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At least 757 records · Page 42

Cause of a Lower-Tropospheric High-Ozone Layer in Spring Over Hanoi

The ozonesonde observations in Hanoi, Vietnam, over fourteen years since 2004 have confirmed the enhancement in lower tropospheric ozone concentration at about 3 km altitude in the spring season. We investigated the evolution of the ozone enhancement from analysis of meteorological data, backward trajectories, and model sensitivity experiments. In spring, air masses over Hanoi exhibit strong height dependence. At 3km, the high-ozone air masses originate from the land area to the west of Hanoi, while low-ozone air masses below about 1.5 km are from the oceanic area to the east. Above 4 km, the air masses are mostly traced back to the farther west area. The chemical transport model simulations revealed that precursor emissions from biomass burning in the inland Indochina Peninsula have the largest contribution to the lower tropospheric ozone enhancement, which is transported upward and eastward and overhangs the clean air intrusion from the ocean to the east of Hanoi. At this height level, the polluted air has the horizontal extent of about 20 degrees in longitude and latitude. The polluted air observed in Hanoi is transported further east and widely spread over the northern Pacific Ocean.

tropospheric ozone↗

Cause of a Lower-Tropospheric High-Ozone Layer in Spring Over Hanoi

The ozonesonde observations in Hanoi, Vietnam, over fourteen years since 2004 have confirmed the enhancement in lower tropospheric ozone concentration at about 3 km altitude in the spring season. We investigated the evolution of the ozone enhancement from analysis of meteorological data, backward trajectories, and model sensitivity experiments. In spring, air masses over Hanoi exhibit strong height dependence. At 3km, the high-ozone air masses originate from the land area to the west of Hanoi, while low-ozone air masses below about 1.5 km are from the oceanic area to the east. Above 4 km, the air masses are mostly traced back to the farther west area. The chemical transport model simulations revealed that precursor emissions from biomass burning in the inland Indochina Peninsula have the largest contribution to the lower tropospheric ozone enhancement, which is transported upward and eastward and overhangs the clean air intrusion from the ocean to the east of Hanoi. At this height level, the polluted air has the horizontal extent of about 20 degrees in longitude and latitude. The polluted air observed in Hanoi is transported further east and widely spread over the northern Pacific Ocean.

Hanoi↗

Computational Aerodynamic Analysis in Support of the CRM Tail Cone Thruster Configuration Wind Tunnel Test

NASA’s Advanced Air Transport Technology (AATT) project is breaching the boundaries of aircraft design in pursuit of eco-friendly solutions that are compatible with urban noise comfort levels. Boundary layer ingesting (BLI) propulsion systems promise to reduce fuel burn with additional potential benefits in noise reduction. Type-II BLI systems of the STARC-ABL type are the subject of a test campaign planned for fiscal year 2022 in the National Transonic Facility (NTF), for which a CRM-based model with a retrofitted tail cone thruster (TCT) has been designed. The present work is a precursor to the NTF test, where the 240 cases planned for the experiment were simulated using the Launch, Ascent and Vehicle Aerodynamics (LAVA)computational framework. Solution sensitivity to angle of attack, engine operating conditions, and the presence of the supporting structure (sting) in the wind tunnel test are analyzed in the extensive dataset. The main flow features contributing to the inlet distortion are identified as the vertical tail wake, wing downwash and fuselage upsweep vortices, with the latter two experiencing the greatest sensitivity to angle of attack. Finally, results from an inlet-guide-vane(IGV) design/integration study are presented. The LAVA team and the turbomachinery design team at NASA’s Ames and Glenn Research Centers are collaborating in an effort to reduce flow distortion upstream of the fan by means of integrating an IGV system into the CRM-TCT model. A significant improvement in flow distortion metrics has been achieved since the initial design iteration. Results employing an actuator zone model with realistic radially-varying thrust profiles to simulate first-order fan effects within LAVA are presented.

