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At least 955 records · Page 53

Tracking Local pH Dynamics during Water Electrolysis via In-Line Continuous Flow Raman Spectroscopy

The performance of electrochemical devices, which play a critical role in decarbonization efforts, is often governed by proton-coupled electron transfer reactions at the electrode–electrolyte interface. These reactions are highly sensitive to the complex and dynamic microenvironment present at the electrode surface. However, characterizing this environment─particularly monitoring interfacial pH and its evolution under reaction conditions─remains challenging, necessitating the development of advanced analytical tools. Here, in this study, we introduce in-line continuous flow Raman spectroscopy (CFRS) as a spectroelectrochemical platform for quantifying interfacial pH swings generated during water-splitting. By monitoring phosphate ion speciation and controlling the hydrodynamics with a flow cell, we measure pH swings as a function of current density, flow rate, and distance from the electrode. Comparison with theoretical models reveals the impact of bulk pH, boundary layer thickness, and bubble dynamics at high current densities. Collectively, these findings establish CFRS as a platform for quantitatively investigating pH dynamics, offering critical insights for advancing electrochemical energy conversion technologies.

Marquez, Raul A. [Univ. of Texas, Austin, TX (Unit↗

NH 3 -Mediated Reactive Capture and Conversion: Integrating CO 2 Absorption from Flue Gas with CO Production via NH 4 HCO 3 Electrolysis

Efficient carbon capture and utilization require strategies that minimize energy penalties of CO 2 regeneration and compression. Reactive capture and conversion (RCC) address this challenge by integrating capture with direct electrochemical conversion. Here, we show an NH3-mediated tandem RCC system that couples capture of CO 2 from simulated flue gas (10% v/v CO 2 in N 2 ) with electroreduction of NH 4 HCO 3 to CO over a Ni single-atom catalyst (Ni-SAC). Speciation modeling and capture experiments revealed that a deep CO 2 capture with C/N ratio of 0.65 was achieved using 2.5 M NH 3 from simulated flue gas. Electrolysis of the resulting NH 4 HCO 3 on the Ni- SAC delivered an 85% CO Faradaic efficiency at 100 mA/cm 2 with excellent tolerance to NH 3 /NH 4 + as confirmed by DFT calculations and ab initio molecular dynamics (AIMD) simulations. Further, the technoeconomic analysis established a levelized total cost of CO manufacturing of $25.43/kmol, gauging the practical viability. Overall, this study holds great potential to decarbonize the chemical manufacturing industry while reducing synthetic production costs.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Challenges and Roadmap for Solar-Thermal Desalination

Decarbonizing desalination systems requires combining renewable energy technologies with desalination systems. Solar thermal desalination, which combines a thermal desalination system (e.g., distillation, multistage flash, etc.) with a concentrated solar system is attractive in geographic regions with an abundance of saline water and solar energy. However, the high economic cost and low efficiency limits its adoption. This review provides an overview of the techno-economic, materials, and performance challenges that need to be overcome to realize solar-desalination. The review describes the four most prominent pathways for overcoming thermodynamic and cost limitations present in current systems. Specifically, methodologies and approaches such as direct solar evaporation structures, low-cost thermal energy storage, solar cogeneration schemes for power and desalination, and solar hybrid desalination are discussed. Furthermore, these strategies can enable solar thermal desalination technologies that are resilient to intermittent solar energy.

14 SOLAR ENERGY↗

Amorphous CeO 2 –Cu Heterostructure Enhances CO 2 Electroreduction to Multicarbon Alcohols

Electrochemical conversion of carbon dioxide (CO 2 ) gas to value-added chemicals such as multicarbon (C 2+ ) alcohols is a promising and attractive decarbonization strategy. However, there are tremendous challenges in tuning the intrinsic activity and selectivity of the catalysts to produce C 2+ alcohols. In this work, we prepared a CeO 2 –Cu composite catalyst via a combination of metallurgy and dealloying method. The interfacial sites of amorphous CeO 2 –Cu heterostructure improve the adsorption of key reaction intermediates *CO and promote the C–C coupling. Significantly, they also stabilize *CH 2 CHO at the bifurcation step, steering the reaction pathway toward the formation of C 2+ alcohols over ethylene. The CeO 2 –Cu catalyst achieves a remarkable faradaic efficiency of 32.9% ± 2.6% for C 2+ alcohols at -0.6 V vs RHE. Overall, this work demonstrates an effective strategy of improving the intrinsic activity and selectivity of the Cu-based catalysts for the generation of C 2+ alcohols.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogen Production from Polyethylene Pyrolysis

