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At least 253 records · Page 14

Energy Spotlight: Advances in Solar Cells and Solar Fuels

Our editorial advisory board members Kai Zhu, Dongling Ma, and Shannon W. Boettcher provide highlights of three articles published in the August issue. They highlight new advances in solar cells and solar fuels that include phenethylammonium iodide treatment on suppressing ion migration in perovskite solar cells, nitride heterostructures for water splitting, and three-dimensional electrode (Si microarray) for CO 2 reduction.

14 SOLAR ENERGY↗

The Feasibility of Direct CO2 Conversion Technologies on Impacting Mid-Century Climate Goals

Recent IPCC modeling suggests that to limit global warming below 2 degrees C, "unprecedented" reductions in CO2 emissions will be required during the 2030-2050 time frame. The direct conversion of CO2 to fuels and chemicals using renewable electricity has garnered interest as one route to draw down emissions with the ability to synthesize products at a significantly lower carbon footprint than conventional methods. However, most direct CO2 conversion pathways are only in the early stages of development and face technical and market hurdles prior to scale-up, bringing into question what role they may play in influencing global CO2 emissions within this critical two-decade window. In this perspective, we highlight low-temperature electrolysis as a promising technology for direct CO2 conversion, including discussion on the products that could most impact global emission levels, and importantly, offer insight into the timeline, required advancements, and specific technical targets needed to successfully scale and deploy these technologies at the commercial level.

chemicals↗

Restructuring and integrity of molecular catalysts in electrochemical CO 2 reduction

Electrocatalysts that start a reaction as molecules do not always end the reaction as molecules, and even when they do, they might not be molecules during catalysis. In this Perspective, we discuss knowledge learned from the study of Cu-based molecularly structured electrocatalysts––including metal coordination complexes, metal-organic frameworks, single-atom catalysts, and polymeric materials––that restructure under electrochemical CO 2 reduction reactions. Recent reports are summarized with an emphasis on the nature and significance of post-mortem and in situ characterization for the proper identification of active sites. We demonstrate that molecular and material structures determine whether electrocatalysts restructure and how they restructure, that understanding of restructuring processes can help us identify active sites for catalysis, and that this knowledge can be leveraged to design precatalysts that generate highly active catalysts under reaction conditions. In addition, we provide recommended practices for studying the integrity of heterogeneous molecular catalysts during and after CO 2 reduction reactions.

CO2 reduction↗

The 2015-2016 El Nino and the Response of the Carbon Cycle: Findings from NASA's OCO-2 Mission

The El Nino Southern Oscillation (ENSO) is the most important mode of tropical climate variability on interannual to decadal time scales. Correlations between atmospheric CO2 growth rate and ENSO activity are relatively well known but the magnitude of this correlation, the contribution from tropical marine vs. terrestrial flux components, and the causal mechanisms, are poorly constrained in space and time. The launch of NASA's Orbiting Carbon Observatory-2 (OCO-2) mission in July 2014 was rather timely given the development of strong ENSO conditions over the tropical Pacific Ocean in 2015-2016. In this presentation, we will discuss how the high-density observations from OCO-2 provided us with a novel dataset to resolve the linkages between El Nino and atmospheric CO2. Along with information from in situ observations of ÎpCO2 from NOAA's Tropical Atmosphere Ocean (TAO) project and atmospheric CO2 from the Scripps CO2 Program, and other remote-sensing missions, we are able to piece together the time dependent response of atmospheric CO2 concentrations over the Tropics. Our findings confirm the hypothesis from studies following the 1997-1998 El Nino event that an early reduction in CO2 outgassing from the tropical Pacific Ocean is later reversed by enhanced net CO2 emissions from the terrestrial biosphere. This implies that a component of the interannual variability (IAV) in the growth rate of atmospheric CO2, which has typically been used to constrain the climate sensitivity of tropical land carbon fluxes, is strongly influenced and modified by ocean fluxes during the early phase of the ENSO event. Our analyses shed further light on the understanding of the marine vs. terrestrial partitioning of tropical carbon fluxes during El Nino events, their relative contributions to the global atmospheric CO2 growth rate, and provide clues about the sensitivity of the carbon cycle to climate forcing on interannual time scales.

