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At least 973 records · Page 54

Guanidinium-Assisted Surface Matrix Engineering for Highly Efficient Perovskite Quantum Dot Photovoltaics

Metal halide perovskite quantum dots (Pe-QDs) are of great interest in new-generation photovoltaics (PVs). However, it remains challenging in the construction of conductive and intact Pe-QD films to maximize their functionality. Herein, a ligand-assisted surface matrix strategy to engineer the surface and packing states of Pe-QD solids is demonstrated by a mild thermal annealing treatment after ligand exchange processing (referred to as “LE-TA”) triggered by guanidinium thiocyanate. The “LE-TA” method induces the formation of surface matrix on CsPbI 3 QDs, which is dominated by the cationic guanidinium (GA+) rather than the SCN-, maintaining the intact cubic structure and facilitating interparticle electrical interaction of QD solids. Consequently, the GA-matrix-confined CsPbI 3 QDs exhibit remarkably enhanced charge mobility and carrier diffusion length compared to control ones, leading to a champion power conversion efficiency of 15.21% when assembled in PVs, which is one of the highest among all Pe-QD solar cells. Additionally, the “LE-TA” method shows similar effects when applied to other Pe-QD PV systems like CsPbBr 3 and FAPbI 3 (FA = formamidinium), indicating its versatility in regulating the surfaces of various Pe-QDs. This work may afford new guidelines to construct electrically conductive and structurally intact Pe-QD solids for efficient optoelectronic devices.

36 MATERIALS SCIENCE↗

Nanoscopic cross-grain cation homogenization in perovskite solar cells

Multiscale cation inhomogeneity has been a major hurdle in state-of-the-art formamidinium–caesium (FA–Cs) mixed-cation perovskites for achieving perovskite solar cells with optimal power conversion efficiencies and durability. Although the field has attempted to homogenize the overall distributions of FA–Cs in perovskite films from both plan and cross-sectional views, our understanding of grain-to-grain cation inhomogeneity and ability to tailor it—that is, spatially resolving the FA–Cs compositional difference between individual grains down to the nanoscale—are lacking. Here we reveal that as fundamental building blocks of a perovskite film, individual grains exhibit cationic compositions deviating from the prescribed ideal composition, severely limiting the interfacial optoelectronic properties and perovskite layer durability. This performance-limiting nanoscopic factor is linked to thermodynamic-driven morphological grooving, leading to a segmented surface landscape. At the grain triple junctions, grooves form nanoscale groove traps that hinder the mixing of solid-state cations across grains and thus retard inter-grain FA–Cs mixing. By rationally modulating the heterointerfacial energies, we reduced the depth of these nanoscale groove traps by a factor of three, significantly improving cation homogeneity. Perovskite solar cells with shallower nanoscale groove traps demonstrate enhanced power conversion efficiencies (25.62%) and improved stability under various standardized international protocols. In conclusion, our work highlights the significance of resolving surface nano-morphologies for homogeneous properties of perovskites.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Novel Lightweight, Low-Cost Heliostat for Concentrating Solar Power (SBIR Phase I Final Report)

