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    Making chemical sense of phase in soft X-ray spectroptychography
    (Elsevier, 7/12/2023) Joseph, Stitsky; Jian, Wang; Stephen, Urquhart
    Spectroptychography is being used to realize a significant improvement in the spatial resolution of x-ray spectromicroscopy, allowing chemical microanalysis at finer spatial scales. The chemical sensitivity of near edge X-ray absorption fine structure (NEXAFS) is familiar to most researchers who use x-ray spectromicroscopy for chemical microanalysis. However, the additional phase information available through ptychography provides additional and tantalizing data, and potentially additional chemical information. This paper explores the chemical information available in phase for a system of silicon dioxide nanospheres.
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    Coal-Based Activated Carbon via Microwave-Assisted ZnCl2 Activation for Methyl Violet 2B Dye Removal: Optimization, Desirability Function, and Adsorption Mechanism
    (MDPI, 2023) Musa, Salis A.; Abdulhameed, Ahmed Saud; Baharin, Siti Nor Atika ; ALOthman, Zeid; Wilson, Lee; Jawad, Ali H.
    In this work, activated carbon (referred to as MCAC) was produced by microwave radiation assisted ZnCl2 activation using Malaysian coal (MC) as a precursor. The Brunauer–Emmett–Teller findings indicate that the MCAC has a relatively large surface area (798.18 m2/g) and a mesoporous structure (average pore diameter of 3.67 nm). The removal of Methylene Violet (MV 2B) a cationic dye model, was employed to investigate the adsorption properties of MCAC. A numerical desirability function in the Box–Behnken design (BBD) was employed to optimize the independent crucial adsorption variables as follows: A: MCAC dose (0.02–0.1 g); B: pH (4–10); and C: time (5–25 min). The results of equilibrium and dynamic adsorption showed that the adsorption of MV 2B followed Freundlich and pseudo-second order models, respectively. The maximum amount of MV 2B dye that the MCAC could adsorb (qmax) was 134.1 mg/g. Electrostatic interactions, π-π stacking, H-bonding, and pore diffusion contribute to the adsorption of MV 2B dye onto the MCAC surface. This study demonstrates the potential to utilize MC as a low-cost precursor for the efficient synthesis of MAC and its utility for the removal of pollutants.
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    Electrocatalytic Oxidation of Nitrophenols via Ag Nanoparticles Supported on Citric-Acid-Modified Polyaniline
    (MDPI, 2023) Khani, Milad; Sammynaiken, Ramaswami; Wilson, Lee
    Citric-acid-modified polyaniline (P-CA) and P-CA modified with Ag nanoparticles (Ag@PCA) were prepared via an in situ reduction method. The physicochemical properties of P-CA and Ag@P-CA were compared to unmodified polyaniline (PANI) and PANI-modified Ag nanoparticles (Ag@PANI). Ag@P-CA had a lower content of aniline oligomers compared to Ag@PANI. P-CA and Ag@P-CA had a greater monolayer adsorption capacity for 2-nitrophenol and lower binding affinity as compared to PANI and Ag@PANI materials. X-ray photoelectron spectroscopy and cyclic voltammetry characterization provided reason and evidence for the higher conductivity of citric-acid-modified materials (P-CA and Ag@P-CA versus PANI and Ag@PANI). These results showed the potential utility for the optimization of adsorption/desorption and electron transfer steps during the electrochemical oxidation of nitrophenols. The oxidation process employs Ag@P-CA as the electrocatalyst by modifying polyaniline with Ag nanoparticles and citric acid, which was successfully employed to oxidize 2-nitrophenol and 4-nitrophenol with comparable selectivity and sensitivity to their relative concentrations. This work is envisaged to contribute significantly to the selective conversion of nitrophenols and electrocatalytic remediation of such waterborne contaminants.
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    Moisture Content and Mechanical Properties of Bio-Waste Pellets for Fuel and/or Water Remediation Applications
    (MDPI, 2023) Anisimov, Yuriy A.; Steiger, Bernd; Cree, Duncan; Wilson, Lee
    The current research is focused on the mutual comparison (mechanical properties, response to humidity) of agro-waste composite materials. The purpose of this work is directed at the valorization of agro-waste biomass products and to investigate their mechanical stability for transport or other applications (in dry and wet states). Three different types of agro-waste (oat hull (Oh), torrefied wheat straw (S), and spent coffee grounds (SCG)) were blended with kaolinite (K) and chitosan (CHT) at variable weight ratios to yield ternary composites. Mechanical properties were represented by measuring hardness (in compression mode) and elastic modulus (under tension mode). Young’s (elastic) modulus was measured both for dried and hydrated samples. The pelletized materials were prepared in two forms: crosslinked (CL) with epichlorohydrin and non-crosslinked (NCL). The hardness of the Oh pellets was poor (75 N) and decreased by four times with greater agro-waste content, while crosslinking affected the hardness only slightly. S pellets had the highest level of hardness at 40% agro-waste content (160 N), with a concomitant decrease to 120 N upon crosslinking. SCG pellets had the least change in hardness for both CL and NCL specimens (105–120 N). The trends of Young’s modulus were similar to hardness. Hydration caused the elastic modulus to decrease ca. 100-fold. In general, S and SCG composites exhibit the greatest hardness and Young’s modulus compared to Oh composites (CL or NCL) in their dry state.
