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DOE OSTI2020

Amorphous Pd-Loaded Ti 4 O 7 Electrode for Direct Anodic Destruction of Perfluorooctanoic Acid

In this work we present a novel Ti 4 O 7 -based electrode loaded with amorphous Pd clusters that achieve efficient anodic destruction of perfluorooctanoic acid (PFOA), a persistent water pollutant with significant environmental and human health concerns. These amorphous Pd clusters were characterized by the disordered, noncrystalline arrangement of Pd single atoms in close proximity, in contrast to crystalline Pd nanoparticles that have been often employed to tailor the electronic properties of an electrode. We found that the Ti 4 O 7 electrode loaded with amorphous Pd clusters significantly outperformed the Ti 4 O 7 electrode loaded with crystalline Pd particles due to enhanced electron transfer through dominant Pd–O bonds. Combined with the efficient binding of PFOA and its degradation intermediates to the fluorinated electrode surface, this electrode was capable of mineralizing PFOA and releasing fluoride as F – . The reaction pathway was found to proceed without involving reactive oxygen species and therefore was not quenched by common anions in complex natural water systems such as chloride ions.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Effect of Adsorbed Carboxylates on the Dissolution of Boehmite Nanoplates in Highly Alkaline Solutions

Understanding the dissolution of boehmite in highly alkaline solutions is important to the processing of the complex nuclear wastes stored at the Hanford (WA) and Savannah River (SC) sites. Here, we report the adsorption of model carboxylate anions on boehmite nanoplates in alkaline solutions and their effects on subsequent boehmite dissolution in 3 M NaOH at 80 °C. Although expectedly lower than at circumneutral pH, adsorption of oxalate at pH 13 at room temperature was significant and remained so through a linear decrease to 3 M NaOH conditions with no evidence for the appearance of new phases. Modeling of the adsorption data and rate were consistent with the formation of outer-sphere surface complexes. By using these conditions to preload the boehmite nanoplates with oxalate, and separately acetate, we measured and compared their dissolution behavior at 80 °C and observed a clear suppression of the dissolution rate for the case of adsorbed oxalate by 23% and for adsorbed acetate by 10% compared to pure solids. Ex situ scanning electron microscopy (SEM) and transmission electron microscopy (TEM) characterization revealed no detectable difference in the morphologic evolution of the dissolving boehmite materials. In conclusion, we nonetheless conclude that pre-adsorbed carboxylate anions, even as nominally weakly bound outer-sphere complexes, can persist on the surface through highly alkaline conditions, decreasing the density of dissolution-active sites and thereby adding an extrinsic control on the dissolution rate.

Adsorption kinetics↗

DOE OSTI2024

The Significant Role of New Particle Composition and Morphology on the HNO 3 -Driven Growth of Particles down to Sub-10 nm

New particle formation and growth greatly influence air quality and the global climate. Recent CERN Cosmics Leaving OUtdoor Droplets (CLOUD) chamber experiments proposed that in cold urban atmospheres with highly supersaturated HNO 3 and NH 3 , newly formed sub-10 nm nanoparticles can grow rapidly (up to 1000 nm h –1 ). Here, we present direct observational evidence that in winter Beijing with persistent highly supersaturated HNO 3 and NH 3 , nitrate contributed less than ~14% of the 8–40 nm nanoparticle composition, and overall growth rates were only ~0.8–5 nm h –1 . To explain the observed growth rates and particulate nitrate fraction, the effective mass accommodation coefficient of HNO 3 (α HNO 3 ) on the nanoparticles in urban Beijing needs to be 2–4 orders of magnitude lower than those in the CLOUD chamber. We propose that the inefficient uptake of HNO 3 on nanoparticles is mainly due to the much higher particulate organic fraction and lower relative humidity in urban Beijing. To quantitatively reproduce the observed growth, we show that an inhomogeneous “inorganic core–organic shell” nanoparticle morphology might exist for nanoparticles in Beijing. Finally, this study emphasized that growth for nanoparticles down to sub-10 nm was largely influenced by their composition, which was previously ignored and should be considered in future studies on nanoparticle growth.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Seasonal Controls on Microbial Depolymerization and Oxidation of Organic Matter in Floodplain Soils

