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At least 37 records · Page 2

High-Entropy Metal-Organic Frameworks (HEMOFs): A New Frontier in Materials Design for CO 2 Utilization

High-entropy materials (HEMs) emerged as promising candidates for a diverse array of chemical transformations, including CO 2 utilization. However, traditional HEMs catalysts are nonporous, limiting their activity to surface sites. Designing HEMs with intrinsic porosity can open the door toward enhanced reactivity while maintaining the many benefits of high configurational entropy. Here, in this study, a synergistic experimental, analytical, and theoretical approach to design the first high-entropy metal-organic frameworks (HEMOFs) derived from polynuclear metal clusters is implemented, a novel class of porous HEMs that is highly active for CO 2 fixation under mild conditions and short reaction times, outperforming existing heterogeneous catalysts. HEMOFs with up to 15 distinct metals are synthesized (the highest number of metals ever incorporated into a single MOF) and, for the first time, homogenous metal mixing within individual clusters is directly observed via high-resolution scanning transmission electron microscopy. Importantly, density functional theory studies provide unprecedented insight into the electronic structures of HEMOFs, demonstrating that the density of states in heterometallic clusters is highly sensitive to metal composition. This work dramatically advances HEMOF materials design, paving the way for further exploration of HEMs and offers new avenues for the development of multifunctional materials with tailored properties for a wide range of applications.

36 MATERIALS SCIENCE↗

Impact of model predictive control-enabled home energy management on large-scale distribution systems with photovoltaics

Residential customers use more than one-quarter of the electricity in the world. Optimally managing home energy consumption is an effective way of easing the operational challenges facing the electric grid with increasing solar photovoltaics (PV). This paper studies the impact of the future proliferation of home energy management systems (HEMS) in the presence of PV on large-scale distribution systems. First, we present a stochastic HEMS model that minimizes residential customers' thermal discomfort and energy costs under uncertainty. The HEMS model schedules the optimal operations of residential appliances in the presence of PV within a mixed-integer linear programming-based model predictive control framework that links the proposed HEMS to a quasi-steady-state time-series simulation tool. Additionally, extensive simulations are conducted for a stand-alone residential home using two tariff structures and for 1977 homes on an 8,500-node distribution feeder. Simulation results quantify the impact of the future proliferation of HEMS on the large-scale distribution system with PV.

14 SOLAR ENERGY↗

Community-scale interaction of energy efficiency and demand flexibility in residential buildings

Demand-side management (DSM) strategies, including energy efficiency (EE) and demand flexibility (DF), contribute to cost-effective operation of the electricity grid. From a system-level perspective, such programs reduce costs, enhance reliability, and reduce network issues. Similarly, DSM programs help participating customers reduce utility bills while maintaining occupant comfort. Understanding the relationship between EE and DF is key to realizing the full potential of DSM programs. In this study, we modeled an all-electric residential community based on a 498-home community that is planned for construction in Fort Collins, Colorado in the United States. We used this community model to study the relationship between different EE measures, including building envelope upgrades and smart appliances, and DF enabled by a home energy management system (HEMS) responding to a time-varying tariff. Various EE levels in the homes – code-minimum, zero energy ready, and even higher levels of envelope efficiency – were simulated. DF is enabled by the HEMS, which coordinates behind-the-meter resources, including flexible building loads, PV, and home battery systems, to minimize utility bills while maintaining occupant comfort. When comparing to the code-minimum homes, EE upgrades alone reduce HVAC energy use during peak hours by up to 50% and the HVAC utility bill by up to $312/year. With the addition of HEMS, the average daily peak demand can be reduced by up to 0.58 MW or 1.2 kW/home in the higher envelope efficiency homes. The combination of EE upgrades, HEMS, and home battery systems is expected to save homeowners up to $590/year while increasing community load flexibility. However, HEMS and home battery systems are less effective in increasing the DF in the more efficient homes due to the lower load.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Home energy management under realistic and uncertain conditions: A comparison of heuristic, deterministic, and stochastic control methods