The overall goal of this Department of Energy (DOE) SBIR Phase I project was to demonstrate the feasibility of the L.Garde, Inc. heliostat mirror facet for use in concentrated solar power applications. Prior to this Phase I project, L.Garde, Inc. developed a design for a lightweight and low cost mirror facet and successfully fabricated small scale (0.667 m 2 ) with a mirror surface flatness of 0.7 mrad. Therefore, the focus of the Phase I effort was to (1) demonstrate scalability by fabricating larger size mirrors while retaining the same mirror surface flatness, (2) demonstrate the design can withstand operating environment conditions through field testing, and (3) perform cost analysis to show the heliostat mirror facet design can meet DoE goals of < 12 kg/m2 and <$30/m 2 . During the Phase I project, L.Garde successfully fabricated large area (1.395 m 2 ) heliostat mirror facets, with a mass per unit area of 8 kg/m 2 and a cost of $29.80/m 2 . Surface flatness measurements (using contact probe technique) were performed on the mirror surface and results showed a flatness of 0.68 mrad, which were in agreement with previously fabricated small scale mirror facets. Slope error measurements was also performed on the mirror surface and results showed a slope error of 0.77 mrad which also was in agreement with previously fabricated small scale mirror facets. One large area mirror facet was subjected to a three (3) month field test. Surface flatness and slope error measurements were performed on the mirror surface after the field test and results were 0.663 mrad and 0.58 mrad respectively. The large scale heliostat mirror facets were also subjected to accelerated aging. However, during this exposure we observed failure due to the breaking of the mirror facets. Further investigation into the source of the failure showed that the mirror component alone showed signs of degradation during the same accelerated aging test. We believe that moisture ingress is occurring when subjected to high humidity, leading to buildup of water with the layers of protective paints and resulting in mirror breakage when water expands in freezing conditions. In order to mitigate or eliminate this issue, a new weatherproofing strategy may be implemented or a new mirror component may be used that is able to survive accelerated aging conditions.

14 SOLAR ENERGY↗

Interfaces and the extended Hilbert space of Chern-Simons theory

The low energy effective field theories of (2 + 1) dimensional topological phases of matter provide powerful avenues for investigating entanglement in their ground states. In [1] the entanglement between distinct Abelian topological phases was investigated through Abelian Chern-Simons theories equipped with a set of topological boundary conditions (TBCs). In the present paper we extend the notion of a TBC to non-Abelian Chern-Simons theories, providing an effective description for a class of gapped interfaces across non-Abelian topological phases. These boundary conditions furnish a defining relation for the extended Hilbert space of the quantum theory and allow the calculation of entanglement directly in the gauge theory. Because we allow for trivial interfaces, this includes a generic construction of the extended Hilbert space in any (compact) Chern-Simons theory quantized on a Riemann surface. Additionally, this provides a constructive and principled definition for the Hilbert space of effective ground states of gapped phases of matter glued along gapped interfaces. Lastly, we describe a generalized notion of surgery, adding a powerful tool from topological field theory to the gapped interface toolbox.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Suppressing strain propagation in ultrahigh-Ni cathodes during fast charging via epitaxial entropy-assisted coating

Surface reconstruction and the associated severe strain propagation have long been reported as the major cause of cathode failure during fast charging and long-term cycling. Despite tremendous attempts, no known strategies can simultaneously address the electro-chemomechanical instability without sacrificing energy and power density. Here we report an epitaxial entropy-assisted coating strategy for ultrahigh-Ni LiNi x Co y Mn 1-x-y O 2 (x ≥ 0.9) cathodes via an oriented attachment-driven reaction between Wadsley-Roth phase-based oxides and the layered-oxide cathodes. Further, the high anti-cracking and anti-corrosion tolerances as well as the fast ionic transport of the entropy-assisted surface effectively improved the fast charging/discharging capability, wide temperature tolerance and thermal stability of the ultrahigh-Ni cathodes. Comprehensive analysis from the primary and secondary particle level to the electrode level using multi-scale in situ synchrotron X-ray probes reveals greatly reduced lattice dislocations, anisotropic lattice strain and oxygen release as well as improved bulk/local structural stability, even when charging beyond the threshold state of charge (75%) of layered cathodes. Layered Ni-rich oxide cathodes are susceptible to challenges with surface reconstruction and strain propagation, limiting their cyclability. The authors propose a solution involving oriented attachment-driven reactions, utilizing Wadsley-Roth nanocrystals and layered oxide to induce an epitaxial entropy-assisted coating, effectively addressing these issues.