CO2↗

The 2015-2016 El Nino and the Response of the Carbon Cycle: Findings from NASA's OCO-2 Mission

The El Nino Southern Oscillation (ENSO) is the most important mode of tropical climate variability on interannual to decadal time scales. Correlations between atmospheric CO2 growth rate and ENSO activity are relatively well known but the magnitude of this correlation, the contribution from tropical marine vs. terrestrial flux components, and the causal mechanisms, are poorly constrained in space and time. The launch of NASA's Orbiting Carbon Observatory-2 (OCO-2) mission in July 2014 was rather timely given the development of strong ENSO conditions over the tropical Pacific Ocean in 2015-2016. In this presentation, we will discuss how the high-density observations from OCO-2 provided us with a novel dataset to resolve the linkages between El Nino and atmospheric CO2. Along with information from in situ observations of CO2 from NOAA's Tropical Atmosphere Ocean (TAO) project and atmospheric CO2 from the Scripps CO2 Program, and other remote-sensing missions, we are able to piece together the time dependent response of atmospheric CO2 concentrations over the Tropics. Our findings confirm the hypothesis from studies following the 1997-1998 El Nino event that an early reduction in CO2 outgassing from the tropical Pacific Ocean is later reversed by enhanced net CO2 emissions from the terrestrial biosphere. This implies that a component of the interannual variability (IAV) in the growth rate of atmospheric CO2, which has typically been used to constrain the climate sensitivity of tropical land carbon fluxes, is strongly influenced and modified by ocean fluxes during the early phase of the ENSO event. Our analyses shed further light on the understanding of the marine vs. terrestrial partitioning of tropical carbon fluxes during El Nino events, their relative contributions to the global atmospheric CO2 growth rate, and provide clues about the sensitivity of the carbon cycle to climate forcing on interannual time scales.

OCO-2↗

Evaluation of Contrail Reduction Strategies Based on Aircraft Flight Distances

This paper evaluates a set of contrail reduction strategies based on the flight range of aircraft as contrail reduction strategies have different impacts on aircraft depending on how they plan to fly. In general, aircraft with longer flight distances cruise at the altitudes where contrails are more likely to form. The concept of the contrail frequency index is used to quantify contrail impacts. The strategy for reducing the persistent contrail formation is to minimize the contrail frequency index by altering the aircraft's cruising altitude. A user-defined factor is used to trade off between contrail reduction and extra CO2 emissions. A higher value of tradeoff factor results in more contrail reduction and extra CO2 emissions. Results show that contrail reduction strategies using various tradeo factors behave differently from short-range flights to long-range ights. Analysis shows that short-distance flights (less than 500 miles) are the most frequent flights but contribute least to contrail reduction. Therefore these aircraft have the lowest priority when applying contrail reduction strategies. Medium-distance flights (500 to 1000 miles) have a higher priority if the goal is to achieve maximum contrail reduction in total; long-distance flights (1000 to 1500 miles) have a higher priority if the goal is to achieve maximum contrail reduction per flight. The characteristics of transcontinental flights (greater than 1500 miles) vary with different weather days so the priority of applying contrail reduction strategies to the group needs to be evaluated based on the locations of the contrail areas during any given day. For the days tested, medium-distance ights contribute up to 42.6% of the reduction among the groups during a day. The contrail frequency index per 1,000 miles for medium-distance, long-distance, and transcontinental flights can be reduced by an average of 75%. The results provide a starting point for developing operational policies to reduce the impact of aviation on climate based on aircraft flight distances.

