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Time-resolved electron paramagnetic resonance (TREPR) combined with pulsed laser excitation is used fot studying the photoexcited states of two 5,10,15-tris(pentafluorophenyl)corroles (tpfc), hosting Rh(III) in their core. The studies have shown that spin-orbit coupling (SOC) in the photoexcited Rh(III) corroles effectively admixes metal centered [super dd]-states to the corroles centered [super 3][pi][pi]*-states.

Here we demonstrate an experimental observation of GHz-scale spin dynamics resolved to sublattice octahedral (Oh) tetrahedral (Td) sites in a spinel ferrimagnet, in this case a Mn-ferrite thin film. X-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) are used, in combination with multiplet calculations, to uniquely identify the spectral signature from Mn2+ and Fe2+,3+ on Oh and Td lattice sites. With the sample under //excitation, the spin alignment of the sublattices is tracked with time-resolved XMCD (TR-XMCD). The spin alignment of the sublattices is mostly antiferromagnetic. The phase difference between the Oh Fe2+ [Oh Fe3+] and Td Mn2+ sites is 181.2 ± 3.8° [183.3° ± 3.7°] at 150 K and 186.6 ± 2.2° [182.0° ± 2.2°] at 300 K. Such direct measurement of the dynamic coupling, exchange stiffness, and damping enabled by TR-XMCD across sublattices will be essential for optimizing the development of future-generation microwave devices. [ABSTRACT FROM AUTHOR]

Here, a recently commissioned five-analyzer Johann spectrometer at the Inner Shell Spectroscopy beamline (8-ID) at the National Synchrotron Light Source II (NSLS-II) is presented. Designed for hard X-ray photon-in/photon-out spectroscopy, the spectrometer achieves a resolution in the 0.5-2 eV range, depending on the element and/or emission line, providing detailed insights into the local electronic and geometric structure of materials. It serves a diverse user community, including fields such as physical, chemical, biological, environmental and materials sciences. This article details the mechanical design, alignment procedures and data-acquisition scheme of the spectrometer, with a particular focus on the continuous asynchronous data-acquisition approach that significantly enhances experimental efficiency., (open access.)

Autonomous methods to align beamlines can decrease the amount of time spent on diagnostics, and also uncover better global optima leading to better beam quality. The alignment of these beamlines is a high-dimensional expensive-to-sample optimization problem involving the simultaneous treatment of many optical elements with correlated and nonlinear dynamics. Bayesian optimization is a strategy of efficient global optimization that has proved successful in similar regimes in a wide variety of beamline alignment applications, though it has typically been implemented for particular beamlines and optimization tasks. In this paper, we present a basic formulation of Bayesian inference and Gaussian process models as they relate to multi-objective Bayesian optimization, as well as the practical challenges presented by beamline alignment. We show that the same general implementation of Bayesian optimization with special consideration for beamline alignment can quickly learn the dynamics of particular beamlines in an online fashion through hyperparameter fitting with no prior information. We present the implementation of a concise software framework for beamline alignment and test it on four different optimization problems for experiments on X-ray beamlines at the National Synchrotron Light Source II and the Advanced Light Source, and an electron beam at the Accelerator Test Facility, along with benchmarking on a simulated digital twin. We discuss new applications of the framework, and the potential for a unified approach to beamline alignment at synchrotron facilities., (open access.)

Supported metal single atom catalysis is a dynamic research area in catalysis science combining the advantages of homogeneous and heterogeneous catalysis. Understanding the interactions between metal single atoms and the support constitutes a challenge facing the development of such catalysts, since these interactions are essential in optimizing the catalytic performance. For conventional carbon supports, two types of surfaces can contribute to single atom stabilization: the basal planes and the prismatic surface; both of which can be decorated by defects and surface oxygen groups. To date, most studies on carbon-supported single atom catalysts focused on nitrogen-doped carbons, which, unlike classic carbon materials, have a fairly well-defined chemical environment. Herein we report the synthesis, characterization and modeling of rhodium single atom catalysts supported on carbon materials presenting distinct concentrations of surface oxygen groups and basal/prismatic surface area. The influence of these parameters on the speciation of the Rh species, their coordination and ultimately on their catalytic performance in hydrogenation and hydroformylation reactions is analyzed. The results obtained show that catalysis itself is an interesting tool for the fine characterization of these materials, for which the detection of small quantities of metal clusters remains a challenge, even when combining several cutting-edge analytical methods., (© 2024 Wiley-VCH GmbH.)

