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At least 73 records · Page 4

Ce IV 70 Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**

Abstract M IV molecular oxo‐clusters (M=Zr, Hf, Ce, Th, U, Np, Pu) are prolific in bottoms‐up material design, catalysis, and elucidating reaction pathways in nature and in synthesis. Here we introduce Ce 70 , a wheel‐shaped oxo‐cluster, [Ce IV 70 (OH) 36 (O) 64 (SO 4 ) 60 (H 2 O) 10 ] 4− . Ce 70 crystallizes into intricate high pore volume frameworks with divalent transition metals and Ce‐monomer linkers. Eight crystal‐structures feature four framework types in which the Ce 70 ‐rings are linked as propellers, in offset‐stacks, in a tartan pattern, and as isolated rings. Small‐angle X‐ray scattering of Ce 70 dissolved in butylamine, with and without added cations (Ce IV , alkaline earths, Mn II ), shows the metals‘ differentiating roles in ring linking, leading to supramolecular assemblies. The large acidic pores and abundant terminal sulfates provide ion‐exchange behavior, demonstrated with U IV and Nd III . Frameworks featuring Ce III/IV ‐monomer linkers demonstrate both oxidation and reduction. This study opens the door to mixed‐metal, highly porous framework catalysts, and new clusters for metal‐organic framework design

Colliard, Ian↗

Ce IV 70 oxosulfate rings, frameworks, supramolecular assembly and redox activity

M IV molecular oxo-clusters (M=Zr, Hf, Ce, Th, U, Np, Pu) are prolific in bottoms-up material design, catalysis, and elucidating reaction pathways in nature and in synthesis. Here we introduce Ce 70 , a wheel-shaped oxo-cluster, [Ce IV 70 -(OH) 36 (O) 64 (SO 4 ) 60 (H 2 O) 10 ] 4- . Ce 70 crystallizes into intricate high pore volume frameworks with divalent transition metals and Ce-monomer linkers. Eight crystal-structures feature four framework types in which the Ce 70 -rings are linked as propellers, in offset-stacks, in a tartan pattern, and as isolated rings. In this work, small-angle X-ray scattering of Ce 70 dissolved in butylamine, with and without added cations (Ce IV , alkaline earths, Mn II ), shows the metals‘ differentiating roles in ring linking, leading to supramolecular assemblies. The large acidic pores and abundant terminal sulfates provide ion-exchange behavior, demonstrated with U IV and Nd III . Frameworks featuring Ce III/IV -monomer linkers demonstrate both oxidation and reduction. Furthermore, this study opens the door to mixed-metal, highly porous framework catalysts, and new clusters for metal-organic framework design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Prediction by Convolutional Neural Networks of CO 2 /N 2 Selectivity in Porous Carbons from N 2 Adsorption Isotherm at 77 K

Abstract Porous carbons are an important class of porous materials with many applications, including gas separation. An N 2 adsorption isotherm at 77 K is the most widely used approach to characterize porosity. Conventionally, textual properties such as surface area and pore volumes are derived from the N 2 adsorption isotherm at 77 K by fitting it to adsorption theory and then correlating it to gas separation performance (uptake and selectivity). Here the N 2 isotherm at 77 K was used directly as input (representing feature descriptors for the porosity) to train convolutional neural networks to predict gas separation performance (using CO 2 /N 2 as a test case) for porous carbons. The porosity space for porous carbons was explored for higher CO 2 /N 2 selectivity. Porous carbons with a bimodal pore‐size distribution of well‐separated mesopores (3–7 nm) and micropores (<2 nm) were found to be most promising. This work will be useful in guiding experimental research of porous carbons with the desired porosity for gas separation and other applications.

Wang, Song↗

Prediction by Convolutional Neural Networks of CO 2 /N 2 Selectivity in Porous Carbons from N 2 Adsorption Isotherm at 77 K

Abstract Porous carbons are an important class of porous materials with many applications, including gas separation. An N 2 adsorption isotherm at 77 K is the most widely used approach to characterize porosity. Conventionally, textual properties such as surface area and pore volumes are derived from the N 2 adsorption isotherm at 77 K by fitting it to adsorption theory and then correlating it to gas separation performance (uptake and selectivity). Here the N 2 isotherm at 77 K was used directly as input (representing feature descriptors for the porosity) to train convolutional neural networks to predict gas separation performance (using CO 2 /N 2 as a test case) for porous carbons. The porosity space for porous carbons was explored for higher CO 2 /N 2 selectivity. Porous carbons with a bimodal pore‐size distribution of well‐separated mesopores (3–7 nm) and micropores (<2 nm) were found to be most promising. This work will be useful in guiding experimental research of porous carbons with the desired porosity for gas separation and other applications.

