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At least 325 records · Page 18

Understanding Instability in Formamidinium Lead Halide Perovskites: Kinetics of Transformative Reactions at Grain and Subgrain Boundaries

Transformative and reconstructive reactions impart significant structural changes at particle boundaries of hybrid perovskites, which influence environmental stability and optoelectronic properties of these materials. Here, we investigate the moisture-induced transformative reactions in formamidinium based perovskites FAPbX 3 (X=I, Br) and show that the ambient stability of these materials can be adjusted from a few hours to several months. For FAPbI 3 , roles of water vapor, particle size, and light illumination on the kinetic pathways of the cubic (a) transformation to the hexagonal (d) phase are analyzed by X-ray diffraction, optical microscopy, photoluminescence and solid-state NMR spectroscopy techniques. The grain and sub-grain boundaries exhibit different α→δ-FAPbI 3 phase transformation kinetics. Our study suggests that the dynamic transformation involves the local water-induced dissolution of the cubic phase occurring at the crystal surfaces followed by precipitation of the hexagonal phase. Insights into structures and dynamics of a kinetically trapped α-|δ-FAPbI 3 are obtained by 1 H, 2 H, and 207 Pb ssNMR spectroscopy.

36 MATERIALS SCIENCE↗

Optimization of Preparation Method, Nucleating Agent, and Stabilizers for Synthesizing Calcium Chloride Hexahydrate (CaCl2.6H2O) Phase Change Material

This study investigates improvements in low-cost latent heat storage material calcium chloride hexahydrate (CaCl2.6H2O). Its melting point is between 25 and 28 °C, with relatively high enthalpy (170–190 J/g); however, this phase change material (PCM) shows supercooling and phase separation. In CaCl2.6H2O incongruent melting causes lower hydrates of CaCl2 to form, which affects the overall energy storage capacity and long-term durability. In this work, PCM performance enhancement was achieved by adding SrCl2.6H2O as a nucleating agent and NaCl/KCl as a stabilizer to prevent supercooling and phase separation, respectively. We investigated the PCM preparation method and optimized the proportions of SrCl2.6H2O and NaCl/KCl. Thermal testing for 25 cycles combined with DSC and T-history testing was performed to observe changes in enthalpy, phase transitions and supercooling over the extended period of usage. X-ray diffraction was used to verify crystalline structure in the compounds. It was found that the addition of 2 wt.% of SrCl2.6H2O reduced supercooling from 12 °C to 0 °C compared to unmodified CaCl2.6H2O. The addition of 5 wt.% NaCl or KCl proved to effectively suppress separation and the melting enthalpy achieved was 169 J/g–178 J/g with congruent melting over 25 cycles, with no supercooling and almost no reduction in the latent heat.

42 ENGINEERING↗

Moisture Stability of Sulfide Solid-State Electrolytes

In this report we detail a comprehensive study on the moisture stability of sulfide solid-state electrolytes in dry room environments. Although sulfide SSEs have many favorable attributes, this class of materials suffers from poor stability with water. Sulfide SSEs react with water to form gaseous H 2 S and a variety of solid byproducts like Li 3 PO 4 and LiOH, which go on to increase the interfacial impedance of solid-state batteries. Lab-scale research typically utilizes gloveboxes with <1 ppm water, however, the large-scale manufacturing of Li-ion batteries occurs in –40°C dewpoint dry rooms with around 126 ppm water. Consequently, the moisture stability of sulfide SSEs must be addressed if the manufacture of solid-state batteries based on sulfide SSEs is to be scaled up. Here, we are the first to characterize the moisture stability of sulfide SSEs according to both H 2 S and the degradation of ionic conductivity at different moisture setpoints ranging from –76°C to –40°C dewpoint. A variety of different SSE compositions are studied; namely, (Li 2 S) 75 (P 2 S 5 ) 25 , (Li 2 S) 70 (P 2 S 5 ) 30 , (Li 2 O) 7 (Li 2 S) 68 (P 2 S 5 ) 25 , (Li 2 O) 7 (Li 2 S) 63 (P 2 S 5 ) 30 , and (Li 2 S) 75 (P 2 S 5 ) 25 + 20 mol% LiI. We find that moisture stability improves with 75 mol% Li2S modifier content and the introduction of a Li 2 O co-modifier. After a 30 min exposure in a –40°C dewpoint dry room environment we found that (Li 2 S) 75 (P 2 S 5 ) 25 + 20 mol% LiI powder generated 0.1 cc/g H 2 S and its ionic conductivity decreased by over 50%. However, when SSE powder was exposed as a slurry in a dodecane carrier the same SSE composition generated 0 cc/g H 2 S and its ionic conductivity only dropped by 14%. Our results show that sulfide SSEs have acceptable moisture stability when appropriately processed in a dry room environment.