Chen, Neil Y.↗

ATD-2 Benefits Mechanism

NASA has been developing and demonstrating a suite of decision support capabilities for integrated arrival, departure, and surface (IADS) operations in a metroplex environment. The effort is being made in three phases, under NASA’s Airspace Technology Demonstration 2 (ATD-2) sub-project, through a close partnership with the Federal Aviation Administration (FAA), air carriers, airport, and general aviation community. The Phase 1 Baseline IADS capabilities provide enhanced operational efficiency and predictability of flight operations through data exchange and integration, tactical surface metering, and automated coordination of release time of controlled flights for overhead stream insertion. The Phase 2 Fused IADS capabilities include the fusion of strategic and tactical surface metering, Atlanta Center airspace tactical scheduling, Electronic Flight Data (EFD) integration, Terminal Flight Data Manager (TFDM) Terminal Publication (TTP) prototype, and Mobile App for General Aviation (GA) community. In the Phase 2 field evaluation, strategic surface metering provides advance notice of metering and additional stability to the assigned gate holds. The users of the IADS system in Phases 1 and 2 include the personnel at Charlotte Douglas International Airport (CLT) air traffic control tower, American Airlines ramp tower, CLT terminal radar approach control (TRACON), and Washington and Atlanta Center. This document describes the ATD-2 benefits mechanism used to assess the Phases 1 and 2 IADS capabilities and field evaluation conducted at CLT since September 2017. The ATD-2 benefits mechanism mainly consists of surface metering and overhead stream insertion. This document provides detailed calculation methods of major benefit metrics, such as fuel savings, gas emissions savings, and engine runtime reduction, which can be obtained through surface metering, gate hold of Approval Request (APREQ) flights prior to pushback, and the renegotiation of release time while taxiing. As of March 31, 2020, it is estimated that 5,075,981 pounds of fuel savings and 15,634,022 pounds of CO2 emission reduction have been achieved so far, with a reduction of 3,832 hours in total engine runtime. The amount of CO2 savings is estimated to be equivalent to planting 116,254 urban trees. The pre- and post-metering comparison results using FAA’s Aviation System Performance Metrics (ASPM) data have also shown that the surface metering had no negative impact on the on-time arrival performance of both outbound and inbound flights at CLT.

ATD-2↗

ATD-2 Benefits Mechanism

NASA has been developing and demonstrating a suite of decision support capabilities for integrated arrival, departure, and surface (IADS) operations in a metroplex environment. The effort is being made in three phases, under NASA’s Airspace Technology Demonstration 2 (ATD-2) sub-project, through a close partnership with the Federal Aviation Administration (FAA), air carriers, airport, and general aviation community. The Phase 1 Baseline IADS capabilities provide enhanced operational efficiency and predictability of flight operations through data exchange and integration, tactical surface metering, and automated coordination of release time of controlled flights for overhead stream insertion. The Phase 2 Fused IADS capabilities include the fusion of strategic and tactical surface metering, Atlanta Center airspace tactical scheduling, Electronic Flight Data (EFD) integration, Terminal Flight Data Manager (TFDM) Terminal Publication (TTP) prototype, and Mobile App for General Aviation (GA) community. In the Phase 2 field evaluation, strategic surface metering provides advance notice of metering and additional stability to the assigned gate holds. The users of the IADS system in Phases 1 and 2 include the personnel at Charlotte Douglas International Airport (CLT) air traffic control tower, American Airlines ramp tower, CLT terminal radar approach control (TRACON), and Washington and Atlanta Center. This document describes the ATD-2 benefits mechanism used to assess the Phases 1 and 2 IADS capabilities and field evaluation conducted at CLT since September 2017. The ATD-2 benefits mechanism mainly consists of surface metering and overhead stream insertion. This document provides detailed calculation methods of major benefit metrics, such as fuel savings, gas emissions savings, and engine runtime reduction, which can be obtained through surface metering, gate hold of Approval Request (APREQ) flights prior to pushback, and the renegotiation of release time while taxiing. As of April 30, 2020, it is estimated that 5,097,173 pounds of fuel savings and 15,699,292 pounds of CO2 emission reduction have been achieved so far, with a reduction of 3,831 hours in total engine runtime. The amount of CO2 savings is estimated to be equivalent to planting 116,739 urban trees. The pre- and post-metering comparison results using FAA’s Aviation System Performance Metrics (ASPM) data have also shown that the surface metering had no negative impact on the on-time arrival performance of both outbound and inbound flights at CLT.