Wang, Song↗

A Three–Dimensional Nanoscale View of Electrocatalyst Degradation in Hydrogen Fuel Cells

The loss of platinum (Pt) electrochemically active surface area (ECSA) is a critical degradation mode that often becomes a limiting factor for heavy-duty proton exchange membrane fuel cell vehicles. High surface area carbon supports have been shown to improve Pt dispersion and limit detrimental ionomer-electrocatalyst interactions due to their large interior pore volume. Here, in this work, using automated scanning transmission electron tomography, the degradation of nanoparticles located on the interior versus exterior surfaces of the carbon support is compared following a catalyst-specific accelerated stress test (AST) of 90,000 voltage cycles between 0.6 V to 0.95 V. The results reveal a notable increase in median particle size for both interior and exterior Pt catalyst particles, with a slightly higher increase in particle size distribution and loss of specific surface area for the particles located on the exterior carbon surface. The fraction of Pt nanoparticles that reside within the interior of the carbon support also increased following the AST test, accompanied by evidence of an increase in average carbon mesopore size. Here, the results shed light on the degradation mechanisms affecting electrochemical properties and the enhanced particle accessibility at lower relative humidity.

08 HYDROGEN↗

Porogen‐Integrated Rapid Oxidation Enables Structured Mesoporous Metal Oxide Films

Structured metal oxide films have promise in optoelectronics, sensing, energy storage, and catalysis but their uptake is predominately limited due to their long and high‐temperature syntheses. Here, in this study, a self‐assembling polymer is used which can act as a chelating fuel source in a solution combustion reaction to generate highly structured mesoporous aluminum oxide films at <250 °C in a matter of minutes through a process termed porogen‐integrated rapid oxidation (PiRO). The resulting films with thicknesses up to 500 nm show an open‐cell, face‐centered cubic structure of spheroidal pores. Further, an additional ligand can be included to control the self‐assembly step to yield both through‐film ordering or tunable disordering for increased pore volume as confirmed by both grazing incidence small angle X‐ray scattering and ellipsometry. Finally, roll‐to‐roll manufacturing with PiRO is demonstrated on flexible polymeric substrates. The method offers a tunable, scalable, low‐temperature, and lower‐cost method to generate large‐area structured mesoporous metal oxide films.

36 MATERIALS SCIENCE↗

A Polymer-Assisted Spinodal Decomposition Strategy toward Interconnected Porous Sodium Super Ionic Conductor-Structured Polyanion-Type Materials and Their Application as a High-Power Sodium-Ion Battery Cathode

A general polymer-assisted spinodal decomposition strategy is used to prepare hierarchically porous sodium super ionic conductor (NASICON)-structured polyanion-type materials (e.g., Na 3 V 2 (PO 4 ) 3 , Li 3 V 2 (PO 4 ) 3 , K 3 V 2 (PO 4 ) 3 , Na 4 MnV(PO 4 ) 3 , and Na 2 TiV(PO 4 ) 3 ) in a tetrahydrofuran/ethanol/H 2 O synthesis system. Depending on the boiling point of solvents, the selective evaporation of the solvents induces both macrophase separation via spinodal decomposition and mesophase separation via self-assembly of inorganic precursors and amphiphilic block copolymers, leading to the formation of hierarchically porous structures. We find that the resulting hierarchically porous Na 3 V 2 (PO 4 ) 3 possessing large specific surface area (≈77 m 2 g -1 ) and pore volume (≈0.272 cm 3 g -1 ) shows a high specific capacity of 117.6 mAh g -1 at 0.1 C achieving the theoretical value and a long cycling life with 77% capacity retention over 1000 cycles at 5 C. This method presented here can open a facile avenue to synthesize other hierarchically porous polyanion-type materials.

36 MATERIALS SCIENCE↗

A Nickel-Decorated Carbon Flower/Sulfur Cathode for Lean-Electrolyte Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries involve a reversible conversion reaction between sulfur and lithium sulfide (Li 2 S) via a series of soluble lithium polysulfide intermediates (LiPSs), enabling a high theoretical specific capacity of 1675 mAh g –1 . However, this process exhibits large polarization and low sulfur utilization and suffers critical capacity fade. The primary approach to tackle the problem has so far been to infiltrate sulfur into nanostructured carbon. Furthermore, most studies using porous carbon as host materials have tested with high electrolyte to sulfur ratios (E/S) (generally > 15 µL mg –1 ) that compromise the cell-level energy density. Here, a flower-shaped porous carbon structure with nickel nanoparticles that can address the problems discussed above is designed. First, the 3D flower-shaped carbon structure enables short ionic transport lengths. Second, the small pore diameters <10 nm and high specific surface areas > 3300 m 2 g –1 with sufficient pore volume are ideal for charging performance for low E/S ratios. Finally, Ni nanoparticles are employed onto the flower-shaped network to improve the reaction kinetics. Collectively, it is successfully demonstrated that the batteries with a high mass loading of 5 mg cm –2 and a 5 µL mg –1 E/S ratio can retain cycle retention of 70% after 150 cycles.