Floodplain soils are vast reservoirs of organic carbon often attributed to anaerobic conditions that impose metabolic constraints on organic matter degradation. What remains elusive is how such metabolic constraints respond to dynamic flooding and drainage cycles characteristic of floodplain soils. Here, in this work, we show that microbial depolymerization and respiration of organic compounds, two rate-limiting steps in decomposition, vary spatially and temporally with seasonal flooding of mountainous floodplain soils (Gothic, Colorado, USA). Combining metabolomics and -proteomics, we found a lower abundance of oxidative enzymes during flooding coincided with the accumulation of aromatic, high-molecular weight compounds, particularly in surface soils. In subsurface soils, we found that a lower oxidation state of carbon coincided with a greater abundance of chemically reduced, energetically less favorable low-molecular weight metabolites, irrespective of flooding condition. Our results suggest that seasonal flooding temporarily constrains oxidative depolymerization of larger, potentially plant-derived compounds in surface soils; in contrast, energetic constraints on microbial respiration persist in more reducing subsurface soils regardless of flooding. Our work underscores that the potential vulnerability of these distinct anaerobic carbon storage mechanisms to changing flooding dynamics should be considered, particularly as climate change shifts both the frequency and extent of flooding in floodplains globally.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Seeding Advanced Treated Wastewater for Purposes of Direct Potable Reuse

Direct potable reuse (DPR) is a promising solution to address water scarcity. However, a better understanding of how introducing advanced treated water (ATW) affects microbial communities present in distribution systems is needed. Here, in this study, we measured changes to the microbial water quality in simulated distribution systems that were conditioned using treated, unimpaired surface water (SW) and then transitioned to ATW. In addition, we investigated whether adding a biological filtration step would seed the microbial community of the ATW and whether the influence would persist in the simulated distribution systems. We found that the bulk water in the ATW-fed distribution systems had lower cell counts and ATP concentrations and a distinct microbial community (based on 16S amplicon sequencing) compared to the SW-fed or the seeded ATW-fed systems. However, biofilm community composition and biomass remained consistent regardless of the feedwater. Increased microbial biomass and diversity were present in the seeded ATW, with several amplicon sequence variants identified as being introduced by the biological filter. Our results suggest that directly introducing ATW to distribution systems could disturb the existing microbial community. Preparing ATW for distribution via biological filtration may deliver more predictable and stable microbial water quality than introducing unseeded ATW.

16S↗

DOE OSTI2026

Optimizing Cryo-Focused Pyrolysis GC/MS for Tracing Soil Organic Matter Across Diverse Ecosystems

The cycling of organic matter in terrestrial soils and sediments is central to a range of biogeochemical processes that regulate nutrient cycling, crop productivity, trace gas emissions, and contaminant transport. Pyrolysis-gas chromatography/mass spectrometry (py-GC/MS) is a powerful tool for characterizing bulk soil organic matter (SOM) at the molecular level. In this study, we used a cryo-focused py-GC/MS system to analyze soil samples from seven diverse ecosystems: vernal pool, prairie pothole, temperate forest, tropical forest, tundra, wildfire-affected boreal forest, and grassland. We addressed a key bottleneck in molecular-level SOM characterization by developing an automated data analysis pipeline to optimize py-GC/MS and complementary evolved gas analysis/mass spectrometry (EGA/MS) methods, incorporating advanced tools for peak deconvolution, developing a custom compound class library, and implementing fragmentation spectrum-based molecular networking for the first time. This improved workflow was applied to soil samples from all seven ecosystems, including multiple depths and density fractions. Our findings demonstrate that ecosystem type plays a dominant role in shaping compositional differences in SOM. We also identified trends in the source of SOM compounds (e.g., microbial vs plantderived) across soil depth and density fractions, which are critical for understanding persistence and turnover of SOM. Our molecular networking analysis indicated that although many compounds are widespread across ecosystems, others are restricted to specific environments, such as wetlands. This underscores the utility of molecular-level data in elucidating the complexity of SOM composition and the environmental drivers that shape it. Such molecular-level insights can deepen our knowledge of biogeochemical SOM cycles.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2026

Dynamic Evolution of Mass and Physical Properties of Atmospheric Organic Aerosol under Solar Irradiance