25 ENERGY STORAGE↗

Numerical analysis of coalescence-induced bubble departure for enhanced boiling heat transfer

Boiling heat transfer plays a crucial role in a wide range of applications, such as power generation, refrigeration, electronics cooling, and pharmaceutics. Among the various factors that influence boiling heat transfer, the dynamics of vapor bubble nucleation, growth, and departure from the heated surface stand out as particularly important. An emerging phenomenon that can promote the departure of bubbles smaller than the Fritz diameter is coalescence-induced departure. If the dynamics of this process are fully understood, then surfaces can be engineered to promote faster bubble departure and substantially increase the performance of boiling heat transfer. Further, this work expands on published results by presenting a detailed numerical analysis of bubble coalescence and departure for a range of initial bubble diameters and size ratios between coalescing bubbles. Analysis of the results is focused on explaining how the release of surface energy and bubble surface dynamics lead to bubble departure, as well as fundamentally distinguishing capillary–inertial jumping and buoyant–inertial departure mechanisms across different bubble sizes and size ratios. The results show that both the initial sizes of the coalescing bubbles and the ratio between their sizes can determine whether the merged bubble will leave the surface through capillary–inertial jumping or buoyant departure. Below a certain bubble size, the release of surface energy by the merger is not sufficient to propel the merged bubble from the surface.

42 ENGINEERING↗

Performance of Spherical Quantum Well Down Converters in Solid State Lighting

We report the color conversion performance of amber and red emitting quantum dots (QDs) on InGaN solid-state lighting (SSL) light emitting diode (LED) packages. Spherical quantum well (SQW) architectures (CdS/CdSe 1- x S x /CdS) were prepared using a library of thio- and selenourea synthesis reagents and high throughput synthesis robotics. CdS/CdSe 1- x S x QDs with narrow luminescence bands were coated with thick CdS shells (thickness = 1.6-7.5 nm) to achieve photoluminescence quantum yields (PLQY) up to 88% at amber and red emission wavelengths (λ max = 600-642 nm, FWHM < 45 nm). The photoluminescence from SQWs encapsulated in silicone and deposited on LED packages was monitored under accelerated aging conditions (oven temperature = 85 °C, relative humidity = 5-85%, blue optical power density = 3-45 W/cm 2 ) by monitoring the red photon output over several hundred hours of continuous operation. The growth of a ZnS shell on the SQW surface increases the stability under long-term operation but also reduces the PLQY, especially of SQWs with thick CdS shells. The results illustrate that the outer ZnS shell layer is key to optimizing the PLQY and the long-term stability of QDs during operation on SSL packages.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvent-induced electrochemistry at an electrically asymmetric carbon Janus particle

Chemical doping through heteroatom substitution is often used to control the Fermi level of semiconductor materials. Doping also occurs when surface adsorbed molecules modify the Fermi level of low dimensional materials such as carbon nanotubes. A gradient in dopant concentration, and hence the chemical potential, across such a material generates usable electrical current. This opens up the possibility of creating asymmetric catalytic particles capable of generating voltage from a surrounding solvent that imposes such a gradient, enabling electrochemical transformations. In this work, we report that symmetry-broken carbon particles comprised of high surface area single-walled carbon nanotube networks can effectively convert exothermic solvent adsorption into usable electrical potential, turning over electrochemical redox processes in situ with no external power supply. The results from ferrocene oxidation and the selective electro-oxidation of alcohols underscore the potential of solvent powered electrocatalytic particles to extend electrochemical transformation to various environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct evidence of microstructure dependence of magnetic flux trapping in niobium