This work demonstrates the mechanocatalytic hydrogenolysis of the ether bond in the lignin model compound benzyl phenyl ether (BPE) and hardwood lignin isolated by hydrolysis with supercritical water. Pd catalysts with 4 wt % loading on Al 2 O 3 and SiO 2 supports achieve 100% conversion of BPE with a toluene production rate of (2.6-2.9) × 10 -5 mol·min -1 . The formation of palladium hydrides under H 2 gas flow contributes to an increase in the turnover frequency by a factor of up to 300 compared to Ni on silica-alumina. While a near-quantitative toluene yield is obtained, some of the phenolic products remain adsorbed on the catalyst., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Use of single-atom catalysts (SACs) has become a popular strategy for tuning activity and selectivity toward specific pathways. However, conventional SAC synthesis methods require high temperatures and pressures, complicated procedures, and expensive equipment. Recently, underpotential deposition (UPD) has been investigated as a promising alternative, yielding high-loading SAC electrodes under ambient conditions and within minutes. Yet only few studies have employed UPD to synthesize SACs, and all have been limited to UPD of Cu. In this work, a flexible UPD approach for synthesis of mono- and bi-metallic Cu, Fe, Co, and Ni SACs directly on oxidized, commercially available carbon electrodes is reported. The UPD mechanism is investigated using in situ X-ray absorption spectroscopy and, finally, the catalytic performance of a UPD-synthesized Co SAC is assessed for electrochemical nitrate reduction to ammonia. The findings expand upon the usefulness and versatility of UPD for SAC synthesis, with hopes of enabling future research toward realization of fast, reliable, and fully electrified SAC synthesis processes., (© 2024 Wiley‐VCH GmbH.)

In recent years, there has been a substantial surge in the investigation of transition-metal dichalcogenides such as MoS 2 as a promising electrochemical catalyst. Inspired by denitrification enzymes such as nitrate reductase and nitrite reductase, the electrochemical nitrate reduction catalyzed by MoS 2 with varying local atomic structures is reported. It is demonstrated that the hydrothermally synthesized MoS 2 containing sulfur vacancies behaves as promising catalysts for electrochemical denitrification. With copper doping at less than 9% atomic ratio, the selectivity of denitrification to dinitrogen in the products can be effectively improved. X-ray absorption characterizations suggest that two sulfur vacancies are associated with one copper dopant in the MoS 2 skeleton. DFT calculation confirms that copper dopants replace three adjacent Mo atoms to form a trigonal defect-enriched region, introducing an exposed Mo reaction center that coordinates with Cu atom to increase N 2 selectivity. Apart from the higher activity and selectivity, the Cu-doped MoS 2 also demonstrates remarkably improved tolerance toward oxygen poisoning at high oxygen concentration. Finally, Cu-doped MoS 2 based catalysts exhibit very low specific energy consumption during the electrochemical denitrification process, paving the way for potential scale-up operations., (© 2024 Wiley-VCH GmbH.)

Stabilization of ions in exotic oxidation states is beneficial for the development of new materials for green energy technologies. Exotic Mn 1+ was proposed to play a role in the function of sodium-based Prussian blue analogues (PBA) batteries, a highly sought-out technology for industrial energy storage. Here, we report the detailed electronic structure characterization of uncharged and charged sodium-based manganese hexacyanomanganate anodes via Mn K-edge X-ray absorption spectroscopy (XAS), Kβ nonresonant X-ray emission (XES), and resonant inelastic X-ray scattering (RIXS). The latter allowed us to obtain site-selective XANES information about two distinct Mn centers. The obtained spectroscopic data represent the first electronic structure characterization of low-spin Mn 1+ using hard X-ray RIXS and XES and allowed us to confirm its role in anode reduction. Our experimental approach can be expanded to analysis of analogues with other 3d transition metals broadening the application of exotic ionic states in materials engineering.

