2 into renewable energy sources is crucial for decarbonization efforts. Formic acid (HCOOH) holds great promise as a hydrogen storage compound due to its high hydrogen density, non‐toxicity, and stability under ambient conditions. However, the electrochemical reduction of CO 2 (CO 2 RR) on conventional carbon black‐supported metal catalysts faces challenges such as low stability through dissolution and agglomeration, as well as suffering from high overpotentials and the necessity to overcome the competitive hydrogen evolution reaction (HER). In this study, we modify the physical/chemical properties of metal surfaces by depositing metal monolayers on graphene (M/G) to create highly active and stable electrocatalysts. Strong covalent bonding between graphene and metal is induced by the hybridization of sp and d orbitals, especially the sharp , , and orbitals of metals near the Fermi level, playing a decisive role. Moreover, charge polarization on graphene in M/G enables the deposition of another thin metallic film, forming metal/graphene/metal (M/G/M) structures. Finally, evaluating overpotentials required for CO 2 reduction to HCOOH, CO, and HER, we find that Pd/G, Pt/G/Ag, and Pt/G/Au exhibit excellent activity and selectivity toward HCOOH production. Our novel 2D hybrid catalyst design methodology may offer insights into enhanced electrochemical reactions through the electronic mixing of metal and other p‐block elements.

Cho, Jinwon↗
DOE OSTI2023

Machine learning-based ethylene and carbon monoxide estimation, real-time optimization, and multivariable feedback control of an experimental electrochemical reactor

Electrochemical reduction of CO 2 gas is a novel CO 2 utilization technique that has the potential to mitigate the global climate crisis caused by anthropogenic CO 2 emissions, and enable the large-scale storage of energy generated from renewable sources in the form of carbon-based chemicals and fuels. However, due to the complexity of the electrochemical reactions, the explicit first-principles models for CO2 reduction are not available yet, and there has been a limited effort to develop process modeling, optimization and control of CO 2 electrochemical reactors. To this end, a rotating cylinder electrode (RCE) reactor has been constructed at UCLA to understand the mass transfer and reaction kinetics effects separately on the productivity. In the RCE reactor, the applied potential strongly influences the reaction energetics and the electrode rotation speed affects the hydrodynamic boundary layer and modifies the film mass transfer coefficient, which involves convective and diffusive transport. Further, the present work aims to develop a multi-input multi-output (MIMO) control scheme for the RCE reactor that integrates techniques from artificial and recurrent neural network modeling, nonlinear optimization, and process controller design. Specifically, production rates of two products from the experimental reactor, ethylene and carbon monoxide, are controlled by manipulating two inputs, applied potential and catalyst rotation speed. Process dynamics and controllability are analyzed, a feedback control strategy is designed and the controllers are tuned accordingly. The experimental electrochemical cell is employed to gather data for process modeling and implement the multivariable control system. Finally, the experimental results are presented which demonstrate excellent closed-loop performance by the control system and regulation of the outputs at three different set-points including an economically-optimal set-point.

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

Proton-Coupled Group Transfer Enables Concerted Protonation Pathways Relevant to Small-Molecule Activation

The mechanistic identification of Nature's use of concerted reactions, in which all bond-breaking and bond-making occurs in a single step, has inspired rational designs for artificial synthetic transformations via pathways that bypass high energy intermediates that would otherwise be thermodynamically and kinetically inaccessible. Here, we electrochemically activate an organometallic Ruthenium(II) complex to show that, in acetonitrile solutions, the movement of protons from weak Brønsted acids, such as water and methanol, is coupled with the transfer of its negatively charged counterpart to carbon dioxide (CO 2 ) - a process termed proton-coupled group transfer - to stoichiometrically produce a metal-hydride complex and a carbonate species. These previously unidentified pathways have played key roles in CO 2 and proton reduction catalysis by enabling the generation of key intermediates such as hydrides and metallocarboxylic acids, while its applicability to carbon acids may provide alternative approaches in the electrosynthesis of chemical commodities via alkylation and carboxylation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