Abstract Elemental type-II superconducting niobium is the material of choice for superconducting radiofrequency cavities used in modern particle accelerators, light sources, detectors, sensors, and quantum computing architecture. An essential challenge to increasing energy efficiency in rf applications is the power dissipation due to residual magnetic field that is trapped during the cool down process due to incomplete magnetic field expulsion. New SRF cavity processing recipes that use surface doping techniques have significantly increased their cryogenic efficiency. However, the performance of SRF Nb accelerators still shows vulnerability to a trapped magnetic field. In this manuscript, we report the observation of a direct link between flux trapping and incomplete flux expulsion with spatial variations in microstructure within the niobium. Fine-grain recrystallized microstructure with an average grain size of 10–50 µm leads to flux trapping even with a lack of dislocation structures in grain interiors. Larger grain sizes beyond 100–400 µm do not lead to preferential flux trapping, as observed directly by magneto-optical imaging. While local magnetic flux variations imaged by magneto-optics provide clarity on a microstructure level, bulk variations are also indicated by variations in pinning force curves with sequential heat treatment studies. The key results indicate that complete control of the niobium microstructure will help produce higher performance superconducting resonators with reduced rf losses 1 related to the magnetic flux trapping.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Two-level systems in nucleated and non-nucleated epitaxial alpha-tantalum films

Building usefully coherent superconducting quantum processors depends on reducing losses in their constituent materials. Tantalum, like niobium, has proven utility as the primary superconducting layer within highly coherent qubits. However, unlike Nb, high temperatures are typically used to stabilize the desirable body-centered-cubic phase, α-Ta, during thin film deposition. It has long been known that a thin Nb layer permits the room-temperature nucleation of α-Ta, but here we observe the epitaxial process and present few-photon microwave loss measurements in Nb-nucleated Ta films. We compare resonators patterned from Ta films grown at high temperature (500 °C) and films nucleated at room temperature, in order to understand the impact of the crystalline order on quantum coherence. In both cases, films grew with Al 2 O 3 (001) ∥ Ta (110), indicating that the epitaxial orientation is independent of temperature and is preserved across the Nb/Ta interface. We use conventional low-power spectroscopy to measure two level system (TLS) loss as well as an electric-field bias technique to measure the effective dipole moments of TLS in the surfaces of resonators. In our measurements, Nb-nucleated Ta resonators had greater loss tangent (1.5 ± 0.1 × 10 -5 ) than non-nucleated (5 ± 1× 10 -6 ) in approximate proportion to defect densities as characterized by x-ray diffraction (0.27° vs 0.18° [110] reflection width) and electron microscopy (30 vs 70 nm domain size). Furthermore, the dependence of the loss tangent on domain size indicates that the development of more ordered Ta films is likely to lead to improvements in qubit coherence times. Moreover, low-temperature α-Ta epitaxy may enable the growth of microstate-free heterostructures, which would not withstand high temperature processing.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Mechanical Analysis of Carbon Fiber Retaining Sleeve for A High-speed Outer Rotor SPM Electric Motor Design

Outer rotor motors can be designed with a larger airgap diameter than inner rotor motors for the same overall diameter and therefore provide higher torque which makes them ideal for high torque space constrained applications. This advantage fits well with the increasing demand of high-speed electric machines in many applications due to their inherent high-power density. However, increasing the motor speed results in significant centrifugal loads for the outer rotor motor design. Layers of carbon fiber sleeve winding on the rotor outer surface is necessary to guarantee its structural integrity without introducing too much weight on the motor itself. In this paper, we studied the mechanical stress of a carbon fiber retaining sleeve in a surface permanent magnet outer rotor motor that spins up to 20,000 RPM. Analytical results from finite element method (FEM) confirmed that the maximum stress experienced by the carbon fiber sleeve was under the material’s yield strength. The proposed sleeve will allow this outer rotor motor to operate at high speeds.