Balancing kinetics, a crucial priority in catalysis, is frequently achieved by sacrificing activity of elementary steps to suppress side reactions and enhance catalyst stability. Dry reforming of methane (DRM), a process operated at high temperature, usually involves fast C-H activation but sluggish carbon removal, resulting in coke deposition and catalyst deactivation. Studies focused solely on catalyst innovation are insufficient in addressing coke formation efficiently. Herein, we develop coke-free catalysts that balance kinetics of elementary steps for overall thermodynamics optimization. Beginning from a highly active cobalt aluminum oxide (CoAl 2 O 4 ) catalyst that is susceptible to severe coke formation, we substitute aluminum (Al) with gallium (Ga), reporting a CoAl 0.5 Ga 1.5 O 4 -R catalyst that performs DRM stably over 1000 hours without observable coke deposition. We find that Ga enhances DRM stability by suppressing C-H activation to balance carbon removal. A series of coke-free DRM catalysts are developed herein by partially substituting Al from CoAl 2 O 4 with other metals., (© 2023. The Author(s).)

Electrochemical nitrate reduction (NO 3 RR) has attracted attention as an emerging approach to mitigate nitrate pollution in groundwater. Here, we report that a highly ordered PdCu alloy-based electrocatalyst exhibits selective (91% N 2 ), stable (480 h), and near complete (94%) removal of nitrate without loss of catalyst. In situ and ex situ XAS provide evidence that structural ordering between Pd and Cu improves long-term catalyst stability during NO 3 RR. In contrast, we also report that a disordered PdCu alloy-based electrocatalyst exhibits non-selective (44% N 2 and 49% NH 4 + ), unstable, and incomplete removal of nitrate. The copper within disordered PdCu alloy is vulnerable to accepting electrons from hydrogenated neighboring Pd atoms. This resulted in copper catalyst losses which were 10× greater than that of the ordered catalyst. The design of stable catalysts is imperative for water treatment because loss of the catalyst adds to the system cost and environmental impacts., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Here, we investigate the stability and performance of single-atom Pd on TiO 2 for the selective dechlorination of 4-chlorophenol. A challenge inherent to single atoms is their high surface free energy, which results in a tendency for the surface migration and aggregation of metal atoms. This work evaluates various factors affecting the stability of Pd single-atoms, including atomic dispersion, coordination environment, and substrate properties, under reductive aqueous conditions. The transition from single atoms to clusters vastly enhanced dechlorination kinetics without diminishing carbon-chlorine bond selectivity. X-ray absorption spectroscopy analysis using both in situ and ex situ conditions followed the dynamic transformation of single atoms into amorphous clusters, which consist of a unique unsaturated coordination environment and few nanometer diameter. The intricate relationship between stability and performance underscores the vital role of detailed characterization to properly determine the true active species for dehalogenation reactions.

The processing and analysis of synchrotron data can be a complex task, requiring specialized expertise and knowledge. Our previous work addressed the challenge of X-ray emission spectrum (XES) data processing by developing a standalone application using unsupervised machine learning. However, the task of analyzing the processed spectra remains another challenge. Although the non-resonant Kβ XES of 3d transition metals are known to provide electronic structure information such as oxidation and spin state, finding appropriate parameters to match experimental data is a time-consuming and labor-intensive process. Here, a new XES data analysis method based on the genetic algorithm is demonstrated, applying it to Mn, Co and Ni oxides. This approach is also implemented as a standalone application, Argonne X-ray Emission Analysis 2 (AXEAP2), which finds a set of parameters that result in a high-quality fit of the experimental spectrum with minimal intervention. AXEAP2 is able to find a set of parameters that reproduce the experimental spectrum, and provide insights into the 3d electron spin state, 3d-3p electron exchange force and Kβ emission core-hole lifetime., (open access.)

