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At least 235 records · Page 13

Sub-volt conversion of activated biochar and water for H 2 production near equilibrium via biochar-assisted water electrolysis

Sluggish water oxidation reactions limit water electrolysis for H 2 production, which can be alleviated by the use of carbon-based ma- terials like agricultural wastes as reducing agents. Biochar from such biomass can reduce equilibrium cell potentials at standard condi- tions from 1.23 V to 0.21 V by avoiding direct water splitting at the anode. However, some challenges hinder biochar oxidation, including poor biochar binding, electrode caking, and surface passivation. We find that enhanced C/O ratio, crystallinity, and negative zeta potential improve biochar oxidation kinetics at mod- erate temperatures. Smaller particle sizes and better mixing pre- vent electrode caking, enhancing biochar stability. Here, we report sub-volt biochar-coupled H 2 production, often referred to as a bio- char-assisted water electrolysis (BAWE), yielding 250 mA/g cat H 2 current at 100% Faradaic efficiency. Over 1 mA current was observed at a near-equilibrium cell potential of 0.2 V cell potential. Using a single-junction solar cell-powered BAWE, 15 mA H 2 is generated at 1 Sun, resulting in 4.8% solar-to-hydrogen efficiency, equivalent to 35% when the energy of H 2 relative to H 2 O (without biochar) is assumed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic Mechanism of Interfacial Water in the Cycloaddition of Quadricyclane and Diethyl Azodicarboxylate

"On-water" catalysis, the unusual activity of water molecules at the organic solvent-water interface, has been demonstrated in many organic reactions. However, the catalytic mechanism has remained unclear, largely because of the irreproducibility of the organic-water interface under the common stirring condition. In this work, the interfacial area was controlled by employing adsorbed water on mesoporous silica nanoparticles as the catalyst. Reliable kinetics of the cycloaddition reaction of quadricyclane and diethyl azodicarboxylate (DEAD) at the toluene-water interface within the nanoparticle pores were measured. Data reveal an Eley-Rideal mechanism, wherein DEAD adsorbs at the toluene-water interface via hydrogen bonds formed with interfacial water, which lower the activation energy of the cycloaddition reaction. The mechanistic insights gained and preparation of surface water in silica pores described herein may facilitate the future design of improved "on-water" catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tracking the dynamics of catalytic Pt/CeO2 active sites during water-gas-shift reaction

Abstract Understanding the atomistic structure of the active site during catalytic reactions is of paramount importance in both fundamental studies and practical applications, but such studies are challenging due to the complexity of heterogeneous systems. Here, we use Pt/CeO 2 as an example to study the dynamic nature of active sites during the water-gas-shift reaction (WGSR) by combining multiple in situ characterization tools. We show that the different concentrations of interfacial Pt δ+ – O – Ce 4+ moieties at Pt/CeO 2 interfaces are responsible for the rank of catalytic performance of Pt/CeO 2 catalysts: Pt/CeO 2 -rod > Pt/CeO 2 -cube > Pt/CeO 2 -oct. For all the catalysts, metallic Pt is formed during the WGSR, leading to the transformation of the active sites to Pt 0 – O v – Ce 3+ and interface reconstruction. These findings shed light on the nature of the active site for the WGSR on Pt/CeO 2 and highlight the importance of combining complementary in situ techniques for establishing structure-performance relationships.

36 MATERIALS SCIENCE↗

The Efficacy of Seasonal Terrestrial Water Storage Forecasts for Predicting Vegetation Activity Over Africa

Terrestrial water storage (TWS) provides important information on terrestrial hydroclimate and may have value for seasonal forecasting because of its strong persistence. We use the NASA Hydrological Forecast and Analysis System (NHyFAS) to investigate TWS forecast skill over Africa and assess its value for predicting vegetation activity from satellite estimates of leaf area index (LAI). Forecast skill is high over East and Southern Africa, extending up to 3–6 months in some cases, with more modest skill over West Africa. Highest skill generally occurs during the dry season or beginning of the wet season when TWS anomalies from the previous wet season are most likely to carry forward in time. In East Africa, this occurs prior to and during the transition into the spring “Long Rains” from January–March, while in Southern Africa this period of highest skill starts at the beginning of the dry season in April and extends through to the start of the wet season in October. TWS is highly and positively correlated with LAI, and a logistic regression model shows high cross-validation skill in predicting above or below normal LAI using TWS. Combining the LAI regression model with the NHyFAS forecasts, 1-month lead LAI predictions have high accuracy over East and Southern Africa, with reduced but significant skill at 3-month leads over smaller sub-regions. This highlights the potential value of TWS as an additional source of information for seasonal forecasts over Africa, with direct applications to some of the most vulnerable agricultural regions on the continent.