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    A Fixed-Bed Column with an Agro-Waste Biomass Composite for Controlled Separation of Sulfate from Aqueous Media
    (MDPI, 2023) Solgi, Mostafa; Steiger, Bernd; Wilson, Lee
    An agro-waste composite with a pelletized form was prepared and characterized via IR and 13C solids NMR spectroscopy. Thermal gravimetry analysis (TGA) was used to study the weight loss profiles, while SEM images provided insight on the biocomposite morphology, along with characterization of the sulfate adsorption properties under equilibrium and dynamic conditions. The sulfate monolayer adsorption capacity (qe = 23 mg/g) of the prepared agro-waste pellets was estimated from the adsorption isotherm results by employing the Langmuir model, and comparable fitting results were obtained by the Freundlich model. The dynamic adsorption properties were investigated via adsorption studies with a fixed bed column at pH 5.2. The effects of various parameters, including flow rate, bed height and initial concentrations of sulfate, were evaluated to estimate the optimal conditions for the separation of sulfate. The experimental data of the breakthrough curves were analyzed using the Thomas and Yoon–Nelson models, which provided satisfactory best-fits for the fixed bed kinetic adsorption results. The predicted adsorption capacities for all samples according to the Thomas model concur with the experimental values. The optimum conditions reported herein afford the highest dynamic adsorption capacity (30 mg/g) as follows: 1100 mg/L initial sulfate concentration, 30 cm bed height and 5 mL/min flow rate. The breakthrough time was measured to be 550 min. This study contributes to a strategy for controlled separation of sulfate using a sustainable biocomposite material that is suitable for fixed-bed column point-of-use water treatment systems.
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    A pyridinium-modified chitosan-based adsorbent for arsenic removal via a coagulation-like methodology
    (Royal Society of Chemistry, 2023) Venegas-García, Deysi J.; Steiger, Bernd; Wilson, Lee
    The goal of this study was to synthesize a chitosan-derived adsorbent that can be used in a coagulation– flocculation (CF) process for facile integration into existing water treatment processes. Therefore, an insoluble pyridinium-modified chitosan (Chi-Py) was prepared. Structural characterization was achieved with spectroscopy (FT-IR, 13C solids NMR, and X-ray photoelectron) methods and thermogravimetric analysis. Approximately 7% di-nitrobenzene and ca. 30% pyridinium moieties were incorporated into the chitosan framework via an adapted, moderate-temperature, Zincke reaction. The arsenic removal efficiency was evaluated by a coagulation-inspired methodology at pH 7.5, where the results were compared against CF systems such as pristine chitosan, FeCl3 and chitosan–FeCl3. The kinetic and van't Hoff thermodynamic parameters for arsenic removal were calculated. Arsenic adsorption was shown to be a spontaneous and exothermic process (ΔG = −4.7 kJ mol−1; ΔH = −75.6 kJ mol−1) with a 76% arsenic removal efficiency at 23 °C and 96% at 5 °C with a maximum effective adsorbent dosage of Chi- Py of 300 mg L−1. The adsorption process for Chi-Py followed pseudo-first order kinetics, where the pyridinium-modified chitosan adsorbent can be successfully employed similar to coagulant-like systems in conventional water treatment processes. In contrast to conventional adsorbents (1–2 g L−1), a dosage of only 300 mg L−1 was required for Chi-Py that offers greater sustainability and recycling of materials. This is contrasted with single-use conventional coagulants such as FeCl3 or binary FeCl3–chitosan CF systems.
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    X-ray Spectroptychography
    (ACS, 3/29/2022) Urquhart, Stephen
    X-ray spectroptychography is an emerging method for the chemical microanalysis of advanced nanomaterials such as catalysts and batteries. This method builds upon established synchrotron X-ray microscopy and spectromicroscopy techniques with added spatial resolution from ptychography, an algorithmic imaging technique. This minireview will introduce the technique of X-ray spectroptychography, where ptychography is performed with variable photon energy, and discuss recent results and prospects for this method.