Organic aerosol (OA) particles constitute a substantial fraction of sub-micron particulate mass in the atmosphere and play a critical role in climate system. OA undergoes dynamic aging processes in the atmosphere, with photolytic aging induced by ultraviolet solar irradiance being an important yet poorly characterized mechanism. Knowledge gaps persist regarding the role of volatility transformations during photolytic aging on the OA mass decay kinetics and the evolution of climate-relevant properties, such as hygroscopicity, hindering the model evaluation of OA spatiotemporal distributions and atmospheric budgets. In this study, we conduct isothermal photolytic aging experiments on both laboratory-generated secondary organic aerosols and ambient-collected particles from urban Atlanta, utilizing a high-sensitivity Quartz Crystal Microbalance. Our results reveal that photolytic aging reduces 40–66% of the low-volatility OA mass with lifetimes ranging from 8 to 200 hours under solar irradiance, and 44–92% of the photolytic mass loss is through slow evaporation of semi- or intermediate-volatile products, kinetically limited by their volatility. We observe up to ±50% changes in OA hygroscopicity with the transformation of fresh OA to photo-recalcitrant low-volatility products, associated with changes in oxygen-to-carbon ratio and molecular weight. A kinetic model incorporating photolytic volatility transformation provides a cohesive explanation for the observed photolysis-induced changes in mass, volatility, and hygroscopicity. Our results can help constrain model representation of the dynamic evolutions of mass and climate-relevant properties during photolytic aging processes of the ambient OA, improving our understanding of OA atmospheric behavior and climate impact.

Bai, Bin↗

DOE OSTI2026

Ion-Specific Precipitation of Extractants Enables Rare-Earth Separation and Wastewater Remediation from Solvent Extraction of Critical Elements

The increasing demand for rare-earth elements (REEs) necessitates sustainable recovery strategies, particularly from secondary sources, such as electronic waste. Solvent extraction is the primary industrial method for REE separation; however, the unintentional dissolution of extractants into wastewater poses serious environmental risks, leading to organic contamination and process inefficiencies. Existing wastewater treatment methods struggle to remove these persistent pollutants, underscoring the need for innovative recovery approaches. Herein, we present a ligand-mediated precipitation strategy that simultaneously recovers REEs and removes dissolved extractants from solvent extraction wastewater. We show that residual extractants in the aqueous phase can selectively bind REEs, inducing their precipitation while leaving transition metals in solution. By integrating FTIR spectroscopy, EDS, XPS, EXAFS, and SAXS, we elucidate the mechanism of ion-specific precipitation and the local coordination environment of metal ions in the precipitate. Importantly, we demonstrate that the precipitated extractants can be efficiently recovered and reused, providing a closed-loop solution that enhances sustainability. Applying this method to leachates from samarium–cobalt (Sm–Co) and neodymium–iron–boron (NdFeB) mixed magnets, we achieve highly selective REE precipitation under mild conditions, demonstrating a scalable and cost-effective pathway for REE recovery, wastewater purification, and extractant recycling. In conclusion, by integrating element-specific ligand-mediated precipitation with extractant reuse, this work offers a transformative approach to REE separation that reduces the environmental impact while improving resource efficiency.

E-waste↗

DOE OSTI2026

Investigating ultrafine aerosol turbulent fluxes during atmospheric new particle formation events

New particle formation (NPF) is an important source of atmospheric aerosols, yet quantitatively predicting its occurrence remains challenging, partly because ground-based measurements cannot capture NPF accurately if they occur in the upper atmosphere. While observations have confirmed the presence of new particles near the top of the planetary boundary layer (PBL), their origins and the direction of their vertical transport have remained ambiguous. Here, we propose and validate an analytical framework using airborne eddy-covariance (EC) and continuous wavelet transform (CWT) to directly quantify the vertical flux of newly formed particles and determine its dominant vertical transportation direction. Analyzing data from a dedicated airborne campaign over the Southern Great Plains, we observed a persistent and strong downward particle flux during NPF events, with a mean value of 133.8 cm?3 m s?¹ downward flux in the entrainment zone, whereas fluxes on non-NPF days were negligible. Our spectral analysis further confirms that these directional fluxes can be reliably captured using standard 1 Hz aerosol instrumentation. These findings suggest that new particle formation, driven by the entrainment of air from the overlying residual/stable layer during PBL growth, is a significant and potentially understudied source of boundary layer aerosols. The framework presented here provides a methodology to correctly attribute NPF events to specific altitudes, thereby improving the mechanistic understanding required for accurate atmospheric models.