AATT↗

Effect of CMAS viscosity on the infiltration depth in thermal barrier coatings of different microstructures

Calcium magnesium aluminum silicate (CMAS) is one of the leading concerns for the gas turbine industry. The effects of CMAS viscosity and the coating microstructure on CMAS infiltration depth were explored by conducting a time dependent interaction study. Three CMAS compositions were used from literature, and their viscosities predicted through FactSage viscosity module were drastically different. The interaction was carried out on three different TBCs synthesized using the solution precursor plasma spray process (SPPS): two of the TBCs were made of yttrium aluminum garnet (YAG) having different microstructures that promote different modes of CMAS infiltration, and one TBC was made of gadolinium zirconate (GZO). All samples had stress relieving vertical cracks and different intensities of horizontally banded porosity, (inter pass boundaries IPBs). A concentration of 100 mg/cm 2 of CMAS was applied on the TBCs which were then subjected to a 5-minute interaction at 1300 °C. Samples were analyzed using scanning electron microscopy (SEM), electron dispersive X-ray spectroscopy (EDXS), and transmission electron microscopy (TEM). Low viscosity CMAS readily penetrated the TBCs while more viscous CMAS showed less penetration. The depth of CMAS infiltration depended on the coating microstructure. In the YAG with IPBs, the CMAS spread horizontally in the IPBs before infiltrating deeper, resulting in reduced infiltration depth compared to other samples in spite of having wider vertical cracks. TEM and EDXS analysis were performed to investigate the phases present in the CMAS-TBC interaction region in YAG. Two regions were chosen, the top TBC surface in direct contact with the sea of CMAS, and the region at the CMAS penetration ended within the coating. Finally, the results showed that no secondary phases like apatite were observed in YAG, thus it can be concluded that the arrest of CMAS happened solely because of CMAS viscosity and the short infiltration time.

36 MATERIALS SCIENCE↗

Lignin conversion to β-ketoadipic acid by Pseudomonas putida via metabolic engineering and bioprocess development

Bioconversion of a heterogeneous mixture of lignin-related aromatic compounds (LRCs) to a single product via microbial biocatalysts is a promising approach to valorize lignin. Here, Pseudomonas putida KT2440 was engineered to convert mixed p-coumaroyl– and coniferyl-type LRCs to β-ketoadipic acid, a precursor for performance-advantaged polymers. Expression of enzymes mediating aromatic O-demethylation, hydroxylation, and ring-opening steps was tuned, and a global regulator was deleted. β-ketoadipate titers of 44.5 and 25 grams per liter and productivities of 1.15 and 0.66 grams per liter per hour were achieved from model LRCs and corn stover-derived LRCs, respectively, the latter representing an overall yield of 0.10 grams per gram corn stover-derived lignin. Technoeconomic analysis of the bioprocess and downstream processing predicted a β-ketoadipate minimum selling price of $\$2.01$ per kilogram, which is cost competitive with fossil carbon-derived adipic acid ($\$1.10$ to 1.80 per kilogram). Overall, this work achieved bioproduction metrics with economic relevance for conversion of lignin-derived streams into a performance-advantaged bioproduct.

09 BIOMASS FUELS↗

Functional analysis of the methylerythritol phosphate pathway terminal enzymes IspG and IspH from Zymomonas mobilis

ABSTRACT Isoprenoids are a diverse family of compounds that are synthesized from two isomeric compounds, isopentenyl diphosphate and dimethylallyl diphosphate. In most bacteria, isoprenoids are produced from the essential methylerythritol phosphate (MEP) pathway. The terminal enzymes of the MEP pathway IspG and IspH are [4Fe-4S] cluster proteins, and in Zymomonas mobilis, the substrates of IspG and IspH accumulate in cells in response to O 2 , suggesting possible lability of their [4Fe-4S] clusters. Here, we show using complementation assays in Escherichia coli that even under anaerobic conditions, Z. mobilis IspG and IspH are not as functional as their E. coli counterparts, requiring higher levels of expression to rescue viability. A deficit of the sulfur utilization factor (SUF) Fe-S cluster biogenesis pathway did not explain the reduced function of Z. mobilis IspG and IspH since no improvement in viability was observed in E. coli expressing the Z. mobilis SUF pathway or having increased expression of the E. coli SUF pathway. Complementation of single and double mutants with various combinations of Z. mobilis and E. coli IspG and IspH indicated that optimal growth required the pairing of IspG and IspH from the same species. Furthermore, Z. mobilis IspH conferred an O 2 -sensitive growth defect to E. coli that could be partially rescued by co-expression of Z. mobilis IspG. In vitro analysis showed O 2 sensitivity of the [4Fe-4S] cluster of both Z. mobilis IspG and IspH. Altogether, our data indicate an important role of the cognate protein IspG in Z. mobilis IspH function under both aerobic and anaerobic conditions. IMPORTANCE Isoprenoids are one of the largest classes of natural products, exhibiting diversity in structure and function. They also include compounds that are essential for cellular life across the biological world. In bacteria, isoprenoids are derived from two precursors, isopentenyl diphosphate and dimethylallyl diphosphate, synthesized primarily by the methylerythritol phosphate pathway. The aerotolerant Z. mobilis has the potential for methylerythritol phosphate pathway engineering by diverting some of the glucose that is typically efficiently converted into ethanol to produce isoprenoid precursors to make bioproducts and biofuels. Our data revealed the surprising finding that Z. mobilis IspG and IspH need to be co-optimized to improve flux via the methyl erythritol phosphate pathway in part to evade the oxygen sensitivity of IspH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A multiwavelength analysis of a collection of short-duration GRBs observed between 2012 and 2015

