Thermally Controlled Activation and Passivation of Surface Chemistry and Oxygen-Exchange Kinetics on a Perovskite Oxide
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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Results for “Active thermal control”
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Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation
It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe3+ to Fe2+) likely bonded with pyridinic N (FeN4) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe–N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M H2SO4), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μgPt/cm2). Enhanced stability is attained with the same catalyst, which loses only 20 mV after 10 000 potential cycles (0.6–1.0 V) in O2 saturated acid. The high-performance atomic Fe PGM-free catalyst holds great promise as a replacement for Pt in future PEMFCs.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Temperature-Gated Thermal Rectifier for Active Heat Flow Control
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solar (photovoltaic), solid state lighting, phonon↗
Infrared triggered dwell and active cooling thermal control effects on microstructural uniformity in DED
Directed Energy Deposition (DED) offers rapid large scale fabrication, but difficulty in delivering consistent microstructures and properties hinders the use of DED fabricated components in safety or performance critical applications. Variability stems from the complex thermal cycles generated by the toolpath used to print the required geometry. Several practical methods have become established in DED to regulate overheating, such as active cooling of the baseplate structure or the use of an infrared camera to inject interlayer pauses to ensure the top layer of the component cools to a set temperature, which have been shown to affect microstructure. However, no critical assessment has been performed as to how effective these controls are in promoting microstructural uniformity in the context of complex layer timing commonly generated by non-prismatic geometries. Here we show how controls influence the thermal field, phase transformations, and dynamic annealing of a low-temperature transformation steel using infrared imaging and operando neutron diffraction. Counterintuitively, common thermal homogenization process controls can reduce microstructural uniformity because these approaches stabilize peak temperature while overlooking temperatures near the solid-state phase transformation fronts. Instead, the cyclic reheating induces spatially-variant dynamically annealed regions which can be modulated via control parameters. We show that these controls have spatially linked effects centimeters away from the active weld, which implies that microstructure control must co-optimize thermal input across many subsequent layers. In conclusion, our results demonstrate the pressing need for higher order controls that integrate predictive elements of simulation data to stabilize printed properties for future qualification of DED components.
Directed energy deposition↗
Vibronically coherent ultrafast triplet-pair formation and subsequent thermally activated dissociation control efficient endothermic singlet fission
Singlet exciton fission (SF), the conversion of one spin-singlet exciton (S 1 ) into two spin-triplet excitons (T 1 ), could provide a means to overcome the Shockley-Queisser limit in photovoltaics. SF as measured by the decay of S 1 has been shown to occur efficiently and independently of temperature even when the energy of S1 is as much as 200 meV less than 2T 1 . Here, we study films of TIPS-tetracene using transient optical spectroscopy and show that the initial rise of the triplet pair state (TT) occurs in 300 fs, matched by rapid loss of S1 stimulated emission, and that this process is mediated by the strong coupling of electronic and vibrational degrees of freedom. This is followed by a slower 10 ps morphology-dependent phase of S1 decay and TT growth. Here we observe the TT to be thermally dissociated on 10-100 ns timescales to form free triplets. This provides a model for "temperature independent", efficient TT formation and thermally activated TT separation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effect of cycling and thermal control on the storage and dynamics of a 40-L monolithic adsorbed natural gas tank
Adsorbed natural gas systems have been proposed as a cost-effective storage alternative to compressed and liquefied natural gas. This has led many groups to search and design sorbent materials with large methane storage capacities since natural gas is approximately 90% methane. The other 10% of natural gas contains larger hydrocarbons which can decrease the useable storage capacity of adsorbent systems. In this work, the effect of large hydrocarbons on the storage and dynamics of a 40-L adsorbed natural gas system, containing 20.5 kg of monolithic carbon adsorbent, produced by the University of Missouri, is reported. It was found that over the course of 20 cycles, due to the retention of 1.9 kg of non-methane components by the monoliths, the useable volumetric storage dropped 16%, and the amount of gas delivered dropped 10%. A second cycling experiment found that by using thermal control while the system discharged, the mass retention decreased to 0.91 kg, and the useable volumetric storage and delivered mass only dropped 7% and 5%, respectively. The effects of the mass retention, storage loss, and thermal control on the system’s charge and discharge dynamics were then analyzed to provide a complete picture of the long-term effects of cycling large scale adsorbed natural gas systems with and without active thermal control.