Understanding and controlling the chemical processes between molten salts and alloys is vital for the safe operation of molten-salt nuclear reactors. Corrosion processes in molten salts are highly dependent on the redox potential of the solution that changes with the presence of fission and corrosion processes, and as such, reactor designers develop electrochemical methods to monitor the salt. However, electrochemical techniques rely on the deconvolution of broad peaks, a process that may be imprecise in the presence of multiple species that emerge during reactor operation. Here, we describe in situ measurements of the concentration and chemical state of corrosion products in molten FLiNaK (eutectic mixture of LiF-NaK-KF) by high-resolution X-ray absorption spectroscopy. We placed a NiCr foil in molten FLiNaK and found the presence of both Ni 2+ ions and metallic Ni in the melt, which we attribute to the foil disintegration due to Cr dealloying., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The occurrence of high concentrations of nitrate in various water resources is a significant environmental and human health threat, demanding effective removal technologies. Single atom alloys (SAAs) have emerged as a promising bimetallic material architecture in various thermocatalytic and electrocatalytic schemes including nitrate reduction reaction (NRR). This study suggests that there exists a stark contrast between thermocatalytic (T-NRR) and electrocatalytic (E-NRR) pathways that resulted in dramatic differences in SAA performances. Among Pd/Cu nanoalloys with varying Pd-Cu ratios from 1:100 to 100:1, Pd/Cu (1:100) SAA exhibited the greatest activity (TOF Pd = 2 min -1 ) and highest N 2 selectivity (94%) for E-NRR, while the same SAA performed poorly for T-NRR as compared to other nanoalloy counterparts. DFT calculations demonstrate that the improved performance and N 2 selectivity of Pd/Cu (1:100) in E-NRR compared to T-NRR originate from the higher stability of NO 3 * in electrocatalysis and a lower N 2 formation barrier than NH due to localized pH effects and the ability to extract protons from water. This study establishes the performance and mechanistic differences of SAA and nanoalloys for T-NRR versus E-NRR., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Atomic dispersion of metal catalysts on a substrate accounts for the increased atomic efficiency of single-atom catalysts (SACs) in various catalytic schemes compared to the nanoparticle counterparts. However, lacking neighboring metal sites has been shown to deteriorate the catalytic performance of SACs in a few industrially important reactions, such as dehalogenation, CO oxidation, and hydrogenation. Metal ensemble catalysts (M n ), an extended concept to SACs, have emerged as a promising alternative to overcome such limitation. Inspired by the fact that the performance of fully isolated SACs can be enhanced by tailoring their coordination environment (CE), we here evaluate whether the CE of M n can also be manipulated in order to enhance their catalytic activity. We synthesized a set of Pd ensembles (Pd n ) on doped graphene supports (Pd n /X-graphene where X = O, S, B, and N). We found that introducing S and N onto oxidized graphene modifies the first shell of Pd n converting Pd-O to Pd-S and Pd-N, respectively. We further found that the B dopant significantly affected the electronic structure of Pd n by serving as an electron donor in the second shell. We examined the performance of Pd n /X-graphene toward selective reductive catalysis, such as bromate reduction, brominated organic hydrogenation, and aqueous-phase CO 2 reduction. We observed that Pd n /N-graphene exhibited superior performance by lowering the activation energy of the rate-limiting step, i.e., H 2 dissociation into atomic hydrogen. The results collectively suggest controlling the CE of SACs in an ensemble configuration is a viable strategy to optimize and enhance their catalytic performance.