We explore the prompt emission and the afterglow properties of short-duration gamma-ray burst (sGRB) 130603B and another eight sGRB events during 2012-2015, observed by several multiwavelength facilities including the Gran Canarias Telescope 10.4 m telescope. Prompt emission high energy data of the events were obtained by INTEGRAL-SPI-ACS, Swift-BAT, and Fermi-GBM satellites. The prompt emission data by INTEGRAL in the energy range of 0.1-10 MeV for sGRB 130603B, sGRB 140606A, sGRB 140930B, sGRB 141212A, and sGRB 151228A do not show any signature of the extended emission or precursor activity and their spectral and temporal properties are similar to those seen in case of other short bursts. For sGRB 130603B, our new afterglow photometric data constrain the pre-jet-break temporal decay due to denser temporal coverage. For sGRB 130603B, the afterglow light curve, containing both our new and previously published photometric data is broadly consistent with the ISM afterglow model. Modeling of the host galaxies of sGRB 130603B and sGRB 141212A using the LePHARE software confirms a scenario in which the environment of the burst is undergoing moderate star formation activity. From the inclusion of our late-time data for eight other sGRBs we are able to: place tight constraints on the non-detection of the afterglow, host galaxy, or any underlying 'kilonova' emission. Our late-time afterglow observations of the sGRB 170817A/GW170817 are also reported on and compared with the sub-set of sGRBs.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

A Multiwave Length Analysis of a Collection of Short-duration GRBs Observed between 2012 and 2015

We investigate the prompt emission and the afterglow properties of short-duration gamma-ray burst (sGRB) 130603B and another eight sGRB events during 2012–2015, observed by several multiwavelength facilities including the Gran Canarias Telescope 10.4 m telescope. Prompt emission high energy data of the events were obtained by INTEGRAL-SPI-ACS, Swift-BAT, and Fermi-GBM satellites. The prompt emission data by INTEGRAL in the energy range of 0.1–10 MeV for sGRB 130603B, sGRB 140606A, sGRB 140930B, sGRB 141212A, and sGRB 151228A do not show any signature of the extended emission or precursor activity and their spectral and temporal properties are similar to those seen in case of other short bursts. For sGRB 130603B, our new afterglow photometric data constrain the pre-jet-break temporal decay due to denser temporal coverage. For sGRB 130603B, the afterglow light curve, containing both our new and previously published photometric data is broadly consistent with the ISM afterglow model. Modeling of the host galaxies of sGRB 130603B and sGRB 141212A using the LePHARE software supports a scenario in which the environment of the burst is undergoing moderate star formation activity. From the inclusion of our late-time data for eight other sGRBs we are able to: place tight constraints on the non-detection of the afterglow, host galaxy, or any underlying ‘kilonova’ emission. Our late-time afterglow observations of the sGRB 170817A/GW170817 are also discussed and compared with the sub-set of sGRBs.

S B Pandey↗

Synthesis of boron-carbide aerogels

We present the synthesis of boron carbide aerogels utilizing nano-boron powder and resorcinol–formaldehyde (RF) organic aerogels as precursors. Monolithic aerogels were fabricated from suspensions of boron nanoparticles and RF via an organic sol-gel process, enabling effective distribution of boron in the gel network. The resulting gels underwent supercritical drying, thermal reduction, and subsequent heat treatment to yield boron carbide aerogels with densities ranging from 37 to 55 mg/cm³. By tuning the boron-to-carbon ratio, heat treatment temperature, and dwell time, surface areas up to 53 m²/g were obtained. X-ray diffraction analysis confirmed the formation of the boron carbide phase and detected the presence of residual carbon within the structure.

