Hydrodeoxygenation of Isoeugenol-derived Model Compound over Carbon-supported Pt and Pt-SnS Catalysts for the Production of Sustainable Jet Fuel.

This study focuses on the sustainable production of bio-jet fuel through the catalytic hydrodeoxygenation (HDO) of isoeugenol (IE). Properties of two spraying synthesis methods (in situ and ex situ metal doping) with different platinum (Pt) loading percentages. The catalyst was characterised using various techniques such as XAS, X-ray photoelectron spectroscopy, X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), field-emission scanning electron microscopy (FESEM) and thermogravimetric analysis. The HRTEM and FESEM results show the successful preparation of a spherical nanoparticle doped over activated carbon, and Pt was dispersed on the outer shell of the particles. The catalytic HDO of IE showed a high yield and conversion as follows: IE conversion of 100%, liquid-phase mass balance of 95.92%, dihydroeugenol conversion of 99.32%, propylcyclohexane yield of 88.94% and HYD yield of 76.19%. Moreover, the catalyst exhibited high reusability with low metal leaching and high coke resistance for 10 cycles. The catalyst was evaluated in a continuous flow reactor for 100 h at different reaction temperatures, and interestingly, the catalyst showed low deactivation with a high half-time.

Effect of straw decomposition on hexavalent chromium removal by straw: Significant roles of surface potential and dissolved organic matter.

Mobility and bioavailability of hexavalent chromium (Cr(VI)) in agricultural soils are affected by interactions between Cr(VI) and returned crop straws. However, the effect of straw decomposition on Cr(VI) removal and underlying mechanisms remain unclear. In this study, Cr(VI) removal by pristine and decomposed rice/rape straws was investigated by batch experiments and a series of spectroscopies. The results showed that straw decomposition inhibited Cr(VI) removal, regardless of straw types. However, the potential mechanisms of the inhibition were distinct for the two straws. For the rice straw, a lower zeta potential after decomposition suppressed Cr(VI) sorption and subsequent reduction. In addition, less Cr(VI) was reduced by the decomposed rice straw-derived dissolved organic matter (DOM) than the pristine one. In contrast, for the rape straw, due to the increased zeta potential after decomposition, the decreased Cr(VI) removal was mainly ascribed to less Cr(VI) reduction by the rape straw-derived DOM. These results emphasized the significant roles of straw surface potential and DOM in Cr(VI) removal, depending on straw types and decomposition, which facilitate the fundamental understanding of Cr(VI) removal by straws and are helpful for predicting the environmental risk of Cr and rational straw return in Cr(VI)-contaminated fields.

The nature of structural defects in ZIF-8 revealed with 1H and 31P MAS NMR and X-ray absorption spectroscopy.

The metal-organic frameworks (MOFs) attract interest as potential catalysts whose catalytic properties are driven by defects. Several methods have been proposed for the defects-inducing synthesis of MOFs. However, the active species formed on the defective sites remain elusive and uncharacterized, as the spectroscopic fingerprints of these species are hidden by the regular structure signals. In this work, we have performed the synthesis of ZIF-8 MOF with defect-inducing procedures using fully deuterated 2-methylimidazolate ligands to enhance the defective sites' visibility. By combining 1H and 31P MAS NMR spectroscopy and X-ray absorption spectroscopy, we have found evidence for the presence of different structural hydroxyl Zn-OH groups in the ZIF-8 materials. It is demonstrated that the ZIF-8 defect sites are represented by Zn-OH hydroxyl groups with the signals at 0.3 and -0.7 ppm in 1H MAS NMR spectrum. These species are of basic nature and may be responsible for the catalytic activity of the ZIF-8 material.

Driving Forces in the Formation of Paracetamol Cocrystals and Solvate with Naphthalene, Quinoline and Acridine.