Discovery of structure-property relationships in thin film alloys of complex metal oxides enabled by high-throughput materials synthesis and characterization facilities is demonstrated here with a case-study. Thin films of binary transition metal oxides (Ti-Zn) are prepared by pulsed laser deposition with continuously varying Ti:Zn ratio, creating combinatorial samples for exploration of the properties of this material family. The atomic structure and electronic properties are probed by spatially resolved techniques including x-ray absorption near edge structures (XANES) and x-ray fluorescence (XRF) at the Ti and Zn K-edge, x-ray diffraction, and spectroscopic ellipsometry. The observed properties as a function of Ti:Zn ratio are resolved into mixtures of five distinguishable phases by deploying multivariate curve resolution analysis on the XANES spectral series, under constraints set by results from the other characterization techniques. First-principles computations based on density function theory connect the observed properties of each distinct phase with structural and spectral characteristics of crystalline polymorphs of Ti-Zn oxide. Continuous tuning of the optical absorption edge as a function of Ti:Zn ratio, including the unusual observation of negative optical bowing, exemplifies a functional property of the film correlated to the phase evolution., (© 2023 IOP Publishing Ltd.)

We report on the giant anisotropy found in the thermoelectric power factor ( S 2 σ) of marcasite structure-type PtSb 1.4 Sn 0.6 single crystal. PtSb 1.4 Sn 0.6 , synthesized using an ambient pressure flux growth method upon mixing Sb and Sn on the same atomic site, is a new phase different from both PtSb 2 and PtSn 2 , which crystallize in the cubic Pa3̅ pyrite and Fm3̅m fluorite unit cell symmetry, respectively. The large difference in S 2 σ for heat flow applied along different principal directions of the orthorhombic unit cell stems mostly from anisotropic Seebeck coefficients.

Two-dimensional magnetic materials (2DMMs) are significant not only for studies on the nature of 2D long-range magnetic order but also for future spintronic devices. Of particular interest are 2DMMs where spins can be manipulated by electrical conduction. Whereas Cr 2 Si 2 Te 6 exhibits magnetic order in few-layer crystals, its large band gap inhibits electronic conduction. Here we show that the defect-induced short-range crystal order in Cr 2 Si 2 Te 6 , on the length scale below 0.6 nm, induces a substantially reduced band gap and robust semiconducting behavior down to 2 K that turns to metallic above 10 GPa. Our results will be helpful in designing conducting states in 2DMMs and call for spin-resolved measurement of the electronic structure in exfoliated ultrathin crystals.

Connections between crystal chemistry and critical temperature T c correlates with the average anion height above the Fe plane, i.e., with the geometry of the FeAs T c correlates with the average anion height above the Fe plane, i.e., with the geometry of the FeAs 4 or FeCh 4 (Ch = Te, Se, or S) tetrahedron. By synthesizing Fe 1- y Se 1 -x S x (0 ≤ x ≤ 1; y ≤ 0.1), we find that in alloyed crystals T c is not correlated with the anion height like it is for most other Fe superconductors. Instead, changes in T c ( x ) and tetragonal-to-orthorhombic (nematic) transition T s ( x ) upon cooling are correlated with disorder in Fe vibrations in the direction orthogonal to Fe planes, along the crystallographic c -axis. The disorder stems from the random nature of S substitution, causing deformed Fe(Se,S) 4 tetrahedra with different Fe-Se and Fe-S bond distances. Our results provide evidence of T c and T s suppression by disorder in anion height. The connection to local crystal chemistry may be exploited in computational prediction of new superconducting materials with FeSe/S building blocks.

Mixed-valence cerium oxide nanoparticles (nanoceria) have been investigated with pronounced interest due to a wide range of biomedical and industrial applications that arises from its remarkable redox catalytic properties. However, there is no understanding of how to control the formation of these two types of nanoceria to obtain Ce 3+ /Ce 4+ ratios required in various applications. In this work, using a soluble borate glass, nanoceria with specific ratios of Ce 3+ /Ce 4+ are created and extracted via controlled glass-melting parameters. Glass embedded with nanoceria as well as nanoceria extracted from the glass were studied via XANES and fitted with the Multivariate Curve Resolution (MCR) technique to calculate the ratio of Ce 3+ /Ce 4+ . Results show that mixed-valence nanoceria with specific ratios are hermetically sealed within the glass for long durations. When the glass dissolves, the mixed-valence nanoceria are released, and the extracted nanoceria have unchanged Ce 3+ /Ce 4+ ratios. Furthermore, TEM investigation on released nanoceria show that the nanoceria consist of several different structures. Although nanocrystal structures of Ce 7 O 12 , Ce 11 O 20 , and Ce 2 O 3 contribute to the reduced state, a new quasi-stable phase of CeO1.66 has been observed as well.