We report home energy management systems (HEMS) have been shown to reduce energy bills and to provide grid services including peak demand reduction and demand flexibility. However, uncertainty in residential energy systems is a significant issue and can reduce the benefits of a HEMS to the homeowner or grid operator. Sources of uncertainty include weather forecasts, predictions of energy-related occupant activities (e.g., hot water draws), and parameter estimation for the building envelope and energy-consuming equipment. This paper tackles the problem of uncertainty by developing a framework that simulates HEMS in uncertain conditions and evaluates the performance of multiple control strategies. A linear, reduced-order residential building model for model predictive control applications is derived and compared to a full-order model. Stochastic model predictive control is shown to perform better than deterministic and heuristic methods when considering realistic forecasts with uncertainty. The framework can evaluate the performance of HEMS in real-world applications, which can help de-risk HEMS deployment.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Modeling Savings for ENERGY STAR Smart Home Energy Management Systems

The objective of this study was to develop a repeatable and defensible methodology to analyze the energy savings for Home Energy Management Systems (HEMS) that meets the minimum requirements for certification under ENERGY STAR ® Smart Home Energy Management System (SHEMS) Version 1. Mandatory connected loads include a smart thermostat, two smart lights, and one smart power strip or smart outlet. Control strategies must include feedback to occupants through an in-home display, user programming, occupancy sensor-based controls, and responsiveness to utility signals such as demand response programs. Several occupant behavior patterns were selected to quantify the range of energy savings potential for a HEMS with this basic functionality. A literature review was conducted to establish realistic room-by-room occupancy levels and usage patterns for connected devices. A series of event-driven hourly profiles were created, followed by adjustments based on application of HEMS control strategies to thermostats, interior lighting, and plug load schedules. EnergyPlus modeling was performed using these hourly schedules in three locations (Boston, Houston, and Phoenix) to examine climate dependence of energy savings. Total site energy savings ranged from 4.3 to 27.1 MBtu/year (7%-35%), and utility bill savings ranged from $\$$123 to $\$$670/year (6%-29%). The highest predicted savings was realized by occupants that were not energy conscious prior to HEMS installation, but highly engaged with the HEMS controls once the system was installed. The smart thermostat accounted for most of the savings, followed by the smart power strip. Smart lighting did not save a significant amount of energy in our analysis, based on an assumption that efficient LEDs with no standby power would normally be installed anyway.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Artificial-Intelligence Aided Design and Synthesis of Novel Layered 2D Multi-Principal Element Materials for Energy Storage (Final Report)

This DOE-EPSCoR project aimed to predict, synthesize, and characterize novel layered two-dimensional (2D) high-entropy materials (HEMs). These 2D-HEMs, composed of multiple principal elements in nearly equal concentrations, are distinct from traditional 2D materials (typically containing two or three elements) and conventional alloys (dominated by a single primary element with minor secondary additions). Their unique structural and compositional features enable significant lattice strain accommodation, resulting in enhanced electrode performance and potential applications in catalysis, hydrogen storage, sensing, quantum information technologies, and flexible electronics. The research focused on addressing four fundamental questions: (i) What combinations of elements can form stable and synthesizable 2D-HEMs? (ii) What mechanisms drive the stability and synthesizability of crystalline single-phase 2D-HEMs? (iii) How do local chemical disorder and defects influence the macroscopic electronic and mechanical properties? and (iv) What charge storage mechanisms are active in selectively synthesized 2D-HEMs for battery and supercapacitor electrode applications? To achieve these goals, the project employed an integrated theory-experiment approach, incorporating high-throughput first-principles calculations, theoretical modeling, data mining, experimental synthesis, and advanced characterization techniques. The advanced computing resources and state-of-the-art experimental characterization facilities at Oak Ridge National Laboratory (ORNL) were leveraged through collaboration. Beyond scientific advancements, the project contributed to workforce development. Two postdoctoral researchers and three graduate students at the University of Maine were trained through co-advising by ORNL scientists and collaborative interactions, strengthening their expertise in cutting-edge materials science.