25 ENERGY STORAGE↗

Improved 140 Nd Production for the 140 Nd/ 140 Pr In Vivo Generator through Target Recycling and Radiochemical Optimization

Theranostic strategies that utilize f-block therapeutic radionuclides, including 161 Tb, 177 Lu, 225 Ac, and 227 Th, suffer from a shortage of positron emission tomography (PET) imaging counterparts in the same chemical space and often rely on 68 Ga as a surrogate. The 140 Nd/ 140 Pr in vivo PET generator, which belongs to the f-block, may address this issue and can be produced via the 141 Pr(p,2n) 140 Nd production route by using medium-energy cyclotrons. However, impurities in the target material, including stable Nd, and the inherent difficulty of adjacent lanthanide separations limit the achievable radionuclidic and chemical purity of 140 Nd. In this work, we address these challenges through the purification and recycling of praseodymium target material and optimization of Nd/Pr separation. The resulting purified 140Nd was evaluated using DOTA and Macropa chelators via radiolabeling and in vitro stability studies. A target material purification and recycling method was developed for the monoisotopic 141 Pr starting material to remove stable Nd impurities, yielding 90.3 ± 4.7% (n = 3) recovery. The purified 141 Pr was isolated as Pr 6 O 11 and irradiated with 24 MeV protons (20.07 MeV at the target surface) at 20 μA for 4 h, which produced 1417.0 ± 83.4 MBq (38.3 ± 2.2 mCi) of 140 Nd at the end of bombardment (EOB). The produced 140 Nd was purified through an optimized DGA normal method to recover 71.6 ± 6.3% pure 140 Nd. The amount of stable Nd reduced progressively in each target purification cycle from >340 ppm without purification to <250 ppb after three cycles, while other measured metallic impurities were below 30 ppb. This improvement in target purity was reflected in the direct increase of apparent molar activity (AMA), when purified 140 Nd was evaluated with DOTA and Macropa chelators. AMA of [ 140 Nd]Nd-DOTA and [ 140 Nd]Nd-Macropa increased from 70.3 MBq/μmol (1.9 mCi/μmol) and 74 MBq/μmol (2.0 mCi/μmol) to 8025.3 MBq/μmol (216.9 mCi/μmol) and 8473.0 MBq/μmol (229.0 mCi/μmol), respectively, after the third target purification cycle. Further evaluation of chelator-labeled 140 Nd showed that [ 140 Nd]Nd-DOTA was stable in phosphate-buffered saline (PBS), saline, human serum, and mouse serum, whereas [140Nd]Nd-Macropa was stable in all except human serum. This work established a practical methodological advance for the production of 140 Nd/ 140 Pr in vivo PET generators, combining optimized target recycling and radiochemical separation to enable scaled-up and high-molar activity 140 Nd suitable for preclinical imaging. These advances support broader development of 140 Nd/ 140 Pr as a robust PET analogue, especially for f-block therapeutics.

Irradiation↗

Eco-friendly, solution-processable and efficient low-energy lighting phosphors: copper halide based hybrid semiconductors Cu 4 X 6 (L) 2 (X = Br, I) composed of covalent, ionic and coordinate bonds

A series of copper halide based inorganic–organic hybrid semiconductors have been synthesized. Structural analysis confirms that all compounds are composed of one-dimensional Cu 4 X 6 2- anionic chains that coordinate to cationic ligands via Cu–N dative bonds. Different coordination affinities of the ligands lead to two types of ligand arrangements with various structural distortions. All compounds are highly resistant to heat and moisture as a result of the combination of coordinate and ionic bonds. Low energy emission with high efficiency is achieved for these compounds and the emission energy (~552–615 nm) and color (yellow-orange) can be tuned by varying the ligand and halogen element. The electronic structure and luminescence mechanism are examined by both experimental and theoretical methods. More importantly, all compounds demonstrate good solubility in polar aprotic solvents, a desired property that is absent in all other CuX hybrid families of extended structures, which is attributed primarily to the ionic nature of this material class. Furthermore, the good solution-processability, and cost effective and easily scalable synthesis coupled with high quantum efficiencies and framework stability make these hybrid materials promising phosphors for general lighting applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of surface coating on electrochemical and thermal behaviors of a Li-rich Li 1.2 Ni 0.16 Mn 0.56 Co 0.08 O 2 cathode