03 NATURAL GAS↗
Thermally Activated Delayed Photoluminescence: Deterministic Control of Excited-State Decay
Thermally activated photophysical processes are ubiquitous in numerous organic and metal-organic molecules, leading to chromophores with excited state properties that can be considered an equilibrium mixture of the available low-lying states. Relative populations of the equilibrated states are governed by temperature. Such molecules have been devised as high quantum yield emitters in modern organic light-emitting diode technology and for deterministic excited state lifetime control to enhance chemical reactivity in solar energy conversion and photocatalytic schemes. This recent discovery of thermally activated photophysics at CdSe nanocrystal-molecule interfaces enables a new paradigm wherein molecule-quantum dot constructs are used to systematically generate material with predetermined photophysical response and excited state properties. Semiconductor nanomaterials feature size-tunable energy level engineering, which considerably expands the purview of thermally activated photophysics beyond what is possible using only molecules. This Perspective is intended to provide a non-exhaustive overview of the advances that led to the integration of semiconductor quantum dots in thermally activated delayed photoluminescence (TADPL) schemes and to identify important challenges moving into the future. The initial establishment of excited state lifetime extension utilizing triplet-triplet excited-state equilibria is detailed. Next, advances involving the rational design of molecules composed of both metal-containing and organic-based chromophores that produce the desired TADPL are described. Lastly, the recent introduction of semiconductor nanomaterials into hybrid TADPL constructs is discussed, paving the way towards the realization of fine-tuned deterministic control of excited state decay. It is envisioned that libraries of synthetically facile composites will be broadly deployed as photosensitizers and light emitters for numerous synthetic and optoelectronic applications in the near future.
14 SOLAR ENERGY↗
Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN 4 Sites for Oxygen Reduction
Abstract FeN 4 moieties embedded in partially graphitized carbon are the most efficient platinum group metal free active sites for the oxygen reduction reaction in acidic proton‐exchange membrane fuel cells. However, their formation mechanisms have remained elusive for decades because the Fe−N bond formation process always convolutes with uncontrolled carbonization and nitrogen doping during high‐temperature treatment. Here, we elucidate the FeN 4 site formation mechanisms through hosting Fe ions into a nitrogen‐doped carbon followed by a controlled thermal activation. Among the studied hosts, the ZIF‐8‐derived nitrogen‐doped carbon is an ideal model with well‐defined nitrogen doping and porosity. This approach is able to deconvolute Fe−N bond formation from complex carbonization and nitrogen doping, which correlates Fe−N bond properties with the activity and stability of FeN 4 sites as a function of the thermal activation temperature.
Li, Jiazhan↗
Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN[subscript 4] Sites for Oxygen Reduction
Abstract not provided
Li, Jiazhan↗
MO-AB-BRA-03: Calorimetry-Based Absorbed Dose to Water Measurements Using Interferometry
Purpose: Interferometry-based calorimetry is a novel technique to measure radiation-induced temperature changes allowing the measurement of absorbed dose to water (ADW). There are no mechanical components in the field. This technique also has the possibility of obtaining 2D dose distributions. The goal of this investigation is to calorimetrically-measure doses between 2.5 and 5 Gy over a single projection in a photon beam using interferometry and compare the results with doses calculated using the TG-51 linac calibration. Methods: ADW was determined by measuring radiation-induced phase shifts (PSs) of light passing through water irradiated with a 6 MV photon beam. A 9×9×9 cm{sup 3} glass phantom filled with water and placed in an arm of a Michelson interferometer was irradiated with 300, 400, 500 and 600 monitor units. The whole system was thermally insulated to achieve sufficient passive temperature control. The depth of measurement was 4.5 cm with a field size of 7×7 cm{sup 2}. The intensity of the fringe pattern was monitored with a photodiode and used to calculate the time-dependent PS curve. Data was acquired 60 s before and after the irradiation. The radiation-induced PS was calculated by taking the difference in the pre- and post-irradiation drifts extrapolated to the midpoint of the irradiation. Results were compared to computed doses. Results: Average comparison of calculated ADW values with interferometry-measured values showed an agreement to within 9.5%. k=1 uncertainties were 4.3% for calculations and 14.7% for measurements. The dominant source of uncertainty for the measurements was a temperature drift of about 30 µK/s caused by heat conduction from the interferometer’s surroundings. Conclusion: This work presented the first absolute ADW measurements using interferometry in the dose range of linac-based radiotherapy. Future work to improve measurements’ reproducibility includes the implementation of active thermal control techniques.