Zhang, Ruoyu↗

DOE OSTI2020

Mechanisms of Enhanced Antibacterial Activity by Reduced Chitosan-Intercalated Nontronite

Previous studies have documented the antibacterial activity of certain iron-containing clays. However, the repulsion between negatively charged bacteria and the clay surface makes this process inefficient. The objective of this study is to improve the bactericidal efficiency of clays by reversing their surface charge from negative to positive. To achieve this objective, here positively charged chitosan, a nontoxic and biodegradable polymer, was intercalated into nontronite NAu-2. Chitosan-intercalated NAu-2 (C-NAu-2) was chemically reduced to obtain reduced C-NAu-2 (rC-NAu-2). Relative to reduced nontronite (rNAu-2), the antibacterial activity of rC-NAu-2 is higher and more persistent over a pH range of 6–8. The close spatial association between positively charged rC-NAu-2 and negatively charged bacteria increases the chances of cell membrane attack by extracellular ROS, the influx of soluble Fe 2+ into the bacterial cell, and the yield of intracellular ROS. All these factors contribute to the enhanced antibacterial activity of rC-NAu-2. In contrast to rNAu-2 treated E. coli cells, where membrane damage and intracellular ROS/Fe accumulation are restricted to the polar regions, the close bacteria–clay association in rC-NAu-2 results in nonselective membrane damage and more uniform intracellular ROS/Fe distribution across whole bacterial cells. These results advance the antibacterial model by highlighting the importance of bacteria–clay interactions to the antibacterial activity of Fe-bearing clays.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

Resolving Nanoscale Processes during Carbon Mineralization Using Identical Location Transmission Electron Microscopy

Basalt reservoirs offer the potential for carbon mineralization, aiding in achieving net-zero emissions. However, debates persist about microscopic crystallization mechanisms due to limited characterization techniques under high-temperature and pressure conditions. By using Identical Location Transmission Electron Microscopy (IL-TEM) and cryo-TEM, this study reveals nanoscale interfacial carbonation processes of forsterite and diopside nanoparticles in water-saturated supercritical carbon dioxide under realistic reservoir conditions. Further, both minerals undergo preferential metal cation dissolution into a thin water film, forming porous Si-rich amorphous layers, supporting the leached layer mechanism as the dominant mineral reactivity process. Diopside’s amorphous layer has lower porosity and growth rate relative to forsterite, likely related to the connectivity of silicate tetrahedra. Kinetically favorable nesquehonite and aragonite nanocrystals form on the amorphous layers. These findings support the development of accurate reservoir simulations and help enable commercial-scale carbon storage deployment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Defluorination Mechanisms and Real-Time Dynamics of Per- and Polyfluoroalkyl Substances on Electrified Surfaces

Per- and polyfluoroalkyl substances (PFAS) are persistent environmental contaminants found in groundwater sources and a wide variety of consumer products. In recent years, electrochemical approaches for the degradation of these harmful contaminants have garnered a significant amount of attention due to their efficiency and chemical-free modular nature. However, these electrochemical processes occur in open, highly non-equilibrium systems, and a detailed understanding of PFAS degradation mechanisms in these promising technologies is still in its infancy. To shed mechanistic insight into these complex processes, we present the first constant-electrode potential (CEP) quantum calculations of PFAS degradation on electrified surfaces. These advanced CEP calculations provide new mechanistic details about the intricate electronic processes that occur during PFAS degradation in the presence of an electrochemical bias, which cannot be gleaned from conventional density functional theory calculations. We complement our CEP calculations with large-scale ab initio molecular dynamics simulations in the presence of an electrochemical bias to provide time scales for PFAS degradation on electrified surfaces. Taken together, our CEP-based quantum calculations provide critical reaction mechanisms for PFAS degradation in open electrochemical systems, which can be used to prescreen candidate material surfaces and optimal electrochemical conditions for remediating PFAS and other environmental contaminants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Design of Experiments for Dynamic Test Runs in Solvent-Based CO 2 Capture Pilot Plants