Lithium-rich layered oxide materials are considered as potential cathode materials for future high-performance lithium-ion batteries (LIBs) owing to their high operating voltage and relatively high specific capacity. However, perceptible issues such as poor rate performance, poor capacity retention, and voltage degradation during cycling need to be improved before the successful commercialization of the material. In this report, zirconia coated Li 1.2 Ni 0.16 Mn 0.56 Co 0.08 O 2 2 = 1.0, 1.5 and 2.0 wt%) materials are synthesized using a sol–gel assisted ball milling approach. A comparison of structural, morphological and electrochemical properties is examined to elucidate the promising role of ZrO 2 coating on the performance of the NMC cathode. A uniform and homogeneous ZrO 2 coating is observed on the surface of NMC particles as evident by TEM elemental mapping images. The ZrO 2 coated NMCs exhibit significantly improved electrochemical performance at a higher C-rate as compared to pristine material. 1.5% ZrO 2 coated NMC demonstrates better cycling stability (95% capacity retention) than pristine NMC (77% capacity retention) after 50 cycles. All ZrO 2 coated NMC materials demonstrated improved thermal stability compared to pristine material. The difference in onset temperature of 2 wt% ZrO 2 coated and pristine NMC is 20 °C. The improved electrochemical performance of ZrO 2 coated NMC can be attributed to the stabilization of its surface structure due to the presence of ZrO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemically-assisted removal of cadmium ions by redox active Cu-based metal-organic framework

An electrochemically-assisted wastewater treatment using Faradaic materials offers a promising technique for the selective removal of hazardous substances. Here, we demonstrate the reversible capture and release of cadmium ions in aqueous solutions, using a redox-active metal-organic framework (MOF) electrode. As-synthesized copper-based MOF (Cu-MOF-74; copper 2,5-dihydroxyterephthalate) is a highly attractive candidate for Faradaic electrosorption due to its large surface area, water stability, and redox-active metal nodes. Our work demonstrates the reversible capture and release of Cd 2+ ions assisted by the electrochemical redox reaction of Cu 2+ /Cu + within the MOF structure. Combined material characterization and electrosorption tests were carried out to determine the operational conditions for maximizing adsorption capacity, energy efficiency, and material stability, thus leading to excellent electrosorption (>100 mg g -1 ) and regeneration efficiency (>90%). This study demonstrates the feasibility of leveraging MOFs containing redox-active metal nodes for the selective separation of toxic cations, and paves the way for promising future applications of these 3-D porous structures for wastewater treatment and environmental remediation.

42 ENGINEERING↗

Metal infiltrated electrodes for solid state batteries

Disclosed are electrochemical devices and methods for making electrochemical devices such as metal infiltrated electrodes for solid state lithium ion and lithium metal batteries. In one method for forming an electrode, a metal is infiltrated into the pore space of the active material of the electrode providing improved electronic conductivity to the electrode. The electrode may also include a solid-state ion conducting material providing improved ion conductivity to the electrode. Before infiltration of the metal, a stabilization coating may be applied to the active material and/or the solid-state ion conducting material to the stabilize electrode interfaces by slowing, but not eliminating, the chemical reactions that occur at elevated temperatures during sintering of the active material and/or the solid-state ion conducting material forming the electrode.