Terrestrial water shortage↗

Multi-hydrophilic functional network enables porous membranes excellent anti-fouling performance for highly efficient water remediation

Membrane technology is believed as a cost-effective approach for solving the water issues, where as it suffers from serious membrane fouling. Surface grafting and surface coating have been proved to be effective in abating the membrane fouling; however, these processes always need additional procedures and compromise the initial permeance of the membranes. Herein, we developed a kind of highly permeable polyacrylonitrile (PAN) membranes with excellent anti-fouling performance through one-step phase inversion of the PAN casting solution containing water-soluble active additives. During the process, the water-soluble active additives could segregate towards the membrane surface and pore walls; thereby finely tailoring the pore structures of the PAN-based membranes. Moreover, the active additives could react with each other to form crosslinked networks containing multi-hydrophilic functional groups including CH2-O-CH2, -OH or-Si-OH. Consequently, the PAN-based membranes exhibited surprising superhydrophilicity with water contact angle below 10. even after soaking in water for one week and the anti-fouling permeance of the membranes increased significantly with permeance recovery rate above 93%. Interestingly, the modified membranes also demonstrated both high permeances and high separation efficiency, thereby showing strong promise in water environmental remediation including wastewater treatment and oil/water emulsion separation.

Anti-fouling↗

Technical Consultation of the International Space Station (ISS) Internal Active Thermal Control System (IATCS) Cooling Water Chemistry

The Internal Active Thermal Control System (IATCS) coolant exhibited unexpected chemical changes during the first year of on-orbit operation following the launch and activation in February 2001. The coolant pH dropped from 9.3 to below the minimum specification limit of 9.0, and re-equilibrated between 8.3 and 8.5. This drop in coolant pH was shown to be the result of permeation of CO2 from the cabin into the coolant via Teflon flexible hoses which created carbonic acid in the fluid. This unexpected diffusion was the result of having a cabin CO2 partial pressure higher than the ground partial pressure (average 4.0 mmHg vs. less than 0.2 mmHg). This drop in pH was followed by a concurrent increasing coolant nickel concentration. No other metal ions were observed in the coolant and based on previous tests, the source of nickel ion was thought to be the boron nickel (BNi) braze intermetallics used in the construction of HXs and cold plates. Specifically, BNi2 braze alloy was used for the IATCS IFHX and BNi3 braze alloy was used for the IATCS Airlock Servicing and Performance Checkout Unit (SPCU) HX and cold plates. Given the failure criticality of the HXs, a Corrosion Team was established by the IATCS CWG to determine the impact of the nickel corrosion on hardware performance life.

Gentz, Steven J.↗

Seasonal Correlations of SST, Water Vapor, and Convective Activity in Tropical Oceans: A New Hyperspectral Data Set for Climate Model Testing

The analysis of the response of the Earth Climate System to the seasonal changes of solar forcing in the tropical oceans using four years of the Atmospheric Infrared Sounder (AIRS) and Advanced Microwave Sounding Unit (AMSU) data between 2002 and 2006 gives new insight into amplitude and phase relationships between surface and tropospheric temperatures, humidity, and convective activity. The intensity of the convective activity is measured by counting deep convective clouds. The peaks of convective activity, temperature in the mid-troposphere, and water vapor in the 0 - 30 N and 0 - 30 S tropical ocean zonal means occur about two months after solstice, all leading the peak of the sea surface temperature by several weeks. Phase is key to the evaluation of feedback. The evaluation of climate models in terms of zonal and annual means and annual mean deviations from zonal means can now be supplemented by evaluating the phase of key atmospheric and surface parameters relative to solstice. The ability of climate models to reproduce the statistical flavor of the observed amplitudes and relative phases for broad zonal means should lead to increased confidence in the realism of their water vapor and cloud feedback algorithms. AIRS and AMSU were launched into a 705 km altitude polar sun-synchronous orbit on the EOS Aqua spacecraft on May 4, 2002, and have been in routine data gathering mode since September 2002.