Test runs in the pilot plants consume significant resources, and therefore, the learning from test runs should be maximized. Test runs conducted in the pilot plants are often steady state. It takes several hours for reaching steady-state in the pilot plants, and thus, the duration of the test runs needs to be long even for collecting few steady-state data points. On the other hand, a large number of measurements can be collected through dynamic test runs in a short span of time. This paper presents a systematic design of dynamic experiments (DoDEs) for identifiability of model parameters, which is achieved by persistently exciting the inputs signals. A pseudorandom binary sequence (PRBS) is designed as the input signal for DoDE due to its efficiency in obtaining sufficient spectral content. However, due to the long sequence size of the PRBS signal, a Schroeder-phase input signal, which is a multisine signal, is also designed. Tests for both types of signals are run in the Pilot Solvent Test Unit (PSTU) at the National Carbon Capture Center in Wilsonville, Alabama. The transient data are used to solve dynamic data reconciliation and parameter estimation problem. The estimated parameters are found to be not only superior to those estimated from using data collected from hundreds of steady-state test runs in a nonreactive (air–water) system, but the parameters could be estimated by using the dynamic data collected for about 24 h from the pilot plant for the MEA-H 2 O–CO 2 system.

CO2 capture↗

DOE OSTI2022

Flux Growth of Cerium Nickel Gallides Studied by In Situ Neutron Diffraction

In this work, reactions of cerium and nickel in excess molten gallium were monitored by neutron diffraction during heating and cooling. The formation of binary intermediates CeGa 2 and Ni 2 Ga 3 was observed during heating. During cooling of the molten mixture from 900 °C, precipitation of BaAl 4 -type CeNi 0.74 Ga 3.26 occurred at 850 °C. Upon cooling to 650 °C, this compound reacted in the flux to form Ce 2 NiGa 10 and then Ce 2 NiGa 12 , the latter of which persisted to room temperature. Making use of this information, subsequent reactions were quenched at 750 °C to isolate crystals of CeNi 0.74 Ga 3.26 for further study. Similar reactions replacing Ce with La and quenching above 750 °C yielded LaNi 0.35 Ga 3.65 crystals. Magnetic susceptibility studies on CeNi 0.74 Ga 3.26 indicate that the cerium is trivalent; the Ce 3+ moments undergo a strongly anisotropic ferromagnetic ordering with moment perpendicular to the c axis below 7 K. Heat capacity data show little evidence of heavy fermion behavior. Resistivity measurements show that both LaNi0.35Ga3.65 and CeNi 0.74 Ga 3.26 exhibit metallic behavior. Density of states calculations support this and indicate that Ni/Ga mixing in the compound stabilizes the structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Vacancy-Driven Disorder and Elevated Dielectric Response in the Pyrochlore Pb 1.5 Nb 2 O 6.5

Lone pair-driven distortions are a hallmark of many technologically important lead (Pb)-based materials. Here, the role of Pb 2+ in polar perovskites is well understood and easily manipulated for applications in piezo- and ferroelectricity, but the control of ordered lone pair behavior in Pb-based pyrochlores is less clear. Crystallographically and geometrically more complex than the perovskite structure, the pyrochlore structure is prone to geometric frustration of local dipoles due to a triangular arrangement of cations on a diamond lattice. The role of vacancies on the O' site of the pyrochlore network has been implicated as an important driver for the expression and correlation of stereochemically active lone pairs in pyrochlores such as Pb 2 Ru 2 O 6.5 and Pb 2 Sn 2 O 6 . In this work we report on the structural, dielectric, and heat capacity behavior of the cation- and anion-deficient pyrochlore Pb 1.5 Nb 2 O 6.5 upon cooling. We find that local distortions are present at all temperatures that can be described by cristobalite-type cation ordering, and this ordering persists to longer length scales upon cooling. From a crystallographic perspective, the material remains disordered and does not undergo an observable phase transition. In combination with density function calculations, we propose that the stereochemical activity of the Pb 2+ lone pairs is driven by proximity to O' vacancies, and the crystallographic site disorder of the O' vacancies prohibits long range correlation of lone pair-driven distortions. This in turn prevents a low-temperature phase transition and results in an elevated dielectric permittivity across a broad temperature range.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Elucidating Actinide–Pertechnetate and Actinide–Perrhenate Bonding via a Family of Th–TcO 4 and Th–ReO 4 Frameworks and Solutions