Sakamoto, Jeffrey↗

Probing Thermal Stability of Li-Ion Battery Ni-Rich Layered Oxide Cathodes by means of Operando Gas Analysis and Neutron Diffraction

Thermal stability is a crucial parameter that must be considered within the overall performance metrics of Ni-rich layered oxide cathodes. While the intrinsic structural stability of the cathode materials under thermal conditions is important, it is also critical to consider their reaction with electrolytes. In this study, operando gas analysis, ex situ neutron diffraction, and differential scanning calorimetry were combined to give a broader picture of the thermal stability of Ni-rich NMC cathodes. Li 1– x Ni 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) composite materials with four different states of charge were investigated with and without the presence of an electrolyte. It has been found that electrolyte can greatly accelerate both the structural and thermal decomposition of the cathode materials. A higher state of charge will also make cathode materials more susceptible to thermal shock. Without an electrolyte, O 2 release inducing a structural change from layered to rock salt was the major observation during thermal runaway. However, all samples retained some levels of layered structure after annealing up to 300 °C without the electrolyte. In comparison, almost all the O3-type layered phase transformed to the rock-salt phase for the cathode materials heated with the electrolyte at the same experimental conditions. Moreover, the amount of CO 2 increased by nearly two orders of magnitude when annealing cathode materials with electrolyte in operando gas analysis experiments. More delithiated NMC811 samples released larger amounts of CO 2 at earlier onset temperatures, resonating well with the differential scanning calorimetry (DSC) results showing that more delithiated samples release more heat during thermal shock.

25 ENERGY STORAGE↗

Stable, Ductile and Strong Ultrafine HT-9 Steels via Large Strain Machining

Beyond the current commercial materials, refining the grain size is among the proposed strategies to manufacture resilient materials for industrial applications demanding high resistance to severe environments. Here, large strain machining (LSM) was used to manufacture nanostructured HT-9 steel with enhanced thermal stability, mechanical properties, and ductility. Nanocrystalline HT-9 steels with different aspect rations are achieved. In-situ transmission electron microscopy annealing experiments demonstrated that the nanocrystalline grains have excellent thermal stability up to 700 °C with no additional elemental segregation on the grain boundaries other than the initial carbides, attributing the thermal stability of the LSM materials to the low dislocation densities and strains in the final microstructure. Nano-indentation and micro-tensile testing performed on the LSM material pre- and post-annealing demonstrated the possibility of tuning the material’s strength and ductility. The results expound on the possibility of manufacturing controlled nanocrystalline materials via a scalable and cost-effective method, albeit with additional fundamental understanding of the resultant morphology dependence on the LSM conditions.

36 MATERIALS SCIENCE↗

Infrared Signatures for Phase Identification in Hafnium Oxide Thin Films

Phase identification in HfO 2 -based thin films is a prerequisite to understanding the mechanisms stabilizing the ferroelectric phase in these materials, which hold great promise in next-generation non-volatile memory and computing technology. While grazing-incidence X-ray diffraction is commonly employed for this purpose, it has difficulty unambiguously differentiating between the ferroelectric phase and other metastable phases that may exist due to similarities in the d-spacings, their low intensities, and the overlapping of reflections. Infrared signatures provide an alternative route. However, their use in phase identification remains limited because phase control has overwhelmingly been accomplished via substituents, thereby convoluting infrared signatures between the substituent and the phase changes they induce. Herein, we report the infrared optical responses of three undoped hafnium oxide films where annealing conditions have been used to create films consisting primarily of the ferroelectric polar orthorhombic Pca2 1 , antipolar orthorhombic Pbca, and monoclinic P2 1 /c phases, as was confirmed via transmission electron microscopy (TEM), UVvisible optical properties, and electrical property measurements. Vibrational signatures acquired from synchrotron nano-Fourier transform infrared spectroscopy (nano-FTIR) are shown to be capable of differentiating between the phases in a non-destructive, rapid, and nanoscale manner. The utility of nano-FTIR is illustrated for a film exhibiting an antiferroelectric polarization response. In this sample, it is proven that this behavior results from the Pbca phase rather than the often-cited tetragonal phase. Here, by demonstrating that IRspectroscopy can unambiguously distinguish phases in this material, this work establishes a tool needed to isolate the factors dictating ferroelectric phase stability in HfO 2 -based materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stability of the interorbital-hopping mechanism for ferromagnetism in multi-orbital Hubbard models