Hydrogen is anticipated to play a pivotal role in the future of clean energy and decarbonization efforts, serving as an energy storage medium, a power generation source, and a clean fuel for transportation. While most hydrogen is produced from carbonaceous fossil feedstocks like natural gas, petroleum, and coal, there is growing interest in using refuse-derived fuels such as waste plastics and municipal solid waste (MSW) as alternative feedstocks. Thermochemical processes such as pyrolysis and catalytic cracking can convert nonrecyclable plastics and organic MSW components to produce hydrogen with lower life cycle greenhouse gas emissions when coupled with CO 2 capture. Such approaches not only address waste-management challenges but also reduce methane emissions from landfills. Furthermore, waste feedstocks are low cost and can support meeting demands for hydrogen across various industries. In this work we examined production of hydrogen from high-density polyethylene (HDPE) as a model polymer using pyrolysis. Analytical studies of pyrolysis utilizing gas chromatography–mass spectrometry (GC/MS) provide insights into conversion pathways for plastic waste, potentially reducing the environmental footprint of traditional hydrogen production methods. This work generates a baseline methodology for hydrogen production from plastic pyrolysis with and without a catalyst and the necessary product distribution baseline from key single plastics. The effect of pyrolysis temperature on the conversion of HDPE was evaluated both with and without a catalyst(s), and the product distributions measured via GC/MS were identified and hydrogen formation was quantified. These results will help guide future research efforts to optimize catalysts and processes for more efficient hydrogen production and mixed plastic waste management.

Catalysts↗

Sustainable Aviation Fuel from High-Strength Wastewater via Membrane-Assisted Volatile Fatty Acid Production: Experimental Evaluation, Techno-economic, and Life-Cycle Analyses

To reduce emissions from combustion of fossil fuels, sustainable aviation fuels (SAFs) have the potential to decarbonize the aviation sector. Redirecting wastes from conventional waste management practices and using them as cost-effective feedstocks for low-carbon fuels can reduce emissions from both waste disposal and fuel combustion. One approach is to upgrade wet wastes to SAF precursors, such as volatile fatty acids (VFAs). Here, in this study, novel membrane-assisted arrested methanogenesis was developed to convert high-strength wastewater to VFAs. Based on experimental results of VFA production, techno-economic and life-cycle analyses were conducted to estimate the potential economic and environmental benefits of SAF production from high-strength wastewater via VFAs. By evaluating three proposed scenarios for VFA production, a minimum production cost of VFA is achieved at $\$$0.60/kg VFA at a wastewater flow rate of 1100 MT/d. For the corresponding VFA-derived SAF, the estimated minimum fuel selling price is $\$$4.64/gasoline gallon equivalent. The life-cycle analysis shows that up to a 71% reduction in greenhouse gas emissions can be achieved relative to its fossil-counterpart along with lower water and fossil-fuel consumption.

09 BIOMASS FUELS↗

Life-Cycle Assessment of Sustainable Aviation Fuel Derived from Paper Sludge

Converting waste paper sludge to sustainable aviation fuel (SAF) offers a circular economy strategy to decarbonize the aviation sector. Here, this study develops a life-cycle assessment (LCA) for converting high-ash paper sludge to SAF in the U.S. using a catalytic sugar upgrading system that consists of ash removal, enzymatic hydrolysis, dehydration, aldol condensation, and hydroprocessing. The LCA is coupled with a process simulation for an industrial-scale biorefinery based on experimental data. We quantified the carbon intensity as 35.7–41.8 gCO 2 eq MJ –1 SAF (–636 to –584 gCO 2 eq per dry kg paper sludge) with acetone as a solvent, renewable fuel, and biobased chemicals; this is further reduced to 5.1–11.1 gCO 2 eq MJ –1 (–925 to –873 gCO 2 eq per dry kg paper sludge) if ash is recycled and used for substituting cement. Converting 1 dry kg paper sludge to SAF with acetone, renewable fuel, and biobased chemicals (–925 to –584 gCO 2 eq) is more climate beneficial than landfilling without landfill gas recovery (791 gCO 2 eq) and with landfill gas recovery (–294 gCO 2 eq). More than 330 million gallons of SAF can be produced annually (>4 million dry t paper sludge/year in the U.S.), resulting in a reduction of 2–7 million tCO 2 eq.