ATD-2↗

Tracking 2020 Decreases in Carbon Dioxide Due to the COVID19 Pandemic in NASA’s GEOS Modeling system: Implications for Space-Based Carbon Monitoring

The COVID19 pandemic led to abrupt, worldwide changes in human activity and related emissions of air pollutants and greenhouse gases that are unprecedented in modern times. NASA satellites have demonstrated their ability to observe some of these impacts, particularly in relation to short-lived gases like nitrogen dioxide (NO2), which is emitted primarily from transportation. Bottom-up analyses of carbon dioxide (CO2) emissions suggest that the growth of atmospheric CO2 has also slowed, but differences are much more subtle than for NO2 because of the lifetime of atmospheric CO2 and sectoral differences in emission reductions. Estimates of CO2 from NASA’s Orbiting Carbon Observatory 2 (OCO-2) provide a unique view of COVID19 impacts, but observed changes in the column-average CO2 can be difficult to interpret because of gaps in spatial coverage. Assimilating these data into the Goddard Earth Observing System (GEOS), an integrated Earth system model with an advanced Constituent Data Assimilation System (CoDAS), helped to reveal changes in CO2 that are consistent with separate, bottom-up analyses of emissions reductions. Both indicate that from February-April of 2020, the growth in CO2 over Europe, North America, and Asia was roughly 0.3 ppm less than during the previous four years. Anomalies derived from gap-filled GEOS OCO-2 CoDAS products contribute to a joint effort by the world’s space agencies to track COVID19 impacts on the Earth. However, attribution of these changes is complicated by interannual variability in atmospheric circulation and the influence of climate on ocean and land carbon sinks. We discuss these results from the perspective of space-based carbon monitoring, which has received considerable support over the past decade from NASA. Our results demonstrate the accomplishments of current sensors and data assimilation systems, but also highlight challenges in providing high quality, low latency information to the public. In particular, understanding and attributing CO2 changes during 2020 requires year-specific information about land and ocean fluxes, which is often delayed for months or even years. We discuss current limitations and potential solutions to address these lags, which would support more reliable and timely space-based carbon monitoring.

COVID-19↗

Development of Hydrogen-Fueled, Highly Energy-Efficient, Electro-Hydraulic Excavator

Regulations for CO2 emissions reduction are driving increasing demand for “zero emissions” off-road vehicles (ORVs). Hydrogen internal combustion engines (H2 ICEs) are closer to commercial viability, and less expensive than fuel cells. The major challenge is the slow torque response of H2 ICEs, that makes it difficult to sustain the harsh torque requirements typical of ORVs. The goal of this paper is to overcome this challenge by proposing an electro-hydraulic hybrid technology with hybrid powertrain and multi-pressure rail technology as fluid power system for an excavator, to enable the use of the H2 ICE, while improving efficiency. The study is based on simulation in MATLAB/Simulink environment, using duty cycle data from a 24-ton excavator. Simulation results show that in respect to the diesel-powered baseline, the proposed electro-hydraulic hybrid allows the use of a H2 ICE, eliminates CO2 emissions and ensures a 52% fuel consumption reduction.

08 HYDROGEN↗

The Temperature of the Earth in 2020

In spite of the confusion in the public discourse about global warming, there is no doubt that the Earth has been warming for the past century. The chemistry of the Earth's atmosphere is complex, and it is sometimes difficult to claim cause-and-effect with certainty. Nevertheless, the evidence seems clear that CO2 and non-CO2 forcings such as methane and air pollution are causally related to this warming trend. Our dependence on fossil fuels make it difficult to expect that massive reductions in CO2 will be feasible in the near-term, however. In this talk I will consider the evidence for global warming, the extent to which we can extrapolate current trends into the future if no changes in global policy are introduced, and those near-term policies that might be realistically introduced to significantly affect those trends.