36 MATERIALS SCIENCE↗

Instrumentation and Methods to Measure Dynamic Forces During Exercise Using the Horizontal Exercise Machine

It is hypothesized that bone loss experienced by astronauts in zero gravity conditions may be curtailed by appropriate exercise. According to Wolf's law, bone regenerates when muscles produce stresses by pulling on the bone during daily activity and/or exercise on Earth. To use this theory to prevent or decrease bone loss, one needs to quantify musculoskeletal loads and relate them to bone density changes. In the context of the space program, it is desirable to determine musculoskeletal loads during exercise so that one may make similar measurements on Earth and in space. In this manner, load measurements on Earth may be used as reference to generate similar loads during exercise in space. A research project to investigate the effects of high-resistive exercise to decrease bone density loss underzero-gravity conditions is being carried out in Life Sciences Research Laboratories at NASA JSC. The project consists of a bed-rest study whereby subjects remain in horizontal position for seventeen weeks. During the study, a subset of those subjects executes a regime of resistive exercises in the horizontal exercise machine (HEM). The HEM was designed so that subjects remain horizontal while exercising to minimize gravity loading even during exercise. Bone density of each subject is measured throughout the duration of their participation. The objective of the study is to determine if the resistive exercises are effective in diminishing or eliminating bone loss. My participation in this project relates to instrumentation, measurement, and processing of signals from displacement sensors (optical encoders) and load-cells. Measurement of displacements will be used to determine the motion of the body during exercise, and load measurements will be used (along with displacement data) to determine forces and torques exerted on each section of the body during exercise. Further, I have assisted in specifying new sensors to be added to the HEM and to a new prototype resistive exercise machine called the Interim Resistive Exercise Device (IRED). New load cells and encoders should be mounted in these devices to obtain more complete kineto-dynamic information. This report includes a description of the instrumentation that was built to perform measurements in the HEM and the IRED, along with the software that was developed to collect the measurements. It also includes examples of measurements taken in the HEM. Finally, a plan is laid out that describes how these measurements may be used to determine forces exerted by muscles for each exercise.

Figueroa, Fernando↗

High-Entropy Oxides in the Mullite-Type Structure

High-entropy materials (HEMs) represent a new class of solid solutions containing at least five different elements. Their compositional diversity makes them promising as platforms for the development of functional materials. We synthesized new HEMs in a mullite-type structure and present five compounds, i.e., Bi 2 (Al 0.25 Ga 0.25 Fe 0.25 Mn 0.25 ) 4 O 9 and A 2 Mn 4 O 10 with variations of A = Nd, Sm, Y, Er, Eu, Ce, and Bi, demonstrating the vast accessible composition space. By combining scattering, microscopy, and spectroscopy techniques, we show that our materials are mixed solid solutions. Remarkably, when following their crystallization in situ using X-ray diffraction and X-ray absorption spectroscopy, we find that the HEMs form through a metastable amorphous phase without the formation of any crystalline intermediates. We expect that our synthesis is excellently suited to synthesizing diverse HEMs and therefore will have a significant impact on their future exploration.

36 MATERIALS SCIENCE↗

A high-performance hydroxide exchange membrane enabled by Cu 2+ -crosslinked chitosan

We report ion exchange membranes are widely used to selectively transport ions in various electrochemical devices. Hydroxide exchange membranes (HEMs) are promising to couple with lower cost platinum-free electrocatalysts used in alkaline conditions, but are not stable enough in strong alkaline solutions. Herein, we present a Cu 2+ -crosslinked chitosan (chitosan-Cu) material as a stable and high-performance HEM. The Cu 2+ ions are coordinated with the amino and hydroxyl groups of chitosan to crosslink the chitosan chains, forming hexagonal nanochannels (similar to 1nm in diameter) that can accommodate water diffusion and facilitate fast ion transport, with a high hydroxide conductivity of 67 ms cm -1 at room temperature. The Cu 2+ coordination also enhances the mechanical strength of the membrane, reduces its permeability and, most importantly, improves its stability in alkaline solution (only 5% conductivity loss at 80 degrees C after 1,000 h). These advantages make chitosan-Cu an outstanding HEM, which we demonstrate in a direct methanol fuel cell that exhibits a high power density of 305 mWcm -2 . The design principle of the chitosan-Cu HEM, in which ion transport channels are generated in the polymer through metal-crosslinking of polar functional groups, could inspire the synthesis of many ion exchange membranes for ion transport, ion sieving, ion filtration and more.