Atmospheric Infrared Sounder↗

Evaluation of Second Target Station Target Streaming for the Preliminary Design of the Target Assembly

This report documents the analysis of dose rate fields from a combination of two sources stemming from the target system of the Oak Ridge National Laboratory (ORNL) Spallation Neutron Source (SNS) Second Target Station (STS). This analysis supports the target drive components’ lifetime estimates and conventional facilities’ preliminary design. The two sources detailed in this report are the radiation generated by the proton beam incident on the target and the activated cooling water in the pipes at the top of the target assembly. The analysis considers the STS target system in operational configuration, with all shielding in place. The dose rate fields are calculated in the target drive room and through the target drive room ceiling. This report calculates the thickness necessary for the target drive room’s high-density concrete ceiling to meet the 0.25 mrem/hr dose limit requirement in the high bay directly above the target drive room. In addition to sizing the target drive room ceiling, this report includes details of the dose field surrounding the target drive assembly to estimate the deposited dose in the target drive assembly components resulting from both streaming and decay of activated water. Prompt neutrons and gammas generated by the proton beam incident on the target primarily stream along the gaps between the target assembly and core vessel shielding. Because the models and analysis detailed in this report are based on the STS preliminary design, future analysis is needed to support the STS final design.

43 PARTICLE ACCELERATORS↗

Seasonal Correlations of SST, Water Vapor, and Convective Activity in Tropical Oceans: A New Hyperspectral Data Set for Climate Model Testing

The analysis of the response of the Earth Climate System to the seasonal changes of solar forcing in the tropical oceans using four years of the Atmospheric Infrared Sounder (AIRS) and Advanced Microwave Sounding Unit (AMSU) data between 2002 and 2006 gives new insight into amplitude and phase relationships between surface and tropospheric temperatures, humidity, and convective activity. The intensity of the convective activity is measured by counting deep convective clouds. The peaks of convective activity, temperature in the mid-troposphere, and water vapor in the 0-30 N and 0-30 S tropical ocean zonal means occur about two months after solstice, all leading the peak of the sea surface temperature by several weeks. Phase is key to the evaluation of feedback. The evaluation of climate models in terms of zonal and annual means and annual mean deviations from zonal means can now be supplemented by evaluating the phase of key atmospheric and surface parameters relative to solstice. The ability of climate models to reproduce the statistical flavor of the observed amplitudes and relative phases for broad zonal means should lead to increased confidence in the realism of their water vapor and cloud feedback algorithms. AIRS and AMSU were launched into a 705 km altitude polar sun-synchronous orbit on the EOS Aqua spacecraft on May 4, 2002, and have been in routine data gathering mode since September 2002.

Atmospheric Infrared Sounder (AIRS)↗

NASA Water Resources Program

With increasing population pressure and water usage coupled with climate variability and change, water issues are being reported by numerous groups as the most critical environmental problems facing us in the 21st century. Competitive uses and the prevalence of river basins and aquifers that extend across boundaries engender political tensions between communities, stakeholders and countries. In addition to the numerous water availability issues, water quality related problems are seriously affecting human health and our environment. The potential crises and conflicts especially arise when water is competed among multiple uses. For example, urban areas, environmental and recreational uses, agriculture, and energy production compete for scarce resources, not only in the Western U.S. but throughout much of the U.S. and also in numerous parts of the world. Mitigating these conflicts and meeting water demands and needs requires using existing water resources more efficiently. The NASA Water Resources Program Element works to use NASA products and technology to address these critical water issues. The primary goal of the Water Resources is to facilitate application of NASA Earth science products as a routine use in integrated water resources management for the sustainable use of water. This also includes the extreme events of drought and floods and the adaptation to the impacts from climate change. NASA satellite and Earth system observations of water and related data provide a huge volume of valuable data in both near-real-time and extended back nearly 50 years about the Earth's land surface conditions such as precipitation, snow, soil moisture, water levels, land cover type, vegetation type, and health. NASA Water Resources Program works closely to use NASA and Earth science data with other U.S. government agencies, universities, and non-profit and private sector organizations both domestically and internationally. The NASA Water Resources Program organizes its projects under five functional themes. I) Streamflow and Flood Forecasting 2) Water Supply and Irrigation (includes evapotranspiration) 3) Drought 4) Water Quality 5) Climate and Water Resources. To maximize this activity NASA Water Resources Program works closely with other government agencies (e.g., the National Oceanic and Atmospheric Administration (NOAA); the U.S. Department of Agriculture (USDA); the U.S. Geological Survey (USGS); the Environmental Protection Agency (EPA), USAID, the Air Force Weather Agency (AFWA)), universities, non-profit national and international organizations, and the private sector. The NASA Water Resources program currently is funding 21 active projects under the functional themes (http://wmp.gsfc.nasa.gov & http://science.nasa.gov/earth-science/applied-sciences/).