Lin, Lianshan↗

The Influence of Anomalous Biomass Emissions on ENSO in CESM2

Abstract The influence of biomass burning (BB) aerosols arising from wildfires and agricultural fires on the transient coupled evolution of El Niño–Southern Oscillation (ENSO) is explored in Community Earth System Model, version 2 (CESM2). For both El Niño and La Niña, two 20-member ensembles are generated from initial states that are predisposed to evolve into ENSO events. For each ENSO phase, one ensemble is forced with the observed BB emissions during satellite-era ENSO events while the other is forced with a climatological annual cycle, with the responses to anomalous BB emissions estimated from interensemble differences. It is found that the regional responses to anomalous BB emissions occur mainly during boreal fall, which is also the time of the climatological seasonal maximum in emissions. Transient responses are identified in precipitation, clouds, and radiation in both the tropics and extratropics. At the onset of El Niño, these include increased precipitation in the northern branch of the intertropical convergence zone (ITCZ) and an enhancement of cloud albedo and amount across the Maritime Continent and eastern subtropical Pacific Ocean. Additional responses are identified through the course of El Niño and successive La Niña events, the net effect of which is to strengthen sea surface temperature (SST) anomalies in the eastern Pacific Ocean during El Niño and warm the tropical Pacific Ocean during La Niña. These responses improve the simulation of ENSO power, diversity, and asymmetry in CESM2. Significance Statement Biomass burning emissions from both wildfires and agricultural fires during ENSO act as a climate feedback, as they are both driven by fire weather anomalies tied to ENSO and influence clouds, radiation, and precipitation on a global scale. While the largest biomass burning (BB) emissions emanate mainly from Indonesia, other regions also exhibit systematic responses. When simulated in CESM2, the emissions collectively impact the flows of energy across the tropical Pacific Ocean in a spatially and temporally complex fashion, with the net effect of improving CESM2’s simulation of ENSO events.

Fasullo, John T. [National Center for Atmospheric ↗

Developing Efficient Perovskite/Silicon Tandem Devices

This project aims at developing highly efficient perovskite/silicon tandem solar cells by developing efficient perovskite top cells, silicon bottom cells, and monolithically integrating the subcells for highly efficient tandem solar cells. The project focused on increasing the efficiency of perovskite solar cells to 20% and understanding related materials science and device physics, as well as developing a compatible bottom high-efficiency c-Si solar cell. The perovskite cells with a wide bandgap of 1.61 eV and 1.84 eV are fabricated by a low-cost, low-temperature, scalable solution process on lower bandgap silicon bottom cells. The bandgaps of perovskite top cells have been tuned between 1.61 eV and 1.84 eV by composition engineering mainly through controlling the halide mixing ratio in perovskite materials. The efficiencies of the wide bandgap perovskite solar cells have been improved to an excellent efficiency of 21.0% for perovskites with a bandgap of 1.63 eV with increased grain size, reduced energy disorder at cathode contact, and defect passivation. We invented a solvent annealing approach with solvent vapor during thermal annealing to enlarge grain size of perovskite film which reduces the charge trap density and improves the device efficiency. Moreover, we discovered that the non-wetting surface could further increase the grain size for perovskite films, because non-wetting surface could prevent the formation of too dense nuclei from heterogeneous nucleation process. We proposed to reduce the energy disorder of organic charge extraction layer to reduce the power loss in perovskite cells. We pioneered defect passivation concept and techniques to suppress the charge non-radiative recombination in perovskite solar cells to boost the efficiency. For the silicon bottom cell development, different from the conventional silicon cell work under full illumination, the light available for the silicon bottom cell in tandem structure is mainly NIR region. We developed a NIR enhanced silicon cell with efficiency of 21.2% by applying a double-layer antireflection coating at the front side and a MgF2 back reflector layer at the rear side. For the perovskite/silicon tandem device, we achieved a highest reported power conversion efficiency of 25.4% in 2018, and further increased the efficiency up to 26.0% in 2019. The research on tandem solar cells focused on reducing reflection loss to <5% at spectrum of 300-1100 nm by antireflection layer, tuning the bandgap of perovskite film for matched current density between sub-cells, and utilizing a ITO layer between perovskite top cell and silicon bottom cell as interconnect layer without Voc loss. Finally, we developed a blading technique to fabricate perovskite films which produces perovskite solar cells with comparable or even superior efficiency to those made by non-scalable spin coating method. This paves the way for scaling up perovskite/silicon tandem solar cells using solution approach.