36 MATERIALS SCIENCE↗

Ionomer Optimization for Hydroxide-Exchange-Membrane Water Electrolyzers Operated with Distilled Water: A Modeling Study

The hydroxide-exchange-membrane water electrolyzer (HEMWE) is a promising means to store intermittent renewable energy in the form of hydrogen chemical energy. The hydroxide-exchange ionomer (HEI) in the gas-evolving electrodes and the hydroxide-exchange membrane (HEM) are key components of HEMWE. In this work, we simulate the cell and examine explicitly the impact of HEI and HEM properties with a focus on improving HEMWE performance when operated with distilled water ( i.e ., no supporting electrolyte). The tradeoff between the ionic conductivity gain and electrochemically active surface area (ECSA) loss is studied. For a constant catalyst loading, distributing more catalyst next to the HEM or making thinner but denser catalyst layer is beneficial for HEMWE performance. The results demonstrate that a higher water diffusion coefficient is desired for HEM to supply reactant water to the cathode. In contrast, a lower water diffusion coefficient is preferred for the cathode HEI to retain the water in the regions with high reaction rates. Overall, the findings provide important insights to optimizing HEI/HEM materials for improved HEMWE performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantification of Load Flexibility in Residential Buildings Using Home Energy Management Systems

With increasing penetration of renewable energy resources, the flexibility of operating behind-the-meter (BTM) resources plays a key role in enhancing grid reliability and resilience. Residential buildings with home energy management systems (HEMS) can provide desired flexibility for the distribution system operator (DSO) while considering customer comfort and preferences. This paper discusses a methodology to quantify the flexibility of BTM resources of residential buildings using HEMS. First, we propose a model predictive control framework to formulate the flexibility band comprising nominal, upper, and lower demand profiles. Second, the paper proposes a dispatch method for HEMS to compute the control signals for each BTM resource (e.g., air conditioner, water heater, home battery system) upon receiving a flexibility service request from the DSO. The case study provides insight into the flexibility provided at the whole-home level with different user preferences and seasons. The results demonstrate that HEMS is capable of providing flexibility service at the request of the DSO while delivering primary services to the building occupants.

41 EE - Solar Energy Technologies Office (EE-4S)↗

Stochastic Home Energy Management Systems with Varying Controllable Resources

This paper studies the performance of a model predictive control (MPC) algorithm in a home energy management system (HEMS) as the set of controllable resources varies and under both a constant and a time-of-use (TOU) electricity price structure. The set of controllable resources includes residentially-owned photovoltaic (PV) panels, a home battery system (HBS), an electric vehicle (EV), and a home heating, ventilation, and air conditioning (HVAC) system. The HEMS optimally schedules the set of controllable resources given user preferences such as indoor thermal comfort and electricity cost sensitivity. The home energy management system is built on a chance constrained, MPC-based algorithm, where the chance constraint ensures the indoor thermal comfort is satisfied with a high probability given uncertainty in the outdoor temperature and solar irradiance forecasts. Simulation results for varying sets of controllable resources under two different electricity price structures demonstrate the variation in the HEMS control with respect to HBS operation, electricity cost, and grid power usage.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Understanding Operando Water Management in Hydroxide‐Exchange‐Membrane Fuel Cells

The water balance in hydroxide-exchange-membrane fuel cells (HEMFCs) is a key challenge for improved performance and durability, intimately linked with the various interfaces and coupled phenomena. For every 4 electrons produced, 4 water molecules are generated in the anode and 2 consumed in the cathode, while electroosmosis transports water across the HEM from the cathode to the anode. Consequently, a concentration gradient drives water back, from anode to cathode. Ineffective water management could lead to cathode dry-out, limiting reaction rate and causing ionomer degradation, or to anode flooding. To address these concerns, it is critical to measure the water transport operando . Herein, a home-built water-flux station is used to measure total water flux during cell operation with different inlet relative humidities and back pressures. Increasing the HEM thickness fourfold decreases the water flux at high current density, and utilizing microporous layers on both the anode and cathode decreases the water flux from the anode to the cathode. However, the most significant variable in changing the water flux was found by increasing the anode back pressure. Furthermore, humidity cycling significantly changed electrochemical performance without affecting the overall water fluxes. These findings can be translated to other devices utilizing an HEM.