Toll, David L.↗

Stability of Mn-Doped TiO 2 Thin-Film Anodes during Water Oxidation Reactions

Incorporating manganese atoms into TiO 2 has been shown to improve its activity for water oxidation. However, its activity has been observed to steadily degrade under constant applied potential, especially at more oxidizing applied potentials. Here, the compositional profile and electrochemical stability of Mn-doped TiO 2 (Mn:TiO 2 ) thin-film electrodes precisely fabricated by atomic layer deposition (ALD) were evaluated to elucidate the mechanisms of electrode degradation. Although ALD enables the deposition of Mn dopants throughout the film thickness, only Mn within 1.5 nm of the surface was observed to be redox active. Annealing Mn:TiO 2 films in air leads to the diffusion of Mn toward the electrode surface and oxidation of the Mn and alters the redox behavior. Annealing endows greater stability to Mn redox behavior but does not fully stabilize the water oxidation current, suggesting that the two electrochemical processes are not precisely correlated. In situ inductively coupled plasma mass spectrometry reveals that Mn is lost from Mn:TiO 2 films at potentials greater than 1.8 V vs RHE. However, the initial Mn loss is equivalent to less than a single ALD layer of MnO x . Longer-term constant potential experiments suggest that Mn is lost from up to 1 nm of the electrode surface but that this loss may account for only a portion of the diminished water oxidation activity.

atomic layer deposition↗

Short Range-Ordered Minerals: Insight into Aqueous Alteration Processes on Mars

Short range-ordered (SRO) aluminosilicates (e.g., allophane) and nanophase ferric oxides (npOx) are common SRO minerals derived during aqueous alteration of basaltic materials. NpOx refers to poorly crystalline or amorphous alteration products that can be any combination of superparamagnetic hematite and/or goethite, akaganeite, schwertmannite, ferrihydrite, iddingsite, and nanometer-sized ferric oxide particles that pigment palagonitic tephra. Nearly 30 years ago, SRO phases were suggested as alteration phases on Mars based on similar spectral properties for altered basaltic tephra on the slopes of Mauna Kea in Hawaii and Martian bright regions measured by Earth-based telescopes. Detailed characterization of altered basaltic tephra on Mauna Kea have identified a variety of alteration phases including allophane, npOx, hisingerite, jarosite, alunite, hematite, goethite, ferrihydrite, halloysite, kaolinite, smectite, and zeolites. The presence of npOx and other Fe-bearing minerals (jarosite, hematite, goethite) was confirmed by the M ssbauer Spectrometer onboard the Mars Exploration Rovers. Although the presence of allophane has not been definitely identified on Mars robotic missions, chemical analysis by the Spirit and Opportunity rovers and thermal infrared spectral orbital measurements suggest the presence of allophane or allophane-like phases on Mars. SRO phases form under a variety of environmental conditions on Earth ranging from cold and arid to warm and humid, including hydrothermal conditions. The formation of SRO aluminosilicates such as allophane (and crystalline halloysite) from basaltic material is controlled by several key factors including activity of water, extent of leaching, Si activity in solution, and available Al. Generally, a low leaching index (e.g., wet-dry cycles) and slightly acidic to alkaline conditions are necessary. NpOx generally form under aqueous oxidative weathering conditions, although thermal oxidative alteration may occasional be involved. The style of aqueous alteration (hydrolytic vs. acid sulfate) impacts which phases will form (e.g., oxides, oxysulfates, and oxyhydroxides). Knowledge on the formation processes of SRO phases in basaltic materials on Earth has allowed significant enhancement in our understanding of the aqueous processes at work on Mars. The 2011 Mars Science Laboratory (MSL) will provide an instrument suite that should improve our understanding of the mineralogical and chemical compositions of SRO phases. CheMin is an X-ray diffraction instrument that may provide broad X-ray diffraction peaks for SRO phases; e.g., broad peaks around 0.33 and 0.23 nm for allophane. Sample Analysis at Mars (SAM) heats samples and detects evolved gases of volatile-bearing phases including SRO phases (i.e., carbonates, sulfates, hydrated minerals). The Alpha Particle X-ray Spectrometer (APXS) and ChemCam element analyzers will provide chemical characterization of samples. The identification of SRO phases in surface materials on MSL will be challenging due to their nanocrystalline properties; their detection and identification will require utilizing the MSL instrument suite in concert. Ultimately, sample return missions will be required to definitively identify and fully characterize SRO minerals with state-of-the-art laboratory instrumentation back on Earth.