25 ENERGY STORAGE↗

Effects of surface species and homogeneous reactions on rates and selectivity in ethane oxidation on oxide catalysts

Selective alkane oxidations on metal oxide catalysts involve complex mechanisms with multiple reactions in series and parallel, different types of reduced and oxidized surface species, and potential contributions from gas-phase reactions. We report kinetics and thermodynamics of elementary steps involved in C 2 H 6 -O 2 reactions on SiO 2 -supported small vanadium oxide domains are determined using density functional theory. These surface reactions together with gas-phase mechanisms are incorporated in kinetic simulations to determine how surface and gaseous reactions interact and contribute to rates and selectivity. The results show that gas-phase reactions within pore volumes in contact with the catalyst contribute significantly to C 2 H 6 activation rates, even at conditions where gas-phase reactions in empty volumes without catalyst are negligible. The majority of C 2 H 6 activations occur on the surface, via H abstraction by vanadium oxo species present at terminal lattice oxygens. The gas-phase activations via H-abstraction by OH radicals also exhibit significant contributions. The reduced centers formed by reactions at vanadium oxo species are re-oxidized rapidly and, therefore, are present in very small concentrations at reaction conditions. The re-oxidation steps lead to the formation of HO 2 radicals and surface peroxo species that are also rapidly consumed and are present in small concentrations. The peroxo species preferentially convert C 2 H 4 to its epoxide product and influence selectivity even at low concentrations. The gas-phase reactions decrease the concentrations of peroxo species and improve selectivity slightly. The effects of reaction conditions and catalyst site density provide further insights into how factors beyond conversions at lattice oxygens influence rates and selectivity in alkane oxidation reactions of significant industrial importance.

42 ENGINEERING↗

Porous Covalent Organic Polymers for Efficient Fluorocarbon‐Based Adsorption Cooling

Abstract Adsorption‐based cooling is an energy‐efficient renewable‐energy technology that can be driven using low‐grade industrial waste heat and/or solar heat. Here, we report the first exploration of fluorocarbon adsorption using porous covalent organic polymers (COPs) for this cooling application. High fluorocarbon R134a equilibrium capacities and unique overall linear‐shaped isotherms are revealed for the materials, namely COP‐2 and COP‐3. The key role of mesoporous defects on this unusual adsorption behavior was demonstrated by molecular simulations based on atomistic defect‐containing models built for both porous COPs. Analysis of simulated R134a adsorption isotherms for various defect‐containing atomistic models of the COPs shows a direct correlation between higher fluorocarbon adsorption capacities and increasing pore volumes induced by defects. Combined with their high porosities, excellent reversibility, fast kinetics, and large operating window, these defect‐containing porous COPs are promising for adsorption‐based cooling applications.

Zheng, Jian↗

Porous Covalent Organic Polymers for efficient Fluorocarbon-based Adsorption Cooling

Adsorption-based cooling is an energy-efficient renewable-energy technology that can be driven using low-grade industrial waste heat and/or solar heat. Here, we report the first exploration of fluorocarbon adsorption using porous covalent organic polymers (COPs) for this cooling application. High fluorocarbon R134a equilibrium capacities and unique overall linear-shaped isotherms are revealed for the materials, namely COP-2 and COP-3. The key role of mesoporous defects on this unusual adsorption behavior was demonstrated by molecular simulations based on atomistic defect-containing models built for both porous COPs. Analysis of simulated R134a adsorption isotherms for various defect-containing atomistic models of the COPs shows a direct correlation between higher fluorocarbon adsorption capacities and increasing pore volumes induced by defects. Combined with their high porosities, excellent reversibility, fast kinetics, and large operating window, these defect-containing porous COPs are promising for adsorption-based cooling applications.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Hierarchical Porous Activated Carbon from Wheat Bran Agro-Waste: Applications in Carbon Dioxide Capture, Dye Removal, Oxygen and Hydrogen Evolution Reactions