60 APPLIED LIFE SCIENCES↗
Binary Atomically Dispersed Metal-Site Catalysts with Core–Shell Nanostructures for O 2 and CO 2 Reduction Reactions
Engineering atomically dispersed metal site catalysts with controlled local coordination environments and 3D nanostructures effectively improves the catalytic performance for the oxygen reduction reaction (ORR) and the carbon dioxide reduction reaction (CO 2 RR), which are critical for clean energy conversion and chemical production. Herein, an innovative approach for preparing core-shell nanostructured catalysts with different single-metal sites in the core and the shell, respectively, is developed. In particular, as the shell precursors, covalent organic polymers with a thin layered structure that is polymerized in situ and coated on a metal-doped ZIF-derived carbon core are used, followed by a controlled thermal activation. The selective combination and construction of different metal sites increase active site density in the surface layers, promote structural robustness, facilitate mass/charge transfer, and yield a possible synergy of active sites in the core and the shell. The p-FeNC(shell)@CoNC(core), consisting of a polymerized FeTPPCl-derived carbon layer (p-FeNC) on a Co-doped ZIF-derived carbon (CoNC), exhibits remarkable ORR activity and stability in acidic media along with encouraging durability in H 2 –air fuel cells. Likewise, a p-FeNC(shell)@NiNC(core) catalyst demonstrates outstanding CO 2 RR activity and stability. Hence, integrating two appropriate single-metal sites in core and shell precursors, respectively, can modulate morphological and catalytic properties for a possible synergy toward different electrocatalysis processes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Insights into the soft brittle-to-ductile transition from discrete dislocation dynamics
The Brittle-to-ductile transition (BDT) in body centered cubic metals exhibits a soft transition wherein the fracture toughness gradually rises to before the onset of ductility. The resultant brittle-to-ductile transition temperature can be described with an Arrhenius relationship whose activation energy is related to plasticity in the material. To provide further insight into the nature of the BDTT, in this work we utilized a discrete dislo- cation dynamics model with a crack to simulate the BDT and how it depends on the thermally activated nature of plasticity. The interrelationship between the BDT activation energy and the dislocation mobility parameters were determined via the calculation of first order sensitivity coefficients. This analysis allows us to demonstrate that the activation energy for the BDT is directly related to the activation energy for plasticity through an effective stress that defines this relationship. This effective stress physically is the average stress on the dislocations that move out of the crack. Lastly, we are able to show that this effective stress is dictated by the low temperature fracture toughness or cleave energy of the material and the source position, the latter of which can be affected by processing. Collectively, these results provide new insight into what controls the thermal activation of the BDT and what are the important parameters to control it.
36 MATERIALS SCIENCE↗
Coupling 2D atomistic information to 3D kink-pair enthalpy models of screw dislocations in bcc metals
The kink-pair activation enthalpy is a fundamental parameter in the theory of plasticity of body-centered cubic (bcc) metals. It controls the thermally activated motion of screw dislocation at low and intermediate temperatures. While direct atomistic calculations of kink pairs on screw dislocations have reached a high degree of accuracy, they can only be practically performed using semiempirical interatomic force fields, as electronic structure methods have not yet reached the level of efficiency needed to capture the system sizes required to model kink-pair structures. In this context, an alternative approach based on standard three-dimensional elastic models, which are efficient but lack atomic-level information, coupled to a substrate potential that represents the underlying lattice, has been widely applied over the past few years. This class of methods, known as ‘line-on-substrate’ (LOS) models, uses the substrate potential to calculate the lattice contribution to the kink-pair energies. In this work, we introduce the stress dependence of the substrate potential into LOS models to evaluate its impact on kink-pair energies. In addition, we include asymmetric dislocation core energies as an extra descriptor of the dislocation character. This asymmetry is also elevated to the continuum level by adding core energies to the general LOS formulation and used to explain potential energy differences known to exist between left and right kinks in bcc metals. Finally, more importantly, by matching the total LOS energies to previously calculated atomistic energies of kink-pair configurations, we issue a rule to establish the value of the so-called core width in nonsingular elasticity theories and reduce its arbitrariness as a mathematical construct.