09 BIOMASS FUELS↗

Electrochemical Conversion of CO 2 to Methyl Formate in a Flow Electrolyzer with Mixed Propylene Carbonate/Methanol Catholyte

Despite the promise of electrochemical carbon dioxide reduction as a technology for the production of clean fuels and decarbonization of the chemical industry, research has mostly focused on aqueous systems with a relatively limited set of products that have been achieved via electrosynthesis. Increasingly, CO 2 electroreduction in nonaqueous solvents is being pursued to develop new avenues for expanding the suite of products that can be made with high selectivity. CO 2 reduction in alcohols coupled with in situ esterification to produce esters is one such route that utilizes nonaqueous electrolyte. To be practical, such electrochemical syntheses need to be translated to a high-performance reactor such as a flow electrolyzer. However, many organic solvents, such as alcohols, wet and flood porous electrodes, thus impeding reactor performance. In this work, methanol was mixed with propylene carbonate as a catholyte for a gas-fed CO 2 flow electrolyzer that avoided cathode flooding. Simultaneously, a dual aqueous anolyte was used for water oxidation as a scalable and sustainable anodic half-reaction. The performance effect of methanol concentration, catholyte acidity, CO 2 flow rate, and dilute water in the catholyte were investigated. With 10 vol % methanol in 90 vol % propylene carbonate, 63% faradaic efficiency for methyl formate ester product was sustained without cathode flooding. However, improvements are still needed to lower the cell resistance and further increase the operating current density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stable-Cycling Sustainable Na-Ion Batteries with Olivine Iron Phosphate Cathode in an Ether Electrolyte

Sustainable batteries using nontoxic, earth-abundant, and low-cost materials are key to decarbonization. Olivine NaFePO 4 fulfills these criteria, is attractive for Na-ion batteries, and can be derived from LiFePO 4 recycled from Li-ion battery wastes. Critical knowledge is needed for transforming LiFePO 4 to NaFePO 4 to enable such a sustainable, green engineering path toward high-performance Na-ion batteries. Herein, we report on the development of a stable-cycling, sustainable olivine iron phosphate-based Na-ion battery empowered by an improved understanding of materials transformation and electrolyte chemistry. First, we found that the conventional carbonate electrolyte with fluoroethylene carbonate additive causes an additional plateau (~2.4 V) at the end of the discharge process of the FePO 4 ||Na metal cell, leading to lower initial discharge capacity and voltage. This result shows that the voltage profile is influenced by not only intrinsic materials phase transformation during battery cycling but also the electrolyte additives and interphases formed. With the 1 M NaPF 6 diglyme electrolyte, we achieved an excellent capacity retention of 96% and 98% after 500 cycles at 1 and 5 C, respectively. Second, we chemically sodiated FePO 4 to form single-phase Na 0.9 FePO 4 . Na 0.9 FePO 4 ||hard carbon full cells demonstrated a remarkable capacity retention of ~84% at 3 and 5 C after 1000 cycles. The successful implementation of hard carbon, which can be derived from biomass waste, will further improve the sustainability of energy storage technologies. Our research demonstrates that electrolyte chemistry influences the voltage profile of phase-changing electrodes and provides effective electrolyte and full-cell design solutions for stable-cycling NaFePO 4 .