14 SOLAR ENERGY↗

SDSS-IV MaNGA: Understanding Ionized Gas Turbulence Using Integral Field Spectroscopy of 4500 Star-forming Disk Galaxies

The Sloan Digital Sky Survey MaNGA program has now obtained integral field spectroscopy for over 10,000 galaxies in the nearby universe. We use the final MaNGA data release DR17 to study the correlation between ionized gas velocity dispersion and galactic star formation rate, finding a tight correlation in which σ Hα from galactic H ιι regions increases significantly from ~18–30 km s –1 , broadly in keeping with previous studies. In contrast, σ Hα from diffuse ionized gas increases more rapidly from 20–60 km s –1 . Using the statistical power of MaNGA, we investigate these correlations in greater detail using multiple emission lines and determine that the observed correlation of σ Hα with local star formation rate surface density is driven primarily by the global relation of increasing velocity dispersion at higher total star formation rate, as are apparent correlations with stellar mass. Assuming H ιι region models consistent with our finding that σ [O III] < σ Hα < σ [O I] , we estimate the velocity dispersion of the molecular gas in which the individual H ιι regions are embedded, finding values σ Mol = 5–30 km s –1 consistent with ALMA observations in a similar mass range. Finally, we use variations in the relation with inclination and disk azimuthal angle to constrain the velocity dispersion ellipsoid of the ionized gas σ z /σ r = 0.84 ± 0.03 and σ Φ /σ r = 0.91 ± 0.03, similar to that of young stars in the Galactic disk. Our results are most consistent with the theoretical models in which turbulence in modern galactic disks is driven primarily by star formation feedback.

79 ASTRONOMY AND ASTROPHYSICS↗

Reactor for hydrothermal growth of structured materials

Design, fabrication, and usage of a reactor are presented for synthesis of structured materials from a liquid-phase precursor by heating. The structured materials are particles, membranes or films of micro-porous molecular sieve crystals such as zeolite and meso-porous materials. The precursor solution and structured materials in the reactor are uniformly heated by a planar heater with characteristic heat transfer dimension in the range of 3 mm to 10 cm. A planar heater having width and length at least three times of the characteristic heat transfer dimension provides at least one surface of uniform temperature distribution for heating purposes. Heating is conducted over a temperature range of 20 to 300° C. The planar heater can be heated by electrical power of by thermal fluid.

36 MATERIALS SCIENCE↗

In situ formed catalysts for active, durable, and thermally stable ammonia protonic ceramic fuel cells at 550 °C

Ammonia protonic ceramic fuel cells (NH 3 -PCFCs) are promising and attractive energy-conversion devices owing to their high energy density, zero-carbon emission, and safety. The development of NH 3 -PCFCs, however, depends largely on the insufficient activity and poor durability of typical Ni-based anodes for ammonia decomposition, especially at low temperatures such as 550 °C. Herein, we report a self-assembled heterostructured Ru 0.95 Cu 0.05 Ni x (RCN) catalyst obtained through an in situ reaction between the surface-decorated Ru 0.95 Cu 0.05 nanoparticles and the Ni grain in the anode under typical processing conditions. At 550 °C, Ni–BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3 anode-supported PCFCs with RCN catalysts exhibit a high peak power density of 0.732 W cm -2 and a significantly enhanced durability of 100 h in NH 3 . Moreover, the cells demonstrate improved thermal stability compared with the bare cell during a 31-cycle thermal cycling test in NH 3 between 550 and 700 °C. In conclusion, the enhanced performance is likely attributed to the synergistic effects of Ru and Cu in RCN for NH 3 decomposition, resulting in a more vital interaction of NH 3 than that of the bare anode surfaces, as confirmed by NH 3 thermal conversion, electrochemical performance, and theoretical simulations.