36 MATERIALS SCIENCE↗
Dynamic re-equilibration controlled multi-step transformations in (Mn, Fe) 2 (P, Si) alloys
In (Mn, Fe) 2 (P, Si) alloys crystallographic first-order phase transformations enable strong coupling of magnetic and entropic properties, potentially leading to high-efficiency energy generation and refrigeration applications. Although hysteresis losses that limit these applications can be reduced through careful control of alloy composition, compositional tuning can also unfavorably influence transformation temperatures and magnetocaloric coupling strength. Hence, exploration of additional processing variables enabling independent control of transformation properties is crucial. In this work, we investigate the role of thermal history as an additional processing variable, exploiting thermally-activated mechanisms to control properties of non-diffusive transformations in (Mn, Fe) 2 (P, Si) alloys. In so doing, we report an unusual transformation-splitting phenomenon following annealing at intermediate times, where a single well-defined magneto-structural transformation evolves towards a multi-step transformation with individual steps occurring at multiple distinct temperatures. Here, on longer annealing at the same temperatures, single-step transformation behavior is recovered. Through additional magnetic and crystallographic characterization, we show that the thermal history-controlled multi-step behavior results from sluggish thermally-activated diffusion. The two-step transformation corresponds to non-equilibrium bimodal composition distributions in the transforming phase, and these develop through a dynamic re-equilibration process as the alloy passes relatively slowly between different thermal equilibria. Together, these results suggest that thermal history primarily controls the transformation properties of (Mn, Fe) 2 (P, Si) alloys indirectly through the composition of one or more transforming phases. Additional investigations are needed to develop thermal history processing for decoupling hysteresis control from other transformation properties.
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
Assessing the Potential of Active Insulation Systems to Reduce Energy Consumption and Enhance Electrical Grid Services
Building envelopes today act as passive systems in a dynamic environment. Traditional energy-saving efforts have mainly tried to improve the performance of building envelope systems by increasing thermal resistance to a set value that reduces energy flow. However, changes in weather and indoor conditions often lead to situations in which a low thermal resistance would decrease energy use. The optimization of thermal resistance that is triggered by changes in temperature, solar radiation, or availability of energy from renewable sources is currently not possible. Controllable active insulation systems (AISs), in which the thermal resistance of the insulation material can be dynamically controlled within a certain range, can expand the capabilities of the building envelope. With AISs the building envelope is no longer only a passive barrier between indoors and outdoors; instead, heat transfer can be controlled. Moreover, when AISs are combined with the thermal mass in the envelope system, these can act as thermal batteries that can be loaded and unloaded on demand. To quantify the benefits of AISs, a literature study of active insulation and achievable thermal conductivity ranges, thermal simulation models, and control logics was performed. Based on this literature study, a simulation model was developed to control the thermal resistance of insulation materials. A methodology to assess the potential of active insulation systems to reduce energy use and enhance electrical grid services was established and applied to identify ideal implementation scenarios for active insulation systems. A significant reduction of total building energy consumption for heating and cooling was found in all climate zones. The savings for the slab-on-ground DOE residential prototype building for eight selected cities in different climate zones range from 4069 kBtu to 8433 kBtu. Depending on the control cooling during peak load hours in Los Angeles could be reduced by more than 80% without a negative impact on thermal comfort conditions.
Antretter, Florian↗
Thermally Activated Exciton Dissociation and Recombination Control the Carrier Dynamics in Organometal Halide Perovskite
Abstract not provided
Savenije, Tom J.↗
Cryogenic hydrogen circulation system of neutron source
Cold neutron sources of reactors and spallation neutron sources are classic high flux neutron sources in operation all over the world. Cryogenic fluids such as supercritical or supercooled hydrogen are commonly selected as a moderator to absorb the nuclear heating from proton beams. By comparing supercritical hydrogen circulation systems and supercooled hydrogen circulation systems, the merits and drawbacks in both systems are summarized. When supercritical hydrogen circulates as the moderator, severe pressure fluctuations caused by temperature changes will occur. The pressure control system used to balance the system pressure, which consists of a heater as an active controller for thermal compensation and an accumulator as a passive volume controller, is preliminarily studied. The results may provide guidelines for design and operation of other cryogenic hydrogen system for neutron sources under construction.
07 ISOTOPE AND RADIATION SOURCES↗
Raman spectroscopy and electrical properties of InAs nanowires with local oxidation enabled by substrate micro-trenches and laser irradiation
The thermal gradients along indium arsenide nanowires were engineered by a combination of fabricated micro-trenches in the supporting substrate and focused laser irradiation. This allowed local spatial control of thermally activated oxidation reactions of the nanowire on the scale of the diffraction limit. The locality of the oxidation was detected by micro-Raman mapping, and the results were found to be consistent with numerical simulations of the temperature profile. Applying the technique to nanowires in electrical devices the locally oxidized nanowires remained conducting with a lower conductance as expected for an effectively thinner conducting core.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