Materials science↗

Enhanced stability of Fe-modified CuO-ZnO-ZrO 2 -Al 2 O 3 /HZSM-5 bifunctional catalysts for dimethyl ether synthesis from CO 2 hydrogenation

In this report a series of iron (Fe) modified CuO-ZnO-ZrO 2 -Al 2 O 3 (CZZA) catalysts, with various Fe loadings, were prepared using a co-precipitation method. A bifunctional catalyst, consisting of Fe-modified CZZA and HZSM-5, was studied for dimethyl ether (DME) synthesis via CO 2 hydrogenation. The effects of Fe loading, reaction temperature, reaction pressure, space velocity, and concentrations of precursor for the synthesis of the Fe-modified CZZA catalyst on the catalytic activity of DME synthesis were investigated. Long-term stability tests showed that Fe modification of the CZZA catalyst improved the catalyst stability for DME synthesis via CO 2 hydrogenation. The activity loss, in terms of DME yield, was significantly reduced from 4.2% to 1.4% in a 100 h run of reaction, when the Fe loading amount was 0.5 (molar ratio of Fe to Cu). An analysis of hydrogen temperature programmed reduction revealed that the introduction of Fe improved the reducibility of the catalysts, due to assisted adsorption of H 2 on iron oxide. The good stability of Fe-modified CZZA catalysts in the DME formation was most likely attributed to oxygen spillover that was introduced by the addition of iron oxide. This could have inhibited the oxidation of the Cu surface and enhanced the thermal stability of copper during long-term reactions.

42 ENGINEERING↗

Thermal Activation of Zirconium(IV) Acetylacetonate Catalysts to Enhance Polyurethane Synthesis and Reprocessing

Carbamate formation and exchange catalysts enable efficient polyurethane (PU) manufacturing, as well as emerging recycling and reprocessing methods for PU thermosets. Zirconium β-diketonate complexes, such as Zr acetylacetonate [Zr(acac) 4 ], are effective alternatives to toxic organotin catalysts that have been used for PU reprocessing. Here, we report that Zr(acac) 4 undergoes a thermally activated process in the PU network during reprocessing that transforms it into a more active carbamate exchange catalyst. This process is associated with the irreversible loss of acetylacetonate ligands and is not observed for the more sterically hindered Zr 2,2,6,6-tetramethyl-3,5-heptanedione [Zr(tmhd) 4 ] complex. Crossover experiments between PU thermoplastics indicated enhanced carbamate exchange after the thermal activation of Zr(acac) 4 in the presence of one of the PUs, whereas a sample of Zr(acac) 4 activated in the absence of the PU had no catalytic activity. Thermal gravimetric analysis suggested that this process is associated with the loss of one protonated acac ligand. Stress relaxation analysis of PU thermosets indicated a distinct change in the characteristic relaxation time associated with the thermal activation of Zr(acac) 4 at temperatures above 140 °C; no such change was observed for samples reprocessed using Zr(tmhd) 4 . Density functional theory and molecular experiments suggest that irreversible ligand exchange of acac with alkoxide or carbamate reduces the activation energy for urethane formation and reversion. Furthermore, the Zr(acac) 4 catalyst activated in the presence of a PU’s polyol precursor provided more porous and less dense PU foams compared to those made using the unactivated Zr(acac) 4 catalyst. Furthermore, these findings are important for developing improved PU synthesis and recycling processes. Thermally activating a catalyst during reprocessing may provide more nuanced control of the in-use and reprocessing characteristics of PU thermosets.

Alcohols↗

SN 2021foa: the bridge between SN IIn and Ibn

ABSTRACT We present the long-term photometric and spectroscopic analysis of a transitioning SN IIn/Ibn from –10.8 d to 150.7 d post V-band maximum. SN 2021foa shows prominent He i lines comparable in strength to the H $\alpha$ line around peak, placing SN 2021foa between the SN IIn and SN Ibn populations. The spectral comparison shows that it resembles the SN IIn population at pre-maximum, becomes intermediate between SNe IIn/Ibn, and at post-maximum matches with SN IIn 1996al. The photometric evolution shows a precursor at –50 d and a light curve shoulder around 17 d. The peak luminosity and colour evolution of SN 2021foa are consistent with most SNe IIn and Ibn in our comparison sample. SN 2021foa shows the unique case of an SN IIn where the narrow P-Cygni in H $\alpha$ becomes prominent at 7.2 d. The H $\alpha$ profile consists of a narrow (500–1200 km s$^{-1}$) component, intermediate width (3000–8000 km s$^{-1}$) and broad component in absorption. Temporal evolution of the H $\alpha$ profile favours a disc-like CSM geometry. Hydrodynamical modelling of the light curve well reproduces a two-component CSM structure with different densities ($\rho \propto$ r$^{-2}$–$\rho \propto$ r$^{-5}$), mass-loss rates (10$^{-3}$–10$^{-1}$ M$_{\odot }$ yr$^{-1}$) assuming a wind velocity of 1000 km s$^{-1}$ and having a CSM mass of 0.18 M$_{\odot }$. The overall evolution indicates that SN 2021foa most likely originated from an LBV star transitioning to a WR star with the mass-loss rate increasing in the period from 5 to 0.5 yr before the explosion or it could be due to a binary interaction.