The emergence of insulating ferromagnetic phase in iron oxychalcogenide chain system has been recently argued to be originated by interorbital hopping mechanism. However, the practical conditions for the stability of such mechanism still prevents the observation of ferromagnetic in many materials. Here, we study the stability range of such ferromagnetic phase under modifications in the crystal fields and electronic correlation strength, constructing a theoretical phase diagram. We find a rich emergence of phases, including a ferromagnetic Mott insulator, a ferromagnetic orbital-selective Mott phase, together with antiferromagnetic and ferromagnetic metallic states. We characterize the stability of the ferromagnetic regime in both the Mott insulator and the ferromagnetic orbital-selective Mott phase forms. We identify a large stability range in the phase diagram at both intermediate and strong electronic correlations, demonstrating the capability of the interorbital hopping mechanism in stabilizing ferromagnetic insulators. Our results may enable additional design strategies to expand the relatively small family of known ferromagnetic insulators.

36 MATERIALS SCIENCE↗

Comparison of the Chemical Composition of Liquids from the Pyrolysis and Hydrothermal Liquefaction of Lignocellulosic Materials

Major differences in thermal stability and hydrotreatment behavior of HTL and pyrolysis oils have been reported in the literature. However, little is known about the variations in the chemical composition of these oils that could explain such differences. Two commercial wood pyrolysis oils (Pyrovac and BTG), and their water-soluble (WS) and water-insoluble fractions (WIS) were analyzed and compared with the aqueous (WS WD-57 ) and oily (WIS WS-57 ) fractions obtained from hydrothermal liquefaction (HTL) of Douglas-fir. The samples were characterized by GC/MS, Karl Fischer titration, carbonyl content, total acid number, elemental composition, calorific value, proximate analysis, Fourier Transform Infrared Spectroscopy (FTIR), Folin-Ciocalteu (FC), and UV fluorescence. All the fractions were also analyzed by Fourier Transform Ion Cyclotron Resonance Mass Spectroscopy (FT-ICR-MS) and by Electrospray Ionization (EI). The most prevalent class of compounds in the water insoluble phases were phenols derived from lignin. Water-soluble phases contain mostly the oxygenated compounds derived from cellulose and hemicellulose and were richer in carbonyl functional groups. The water content of the resulting aqueous phases were between: 65 (WS BTG ) and 96 (WS Pyrovac ) wt. %. The bio-oil from BTG has higher water content and lower HHV, compared to Pyrovac oil. The GC/MS results of BTG oil show the presence of a more prominent acetic acid peak and higher TAN number than the Pyrovac oil. The GC/MS of Pyrovac oil showed more obvious mono-phenol peaks. The quantification of this family by Folin-Ciocalteu method confirmed higher content of monophenolic compounds compared with the BTG oil. The lower thermal stability of pyrolysis oils compared with HTL biocrudes can be partially explained by the fact that pyrolysis oils (BTG and Pyrovac) contain carbohydrates while HTL biocrude (WIS WD-57 ) doesn’t. Thus, we decided to further investigate the chemical differences between the phenolic rich fractions insoluble in water and the holocellulose derived compounds soluble in water. Even after water extraction, the acid content of the water insoluble fraction from BTG (WISBTG) was higher than the acid content of the water insoluble fraction obtained by HTL (WISWSD-57). Likewise, the acid content of the aqueous phases derived from pyrolysis oils (WS Pyrovac , WS BTG ) was also higher than for the aqueous phase obtained by HTL (WSWSD-57). This result is in part due to the use of bases in the HTL process that neutralizes the acid formed in that process. Moreover, the starting feedstock may also influence the differences between the oils. Although, the UV-Fluorescence spectra, ICR-MS and the EI analyses showed some minor differences in the molecular weight and chemical make-up of the oligomers soluble and insoluble in water from pyrolysis and HTL; the differences observed were not large enough to justify the differences in behavior between these oils reported in the literature. Our results suggest that the differences observed between HTL biocrudes and pyrolysis oils are likely partially due to the presence of holocellulose derived products in the pyrolysis oils and higher acid contents.

09 BIOMASS FUELS↗

High temperature thermochemical energy storage materials

Disclosed are high enthalpy thermochemical energy storage materials that exhibit high thermal conductivity and stability at high temperature reaction conditions. Disclosed materials include hydride-based alloys that can undergo high temperature reversible hydrogenation/dehydrogenation reactions without phase change of any metal or metalloid components of the alloy. The materials undergo a reversible exothermic hydrogenation reaction to form a metal hydride and a ternary alloy that includes a high thermal conductivity metal that, in its pure state, would exhibit a phase change at the hydrogenation reaction conditions.