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    Internal molecular conformation of organic glasses: A NEXAFS study
    (American Institute of Physics, 7/16/2021) Zuhaib, Amara; Urquhart, Stephen
    The origin of the exceptional stability of molecular glasses grown by physical vapor deposition (PVD) is not well understood. Differences in glass density have been correlated with thermodynamic stability for thin films of N,N′-Bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD) grown by PVD at specific substrate temperatures below the glass transition temperature. However, the relationship between the internal conformation of glass molecules and the thermodynamic properties of molecular glasses is not well studied. We use carbon 1s near edge x-ray absorption fine structure (NEXAFS) spectroscopy to examine different TPD sample preparations in which differences in the thermodynamic stability of the glass are known. Density functional theory simulations of the NEXAFS spectra of TPD allow us to attribute spectroscopic differences to changes in the internal conformation of the TPD molecule and relate this conformation to the stability of the TPD glass. This provides a direct experimental measurement of the internal conformation of molecules forming an organic glass.
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    Oxazolium Salts as Organocatalysts for the Umpolung of Aldehydes
    (ACS Publications, 10/1/2018) Garapati, Venkata Krishna Rao; Gravel, Michel
    Oxazolium salts were successfully employed for the first time as organocatalysts for benzoin, Stetter, and redox esterification reactions. An N-mesityl oxazolium salt catalyzed homobenzoin reaction of aromatic, heteroaromatic, and aliphatic aldehydes delivered α-hydroxy ketones in high yields. This new type of catalyst proved remarkably effective for the Stetter reaction of challenging substrates such as β-alkyl-α,β-unsaturated ketones and electron-rich aromatic aldehydes in comparison to common thiazolium and triazolium salts.
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    Enantioselective Stetter Reactions Catalyzed by Bis(amino)cyclopropenylidenes: Important Role for Water as an Additive
    (ACS Publications, 12/15/2020) Rezazadeh Khalkhali, Mehran; Wilde, Myron M. D.; Gravel, Michel
    The first highly enantioselective intermolecular Stetter reaction using simple enones is reported. A series of novel chiral BAC structures were designed and prepared. They were tested in the Stetter reaction with simple aldehydes and enones. The products were generated in excellent yields and enantioselectivities (up to 92% ee). Surprisingly, a substoichiometric amount of water was crucial to obtain high enantioselectivities. Chiral BACs were also shown to catalyze 1,6-conjugate addition reactions with paraquinone methides enantioselectively.
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    Microsecond Resolved Infrared Spectroelectrochemistry Using Dual Frequency Comb IR Lasers
    (American Chemical Society, 4/1/2020) Burgess, Ian
    A dual infrared frequency comb spectrometer with heterodyne detection has been used to perform time resolved electrochemical attenuated total reflectance surface enhanced infrared absorption spectroscopy (ATR-SEIRAS). The measurement of the potential dependent desorption of a monolayer of a pyridine derivative (4-dimethylaminopyridine, DMAP) with time resolution as high as 4 μs was achieved without the use of step-scan interferometry. An analysis of the detection limit of the method as a function of both time resolution and measurement co-additions is provided and compared to step-scan experiments of an equivalent system. Dual frequency comb spectroscopy is shown to be highly amenable to time-resolved ATR-SEIRAS. Microsecond resolved spectra can be obtained with high spectral resolution and fractional monolayer detection limits in a total experimental duration that is two orders of magnitude less than the equivalent step-scan experiment.
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    Silicon 1s Near Edge X-ray Absorption Fine Structure Spectroscopy of Functionalized Silicon Nanocrystals
    (American Chemical Society, 2016) Ritchie, Andrew; Cao, Wei; Dasog, Mita; Purkait, T.K.; Senger, Curtis; HU, Yongfeng; Xiao, Q.F.; Veinot, Jon; Urquhart, Stephen; Urquhart, Stephen
    Silicon 1s Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra of silicon nanocrystals have been examined as a function of nanocrystal size (3 – 100 nm), varying surface functionalization (hydrogen or 1-pentyl termination), or embedded in oxide. The NEXAFS spectra are characterized as a function of nanocrystal size and surface functionalization. Clear spectroscopic evidence for long range order is observed Si-NCs that are 5-8 nm in diameter or larger. Energy shifts in the silicon 1s NEXAFS spectra of covalently functionalized silicon nanocrystals with changing size are attributed to surface chemical shifts and not to quantum confinement effects.