Paracetamol is an important analgesic and antipyretic drug showing poor tabletability. Among the various approaches used to improve this property, understanding the forces that govern the crystal packing is revealed to be crucial. We prepared three stable compounds: (par)2∙(nap) (1), (par)∙(quin) (2), and (par)∙(acr) (3) (nap-naphthalene, quin-quinoline, acr-acridine) being cocrystals or solvate. The structural studies showed that all the reported compounds are composed of alternately arranged layers of paracetamol and coformer. Several supramolecular motifs in the paracetamol layer were identified: R44(22) in (1); R64(20) and R22(8) in (2); and R22(8), R42(12), and R44(26) rings in (3). The stability of the crystal network was studied by interactions analysis performed by Hirshfeld surface and fingerprint approaches and the energy between the closest units in the crystal network was calculated. It showed that the strongest interactions were found between blocks connected by N-H⋯O=C and O-H⋯O/N hydrogen bonds due to an important coulombic factor. The dispersive energy becomes important for tail-to-tail (and head-to-tail) arranged paracetamol units, and it prevails in the case of stacking interactions between coformer molecules. The importance of dispersive forces increases with the size of the aromatic system of the coformer. XAS studies confirmed the successful preparation of compounds and provided some details about electron structure.

Detangling past and modern zinc anthropogenic source contributions in an urbanized coastal river by combining elemental, isotope and speciation approaches.

The accumulation of trace metals in the environmental compartments of coastal rivers is a global and complex environmental issue, requiring multiple tools to constrain the various anthropogenic sources and biogeochemical processes affecting the water quality of these environments. The Valao fluvio-estuarine system (Rio de Janeiro, Brazil) presents a challenging case of a coastal river contaminated by both modern and historical anthropogenic metal sources, located in the land and in the intra-estuary, continuously mixed by tidal cycles. This study employed a combination of spatial distribution analysis of trace metals including gadolinium (Gd), zinc (Zn) isotopic analyses, and X-ray absorption spectroscopy (XAS) to distinguish between these sources. The concentrations of metals in both dissolved (water samples) and surficial sediment compartments (Suspended Particulate Matter and sediment samples) display an overall enrichment trend from upstream to downstream. Multivariate statistical analysis allows to discriminate geogenic elements derived from watershed geology (Ti, K, and Mg) vs anthropogenic contaminants from urban runoff and domestic sewage discharges (Cu, Cr, Pb, Zn, and Gd); and legacy metal contaminants (Zn and Cd) remobilized from ancient metallurgical wastes and transported upstream in the estuary during tidal cycles. The anthropogenic Gd concentration in the dissolved compartment increases along the watercourse, highlighting continuous ongoing sewage discharge. Zinc solid speciation also indicates that Zn contribution from legacy metallurgy waste is primarily associated with sulfide-Zn and Zn-phyllosilicate in the outlet estuary, while in upstream sediments of fluvio-estuarine system, Zn is found bound to organic matter. Zinc isotope systematically reveals a progressive downstream shift to heavier isotope compositions. Upstream, the relatively pristine site and the urbanized section of the river exhibit a relatively uniform δ66/64Zn value (+0.20 ± 0.07 ‰) in suspended particulate matter (SPM) and surficial sediments. These results indicate that domestic sewage discharges contribute to Zn enrichment in sediments of the Valao fluvio-estuarine system but without modifying its isotope signature in sediments. The sediment of the downstream estuarine section shows a heavier δ66/64Zn value (+0.48 ± 0.08 ‰), indicating the strong influence of the intra-estuarine source identified as the historical metallurgic contamination. An integrated view of the geochemical tracers allows thus inferring that the untreated sewage and legacy metallurgical contamination are the primary sources of anthropogenic Zn contamination. It highlights the progressive mixing along the estuarine gradient under tidal dynamics. The influence of the former source continuously expands from the headland towards the estuary.

Electronic structure of light-induced nitrosyl linkage isomers revealed by X-ray absorption spectroscopy at Ru L3,2-edges.

X-ray absorption spectroscopy (XAS) is a powerful tool for examining changes of the electronic and molecular structure following light-induced excitation of a molecule. Specifically, this method can be applied to investigate the ground (GS, RuNO) and metastable states (MS1, RuON and MS2, Ruη2(NO)) of the nitrosyl ligand (NO), which differ in their coordination mode to the metal. In this work, we report for the first time experimental and theoretical (DFT) Ru L3,2-edge XA spectra for the octahedral complex trans-[RuNOPy4F](ClO4)2 (1, Py = pyridine) in both ground and metastable states. The transition from GS to MS1 using 420 nm light excitation leads to a significant downshift of the 2p â†’ LUMO(+1) peaks by about 0.5-0.8 eV, attributed to the destabilisation of 2p orbitals and stabilization of LUMO(+1). Subsequent irradiation of MS1 at 920 nm produces isomer MS2, for which even greater stabilization of LUMO occurs, though without a significant change in 2p energy. The change in 2p energy is attributed to a variation in the charge on the Ru atom after NO isomerization, while LUMO(+1) stabilization is related to changes in the Ru(NO) bond length and the composition of this orbital.