36 MATERIALS SCIENCE↗

Greenhouse Gas Emissions Associated with Pretreatment Techniques Utilized for Biosugar Production

Less carbon-intensive production of biosugars from lignocellulosic materials can lead to improved manufacturing of biofuels and bioproducts. In this study, the production of biosugars is analyzed to understand the potential of producing bioproducts from biosugars with a low carbon intensity. Life-cycle assessment is conducted on five lignocellulosic feedstocks along with seven pretreatment techniques to produce biosugars as an important platform intermediate for producing bioproducts. The production of electricity using lignin with and without heat integration was also incorporated. In addition, seven bioproducts are analyzed for the estimation of the GHG emissions budget, which represents the emissions available to convert, separate, and upgrade biosugars into bioproducts within the 70% emissions reduction target. Corn stover-deacetylation and dilute acid pretreatment (CS-DDA) provide the lowest GHG emissions for biosugar (0.03 kg CO 2 eq/kg biosugar) and thereby the highest GHG emissions budget for the case of lactic acid production (3.76 kg CO 2 eq/kg lactic acid). Natural gas and chemicals are the major contributors to all of the pretreatment techniques under study. The outcomes from this study can benefit the advancement of upcoming biobased processes that meet decarbonization targets.

Biopolymers↗

Light-Duty Vehicle Transportation Policy and Implication on Greenhouse Gas Emissions

The transportation sector accounts for 16% of global greenhouse gas (GHG) emissions and is under formidable pressure to decarbonize. With a growing number of countries making commitments to achieve carbon neutrality or “net-zero” emissions within the next few decades, it is imperative for transportation researchers and policymakers to understand the viable pathways towards achieving carbon neutrality for light-duty transport. This chapter discusses the transportation policies and GHG emissions of the three largest markets in the world—the U.S., China, and the European Union. The life cycle GHG emissions of various vehicle technologies are evaluated while highlighting the regional and temporal differences. We then use market penetration and fleet models, developed specifically for each market, to comprehensively assess the light-duty transport energy demand and GHG emissions under various scenarios. The modeling results show that battery electric vehicles (BEVs) will increase in market share, but internal combustion engine vehicles (ICEV) will continue to dominate the passenger vehicle stock in the next 20 years under most scenarios. Improving ICEV efficiency can play a critical role in meeting GHG regulations in the near- and medium-term. BEVs, whose GHG emissions are highly dependent on the source of electricity generation, will play an essential role in the long-term as the electric grid becomes cleaner. In summary, transportation policies should be technology agnostic and consider emissions based on the whole life cycle. Moreover, a holistic approach to reducing transportation GHG emissions is key to achieving global environmental goals.

Ou, Shawn↗

Dynamic Bubbling Balanced Proactive CO 2 Capture and Reduction on a Triple-Phase Interface Nanoporous Electrocatalyst

The formation and preservation of the active phase of the catalysts at the triple-phase interface during CO 2 capture and reduction is essential for improving the conversion efficiency of CO 2 electroreduction toward value-added chemicals and fuels under operational conditions. Designing such ideal catalysts that can mitigate parasitic hydrogen generation and prevent active phase degradation during the CO 2 reduction reaction (CO 2 RR), however, remains a significant challenge. Herein, we developed an interfacial engineering strategy to build a new SnO x catalyst by invoking multiscale approaches. This catalyst features a hierarchically nanoporous structure coated with an organic F-monolayer that modifies the triple-phase interface in aqueous electrolytes, substantially reducing competing hydrogen generation (less than 5%) and enhancing CO 2 RR selectivity (~90%). This rationally designed triple-phase interface overcomes the issue of limited CO 2 solubility in aqueous electrolytes via proactive CO 2 capture and reduction. Concurrently, we utilized pulsed square-wave potentials to dynamically recover the active phase for the CO 2 RR to regulate the production of C1 products such as formate and carbon monoxide (CO). This protocol ensures profoundly enhanced CO 2 RR selectivity (~90%) compared with constant potential (~70%) applied at -0.8 V (V vs RHE). We further achieved a mechanistic understanding of the CO 2 capture and reduction processes under pulsed square-wave potentials via in situ Raman spectroscopy, thereby observing the potential-dependent intensity of Raman vibrational modes of the active phase and CO 2 RR intermediates. Finally, this work will inspire material design strategies by leveraging triple-phase interface engineering for emerging electrochemical processes, as technology moves toward electrification and decarbonization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Robust Methodology to Elucidate Kinetics of Room Temperature Electrochemical Propane Adsorption on Platinum