AEMFC↗

Across the Board: Sheng Dai on Catalyst Design by Entropic Factors

In this series of articles, the board members of ChemSusChem discuss recent research articles that they consider of exceptional quality and importance for sustainability. This entry features Dr. S. Dai, who discusses high-entropy materials (HEMs) as new materials in catalysis. In this viewpoint, two types of HEMs (alloy and non-alloy HEMs), their synthesis, and their application in various catalytic reactions are presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxidative instability of ionomers in hydroxide-exchange-membrane water electrolyzers

Hydroxide-exchange membrane (HEM) electrolyzers can produce green H 2 with only earth-abundant catalysts and electrolyte-free (nominally pure) water feed, significantly decreasing system cost and complexity. However, HEM technology suffers from short lifetimes, attributed in part to poor stability of anion-exchange polymers used in the membrane and catalyst layers. We use electrochemical analysis and ex situ characterization techniques to study anion-exchange-polymer degradation in electrolyzers. Using multiple ionomers, catalyst-layer additives, and electrolyte feed, we show how anode-ionomer oxidation is the dominant degradation mechanism for all HEM-based electrolyzer cells tested. Here, we find improved device stability using oxidation-resistant catalyst-layer binders and propose new design strategies for advanced ionomer and catalyst-layer development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Beyond the four core effects: revisiting thermoelectrics with a high-entropy design

Low-exergy waste heat, which constitutes the majority of industrial-scale thermal losses, remains largely unrecoverable with conventional technologies. Thermoelectrics offer a solid-state solution for converting this hard-to-access energy into electricity, making them attractive for decentralized power generation and sensor applications. High-entropy materials (HEMs) have gained traction as a strategy for better-performing thermoelectrics, but the mechanisms driving their benefits require further exploration. This article highlights key insights for heat and electronic transport in HEMs. For heat transport, we argue that reduced, and often ultralow, lattice thermal conductivity in HEMs—with respect to ordered counterparts—can be taken for granted, emerging naturally as a fifth core effect of high-entropy systems. While band convergence is often considered beneficial for electronic transport, its impact depends strongly on the electronic structure. We summarize the scenarios where it can be detrimental to thermoelectric performance. These insights motivate strategies that align seamlessly with advancements in artificial intelligence and data-driven approaches, helping accelerate the discovery of next-generation thermoelectric materials.

Oses, Corey [Johns Hopkins Univ., Baltimore, MD (U↗

Era of entropy: Synthesis, structure, properties, and applications of high-entropy materials

The field of high-entropy materials (HEMs) has emerged as a dynamic area of scientific exploration, driven by the exceptional properties arising from their compositional complexity. Encompassing both high-entropy alloys (HEAs) and high-entropy ceramics (HECs), these materials have garnered significant attention across diverse research domains. From investigations into phase evolution and mechanical characteristics to studies of ionic, electronic, and magnetic behaviors, HEMs demonstrate remarkable potential for a wide array of applications. These range from catalysis and tribology to energy storage and superconductivity. Fundamental research has shed light on crucial phenomena such as configurational entropy, lattice distortion, and sluggish diffusion. These discoveries are paving the way for materials design strategies that enable new functional tunability and resistance to application-specific harsh environments. This burgeoning field promises to revolutionize material design and performance across numerous technological sectors. Here, this special collection between Applied Physics Letters and the Journal of Applied Physics provides a timely overview of the latest research in this area. It highlights the growing interest in understanding the impact of high compositional complexity on conventional structure–process–property–performance relationships in HEMs.

36 MATERIALS SCIENCE↗

Silicon Sheet Growth Development for the Large Area Sheet Task of the Low Cost Solar Array Project. Heat Exchanger Method - Ingot Casting Fixed Abrasive Method - Multi-Wire Slicing

Solar cells fabricated from HEM cast silicon yielded up to 15% conversion efficiencies. This was achieved in spite of using unpurified graphite parts in the HEM furnace and without optimization of material or cell processing parameters. Molybdenum retainers prevented SiC formation and reduced carbon content by 50%. The oxygen content of vacuum cast HEM silicon is lower than typical Czochralski grown silicon. Impregnation of 45 micrometers diamonds into 7.5 micrometers copper sheath showed distortion of the copper layer. However, 12.5 micrometers and 15 micrometers copper sheath can be impregnated with 45 micrometers diamonds to a high concentration. Electroless nickel plating of wires impregnated only in the cutting edge showed nickel concentration around the diamonds. This has the possibility of reducing kerf. The high speed slicer fabricated can achieve higher speed and longer stroke with vibration isolation.

Schmid, F.↗