Web-CONEXS: an inroad to theoretical X-ray absorption spectroscopy.

Accurate analysis of the rich information contained within X-ray spectra usually calls for detailed electronic structure theory simulations. However, density functional theory (DFT), time-dependent DFT and many-body perturbation theory calculations increasingly require the use of advanced codes running on high-performance computing (HPC) facilities. Consequently, many researchers who would like to augment their experimental work with such simulations are hampered by the compounding of nontrivial knowledge requirements, specialist training and significant time investment. To this end, we present Web-CONEXS, an intuitive graphical web application for democratizing electronic structure theory simulations. Web-CONEXS generates and submits simulation workflows for theoretical X-ray absorption and X-ray emission spectroscopy to a remote computing cluster. In the present form, Web-CONEXS interfaces with three software packages: ORCA, FDMNES and Quantum ESPRESSO, and an extensive materials database courtesy of the Materials Project API. These software packages have been selected to model diverse materials and properties. Web-CONEXS has been conceived with the novice user in mind; job submission is limited to a subset of simulation parameters. This ensures that much of the simulation complexity is lifted and preliminary theoretical results are generated faster. Web-CONEXS can be leveraged to support beam time proposals and serve as a platform for preliminary analysis of experimental data.

Highly efficient uranium uptake by the eco-designed cocamidopropyl betaine-decorated Na-P1 coal fly-ash zeolite.

In some locations around the globe, the U concentrations may exceed WHO standards by 2-folds therefore, effective yet environmentally wise solutions to purify radioactive waters are of significant importance. Here, the optimized and fully controlled coal-fly-ash based Na-P1 zeolite functionalization by employing novel, biodegradable biosurfactant molecule - cocamidopropyl betaine (CAPB) is showcased. The zeolite's surface decoration renders three composites with varying amounts of introduced CAPB molecule (Na-P1 @ CAPB), with 0.44, 0.88, and 1.59-times External Cation Exchange Capacity (ECEC). Wet-chemistry experiments revealed extremely high U adsorption capacity (qmax = 137.1 mg U/g) unveiling preferential interactions of uranyl dimers with CAPB molecules coupled with ion-exchange between Na+ ions. Multimodal spectroscopic analyses, including Fourier-Transformed Infra-Red (FT-IR), X-ray Photoelectron (XPS), and X-ray Absorption Fine Structure (XAFS), showed the hexavalent oxidation state of U, and no secondary release of the CAPB molecule from the composite. The EXAFS signals fingerprint changes in the interatomic distances of adsorbed U, showing the impact of the O and N, heteroatoms present in the CAPB molecule on U binding mechanism. The presented research outcomes showcase the easy, scalable, optimized, and environmentally friendly synthesis of biofunctional zeolite effectively purifying the real-life U-bearing wastewaters from the vicinity of the Pribram deposit (Czech Republic).

The identification of arsenic species produced in the dissolution of crystalline orpiment under anoxic conditions: XAS evidence.

The orpiment (As2S3) is an important secondary mineral in the geochemical process of arsenic (As) in the environment. The dissolution of orpiment has a close relationship with the migration and transformation of As. The dissolved species of As2S3 is closely related to sulfide (S-II) in the anoxic and sulfidic environment. This paper focuses on the various As species formed when As2S3 dissolved in the presence and absence of excess S-II under anoxic conditions with simulation tests via X-ray absorption spectroscopy (XAS), liquid chromatography with (hydride generation) atomic fluorescence spectrophotometry, and Raman spectroscopy. The results showed that the As produced when As2S3 dissolved in the excess S-II contained a mixture of arsenite and thioarsenite (ThioAsIII). Based on the linear combination fitting, ThioAsIII is the dominant As species (88.2 %) with arsenite as the leftover component. However, the percentage of ThioAsIII decreased to 43.7 % if As2S3 dissolved in the absence of excess S-II, indicting ThioAsIII favored under sulfidic conditions. The findings may give further insights about the role and formation mechanism of ThioAsIII in the dissolution process of As2S3. ENVIRONMENTAL IMPLICATION: The dissolution of crystallization orpiment has a close relationship with the transport of As in the environment. Qualitatively and quantitatively identification of the dissolved species of As2S3 in the presence and absence of excess S-II may be helpful for a better understanding and predicting the fate of As. The formed trithioarsenite was the dominant dissolved species compared to arsenite in the sulfidic system. It has higher mobility than AsV and AsIII, and has been found in many As-related adsorption/desorption and redox reactions. Therefore, great cautions should be given when choosing technologies to remediate the As contaminated soils and waters.