Here this work reports an efficient method for facile synthesis of hierarchically porous carbon (WB-AC) utilizing wheat bran waste. Obtained carbon showed 2.47 mmol g -1 CO 2 capture capacity with good CO 2 /N 2 selectivity and 27.35 to 29.90 kJ mol -1 isosteric heat of adsorption. Rapid removal of MO dye was observed with a capacity of ~555 mg g -1 . Moreover, WB-AC demonstrated a good OER activity with 0.35 V low overpotential at 5 mA cm -2 and a Tafel slope of 115 mV dec -1 . It also exhibited high electrocatalytic HER activity with 57 mV overpotential at 10 mA cm -2 and a Tafel slope of 82.6 mV dec -1 . The large SSA (757 m 2 g -1 ) and total pore volume (0.3696 cm 3 g -1 ) result from N 2 activation contributing to selective CO 2 uptake, high and rapid dye removal capacity and superior electrochemical activity (OER/HER), suggesting the use of WB-AC as cost effective adsorbent and metal free electrocatalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Adsorption of methylene blue by bismuth impregnated biochar of different biomass materials: pore structure and surface chemistry characteristics

Abstract In this study, three different types of biochar (biomass materials were beech wood, corncob, and bamboo) were loaded with bismuth to form bismuth impregnated biochars (named respectively as Bi@WBC, Bi@CBC, and Bi@BBC) to investigate their properties (pore structure and surface chemistry characteristics) on methylene blue (MB) removal capacities. Three bismuth impregnated biochars made from different biomass materials were ranked for their adsorption capacity of MB as follows: Bi@WBC > Bi@CBC > Bi@BBC, in which Bi@WBC showed the largest Langmuir adsorption capacity of 178.59 mg g −1 . While the specific surface area (SSA) and pore volume of Bi@WBC were the largest (accounting for 477.74 m 2 g −1 and 0.15 cm 3 g −1 , respectively), according to the FTIR and XPS results, Bi@WBC (72.3%) exhibited a higher proportion of BiO bonds than the Bi@CBC (52.3%) and Bi@BBC (48.4%) did. Conclusively, the rich porous structure and surface functional groups of Bi@WBC affected the adsorption capacity of MB, and the chemical adsorption provided the main contribution. © 2022 Society of Chemical Industry (SCI).

Li, Peiyi↗

Mafic explosive volcanism at Llaima Volcano: 3D x-ray microtomography reconstruction of pyroclasts to constrain shallow conduit processes

Abstract Mafic volcanic activity is dominated by effusive to mildly explosive eruptions. Plinian and ignimbrite-forming mafic eruptions, while rare, are also possible; however, the conditions that promote such explosivity are still being explored. Eruption style is determined by the ability of gas to escape as magma ascends, which tends to be easier in low-viscosity, mafic magmas. If magma permeability is sufficiently high to reduce bubble overpressure during ascent, volatiles may escape from the magma, inhibiting violent explosive activity. In contrast, if the permeability is sufficiently low to retain the gas phase within the magma during ascent, bubble overpressure may drive magma fragmentation. Rapid ascent may induce disequilibrium crystallization, increasing viscosity and affecting the bubble network with consequences for permeability, and hence, explosivity. To explore the conditions that promote strongly explosive mafic volcanism, we combine microlite textural analyses with synchrotron x-ray computed microtomography of 10 pyroclasts from the 12.6 ka mafic Curacautín Ignimbrite (Llaima Volcano, Chile). We quantify microlite crystal size distributions (CSD), microlite number densities, porosity, bubble interconnectivity, bubble number density, and geometrical properties of the porous media to investigate the role of magma degassing processes at mafic explosive eruptions. We use an analytical technique to estimate permeability and tortuosity by combing the Kozeny-Carman relationship, tortuosity factor, and pyroclast vesicle textures. The groundmass of our samples is composed of up to 44% plagioclase microlites, > 85% of which are < 10 µm in length. In addition, we identify two populations of vesicles in our samples: (1) a convoluted interconnected vesicle network produced by extensive coalescence of smaller vesicles (> 99% of pore volume), and (2) a population of very small and completely isolated vesicles (< 1% of porosity). Computed permeability ranges from 3.0 × 10 −13 to 6.3 × 10 −12 m 2 , which are lower than the similarly explosive mafic eruptions of Tarawera (1886; New Zealand) and Etna (112 BC; Italy). The combination of our CSDs, microlite number densities, and 3D vesicle textures evidence rapid ascent that induced high disequilibrium conditions, promoting rapid syn-eruptive crystallization of microlites within the shallow conduit. We interpret that microlite crystallization increased viscosity while simultaneously forcing bubbles to deform as they grew together, resulting in the permeable by highly tortuous network of vesicles. Using the bubble number densities for the isolated vesicles (0.1-3 −3 × 10 4 bubbles per mm 3 ), we obtain a minimum average decompression rate of 1.4 MPa/s. Despite the textural evidence that the Curacautín magma reached the percolation threshold, we propose that rapid ascent suppressed outgassing and increased bubble overpressures, leading to explosive fragmentation. Further, using the porosity and permeability of our samples, we estimated that a bubble overpressure > 5 MPa could have been sufficient to fragment the Curacautín magma. Other mafic explosive eruptions report similar disequilibrium conditions induced by rapid ascent rate, implying that syn-eruptive disequilibrium conditions may control the explosivity of mafic eruptions more generally.