Hansen, James↗

EMS-Induced Mutagenesis of Clostridium carboxidivorans for Increased Atmospheric CO 2 Reduction Efficiency and Solvent Production

Clostridium carboxidivorans (P7) is one of the most important solvent-producing bacteria capable of fermenting syngas (CO, CO 2 , and H 2 ) to produce chemical commodities when grown as an autotroph. This study aimed to develop ethyl methanesulfonate (EMS)-induced P7 mutants that were capable of growing in the presence of CO 2 as a unique source of carbon with increased solvent formation and atmospheric CO 2 reduction to limit global warming. Phenotypic analysis including growth and end product characterization of the P7 wild type (WT) demonstrated that this strain grew better at 25 °C than 37 °C when CO 2 served as the only source of carbon. In the current study, 55 mutagenized P7-EMS mutants were developed by using 100 mM and 120 mM EMS. Interestingly, using a forward genetic approach, three out of the 55 P7-EMS mutants showed a significant increase in ethanol, butyrate, and butanol production. The three P7-EMS mutants presented on average a 4.68-fold increase in concentrations of ethanol when compared to the P7-WT. Butyric acid production from 3 P7-EMS mutants contained an average of a 3.85 fold increase over the levels observed in the P7-WT cultures under the same conditions (CO 2 only). In addition, one P7-EMS mutant presented butanol production (0.23 ± 0.02 g/L), which was absent from the P7-WT under CO 2 conditions. Most of the P7-EMS mutants showed stability of the obtained end product traits after three transfers. Most importantly, the amount of reduced atmospheric CO 2 increased up to 8.72 times (0.21 g/Abs) for ethanol production and up to 8.73 times higher (0.16 g/Abs) for butyrate than the levels contained in the P7-WT. Additionally, to produce butanol, the P7-EMSIII-J mutant presented 0.082 g/Abs of CO 2 reduction. This study demonstrated the feasibility and effectiveness of employing EMS mutagenesis in generating solvent-producing anaerobic bacteria mutants with improved and novel product formation and increased atmospheric CO 2 reduction efficiency.

59 BASIC BIOLOGICAL SCIENCES↗

Promoting electrochemical reduction of CO 2 to ethanol by B/N-doped sp 3 /sp 2 nanocarbon electrode

Electrochemical reduction of CO 2 to value-added chemicals holds promise for carbon utilization and renewable electricity storage. However, selective CO 2 reduction to multi-carbon fuels remains a significant challenge. Here, we report that B/N-doped sp 3 /sp 2 hybridized nanocarbon (BNHC), consisting of ultra-small nanoparticles with a sp 3 carbon core covered by a sp 2 carbon shell, is an efficient electrocatalyst for electrochemical reduction of CO 2 to ethanol at relatively low overpotentials. CO 2 reduction occurs with a Faradaic efficiency of 58.8%-69.1% for ethanol and acetate production at –0.5 ~ –0.6 V (vs. RHE), among which 51.6%-56.0% is for ethanol. The high selectivity for ethanol is due to the integrated effect of sp 3 /sp 2 carbon and B/N doping. Finally, both sp 3 carbon and B/N doping contribute to enhanced ethanol production with sp 2 carbon reducing the overpotential for CO 2 reduction to ethanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrocatalytic CO 2 Reduction to Fuels: Progress and Opportunities

The electrochemical reduction of CO 2 continues to be an appealing option for storing renewable energy in a chemical form. In this review, we assess progress in designing catalysts that convert CO 2 to high energy density products. We explain how reaction data can be reported to reflect the intrinsic properties of the catalyst. This analysis shows that limited advances have been made in improving the performance of Cu. We suggest that opportunities remain using bimetallic catalysts that are resistant to dealloying. While aqueous systems are instrumental to developing our understanding of this chemistry, gas-fed systems that operate at high current densities must be developed. Although obstacles remain for practical application of CO 2 reduction, advances in fundamental understanding made over the years give reason for optimism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microalgae Biomass Production for Utilization of CO2 and Mitigation of Greenhouse Gas Emissions