Interfacial Interaction in MeOx/MWNTs (Me-Cu, Ni) Nanostructures as Efficient Electrode Materials for High-Performance Supercapacitors.

Due to their unique physical and chemical properties, complex nanostructures based on carbon nanotubes and transition metal oxides are considered promising electrode materials for the fabrication of high-performance supercapacitors with a fast charge rate, high power density, and long cycle life. The crucial role in determining their efficiency is played by the properties of the interface in such nanostructures, among them, the type of chemical bonds between their components. The complementary theoretical and experimental methods, including dispersion-corrected density functional theory (DFT-D3) within GGA-PBE approximation, scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman, X-ray photoelectron, and X-ray absorption spectroscopies, were applied in the present work for the comprehensive investigation of surface morphology, structure, and electronic properties in CuOx/MWCNTs and NiOx/MWCNTs. As a result, the type of interfacial interaction and its correlation with electrochemical characteristics were determined. It was found that the presence of both Ni-O-C and Ni-C bonds can increase the contact between NiO and MWCNTs, and, through this, promote electron transfer between NiO and MWCNTs. For NiOx/MWCNTs, better electrochemical characteristics were observed than for CuOx/MWCNTs, in which the interfacial interaction is determined only by bonding through Cu-O-C bonds. The electrochemical properties of CuOx/MWCNTs and NiOx/MWCNTs were studied to demonstrate the effect of interfacial interaction on their efficiency as electrode materials for supercapacitor applications.

Revealing the structure of the active sites for the electrocatalytic CO2 reduction to CO over Co single atom catalysts using operando XANES and machine learning.

Transition-metal nitrogen-doped carbons (TM-N-C) are emerging as a highly promising catalyst class for several important electrocatalytic processes, including the electrocatalytic CO2 reduction reaction (CO2RR). The unique local environment around the singly dispersed metal site in TM-N-C catalysts is likely to be responsible for their catalytic properties, which differ significantly from those of bulk or nanostructured catalysts. However, the identification of the actual working structure of the main active units in TM-N-C remains a challenging task due to the fluctional, dynamic nature of these catalysts, and scarcity of experimental techniques that could probe the structure of these materials under realistic working conditions. This issue is addressed in this work and the local atomistic and electronic structure of the metal site in a Co-N-C catalyst for CO2RR is investigated by employing time-resolved operando X-ray absorption spectroscopy (XAS) combined with advanced data analysis techniques. This multi-step approach, based on principal component analysis, spectral decomposition and supervised machine learning methods, allows the contributions of several co-existing species in the working Co-N-C catalysts to be decoupled, and their XAS spectra deciphered, paving the way for understanding the CO2RR mechanisms in the Co-N-C catalysts, and further optimization of this class of electrocatalytic systems.

Site-Selective Zn-Metalation in Poly-Triphenyl Amine-based Porous Organic Polymer for Solid-Gas Phase CO2 Photoreduction.

Harvesting solar energy to produce value-added chemicals from carbon dioxide (CO2) presents a promising route for addressing the complexities of sustainable energy systems and environmental issues. In this context, the development of metal-coordinated porous organic polymers (POPs) offers a vital avenue for improving the photocatalytic performance of organic motifs. The current study presents a metal-integrated photocatalytic system (namely, Zn@BP-POP) developed via a one-pot Friedel-Crafts (F.C.) acylation strategy, for solid-gas phase photochemical CO2 reduction to CO (CO2RR). The postsynthetic incorporation of metal (Zn) active sites on the host polymeric backbone of BP-POP significantly influences the catalytic activity. Notably, Zn@BP-POP demonstrates good photocatalytic performance in the absence of any cocatalyst and photosensitizer yielding CO while impeding the competitive hydrogen evolution reaction (HER) from water. The experimental findings collectively propose that the observed catalytic activity and selectivity arise from the synergistic interplay between the singular zinc catalytic centers and the light-harvesting capacity of the highly conjugated polymeric backbone. Further, X-ray absorption spectroscopy (XAS) analysis has significantly highlighted the prominent role played by the ZnN2O4 single sites in the polymeric framework for activating the gaseous CO2 molecules. Further, time-dependent density functional theory (DFT) analysis also reveals the thermodynamic feasibility of CO2RR over HER under optimized reaction conditions. This work cumulatively presents an effective strategy to demonstrate the importance of metal-active sites and effectively establish their structure-activity relationship during photocatalysis.