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    Systematic Investigation of π–π Interactions in Near-Edge X-ray Fine Structure (NEXAFS) Spectroscopy of Paracyclophanes
    (2017) Perera, Sahan; Urquhart, Stephen
    NEXAFS spectroscopy has potential for study of packing and order in organic materials but only if intermolecular effects are understood. This work studies how π–π interactions between adjacent unsaturated groups affect their NEXAFS spectra, with a broader goal of building a general understanding of the role of intermolecular effects in NEXAFS spectroscopy. These effects are examined using paracyclophane (PCP) molecules, in which the benzene–benzene separation distance is controlled by varying the length of the alkyl groups separating the benzene rings. NEXAFS spectroscopy and density functional theory (DFT) simulations are used to examine spectroscopic changes related to the strength of these π–π interactions. A characteristic red shift is observed as adjacent benzene rings get closer together. This shift is attributed to Coulombic and orbital interactions between the adjacent benzene rings, mediated through overlapping π/π* orbitals.
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    Connecting Molecular Conformation to Aggregation in P3HT Using Near Edge X-ray Absorption Fine Structure Spectroscopy
    (American Chemical Society, 10/11/2017) Martinson, Mercedes; Urquhart, Stephen; Eger, Shaylin; Murcia, Victor; Ade, Harald; Collins, Brian
    Carbon 1s Near Edge X-ray Absorption Fine Structure (NEXAFS) and UV-vis spectroscopy are used to examine differences between highly aggregated and poorly aggregated forms of the polymer poly(3-hexylthiophene) (P3HT), based on as-cast and annealed regio-random and regio-regular P3HT samples. UV-vis spectra show characteristic signatures of unaggregated P3HT in regio-random P3HT, and of H-aggregation in regio-regular P3HT samples. Distinct spectroscopic differences, including energy shifts, are observed in the NEXAFS spectra of aggregated P3HT relative to the unaggregated forms. These differences are reproduced with Transition – Potential Density Functional Theory (TP-DFT) calculations which explore aggregation and molecular confirmation. Differences in the NEXAFS spectra of P3HT are assigned to thiophene backbone twisting in the unaggregated forms of P3HT, and to various degrees of chain planarization in aggregated forms of P3HT that also correlate to the exciton bandwidth. These results open up the prospect of charactering conformation and related difficult to assess structural details through NEXAFS spectroscopy and correlative theory and electronic structure analysis.
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    Temperature Dependence in the NEXAFS Spectra of n-Alkane
    (American Chemical Society, 11/16/2018) Urquhart, Stephen; Perera, Sahan; Sadegh, Shokatian; Wang, Jian
    The near edge X-ray absorption fine structure (NEXAFS) spectra of orthorhombic single crystals of n-octacosane (n-C28H58), recorded at room temperature (298 K) and at cryogenic temperatures (93 K), show distinct differences. The characteristic carbon 1s → σ*C–H band in the NEXAFS spectrum of n-C28H58 is broader and has a lower-energy onset in its room temperature spectrum than in its NEXAFS spectrum recorded at cryogenic temperatures. Density functional theory simulations show that nuclear motion and molecular disorder contribute to the observed spectral broadness and are the origin of the low-energy onset of the C–H band in the room temperature spectrum
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    Linear Dichroism in the NEXAFS Spectra of n-Alkane Crystalline Polymorphs
    (Elsevier, 2019-04) Perera, Sahan; Wang, Jian; Urquhart, Stephen
    Linear Dichroism in Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy is a useful tool for studying molecular orientation and for clarifying spectroscopic assignments. n- Alkane molecules can form single crystals with different polymorphs; orthorhombic and monoclinic in the case of even chain lengths between n-C28H58 and n-C40H82. These polymorphs exhibit different linear dichroism in their NEXAFS spectra; in particular a backbone-oriented transition contributes to the low-energy “C-H” band in the monoclinic polymorph.
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    Near Edge X-ray Absorption Fine Structure Spectra of Linear n- Alkanes: Variation with Chain Length
    (Elsevier, 2019) Shokatian, Sadegh; Urquhart, Stephen
    The effect of chain length on the carbon 1s Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra of linear n-alkanes has been examined with Transition Potential Density Functional Theory (TP-DFT) calculations. Species from propane (C3H8) to n-icosane (n-C20H42) and selected longer chains were examined. This study focuses on the prominent ‘C-H band’ (287 - 288 eV) in these NEXAFS spectra. TP-DFT calculations show that contributions from interior methylene groups (3 or more positions from the chain end) are similar, while contributions from the terminal methyl and the first methylene groups differ. The evolution of the angle dependent and Rydberg-valence mixing with chain length are also examined.