Ming, Douglas W.↗

Stabilization of Catalytically Active Surface Defects on Ga-doped La–Sr–Mn Perovskites for Improved Solar Thermochemical Generation of Hydrogen

Solar thermochemical hydrogen (STCH) production from water splitting typically requires performing redox cycles at temperatures above 1200 °C to reduce and re-oxidize the bulk of a reversible material. Bulk processes such as oxygen vacancy formation and oxygen diffusion energies dictate the viability of a material for STCH. The surface plays an important role in the formation and destruction of vacancies and interacts with gas phase water and surface adsorbed species. These surface processes can lead to surface reconfigurations and even the formation of surface phases with stoichiometry and oxygen content very different from the bulk composition. Understanding in-situ the surface chemical state and its evolution under water splitting is important to design nonstoichiometric oxides capable of longer-lasting STCH generation at lower temperatures. In this work, we describe the water splitting active defect sites in LSM ((La 0.65 Sr 0.35 ) 0.95 MnO 3–δ ) and Ga-doped LSM ((La 0.6 Sr 0.4 ) 0.95 (Mn 0.8 Ga 0.2 )O 3–δ ) perovskites during Operando thermochemical water splitting conditions using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) experiments at 800 °C under steam. We show that sub-stoichiometric La +3 in the oxygen-vacancy rich surface at operating conditions can be used to correlate surface water splitting activity and the creation of surface hydroxide intermediates. The addition of Ga in LSM is shown to drastically stabilize the surface chemical composition by preventing Sr segregation and stabilizing catalytically active surface defects that promote the binding of adsorbed hydroxides. Here, we use Operando AP-XPS quantification of metastable surface hydroxide intermediates (La(OH) 3 ) to determine the amount of catalytically active surface sites in LSM (2.9%) and in LSMG (7.8–8.1%, depending on the bulk oxidation state).

08 HYDROGEN↗

Electrification in Hurricanes over the Tropical Americas: Implication for Stratospheric Water Vapor