Electrocatalytic activation of alkanes can further decarbonize chemical manufacturing by leveraging affordable renewable electricity and readily available shale gas reserves in the United States. Earlier works have identified the unique role of Pt in adsorbing and activating alkanes, like propane, at room temperature in acidic, aqueous electrolytes, revealing spontaneous formation of deeply dehydrogenated propane-derived surface species with an intact C 3 - backbone. Although an adsorption mechanism was hypothesized, it has not been explicitly investigated to date, preventing the quantification of kinetic rate parameters. A robust methodology to investigate and benchmark propane adsorption kinetics on Pt is critical for the rational design of electrocatalysts that exhibit higher selectivity toward desired partially oxidized products. Herein, we analyze an oxidative current transience that appears during the adsorption of propane on Pt in aqueous electrochemical conditions and develop a methodology that elucidates the adsorption mechanism and enables quantification of rate parameters such as order dependences and apparent activation barriers. This method yields an expected first-order dependence with respect to propane concentration at low coverage and reveals a second-order dependence with respect to the concentration of surface active sites. Additionally, the apparent activation barrier for propane adsorption was calculated using an Arrhenius analysis of the current transience under temperature control. The experimentally measured activation barrier of 35 kJ mol –1 is in excellent agreement with the theoretical barrier calculated by density functional theory (DFT). The kinetic analysis was extended, via the use of transition state theory, to extract entropy and enthalpy of activation, yielding consistent results with the proposed two-step adsorption mechanism and DFT calculations. These results demonstrate reliable quantification of kinetic parameters for electrocatalytic activation of C–H bonds in alkanes that can be employed for rational catalyst development for a versatile range of electrocatalytic conditions.

alkane activation↗

Carbon‐Neutral Pathways for the United States

Abstract The Intergovernmental Panel on Climate Change (IPCC) Special Report on Global Warming of 1.5°C points to the need for carbon neutrality by mid‐century. Achieving this in the United States in only 30 years will be challenging, and practical pathways detailing the technologies, infrastructure, costs, and tradeoffs involved are needed. Modeling the entire U.S. energy and industrial system with new analysis tools that capture synergies not represented in sector‐specific or integrated assessment models, we created multiple pathways to net zero and net negative CO 2 emissions by 2050. They met all forecast U.S. energy needs at a net cost of 0.2–1.2% of GDP in 2050, using only commercial or near‐commercial technologies, and requiring no early retirement of existing infrastructure. Pathways with constraints on consumer behavior, land use, biomass use, and technology choices (e.g., no nuclear) met the target but at higher cost. All pathways employed four basic strategies: energy efficiency, decarbonized electricity, electrification, and carbon capture. Least‐cost pathways were based on >80% wind and solar electricity plus thermal generation for reliability. A 100% renewable primary energy system was feasible but had higher cost and land use. We found multiple feasible options for supplying low‐carbon fuels for non‐electrifiable end uses in industry, freight, and aviation, which were not required in bulk until after 2035. In the next decade, the actions required in all pathways were similar: expand renewable capacity 3.5 fold, retire coal, maintain existing gas generating capacity, and increase electric vehicle and heat pump sales to >50% of market share. This study provides a playbook for carbon neutrality policy with concrete near‐term priorities.

Williams, James H.↗

Technology Pathways Could Help Drive the U.S. West Coast Grid's Exposure to Hydrometeorological Uncertainty

Abstract Previous studies investigating deep decarbonization of bulk electric power systems and wholesale electricity markets have not sufficiently explored how future grid pathways could affect the grid's vulnerability to hydrometeorological uncertainty on multiple timescales. Here, we employ a grid operations model and a large synthetic weather ensemble to “stress test” a range of future grid pathways for the U.S. West Coast developed by ReEDS, a well‐known capacity planning model. Our results show that gradual changes in the underlying capacity mix from 2020 to 2050 can cause significant “re‐ranking” of weather years in terms of annual wholesale electricity prices (with “good” years becoming bad, and vice versa). Nonetheless, we find the highest and lowest ranking price years in terms of average electricity price remain mostly tied to extremes in hydropower availability (streamflow) and load (summer temperatures), with the strongest sensitivities related to drought. Seasonal dynamics seen today involving spring snowmelt and hot, dry summers remain well‐defined out to 2050. In California, future supply shortfalls in our model are concentrated in the evening and occur mostly during periods of high temperature anomalies in late summer months and in late winter; in the Pacific Northwest, supply shortfalls are much more strongly tied to negative streamflow anomalies. Under our more robust sampling of stationary hydrometeorological uncertainty, we also find that the ratio of dis‐patchable thermal (i.e., natural gas) capacity to wind and solar required to ensure grid reliability can differ significantly from values reported by ReEDS.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Modeling the Water Systems of the Western US to Support Climate‐Resilient Electricity System Planning