Technetium-99, a β-emitter produced from 235 U fission, poses a challenge for the nuclear industry due to co-extraction of pertechnetate (TcO 4 – ) with the actinides (An) during nuclear fuel reprocessing. Previous studies suggested that direct coordination of pertechnetate with An plays an important role in the coextraction process. However, few studies have provided direct evidence for An–TcO 4 – bonding in the solid state, and even fewer in solution. The present study describes synthesis and structural elucidation of a family of thorium(IV)-pertechnetate/perrhenate (ReO 4 – , nonradioactive surrogate) compounds, which is obtained by dissolution of thorium oxyhydroxide in perrhenic/pertechnic acid followed by crystallization, with or without heating. For reaction ratios of 3:1, 4:1, and 6:1 MO 4 – /Th(IV) (M = Tc, Re), the crystallized compounds reflect the same ratio, suggesting facile and flexible coordination. Furthermore, nine structures reveal 1-dimensional and 2-dimensional frameworks with varying topologies. While a multitude of compounds isolated from 4:1 (and 6:1) reaction solutions feature Th monomers linked by MO 4 – , the 3:1 reaction solution yielded the well-known dihydroxide-bridged thorium dimer, linked, and capped by MO 4 – . Density functional theory calculations on ReO 4 – /TcO 4 – isomorphs suggest similar bonding characteristics in the solid state, but experimental solution characterization noted differences. Specifically, small-angle X-ray scattering studies suggest the bonding of Th–TcO 4 – persists in solution, while Th–ReO 4 – bonding is less apparent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Determining the Effects of Zero-Field Splitting and Magnetic Exchange in Dimeric Europium(II) Complexes

Related BAP [BAP = bis(acyl)phosphide] and Acac (Acac = β-diketonate) molecules perform as robust supports for both lanthanide and actinide metals. Here, a molecular bimetallic Eu 2+ complex was successfully targeted and isolated by employing sodium bis(mesitoyl)phosphide [Na( mes BAP)] in a salt metathesis with EuI 2 , producing [Eu( mes BAP) 2 (et 2 o)] 2 (et 2 o = metal-coordinated diethyl ether). The corresponding Acac-Eu 2+ complex was targeted using mes Acac– (1,3-dimesityl-1,3-propanedione), generating [Eu( mes Acac) 2 (et 2 o)] 2 . Both complexes were characterized by single-crystal X-ray diffraction, UV–vis, IR, and NMR spectroscopies, and variable-temperature magnetic susceptibility. [Eu( mes BAP) 2 (et 2 o)] 2 was persistent under anaerobic, anhydrous conditions, whereas the analogous [Eu( mes Acac) 2 (et 2 o)] 2 showed evidence of decomposition under identical conditions. Finally, variable-temperature magnetic susceptibility and magnetization studies of [Eu( mes BAP) 2 (et 2 o)] 2 and [Eu( mes Acac) 2 (et 2 o)] 2 were performed, resulting in similar magnetic exchange coupling values of J ex = –0.018 and –0.023 cm –1 and axial zero-field-splitting D values of –0.38 and –0.51 cm –1 , respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Ligand–Metal Complementarity in Rare-Earth and Actinide Chemistry

In this article, the rare-earths are comprised of scandium, yttrium, and the lanthanides (atomic numbers 21, 39, and 57–71). (1) While these elements are essential to modern life, they were historically characterized as simple, perhaps dull, compared to the rich multielectron chemistry of d-block metals in catalysts and enzymes. These descriptions were quite fair and largely true at the time that these elements were being discovered and the first compounds containing them were being synthesized, although much progress has been made to overturn this view of the rare earths. Similarly, discussions about actinide chemistry are sometimes limited to research pertinent to the nuclear industry, which, while comprising technologies vital to modern society, does not celebrate the fascinating chemical space that much of the actinide series occupies. These historic characterizations of most of the rare-earth and actinide elements persist in some textbooks, and we acknowledge that it is a helpful place to start; however, altogether these series comprise 32 elements-27% of the 118 known by 2024-and we suggest it would be an unfortunate twist of physics if such a large proportion of the Periodic Table were genuinely dull. Indeed, as this Inorganic Chemistry Forum Issue “Ligand-Metal Complementarity in Rare-Earth and Actinide Chemistry” highlights, the chemistry-let alone the physics, that is, spectroscopy and magnetism-of these elements is rich and depends on ligands!

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