Gangopadhyay, Anjasha (ORCID:0000000238845637)↗

Descriptor-Based Analysis of Atomic Layer Deposition Mechanisms on Spinel LiMn 2 O 4 Lithium-Ion Battery Cathodes

Protective coatings have been shown to effectively suppress Mn ion dissolution from the spinel LiMn 2 O 4 lithium-ion battery cathode by stabilizing the surface against undesired side reactions with the electrolyte. In spite of extensive study, however, there remains a lack of atomic-scale understanding of how such coatings are deposited, and no molecular-level descriptor to predict trends in deposition mechanisms has been identified. We have recently shown that Al 2 O 3 coatings grown by atomic layer deposition (ALD) with alternating trimethylaluminum (TMA) and water exposures exhibit submonolayer growth because of precursor decomposition on the lithium manganate spinel (LMO) surface during early ALD pulses. In the present work, we elucidate the underlying mechanisms of this Al 2 O 3 ALD process using density functional theory (DFT) calculations and X-ray photoelectron spectroscopy (XPS) experiments, and we introduce a generalized descriptor-based framework to understand the resulting trends across a spectrum of surface structures and functionalities. We demonstrate that all decomposition products, including CH 3 -aluminum adducts and dissociated CH 3 groups, are Lewis bases and are coordinated to oxygen atoms on the LMO surface, leading to charge transfer to Lewis acidic Mn 3d states. Inert-transfer XPS supports these theoretical predictions, showing an increase in near-surface Mn 3+ content following TMA exposure and shifts in C is spectra consistent with C-O bond formation. We extend the DFT studies to various low- and high-index LMO surface facets, as a proxy for tuning the Lewis acid-base interactions between surface-bound CH 3 * and near-surface Mn ions. The thermochemistry for TMA reactions on these chemically distinct LMO surfaces demonstrates that ALD is structure-sensitive and that there is higher reactivity for TMA decomposition and Al 2 O 3 nucleation near LMO steps and defects. Motivated by the Lewis basic character of the decomposition products, we introduce the oxygen vacancy formation energy as a descriptor for decomposition energetics, and we demonstrate that all energetics are correlated to this quantity through the number of electrons that are transferred along the reaction coordinate. Finally, based on these findings, we hypothesize that improved electrochemical cycling with only 1-2 ALD cycles may be due to selective passivation of defect sites on the LMO surface that are more susceptible to Mn dissolution, and we suggest that similar descriptor-based analyses could be useful for the study of other ALD coatings on oxide substrates.

25 ENERGY STORAGE↗

Analysis of Base-Heating Environment During Ground Testing of a Lunar Lander Demonstrator

A three-dimensional, unstructured-grid, pressure-based, reacting flow, computational fluid dynamics (CFD) and heat transfer methodology was employed to study the base-heating environment of a lunar lander demonstrator, during terrestrial ground testing. Two base-heating environments were investigated: lunar lander demonstrator sitting on pad, and lunar lander demonstrator hovering at a distance above ground. Two unique and quite different base-flow physics are found for these two cases. In the case of demonstrator sitting on pad, the computed heat fluxes are high and the base flow is unsteady, caused by a Coanda effect precursor that makes the fountain jet oscillate about the center of the base. For the second case, due to the higher elevation of the demonstrator and the layout of the nozzles, the Coanda effect forces the fountain jet to be attached to two of the nozzle plumes, resulting in much lower computed base heat fluxes.

Wang, T. S.↗

Mesoporous PdAg Nanospheres for Stable Electrochemical CO 2 Reduction to Formate

Palladium is a promising material for electrochemical CO 2 reduction to formate with high Faradaic efficiency near the equilibrium potential. It unfortunately suffers from problematic operation stability due to CO poisoning on surface. In this work, it is demonstrated that alloying is an effective strategy to alleviate this problem. Mesoporous PdAg nanospheres with uniform size and composition are prepared from the co-reduction of palladium and silver precursors in aqueous solution using dioctadecyldimethylammonium chloride as the structure-directing agent. The best candidate can initiate CO 2 reduction at zero overpotential and achieve high formate selectivity close to 100% and great stability even at <-0.2 V versus reversible hydrogen electrode. The high selectivity and stability are believed to result from the electronic coupling between Pd and Ag, which lowers the d-band center of Pd and thereby significantly enhances its CO tolerance, as evidenced by both electrochemical analysis and theoretical simulations.