The Inner Shell Spectroscopy (ISS) beamline on the 8-ID station at the National Synchrotron Light Source II (NSLS-II), Upton, NY, USA, is a high-throughput X-ray absorption spectroscopy beamline designed for in situ, operando, and time-resolved material characterization using high monochromatic flux and scanning speed. This contribution discusses the technical specifications of the beamline in terms of optics, heat load management, monochromator motion control, and data acquisition and processing. Results of the beamline tests demonstrating the quality of the data obtainable on the instrument, possible energy scanning speeds, as well as long-term beamline stability are shown. The ability to directly control the monochromator trajectory to define the acquisition time for each spectral region is highlighted. Examples of studies performed on the beamline are presented. The paper is concluded with a brief outlook for future developments., (open access.)

In this study, we demonstrate three-dimensional (3D) hollow nanosphere electrocatalysts for CO 2 conversion into formate with excellent H-Cell performance and industrially-relevant current density in a 25 cm 2 membrane electrode assembly electrolyzer device. Varying calcination temperature maximized formate production via optimizing the crystallinity and particle size of the constituent SnO 2 nanoparticles. The best performing SnO 2 nanosphere catalysts contained ~ 7.5 nm nanocrystals and produced 71-81% formate Faradaic efficiency (FE) between -0.9 V and -1.3 V vs. the reversible hydrogen electrode (RHE) at a maximum formate partial current density of 73 ± 2 mA cm geo -2 at -1.3 V vs. RHE. The higher performance of nanosphere catalysts over SnO 2 nanoparticles and commercially-available catalyst could be ascribed to their initial structure providing higher electrochemical surface area and preventing extensive nanocrystal growth during CO 2 reduction. Our results are among the highest performance reported for SnO 2 electrocatalysts in aqueous H-cells. We observed an average 68 ± 8% FE over 35 h of operation with multiple on/off cycles. In situ Raman and time-dependent X-ray diffraction measurements identified metallic Sn as electrocatalytic active sites during long-term operation. Further evaluation in a 25 cm 2 electrolyzer cell demonstrated impressive performance with a sustained current density of 500 mA cm geo -2 and an average 75 ± 6% formate FE over 24 h of operation. Our results provide additional design concepts for boosting the performance of formate-producing catalysts., (© 2022. The Author(s).)

A capacitance increase phenomenon is observed for MoO 3 electrodes synthesized via a sol-gel process in the presence of dopamine hydrochloride (Dopa HCl) as compared to α-MoO 3 electrodes in 5M ZnCl 2 aqueous electrolyte. The synthesis approach is based on a hydrogen peroxide-initiated sol-gel reaction to which the Dopa HCl is added. The powder precursor (Dopa) x MoO y , is isolated from the metastable gel using freeze-drying. Hydrothermal treatment (HT) of the precursor results in the formation of MoO 3 accompanied by carbonization of the organic molecules; designated as HT-MoO 3 /C. HT of the precipitate formed in the absence of dopamine in the reaction produced α-MoO 3 , which was used as a reference material in this study (α-MoO 3 -ref). Scanning electron microscopy (SEM) images show a nanobelt morphology for both HT-MoO 3 /C and α-MoO 3 -ref powders, but with distinct differences in the shape of the nanobelts. The presence of carbonaceous content in the structure of HT-MoO 3 /C is confirmed by FTIR and Raman spectroscopy measurements. X-ray diffraction (XRD) and Rietveld refinement analysis demonstrate the presence of α-MoO 3 and h-MoO 3 phases in the structure of HT-MoO 3 /C. The increased specific capacitance delivered by the HT-MoO 3 /C electrode as compared to the α-MoO 3 -ref electrode in 5M ZnCl 2 electrolyte in a -0.25-0.70 V vs. Ag/AgCl potential window triggered a more detailed study in an expanded potential window. In the 5M ZnCl 2 electrolyte at a scan rate of 2 mV s -1 , the HT-MoO 3 /C electrode shows a second cycle capacitance of 347.6 F g -1 . The higher electrochemical performance of the HT-MoO 3 /C electrode can be attributed to the presence of carbon in its structure, which can facilitate electron transport. Our study provides a new route for further development of metal oxides for energy storage applications., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Norouzi, Omo-Lamai, Alimohammadi, Averianov, Kuang, Yan, Wang, Stavitski, Leshchev, Takeuchi, Takeuchi, Marschilok, Bock and Pomerantseva.)