X-ray Spectroscopy at the SuperXAS and Debye Beamlines: from in situ to Operando.

Understanding structure-performance relationships are essential for the rational design of new functional materials or in the further optimization of (catalytic) processes. Due to the high penetration depth of the radiation used, synchrotron-based hard X-ray techniques (with energy > 4.5 keV) allow the study of materials under realistic conditions (in situ and operando) and thus play an important role in uncovering structure-performance relationships. X-ray absorption and emission spectroscopies (XAS and XES) give insight into the electronic structure (oxidation state, spin state) and local geometric structure (type and number of nearest neighbor atoms, bond distances, disorder) up to ~5 Å around the element of interest. In this mini review, we will give an overview of the in situ and operando capabilities of the SuperXAS beamline, a facility for hard X-ray spectroscopy, through recent examples from studies of heterogeneous catalysts, electrochemical systems, and photoinduced processes. The possibilities for time-resolved experiments in the time range from ns to seconds and longer are illustrated. The extension of X-ray spectroscopy at the new Debye beamline combined with operando X-ray scattering and diffraction and further developments of time-resolved XES at SuperXAS will open new possibilities after the Swiss Light Source upgrade mid 2025.

Iridium Single Atoms to Nanoparticles: Nurturing the Local Synergy with Cobalt-Oxide Supported Palladium Nanoparticles for Oxygen Reduction Reaction.

A ternary catalyst comprising Iridium (Ir) single-atoms (SA)s decorated on the Co-oxide supported palladium (Pd) nanoparticles (denoted as CPI-SA) is developed in this work. The CPI-SA with 1 wt.% of Ir exhibits unprecedented high mass activity (MA) of 7173 and 770 mA mgIr -1, respectively, at 0.85 and 0.90 V versus RHE in alkaline ORR (0.1 m KOH), outperforming the commercial Johnson Matthey Pt catalyst (J.M.-Pt/C; 20 wt.% Pt) by 107-folds. More importantly, the high structural reliability of the Ir single-atoms endows the CPI-SA with outstanding durability, where it shows progressively increasing MA of 13 342 and 1372 mA mgIr -1, respectively, at 0.85 and 0.90 V versus RHE up to 69 000 cycles (3 months) in the accelerated degradation test (ADT). Evidence from the in situ partial fluorescence yield X-ray absorption spectroscopy (PFY-XAS) and the electrochemical analysis indicate that the Ir single-atoms and adjacent Pd domains synergistically promote the O2 splitting and subsequent desorption of hydroxide ions (OH-), respectively. Whereas the Co-atoms underneath serve as electron injectors to boost the ORR activity of the Ir single-atoms. Besides, a progressive and sharp drop in the ORR performance is observed when Ir-clusters and Ir nanoparticles are decorated on the Co-oxide-supported Pd nanoparticles.

Correlative In Situ Spectro-Microscopy of Supported Single CuO Nanoparticles: Unveiling the Relationships between Morphology and Chemical State during Thermal Reduction.

The activity, selectivity, and lifetime of nanocatalysts critically depend on parameters such as their morphology, support, chemical composition, and oxidation state. Thus, correlating these parameters with their final catalytic properties is essential. However, heterogeneity across nanoparticles (NPs) is generally expected. Moreover, their nature can also change during catalytic reactions. Therefore, investigating these catalysts in situ at the single-particle level provides insights into how these tunable parameters affect their efficiency. To unravel this question, we applied spectro-microscopy to investigate the thermal reduction of SiO2-supported copper oxide NPs in ultrahigh vacuum. Copper was selected since its oxidation state and morphological transformations strongly impact the product selectivity of many catalytic reactions. Here, the evolution of the NPs' chemical state was monitored in situ during annealing and correlated with their morphology in situ. A reaction front was observed during the reduction of CuO to Cu2O. From the temperature dependence of this front, the activation energy was extracted. Two parameters were found to strongly influence the NP reduction: the initial nanoparticle size and the chemical state of the SiO2. substrate. The CuOx reduction was found to be completed first on smaller NPs and was also favored over partially reduced SiOx regions that resulted from X-ray beam irradiation. This methodology with single-particle level spectro-microscopy resolution provides a way of isolating the influence of diverse morphologic, electronic, and chemical influences on a chemical reaction. The knowledge gained is crucial for the future design of more complex multimetallic catalytic systems.