30 DIRECT ENERGY CONVERSION↗

Residential Vehicle-to-Home Backup Power Capabilities: Key Findings from a ComEd Beneficial Electrification R&D Pilot

This report summarizes key findings from a collaborative technical study of residential, non-grid-tied vehicle-to-home (V2H) backup power systems in Commonwealth Edison’s (ComEd’s) service territory. The work integrates (1) a feeder-level technoeconomic analysis (TEA) using historical outage-event data and simulated electric-vehicle (EV) driving/charging profiles to estimate potential reliability and customer interruption-cost impacts under V2H and vehicle-to-grid (V2G) adoption scenarios; (2) controlled laboratory performance testing of a representative V2H backup ecosystem to characterize transfer-to-backup behavior, sustained power delivery, efficiency trends, and repeatable reliability limitations; and (3) a cybersecurity assessment aligned with NIST Cybersecurity Framework (CSF) 2.0 and ISO/SAE 21434 to evaluate interface-level risk drivers and identify program-relevant mitigations. Results indicate that V2H can provide measurable resilience value, but outcomes are strongly context dependent on outage patterns and the share of events that are “V2H-applicable.” Typical transfer-to-backup behavior clustered on the order of minutes, but rare long-delay edge cases were observed (including an event approaching 30 minutes) and should be treated as a reliability risk. High-power testing showed that peak-rated output is not necessarily continuously deliverable; stable operation may require operation below nameplate ratings and attention to thermal and installation constraints. The cybersecurity assessment highlights a broad attack surface spanning commissioning, home networks, embedded services, and cloud/OTA pathways, motivating minimum controls for secure onboarding, signed updates, patch cadence, and coordinated vulnerability response for any scaled deployment.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Emerging Electrochemical Techniques for Probing Site Behavior in Single-Atom Electrocatalysts

Single-atom catalysts (SACs) have aroused tremendous interest over the past decade, particularly in the community of energy and environment-related electrocatalysis. A rapidly growing number of recent publications have recognized it as a promising candidate with maximum atomic utilization, distinct activity, and selectivity in comparison to bulk catalysts and nanocatalysts. However, the complexity of localized coordination environments and the dispersion of isolated sites lead to significant difficulties when it comes to gaining insight into the intrinsic behavior of electrocatalytic reactions. Furthermore, the low metal loadings of most SACs make conventional ensemble measurements less likely to be accurate on the subnanoscale. Thus, it remains challenging to probe the activity and properties of individual atomic sites by available commercial instruments and analytical methods. In spite of this, continuing efforts have lately focused on the development of advanced measurement methodologies, which are very useful to the fundamental understanding of SACs. There have recently been a number of in situ/operando techniques applied to SACs, such as electron microscopy, spectroscopy, and other analysis methods, which support relevant functions to identify the active sites and reaction intermediates and to investigate the dynamic behavior of localized structures of the catalytic sites. This Account aims to present recent electrochemical probing techniques which can be used to identify single-atomic catalytic sites within solid supports. First, we describe the basic principles of molecular probe methods for the study and analysis of electrocatalytic site behavior. In particular, the in situ probing technique enabled by surface interrogation scanning electrochemical microscopy (SISECM) can measure the active site density and kinetic rate with high resolution. An alternative electrochemical probing technique is further demonstrated on the basis of single-entity electrochemistry, which allows the unique electrochemical imaging of the size and catalytic rate of single atoms, molecules, and clusters. Next, the merits and limitations of different electrochemical techniques are then discussed, along with perspectives for future prospects. Apart from this, we further showcase the powerful capability of emerging electrochemical probing techniques for determining significant effects and properties of SACs for various electrocatalytic reactions, including oxygen reduction and evolution, hydrogen evolution, and nitrate reduction. Overall, electrochemical techniques with atomic resolution have greatly increased opportunities for observing, measuring, and understanding the surface and interface chemistry during energy conversion. In the future, it is anticipated that the development of electrochemical probing techniques will be advanced with innovative perspectives on the behavior and features of SACs. We hope that this Account can contribute in several ways to promoting the fundamental knowledge and technical progress of emerging electrochemical measurements for studying SACs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