We introduce a new graphene oxide (GO)-based membrane architecture that hosts cobalt catalysts within its nanoscale pore walls. Such an architecture would not be possible with catalysts in nanoscale, the current benchmark, since they would block the pores or alter the pore structure. Therefore, we developed a new synthesis procedure to load cobalt in an atomically dispersed fashion, the theoretical limit in material downsizing. The use of vitamin C as a mild reducing agent was critical to load Co as dispersed atoms (Co 1 ), preserving the well-stacked 2D structure of GO layers. With the addition of peroxymonosulfate (PMS), the Co 1 -GO membrane efficiently degraded 1,4-dioxane, a small, neutral pollutant that passes through nanopores in single-pass treatment. The observed 1,4-dioxane degradation kinetics were much faster (>640 times) than the kinetics in suspension and the highest among reported persulfate-based 1,4-dioxane destruction. The capability of the membrane to reject large organic molecules alleviated their effects on radical scavenging. Furthermore, the advanced oxidation also mitigated membrane fouling. The findings of this study present a critical advance toward developing catalytic membranes with which two distinctive and complementary processes, membrane filtration and advanced oxidation, can be combined into a single-step treatment.

In this study, we loaded Pd catalysts onto a reduced graphene oxide (rGO) support in an atomically dispersed fashion [i.e., Pd single-atom catalysts (SACs) on rGO or Pd 1 /rGO] via a facile and scalable synthesis based on anchor-site and photoreduction techniques. The as-synthesized Pd 1 /rGO significantly outperformed the Pd nanoparticle (Pd nano ) counterparts in the electrocatalytic hydrodechlorination of chlorinated phenols. Downsizing Pd nano to Pd 1 leads to a substantially higher Pd atomic efficiency (14 times that of Pd nano ), remarkably reducing the cost for practical applications. The unique single-atom architecture of Pd 1 additionally affects the desorption energy of the intermediate, suppressing the catalyst poisoning by Cl - , which is a prevalent challenge with Pd nano . Characterization and experimental results demonstrate that the superior performance of Pd 1 /rGO originates from (1) enhanced interfacial electron transfer through Pd-O bonds due to the electronic metal-support interaction and (2) increased atomic H (H*) utilization efficiency by inhibiting H 2 evolution on Pd 1 . This work presents an important example of how the unique geometric and electronic structure of SACs can tune their catalytic performance toward beneficial use in environmental remediation applications.

Single atom catalysts have been found to exhibit superior selectivity over nanoparticulate catalysts for catalytic reactions such as hydrogenation due to their single-site nature. However, improved selectively is often accompanied by loss of activity and slow kinetics. Here we demonstrate that neighboring Pd single atom catalysts retain the high selectivity merit of sparsely isolated single atom catalysts, while the cooperative interactions between neighboring atoms greatly enhance the activity for hydrogenation of carbon-halogen bonds. Experimental results and computational calculations suggest that neighboring Pd atoms work in synergy to lower the energy of key meta-stable reactions steps, i.e., initial water desorption and final hydrogenated product desorption. The placement of neighboring Pd atoms also contribute to nearly exclusive hydrogenation of carbon-chlorine bond without altering any other bonds in organohalogens. The promising hydrogenation performance achieved by neighboring single atoms sheds light on a new approach for manipulating the activity and selectivity of single atom catalysts that are increasingly studied in multiple applications., (© 2021. The Author(s).)