Synergistic Effect of He for the Fabrication of Ne and Ar Gas-Charged Silicon Thin Films as Solid Targets for Spectroscopic Studies.

Sputtering of silicon in a He magnetron discharge (MS) has been reported as a bottom-up procedure to obtain He-charged silicon films (i.e., He nanobubbles encapsulated in a silicon matrix). The incorporation of heavier noble gases is demonstrated in this work with a synergistic effect, producing increased Ne and Ar incorporations when using He-Ne and He-Ar gas mixtures in the MS process. Microstructural and chemical characterizations are reported using ion beam analysis (IBA) and scanning and transmission electron microscopies (SEM and TEM). In addition to gas incorporation, He promotes the formation of larger nanobubbles. In the case of Ne, high-resolution X-ray photoelectron and absorption spectroscopies (XPS and XAS) are reported, with remarkable dependence of the Ne 1s photoemission and the Ne K-edge absorption on the nanobubble's size and composition. The gas (He, Ne and Ar)-charged thin films are proposed as "solid" targets for the characterization of spectroscopic properties of noble gases in a confined state without the need for cryogenics or high-pressure anvils devices. Also, their use as targets for nuclear reaction studies is foreseen.

Nanostructure and dynamics of N-truncated copper amyloid-ß peptides from advanced X-ray absorption fine structure.

An X-ray absorption spectroscopy (XAS) electrochemical cell was used to collect high-quality XAS measurements of N-truncated Cu:amyloid-ß (Cu:Aß) samples under near-physiological conditions. N-truncated Cu:Aß peptide complexes contribute to oxidative stress and neurotoxicity in Alzheimer's patients' brains. However, the redox properties of copper in different Aß peptide sequences are inconsistent. Therefore, the geometry of binding sites for the copper binding in Aß4-8/12/16 was determined using novel advanced extended X-ray absorption fine structure (EXAFS) analysis. This enables these peptides to perform redox cycles in a manner that might produce toxicity in human brains. Fluorescence XAS measurements were corrected for systematic errors including defective-pixel data, monochromator glitches and dispersion of pixel spectra. Experimental uncertainties at each data point were measured explicitly from the point-wise variance of corrected pixel measurements. The copper-binding environments of Aß4-8/12/16 were precisely determined by fitting XAS measurements with propagated experimental uncertainties, advanced analysis and hypothesis testing, providing a mechanism to pursue many similarly complex questions in bioscience. The low-temperature XAS measurements here determine that CuII is bound to the first amino acids in the high-affinity amino-terminal copper and nickel (ATCUN) binding motif with an oxygen in a tetragonal pyramid geometry in the Aß4-8/12/16 peptides. Room-temperature XAS electrochemical-cell measurements observe metal reduction in the Aß4-16 peptide. Robust investigations of XAS provide structural details of CuII binding with a very different bis-His motif and a water oxygen in a quasi-tetrahedral geometry. Oxidized XAS measurements of Aß4-12/16 imply that both CuII and CuIII are accommodated in an ATCUN-like binding site. Hypotheses for these CuI, CuII and CuIII geometries were proven and disproven using the novel data and statistical analysis including F tests. Structural parameters were determined with an accuracy some tenfold better than literature claims of past work. A new protocol was also developed using EXAFS data analysis for monitoring radiation damage. This gives a template for advanced analysis of complex biosystems.

Synergizing Fe2O3 Nanoparticles on Single Atom Fe-N-C for Nitrate Reduction to Ammonia at Industrial Current Densities.