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    in situ X-ray Absorption Spectroscopic Analysis of Gold-Palladium Bimetallic Nanoparticle Catalysts
    (American Chemical Society, 2013) MacLennan, Aimee; Banerjee, Abhinandan; Hu, Yongfeng; Miller, Jeffrey T; Scott, Robert WJ
    Gold–palladium core–shell nanoparticles have been previously shown to be extremely effective catalysts for a number of oxidation reactions including the aerobic oxidation of alcohols. However, the novel activity and durability of such catalysts are still poorly understood, and there are several putative mechanisms by which oxidation reactions can proceed. Previously we showed that Pd(II) salts in the presence of Au nanoparticles were also effective catalysts for the room temperature oxidation of crotyl alcohol. Herein we show an in situ X-ray absorption spectroscopy (XAS) study at both the Pd–K and Pd-LIII edges of Au nanoparticle/Pd(II) salt solutions in the presence of crotyl alcohol. Liquid cells with X-ray permeable windows were used to obtain quick-scan XAS data during the oxidation of crotyl alcohol, allowing for time-resolved Pd speciation information and information about the reaction mechanism and kinetics. XAS measurements definitively show that the first step of this reaction involves Pd reduction onto the Au nanoparticles; in addition, further studies of the stability of the resulting Au–Pd core–shell nanoparticles toward oxygen gas suggests that the role of Au in such catalysts is to prevent the reoxidation of the catalytically active surface Pd atoms. Catalytic crotyl alcohol oxidation measurements were done which validated that the in situ reduction of Pd(II) in the presence of Au nanoparticles did indeed result in catalytically active AuPd bimetallic catalysts.
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    Following the Thermal Activation of Au25(SR)18 Clusters for Catalysis by X-Ray Absorption Spectroscopy
    (American Chemical Society, 2013) Shivhare, Atal; Chevrier, Daniel; Purves, Randy W; Scott, Robert WJ
    We show the thermal activation of phenylethanethiolate (L = SC8H9) and hexanethiolate (L = SC6H13) Au25L18 monolayer protected clusters (MPCs) on carbon black supports, followed by characterization with extended X-ray absorption fine structure (EXAFS) spectroscopy and transmission electron microscopy (TEM). EXAFS analysis shows that the thiolate stabilizers can be partially removed from the surface under mild heating conditions without significant changes in the cluster size. The resulting clusters are shown to be catalytically active for the reduction catalysis of 4-nitrophenol. EXAFS and TEM data show that thermal treatment under air at 200 °C leads to nearly complete removal of all of the thiolate stabilizers with little to no growth in cluster size, while cluster sintering was seen at higher calcination temperatures. The maximum catalytic activity for Au25(SC8H9)18 MPCs was seen at 250 °C activation conditions. These results are consistent with results reported earlier for Au25(SR)18 clusters on ceria by Jin et al., who suggested that cluster integrity was maintained during mild activation conditions. Here, EXAFS data unambiguously show that while the cluster size does not grow significantly, such mild heating conditions do lead to nearly complete removal of the thiolate stabilizers.
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    Design, synthesis, catalytic application, and strategic redispersion of plasmonic silver nanoparticles in ionic liquid media
    (Elsevier, 2014) Banerjee, Abhinandan; Theron, Robin; Scott, Robert WJ
    Silver nanoparticles synthesized in tetraalkylphosphonium ionic liquids are found to be excellent catalysts for borohydride-induced reductive degeneration of Eosin-Y, a dye that has been classified as a Class 3 carcinogen by the International Agency for Research on Cancer. TEM images indicated that the size of the Ag nanoparticles was significantly influenced by heat-induced sintering. A strategy was devised to redisperse smaller Ag nanoparticles from their aggregated/sintered counterparts via a two-step protocol that involved oxidative etching of Ag nanoparticles, followed by a re-reduction step. This protocol led to a reduction in the sintered Ag nanoparticle size from 15.7 ± 6.1 nm to 3.7 ± 0.8 nm, which was consistent with the size of the as-synthesized nanoparticles. The as-synthesized and the redispersed Ag nanoparticles were found to catalyze the bleaching of Eosin-Y with comparable efficiencies; first order rate constants for Eosin Y reduction were ∼8 times higher for smaller Ag nanoparticles compared to their sintered counterparts. An examination of the kinetics of Ag nanoparticle etching was performed via temperature-controlled UV–vis spectroscopy. Changes in the oxidation state of Ag during this sequence of events were also followed by in situ X-ray absorption spectroscopy of Ag nanoparticles in the ionic liquid.