Valdivia, Pedro↗

Evaluation of engineered sorbents for the sorption of mercury from contaminated bank soils: a column study

Abstract As a global environmental pollutant, mercury (Hg) threatens our water resources and presents a substantial risk to human health. The rate and extent of immobilization of Hg 2+ (hereafter, Hg) on engineered sorbents (Thiol-SAMMS®, pine biochar, SediMite™, Organoclay™ PM-199, and quartz sand as a control) was evaluated using flow-through column experiments. The effectiveness of the sorbents was based on (1) the percentage of Hg removed in relation to the total amount of Hg passing the sorbent column, and (2) the rate of Hg uptake compared to the nonreactive tracer bromide (Br − ). All sorbents removed Hg to a certain extent, but none of the sorbents removed all the Hg introduced to the columns. Thiol-SAMMS showed the highest mean percentage of Hg removed (87% ± 2.9%), followed by Organoclay PM-199 (71% ± 0.4%), pine biochar (57% ± 22.3%), SediMite (61% ± 0.8%), and the control quartz sand (11% ± 5.6%). Thiol-SAMMS was the only sorbent to exhibit retardation of Hg in comparison to the conservative tracer Br − . For the remaining sorbents, Br − along with low concentrations of Hg were eluted within the first 3 pore volumes, indicating limited retardation of Hg. Overall, removal of Hg by sorbents was substantial, suggesting that sorbents might be suitable for deployment in contaminated environments. High concentrations of DOM leaching from the soil columns likely influenced the speciation of Hg and inhibited sorption to the sorbents. Incomplete removal of Hg by any sorbent suggests that additional optimization is needed to increase efficiency.

54 ENVIRONMENTAL SCIENCES↗

Impact of Mg on Pd-based Methane Oxidation Catalysts for Lean-burn Natural Gas Emissions Control

More efficient lean-burn, natural gas engines are limited by greenhouse gas emissions due to methane oxidation catalysts (MOC) that suffer from water inhibition and high temperature activation. Herein, we report that the addition of Mg to supported 1 wt.% Pd MOCs improved hydrothermal stability even after severe hydrothermal aging. The superior methane oxidation activity compared to the corresponding Mg-free catalyst was attributed to (1) influence of Mg during surface roughening and restructuring at 700 °C on metal-support interaction, (2) reducibility of PdOx sites and (3) preferential stabilization of active Pd (1 0 0) facets in the sample as was evidenced by H 2 TPR and CO TPD characterization experiments. Methane conversion under synthetic exhaust conditions relevant to natural gas, lean-burn engines were investigated. In conclusion, BET, TPR, CO pulse chemisorption followed by TPD provided valuable insights into the surface area, pore volume, reducibility, Pd dispersion and Pd particle size of the selected catalyst samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Broad range material-to-system screening of metal–organic frameworks for hydrogen storage using machine learning

Hydrogen is pivotal in the transition to sustainable energy systems, playing major roles in power generation and industrial applications. Metal–organic frameworks (MOFs) have emerged as promising mediums for efficient hydrogen storage. However, identifying potential candidates for deployment is challenging due to the vast number of currently available synthesized MOFs. This study integrates molecular simulations, machine learning, and techno-economic analysis to evaluate the performance of MOFs across broad operation conditions for hydrogen storage applications. While previous screenings of MOF databases have predominantly emphasized high hydrogen capacities under cryogenic conditions, this study reveals that optimal temperatures and pressures for cost minimization depend on the raw price of the MOF. Specifically, when MOFs are priced at $15/kg, among the 9720 MOFs tested, 9692 MOFs achieve the lowest cost at temperatures between 170 K and 250 K and a pressure of 150 bar. Under these optimal conditions, 362 MOFs deliver a lower levelized cost of storage than 350 bar compressed gas hydrogen storage. Furthermore, this study reveals key material properties that result in low system cost, such as high surface areas (>3000 m2/g), large void fractions (>0.78), and large pore volumes (>1.1 cm3/g).

Hydrogen storage↗