Abstract Electricity and water systems in the Western US (WUS) are closely connected, with hydropower comprising 20% of total annual WUS generation, and electricity related to water comprising about 7% of total WUS electricity use. Because of these interdependencies, the threat of climate change to WUS resources will likely have compounding electricity impacts on the Western Interconnect grid. This study describes a WUS‐wide water system model with a particular emphasis on estimating climate impacts on hydropower generation and water‐related electricity use, which can be linked with a grid expansion model to support climate‐resilient electricity planning. The water system model combines climatically‐driven physical hydrology and management of both water supply and demand allocation, and is applied to an ensemble of 15 climate scenarios out to 2050. Model results show decreasing streamflow in key basins of the WUS under most scenarios. Annual water‐related electricity use increases up to 4%, and by up to 6% during the summer months, driven by growing agricultural demands met increasingly through a shift toward energy‐intensive groundwater to replace declining surface water. Total annual hydropower generation changes by +5% to −20% by mid‐century but declines in most scenarios, with decreases in summer generation by up to nearly −30%. Water‐related electricity use increases tend to coincide with hydropower generation declines, annually and seasonally, demonstrating the importance of concurrently evaluating the climate signal on both water‐for‐energy and energy‐for‐water to inform planning for grid reliability and decarbonization goals.

13 HYDRO ENERGY↗

Multi‐Layered Systems for Permanent Geologic Storage of CO 2 at the Gigatonne Scale

Abstract The effectiveness of Carbon Capture and Storage (CCS) as an imperative decarbonization technology relies on the sealing capacity of a fine‐grained caprock to permanently store CO 2 deep underground. Uncertainties in assessing the caprock sealing capacity increase with the spatial and temporal scales and may delay CCS deployment at the gigatonne scale. We have developed a computationally efficient transport model to capture the dynamics of basin‐wide upward CO 2 migration in a multi‐layered setting over geological time scales. We find that massive capillary breakthrough and viscous flow of CO 2 , even through pervasively fractured caprocks, are unlikely to occur and compromise the storage security. Potential leakage from the injection reservoir is hampered by repetitive layering of overlying caprocks. This finding agrees with geologic intuition and should be understandable by the public, contributing to the development of climate policies around this technology with increased confidence that CO 2 will be indefinitely contained in the subsurface.

58 GEOSCIENCES↗

Dual Impacts of Space Heating Electrification and Climate Change Increase Uncertainties in Peak Load Behavior and Grid Capacity Requirements in Texas

Around 60% of households in Texas currently rely on electricity for space heating. As decarbonization efforts increase, non‐electrified households could adopt electric heat pumps, significantly increasing peak (highest) electricity demand in winter. Simultaneously, anthropogenic climate change is expected to increase temperatures, the potential for summer heat waves, and associated electricity demand for cooling. Uncertainty regarding the timing and magnitude of these concurrent changes raises questions about how they will jointly affect the seasonality of peak demand, firm capacity requirements, and grid reliability. This study investigates the net effects of residential space heating electrification and climate change on long‐term demand patterns and load shedding potential, using climate change projections, a predictive load model, and a direct current optimal power flow (DCOPF) model of the Texas grid. Results show that full electrification of residential space heating by replacing existing fossil fuel use with higher efficiency heat pumps could significantly improve reliability under hotter futures. Less efficient heat pumps may result in more severe winter peaking events and increased reliability risks. As heating electrification intensifies, system planners will need to balance the potential for greater resource adequacy risk caused by shifts in seasonal peaking behavior alongside the benefits (improved efficiency and reductions in emissions).

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