Ward, Patrick A.↗

Concentrating Rare Earth Elements in Coal mine drainage Using Coal Combustion Products through Abandoned Mine Land Reclamation

Rare earth elements (REEs) (including scandium, yttrium and a group of 15 lanthanides) are often considered to be critical components in the productions of renewable energy hardware, electric vehicles, health care and military equipment, and consumer electronic products. The demand of REEs has been projected to be growing at an annual rate of 5-9% in the next 25 years. In 2011, the global demand of total rare earth oxides (REOs) was estimated to be approximately 105,000 tons, which is expected to grow to 210,000 tons by 2025. China overwhelmingly dominates the current worldwide rare earth productions but has strategically restricted its exports, causing significant instability for the global market. In response to the increasing demand for REEs and the supply dominance of China, identifying alternative sources of REEs has become a critical issue for the United States and other countries. Coal, coal ash, and coal mine drainage (CMD) are considered to be the alternative sources of REEs. In the U.S., high REE concentrations have been reported to be closely associated with coal deposits, including the Appalachian Basins. When surface and/or groundwater come in contact with geologic strata containing sulfide minerals exposed by coal mining, the accelerated oxidation of sulfide minerals in the presence of ferric iron and/or oxygen can produce sulfuric acid. The process promotes the weathering of REE-bearing rocks and minerals in the host geologic strata. Compared to average river water and seawater, the concentrations of REEs can be orders of magnitude higher in CMD. In this study, we demonstrated a trap-extract-precipitate (TEP) process that can effectively recover REEs from CMD. The three-stage TEP process uses alkaline industrial by-products to capture REEs from CMD and then applies an extraction/precipitation procedure to produce a feedstock that can be economically processed to produce marketable rare earth oxides. The alkaline industrial by-products tested in this study include the residual from a water softening process (DRWP sludge) and two types of stabilized flue gas desulfurization materials (sFGDs). sFGD material is a mixture of lime (CaO) and two coal combustion by-products, calcium sulfite FGD by-product and fly ash. The objectives of this study are to (1) validate the effectiveness and feasibility; (2) determine mechanisms controlling the rare earth recovery, (3) quantify the associated economic and environmental benefits, and (4) evaluate the full-scale application. To achieve these objectives, tasks to be carried out in this proposed project are organized into three phases. In the first phase, the research team collaborated with Ohio Department of Natural Resources, American Electric Power, The Wilds (a nonprofit wildlife conservation organization), and a private landowner to carry out field investigations aimed to screen and evaluate the seasonal changes of rare earths in the CMD discharges that have high recovery potentials. Next, the recovery of REEs from CMD was tested using a series of lab-scale column and batch tests under, respectively, percolation and completely mixed conditions. Results obtained from these lab-scale studies show that all three tested solids are very effective in retaining REEs. Over 98% of the CMD REEs that contacted the solids were captured before the solids exhausted their neutralization capacities. We also determined an extraction process using a non-acid, organic ligand extraction solution that can effectively remobilize the retained REEs from the spent solids (over 90%). The REE concentrate (>7.5 wt. % of total REEs) is then formed in an aeration process. The TEP process uses environmentally benign industrial by-products and a naturally-occurring organic ligand to mitigate CMD and recover REEs. Techno-economic analysis (TEA) and life-cycle assessment (LCA) was carried out in the third phase. The engineering-economic costs and net energy, net CO2 emissions, and water and other requirements were investigated to understand the economic and environmental implications of this process. This work uses mass and energy balances from laboratory-scale experiments to estimate the economic costs and environmental impacts. The results suggest that passive treatment systems that use DRWP sludge are preferred over those that use sFGD material, because of lower economic costs ($89,300/yr with a unit cost of $86/gT-REE vs. $89,800/yr, or $278/gT-REE) and improved environmental performance across all indicators from two different impact assessment methods. These differences are largely attributable to the larger capacity of DRWP sludge in the passive treatment application. We envision this TEP process can be integrated with abandoned mine land (AML) reclamation to create an approach that can add economic incentives for AML reclamation, remediate CMD discharge, and eliminate public safety hazards and threats to local environment and ecological systems posed by AMLs. It can restore lands and communities that are adversely impacted by legacy mining.