The electrochemical reduction of nitrates (NO3 -) enables a pathway for the carbon neutral synthesis of ammonia (NH3), via the nitrate reduction reaction (NO3RR), which has been demonstrated at high selectivity. However, to make NH3 synthesis cost-competitive with current technologies, high NH3 partial current densities (jNH3) must be achieved to reduce the levelized cost of NH3. Here, the high NO3RR activity of Fe-based materials is leveraged to synthesize a novel active particle-active support system with Fe2O3 nanoparticles supported on atomically dispersed Fe-N-C. The optimized 3×Fe2O3/Fe-N-C catalyst demonstrates an ultrahigh NO3RR activity, reaching a maximum jNH3 of 1.95 A cm-2 at a Faradaic efficiency (FE) for NH3 of 100% and an NH3 yield rate over 9 mmol hr-1 cm-2. Operando XANES and post-mortem XPS reveal the importance of a pre-reduction activation step, reducing the surface Fe2O3 (Fe3+) to highly active Fe0 sites, which are maintained during electrolysis. Durability studies demonstrate the robustness of both the Fe2O3 particles and Fe-Nx sites at highly cathodic potentials, maintaining a current of -1.3 A cm-2 over 24 hours. This work exhibits an effective and durable active particle-active support system enhancing the performance of the NO3RR, enabling industrially relevant current densities and near 100% selectivity.

Exploring the Role of an Electrolyte Additive in Suppressing Surface Reconstruction of a Ni-Rich NMC Cathode at Ultrahigh Voltage via Enhanced In Situ and Operando Characterization Methods.

Vinylene carbonate (VC) is a widely used electrolyte additive in lithium-ion batteries for enhanced solid electrolyte interphase formation on the anode side. However, the cathode electrolyte interphase (CEI) formation with VC has received a lot less attention. This study presents a comprehensive investigation employing advanced in situ/operando-based Raman and X-ray absorption spectroscopy (XAS) to explore the effect of electrolyte composition on the CEI formation and suppression of surface reconstruction of LixNiyMnzCo1-y-zO2 (NMC) cathodes. A novel chemical pathway via VC polymerization is proposed based on experimental results. In situ Raman spectra revealed a new peak at 995 cm-1, indicating the presence of C-O semi-carbonates resulting from the radical polymerization of VC. Operando Raman analysis unveiled the formation of NiO at 490 cm-1 in the baseline system under ultrahigh voltage (up to 5.2 V). However, this peak was conspicuously absent in the VC electrolyte, signifying the effectiveness of VC in suppressing surface reconstruction. Further investigation was carried out utilizing in situ XAS compared X-ray absorption near edge structure spectra from cells of 3 and 20 cycles in both electrolytes at different operating voltages. The observed shift at the Ni K-edge confirmed a more substantial reduction of Ni in the baseline electrolyte compared to that in the VC electrolyte, thus indicating less CEI protection in the former. A sophisticated extended X-ray absorption fine structure analysis quantitatively confirmed the effective suppression of rock-salt formation with the VC electrolyte during the charging process, consistent with the operando Raman results. The in situ XAS results thus provided additional support for the key findings of this study, establishing the crucial role of VC polymerization in enhancing CEI stability and mitigating surface reconstruction on NMC cathodes. This work clarifies the relationship between the enhanced CEI layer and NMC degradation and inspires rational electrolyte design for long-cycling NMC cathodes.

Li+ Cations Activate NiFeOOH for Oxygen Evolution in Sodium and Potassium Hydroxide.

The efficiency of electrolysis is reduced due to the sluggish oxygen evolution reaction (OER). Besides catalyst properties, electrocatalytic activity also depends on the interaction of the electrocatalyst with the electrolyte. Here, we show that the addition of small amounts of Li+ to Fe-free NaOH or KOH electrolytes activates NiFeOOH for the OER compared to single-cation electrolytes. Moreover, the activation was maintained when the solution was returned to pure NaOH. Importantly, we show that the origin of activation by Li+ cations is primarily non-kinetic in nature, as the OER onset for the mixed electrolyte does not change and the Tafel slope at low current density is ~30 mV/dec in both electrolytes. However, the increase of the apparent Tafel slope remains lower at increasing current densities in the presence of Li+. Based on electrochemical quartz crystal microbalance and in situ X-ray absorption spectroscopy measurements, we show that this reduction of non-kinetic effects is due to enhanced intercalation of sodium, water and hydroxide. This enhanced electrolyte penetration facilitates the OER, especially at higher current densities and for increased catalyst loading. Our work shows that mixed electrolytes where distinct cations can have different roles provide a simple and promising strategy towards improved OER rates.