36 MATERIALS SCIENCE↗

Green synthesis of sulfur‐doped g‐C 3 N 4 nanosheets for enhanced removal of oxytetracycline under visible‐light irradiation and reduction of its N ‐nitrosodimethylamine formation potential

Abstract BACKGROUND In this study, sulfur‐doped g‐C 3 N 4 (SCN) nanosheets were synthesized using thiourea as a precursor, and then used to catalyze the degradation of oxytetracycline (OTC) under visible‐light irradiation. OTC was chosen as target contaminant because of it being an important precursor of N ‐nitrosodimethylamine (NDMA). RESULTS The removal of OTC was influenced by its initial concentration, initial pH, SCN dosage and water matrices. OTC (≤10 mg L −1 ) was almost completely removed in 40 min under the conditions of an initial pH of 7.0 and a SCN dose of 1.0 g L −1 , and its degradation was well described by the pseudo‐first‐order kinetics model. Water matrices would also influence the degradation of OTC in the system. Electron paramagnetic resonance analysis and trapping experiments confirmed that the function of the radicals for OTC removal followed the order of • O 2 − > • OH > h + . Eight transformation products were determined during the degradation of OTC, it being removed through four pathways: methyl oxidization, demethylation, decarbonylation and secondary alcohol oxidation. SCN was stable in the system, as the removal efficiency of OTC was not significantly reduced even after three recycles. In addition, 55.5% of NDMA formation potential of OTC was reduced after SCN catalytic oxidation. CONCLUSIONS The results imply that the visible‐light‐driven SCN catalytic oxidation is an effective technology not only for the removal of OTC but also for the reduction of NDMA formation potential. © 2021 Society of Chemical Industry

Dou, Yicheng↗

Marginal Damage of Methane Emissions: Ozone Impacts on Agriculture

Methane directly contributes to air pollution, as an ozone precursor, and to climate change, generating physical and economic damages to different systems, namely agriculture, vegetation, energy, human health, or biodiversity. The methane-related damages to climate, measured as the Social Cost of Methane, and to human health have been analyzed by different studies and considered by government rulemaking in the last decades, but the ozone-related damages to crop revenues associated to methane emissions have not been incorporated to policy agenda. Using a combination of the Global Change Analysis Model and the TM5-FASST Scenario Screening Tool, we estimate that global marginal agricultural damages range from ~ 423 to 556 $2010/t-CH 4 , of which 98 $2010/t-CH 4 occur in the USA, which is the most affected region due to its role as a major crop producer, followed by China, EU-15, and India. These damages would represent 39–59% of the climate damages and 28–64% of the human health damages associated with methane emissions by previous studies. The marginal damages to crop revenues calculated in this study complement the damages from methane to climate and human health, and provides valuable information to be considered in future cost-benefits analyses.

54 ENVIRONMENTAL SCIENCES↗

Coupling Amorphization and Compositional Optimization of Ternary Metal Phosphides toward High-Performance Electrocatalytic Hydrogen Production

Amorphous materials, with abundant active sites and unique electronic configurations, have the potential to outperform their crystalline counterparts in high-performance catalysis for clean energy. However, their synthesis and compositional optimization remain underexplored due to the strict conditions required for their formation. Here, in this study, we report the synthesis of ternary platinum-nickel-phosphorus (PtNiP) amorphous nanoparticles (ANPs) within milliseconds by flash Joule heating, which features ultrafast cooling that enables the vitrification of metal precursors. Through compositional optimization, the Gibbs free energy of hydrogen adsorption for Pt 4 Ni 4 P 1 ANPs is optimized at 0.02 eV, an almost ideal value, even surpassing that of the benchmark metallic platinum catalyst. As a result, the PtNiP ANPs exhibited superior activity in electrocatalytic hydrogen evolution in acid electrolyte (η 10 ∼ 14 mV, Tafel slope ∼ 18 mV dec –1 , and mass activity 5× higher than state-of-the-art Pt/C). Life-cycle assessment and technoeconomic analysis suggest that, compared to existing processes, our approach enables notable reductions in greenhouse gas emission, energy consumption, and production cost for practical electrolyzer catalyst manufacturing.

36 MATERIALS SCIENCE↗