We report synthetic strategies for installing platinum group metals (PGMs: Pd, Rh, Ir, and Pt) on a scorpionate-derived linker (TpmC*) within a metal-organic framework (MOF), both by room-temperature postsynthetic metalation and by direct solvothermal synthesis, with a wide range of metal loadings relevant for fundamental studies and catalysis. In-depth studies for the palladium adduct Pd(II)@Zr-TpmC* by density-functional-theory-assisted extended X-ray absorption fine structure spectroscopy reveals that the rigid MOF lattice enforces a close Pd(II)-N apical interaction between the bidentate palladium complex and the third uncoordinated pyrazole arm of the TpmC* ligand (Pd-N apical = 2.501 ± 0.067 Å), an interaction that is wholly avoided in molecular palladium scorpionates.

Heterogeneous advanced oxidation processes (AOPs) allow for the destruction of aqueous organic pollutants via oxidation by hydroxyl radicals ( • OH). However, practical treatment scenarios suffer from the low availability of short-lived • OH in aqueous bulk, due to both mass transfer limitations and quenching by water constituents, such as natural organic matter (NOM). Herein, we overcome these challenges by loading iron oxychloride catalysts within the pores of a ceramic ultrafiltration membrane, resulting in an internal heterogeneous Fenton reaction that can degrade organics in complex water matrices with pH up to 6.2. With • OH confined inside the nanopores (∼ 20 nm), this membrane reactor completely removed various organic pollutants with water fluxes of up to 100 L m -2 h -1 (equivalent to a retention time of 10 s). This membrane, with a pore size that excludes NOM (>300 kDa), selectively exposed smaller organics to • OH within the pores under confinement and showed excellent resiliency to representative water matrices (simulated surface water and sand filtration effluent samples). Moreover, the membrane exhibited sustained AOPs (>24 h) and could be regenerated for multiple cycles. Our results suggest the feasibility of exploiting ultrafiltration membrane-based AOP platforms for organic pollutant degradation in complex water scenarios.

The ability of transition metal chitosan complexes (TMCs) of varying valence and charge to selectively adsorb As(III) and As(V) over their strongest adsorptive competitor, phosphate is examined. Fe(III)-chitosan, Al(III)-chitosan, Ni(II)-chitosan, Cu(II)-chitosan, and Zn(II)-chitosan are synthesized, characterized via Attenuated Total Reflectance-Fourier Transform Infrared spectroscopy (ATR-FTIR) and X-ray Diffractometry (XRD), and their selective sorption capabilities towards As(III) and As(V) in the presence of phosphate are evaluated. It was found that the stability of the metal-chitosan complexes varied, with Al(III)- and Zn(II)-chitosan forming very unstable complexes resulting in precipitation of gibbsite, and Wulfingite and Zincite, respectively. Cu(II)-, Ni(II)-, and Fe(III)-chitosan formed a mixture of monodentate and bidentate complexes. The TMCs which formed the bidentate complex (Cu(II)-, Ni(II)-, and Fe(III)-) showed greater adsorption capability for As(V) in the presence of phosphate. Using the binary separation factor ∝ t / c , it can be shown that only Fe(III)-chitosan is selective for As(V) and As(III) over phosphate. Density Functional Theory (DFT) modeling and extended X-ray adsorption fine structure (EXAFS) determined that Fe(III)-chitosan and Ni(II)-chitosan adsorbed As(V) and As(III) via inner-sphere complexation, while Cu(II)-chitosan formed mainly outer-sphere complexes with As(V) and As(III). These differences in complexation likely result in the observed differences in selective adsorption capability towards As(V) and As(III) over phosphate. It is hypothesized that the greater affinity of Fe(III)- and Ni(II)-chitosan towards As(V) and As(III) compared to Cu(II)-chitosan is due to their forming less-stable, more reactive chitosan complexes as predicted by the Irving Williams Series.