Microalgal cultivation processes for production of foods, feeds, fuels, fertilizers and other bioproducts and wastewater treatment are being considered for reducing CO2 and other greenhouse gas emissions. Major differences between microalgae and higher plant biomass cultivation are include their potential for much higher productivities, their higher content of major (N-P-K) and minor nutrients, and the challenge of harvesting such microscopic plants. Most critical, microalgal mass cultures, unlike higher plants, currently require fertilization with concentrated sources of CO2. As practically all of the C fixed into algal biomass will be re-emitted into the atmosphere in short order, algae processes do not sequester carbon. Their potential for CO2 emissions reductions must thus be based on comparisons with current technologies for the production of competing products, such as biofuels or animal feeds, or in wastewater treatment. Further, due to economic limitations to flue gas transport (3 to 12 % CO2), as well as highly variable diurnal and seasonal CO2 utilization and limited land and water availability near most CO2 sources, only a small fraction of waste CO2 emissions will be directly utilizeable for microalgae biomass production. However, for long-distance transport, flue gas CO2 capture by chemical processes would greatly increase the costs of flue gas utilization. More concentrated, sources of CO2 from refineries, fertilizer, chemical plants, and fermentations are available, but are also very limited relative to the quantities required for commodity production. Microalgae can also be cultivated on organic wastes, which provide both nutrients (N, P, K, etc.) and organic and inorganic carbon for algal growth, reducing greenhouse gas emissions compared to conventional treatment processes. To maximize the potential for algae biomass production and CO2 utilization, direct capture of CO2 from air will be required. This could be accomplished with the algal cultivation process itself in large open-raceway ponds, through chemical and biological enhancements of CO2 transfer into algal cutures. The relative productivities, economics, greenhouse gas balances, and resource potentials of these alternative CO2 sources for large-scale production of microalgae will be reviewed.

09 BIOMASS FUELS↗

Steering CO 2 electroreduction toward ethanol production by a surface-bound Ru polypyridyl carbene catalyst on N-doped porous carbon

Significance Electrochemical reduction of CO 2 can convert CO 2 emission back to value-added fuels and chemicals and store renewable electricity. Reducing CO 2 to multicarbon products has attracted great interest because of their higher energy densities and associated economic values. We report here a promising strategy for steering CO 2 electroreduction toward ethanol production by exploiting a surface-bound Ru polypyridyl carbene catalyst on an N-doped porous carbon electrode. We show the synergistic effects of Ru polypyridyl carbene for CO intermediate production with a porous carbon for C–C coupling that could boost ethanol production at relatively low overpotentials. The strategy provides insights on how to improve selectivity and efficiency for CO 2 reduction toward multicarbon products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure Activity Relationships for Second‐Coordination Sphere Functional Group Dependent CO 2 Reduction by Manganese Bipyridyl Electrocatalysts

Abstract A series of twelve second coordination sphere (SCS) functionalized manganese tricarbonyl bipyridyl complexes are investigated for their electrocatalytic CO 2 reduction properties in acetonitrile. A qualitative and quantitative assessment of the SCS functional groups is discussed with respect to the catalysts’ thermodynamic and kinetic efficiencies, and their product selectivities. In probing a broad scope of functional groups, it is clear that only the aprotic ortho‐arylester SCS is capable of promoting the highly desired low‐overpotential proton‐transfer electron‐transfer (PT‐ET) pathway for selective CO production. The ortho‐phenolic analogues cause an increase in overpotential with a product selectivity favoring H 2 evolution, consistent with a high‐overpotential pathway via the anionic [Mn−H] − intermediate. Alternative aprotic Lewis base functional groups such as trifluoromethyl, morpholine and acetamide are shown to also be capable of intermediate manganese hydride generation. The tertiary amine substituent, 2‐morpholinophenyl, exhibits a desirable product distribution characteristic of syn‐gas (CO : H 2 =30 : 48) with an impressive turnover frequency, while the secondary amine group, 2‐acetamidophenyl, induces a notable shift in selectivity with a faradaic yield of 55 % for the formate (HCO 2 − ) product. In addition to their catalytic properties, cyclic voltammetry and infrared spectroelectrochemistry (IR‐SEC) studies are presented to probe pre‐catalyst electronic properties and the two‐electron reduction activation pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