01 COAL, LIGNITE, AND PEAT↗

Gradient synthesis of carbon quantum dots and activated carbon from pulp black liquor for photocatalytic hydrogen evolution and supercapacitor

Black liquor (BL) is a by-product of the chemical pulping industry and is mainly used as a low-value fuel; however, its potential to produce high-value products has not been fully exploited. In this study, a green and simple strategy is reported for the gradient production of Na + -functionalized carbon quantum dots (Na + -CQDs) for the first time, N and S co-doped CQDs (N/S-CQDs), and N and S co-doped KOH-activated carbon (N/S-KAC) from BL by dialysis, hydrothermal carbonization and activation-carbonization, respectively. Due to the good electron trapping ability, photoluminescence and promising up-conversion luminescence of CQDs, the hydrogen evolution efficiency of Na + -CQDs/TiO 2 and N/S-CQDs/TiO 2 photocatalysts was improved by 2.45 and 1.46 times, respectively, compared with pure TiO 2 . N/S-KAC with a high specific surface area of 2294 m 2 g -1 provides an excellent specific capacitance of 253 F g -1 at 0.5 A g -1 and a promising energy density of 26.92 Wh kg -1 under a power density of 566 W kg -1 for the fabricated symmetrical supercapacitor. Moreover, the electrode material has good cycling stability with a capacitance retention of ~ 93.91% after 5000 cycles. In conclusion, this pathway provides a versatile and scalable approach for the construction and co-production of nanostructured materials, photocatalysts and energy storage devices.

36 MATERIALS SCIENCE↗

Magnesium Todorokite: Influence of Morphology on Electrochemistry in Lithium, Sodium and Magnesium Based Batteries

Samples of Mg-todorokite with mixed nanosheet & nanowire (referred to as nanosheets for the sake of simplicity) and pure nanowire morphology were prepared to probe the morphological impact on battery relevant electrochemistry. The samples had similar physicochemical properties where the Mg-todorokite nanosheets had a composition of Mg 0.20 MnO 2 with a crystallite size of 9 nm and water content of 0.29 moles of H 2 O per formula unit, while the nanowires had a composition of Mg 0.19 MnO 2 with a crystallite size of 14 nm and water content of 0.28. The electrochemistry of the Mg-todorokite materials was evaluated using cyclic voltammetry, galvanostatic cycling, and rate capability testing. The Mg-todorokite nanosheets showed higher discharge capacity than the nanowires in lithium, sodium and magnesium-based electrolytes. Notably, the nanowire materials exhibited excellent cycling stability compared to the nanosheets in lithium and sodium-based batteries. Finally, x-ray absorption spectroscopy (XAS) of lithiated samples suggests that Mn in the nanosheet containing material was more highly reduced to Mn 3+ after the 1st full discharge explaining the higher initial capacities observed. However, a MnO-like structural distortion was observed after extended cycling in the nanosheet material consistent with its poorer capacity retention.

25 ENERGY STORAGE↗

Novel Ultrabright and Air-Stable Photocathodes Discovered from Machine Learning and Density Functional Theory Driven Screening

The high brightness, low emittance electron beams achieved in modern X-ray free-electron lasers (XFELs) have enabled powerful X-ray imaging tools, allowing molecular systems to be imaged at picosecond time scales and sub-nanometer length scales. One of the most promising directions for increasing the brightness of XFELs is through the development of novel photocathode materials. Whereas past efforts aimed at discovering photocathode materials have typically employed trial-and-error-based iterative approaches, this work represents the first data-driven screening for high brightness photocathode materials. Through screening over 74 000 semiconducting materials, a vast photocathode dataset is generated, resulting in statistically meaningful insights into the nature of high brightness photocathode materials. This screening results in a diverse list of photocathode materials that exhibit intrinsic emittances that are up to 4x lower than currently used photocathodes. In a second effort, multiobjective screening is employed to identify the family of M 2 O (M = Na, K, Rb) that exhibits photoemission properties that are comparable to the current state-of-the-art photocathode materials, but with superior air stability. This family represents perhaps the first intrinsically bright, visible light photocathode materials that are resistant to reactions with oxygen, allowing for their transport and storage in dry air environments.

36 MATERIALS SCIENCE↗