This study explores the relation between lightning activity and water vapor in the Tropical Tropopause Layer (TTL) over hurricane systems in the Tropical Americas. The hypothesis herein is that hurricanes that exhibit enhanced lightning activity are associated with stronger updrafts that can transport more moisture directly into the TTL (and subsequently into the tropical stratosphere) or even directly into the tropical stratosphere over this region. The TTL over the Tropical Americas, which includes the Caribbean and Gulf of Mexico, is of particular interest, because summertime cold point tropopause is the lowest in height and thus the warmest in temperature over the tropics. The latter condition implies higher saturation values and thus potential for more water vapor to enter the stratosphere. Climate forecast is very sensitive to stratospheric water vapor abundance, because of the key role that water vapor plays in regulating the chemical and radiative properties of the stratosphere. Given the potential for increases in hurricane intensity and frequency under predicted warmer conditions, it becomes essential to understand the effect of hurricanes on stratospheric water vapor. In this study, we use a combination of ground and space-borne observations as well as trajectory calculations. The observations include: cloud-to-ground (CG) lightning data from the U.S. National Lightning Detection Network (NLDN), geostationary infrared observations from the National Climatic Data Center Hurricane Satellite (HURSAT) data set, cloud properties from Aqua-MODIS, and water vapor from Aura-MLS. We analyze hurricanes from the 2005 season when Aura-MLS data are available, namely: Dennis, Emily, Katrina, Rita, and Wilma. Our analysis consists of examining CG lightning, cloud-top properties, and TTL water vapor (i.e., 100 and 147 mb) over the hurricane while it remains over water in the Tropical Americas region. We investigate daily as well as diurnal statistical properties. The hurricanes analyzed in this study showed that lightning activity is negatively correlated with minimum infrared brightness temperature and positively correlated with 100-mb water vapor. An examination of the maxima in water vapor observed over the hurricane not only shows larger magnitudes, but also larger differences between water vapor averages and water vapor maxima over the hurricane as lightning activity increases. Trajectory calculations are performed using the Flextra model in order to investigate the fate of the moister air masses found in the TTL.

Pittman, Jasna V.↗

Engineering PdAu/CeO 2 Alloy/Oxide Interfaces for Selective Methane‐to‐Methanol Conversion with Water

The direct conversion of methane-to-methanol remains a critical challenge in methane valorization. In this study, we unveil the crucial role of PdAu/CeO 2 catalysts in enabling selective methane transformation under mild conditions, using only water as the sole oxidant. Through a combination of experimental techniques, including XPS and catalytic testing, alongside density functional theory (DFT) calculations, we demonstrate that a Pd 0.3 Au 0.7 /CeO 2 catalyst, which predominantly exposes isolated Pd atoms, achieves remarkable methanol selectivity (∼80%) at 500 K with a 1:1 methane-to-water ratio. While Pd/CeO 2 efficiently activates methane, its tendency for overreaction leads to complete methanol decomposition, thereby limiting selectivity. Alloying Pd with Au on ceria mitigates this over-reactivity, preventing methanol degradation while maintaining sufficient catalytic activity. The PdAu/CeO 2 composite exhibits a synergistic effect: Pd in contact with the ceria support facilitates methane activation and water dissociation, while Au fine-tunes reactivity to promote methanol formation. DFT calculations confirm that isolated Pd sites at the PdAu/CeO 2 interface play a key role in balancing activity and selectivity. This work underscores the importance of alloy/oxide interfaces in controlling selective methane conversion with water and offers valuable insights for designing highly efficient catalysts for methanol synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A bioinspired cobalt catalyst based on a tripodal imidazole/pyridine platform capable of water reduction and oxidation

The prototypical drug carrier [Co II (L 1 )Cl]PF 6 (1), where L 1 is a tripodal amine bound to pyridine and methyl-imidazoles, had its electrocatalytic water splitting activity studied under different pH conditions. This species contains a high-spin 3d 7 Co II metal center, and is capable of generating both H 2 from water reduction and O 2 from water oxidation. Turnover numbers reach 390 after 3 h for water reduction. Initial water oxidation activity is molecular, with TONs of 71 at pH 7 and 103 at pH 11.5. The results reveal that species 1 can undergo several redox transformations, including reduction to the 3d 8 Co I species that precedes a LS 3d 6 hydride for water reduction, as well as nominal Co IV $=$O and Co III -OOH species required for water oxidation. Finally, post-catalytic analyses confirm the molecular nature of reduction and support initial molecular activity for oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanochemically accelerated deconstruction of chemically recyclable plastics

Plastics redesign for circularity has primarily focused on monomer chemistries enabling faster deconstruction rates concomitant with high monomer yields. Yet, during deconstruction, polymer chains interact with their reaction medium, which remains underexplored in polymer reactivity. Here, we show that, when plastics are deconstructed in reaction media that promote swelling, initial rates are accelerated by over sixfold beyond those in small-molecule analogs. This unexpected acceleration is primarily tied to mechanochemical activation of strained polymer chains; however, changes in the activity of water under polymer confinement and bond activation in solvent-separated ion pairs are also important. Together, deconstruction times can be shortened by seven times by codesigning plastics and their deconstruction processes.

36 MATERIALS SCIENCE↗