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The ability to study chemical dynamics on ultrafast timescales has greatly advanced with the introduction of X-ray free electron lasers (XFELs) providing short pulses of intense X-rays tailored to probe atomic structure and electronic configuration. Fully exploiting the full potential of XFELs requires specialized experimental endstations along with the development of techniques and methods to successfully carry out experiments. The liquid jet endstation (LJE) at the Linac Coherent Light Source (LCLS) has been developed to study photochemistry and biochemistry in solution systems using a combination of X-ray solution scattering (XSS), X-ray absorption spectroscopy (XAS), and X-ray emission spectroscopy (XES). The pump-probe setup utilizes an optical laser to excite the sample, which is subsequently probed by a hard X-ray pulse to resolve structural and electronic dynamics at their intrinsic femtosecond timescales. The LJE ensures reliable sample delivery to the X-ray interaction point via various liquid jets, enabling rapid replenishment of thin samples with millimolar concentrations and low sample volumes at the 120 Hz repetition rate of the LCLS beam. This paper provides a detailed description of the LJE design and of the techniques it enables, with an emphasis on the diagnostics required for real-time monitoring of the liquid jet and on the spatiotemporal overlap methods used to optimize the signal. Additionally, various scientific examples are discussed, highlighting the versatility of the LJE.
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The oxygen evolution reaction is central to making chemicals and energy carriers using electrons. Combining the great tunability of enzymatic systems with known oxide-based catalysts can create breakthrough opportunities to achieve both high activity and stability. Here we report a series of metal hydroxide-organic frameworks (MHOFs) synthesized by transforming layered hydroxides into two-dimensional sheets crosslinked using aromatic carboxylate linkers. MHOFs act as a tunable catalytic platform for the oxygen evolution reaction, where the π-π interactions between adjacent stacked linkers dictate stability, while the nature of transition metals in the hydroxides modulates catalytic activity. Substituting Ni-based MHOFs with acidic cations or electron-withdrawing linkers enhances oxygen evolution reaction activity by over three orders of magnitude per metal site, with Fe substitution achieving a mass activity of 80 A [Formula: see text] at 0.3 V overpotential for 20 h. Density functional theory calculations correlate the enhanced oxygen evolution reaction activity with the MHOF-based modulation of Ni redox and the optimized binding of oxygenated intermediates.
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Estruturas Metalorgânicas , Oxigênio , Catálise , HidróxidosRESUMO
Photocatalysis is a promising concept for the direct conversion of solar energy into fuels and chemicals. The design, experimental protocol, and performance of a multimodal and versatile flow reactor for the characterization of powdered and immobilized photocatalysts are herein presented. Ultimately, this instrument enables rigorous evaluation of photocatalysis performance metrics. The apparatus quantifies transient gas-phase reaction products via online real-time gas analyzer mass spectrometry (RTGA-MS). For H2, the most challenging gas, the photocatalytic system's RTGA-MS gas detection sensitivity spans over three orders of magnitude and can detect down to tens of parts per million under atmospheric conditions. Using Pt nanoparticles supported on anatase TiO2 photocatalyst via wet impregnation, the instrument's capability for the characterization of photocatalytic H2 evolution is demonstrated, resulting in an apparent quantum yield (AQY) of 48.1% ± 0.9% at 320 nm, 45.7% ± 0.3% at 340 nm and 31% ± 1% at 360 nm. The photodeposition of Pt on anatase TiO2 was employed to demonstrate the instrument's capability to track the transient behavior of photocatalysts, resulting in an improved 55% ± 2% AQY for H2 evolution at 340 nm from aqueous methanol. This photocatalytic instrument enables systematic study of a wide variety of photocatalytic reactions such as water splitting and CO2 reduction to valuable C2+ fuels and chemicals.
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Femtosecond-resolved Extended X-ray Absorption Fine Structure (EXAFS) measurements of solvated transition metal complexes are successfully implemented at the X-ray Free Electron Laser LCLS. Benchmark experiments on [Fe(terpy)2]2+ in solution show a signal-to-noise ratio on the order of 500, comparable to typical 100 ps-resolution synchrotron measurements. In the few femtoseconds after photoexcitation, we observe the EXAFS fingerprints of a short-lived (â¼100 fs) intermediate as well as those of a vibrationally hot long-lived (â¼ns) excited state.
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Metal-organic frameworks (MOFs) provide highly designable platforms to construct complex coordination architectures for targeted applications. Herein, we demonstrate that trans-coordinated metal centers with exposed equatorial positions can be placed in a MOF matrix. A Zr-based MOF, namely, PCN-160, was initially synthesized as a scaffold structure. Postsynthetic linker labilization was subsequently implemented to partially remove the original dicarboxylate linkers and incorporate pyridinecarboxylates. A pair of neighboring pyridyl groups was arranged at proper proximity within the framework to form trans-binding sites that accommodate different metal cations including Mn2+, Fe2+, Co2+, Ni2+, Cu2+, and Pd2+. Furthermore, the trans-coordinated Ni2+ sites in porous frameworks can be readily accessed by substrates along the equatorial plane, facilitating the catalysis as manifested by the superior activity in ethylene dimerization over that observed for a cis-chelated catalyst.
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For overall water-splitting systems, it is essential to establish O2 -insensitive cathodes that allow cogeneration of H2 and O2 . An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H2 evolution in the presence of O2 . Inâ operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O2 gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoOx /Pt/SrTiO3 with inhibited water formation from H2 and O2 , which is the prevailing back reaction on the bare Pt/SrTiO3 photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis.
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Photocatalytic CO2 reduction to CO under unassisted (unbiased) conditions was recently demonstrated using heterostructure catalysts that combine p-type GaN with plasmonic Au nanoparticles and Cu nanoparticles as cocatalysts (p-GaN/Al2O3/Au/Cu). Here, we investigate the mechanistic role of Cu in p-GaN/Al2O3/Au/Cu under unassisted photocatalytic operating conditions using Cu K-edge X-ray absorption spectroscopy and first-principles calculations. Upon exposure to gas-phase CO2 and H2O vapor reaction conditions, the composition of the Cu nanoparticles is identified as a mixture of CuI and CuII oxide, hydroxide, and carbonate compounds without metallic Cu. These composition changes, indicating oxidative conditions, are rationalized by bulk Pourbaix thermodynamics. Under photocatalytic operating conditions with visible light excitation of the plasmonic Au nanoparticles, further oxidation of CuI to CuII is observed, indicating light-driven hole transfer from Au-to-Cu. This observation is supported by the calculated band alignments of the oxidized Cu compositions with plasmonic Au particles, where light-driven hole transfer from Au-to-Cu is found to be thermodynamically favored. These findings demonstrate that under unassisted (unbiased) gas-phase reaction conditions, Cu is found in carbonate-rich oxidized compositions rather than metallic Cu. These species then act as the active cocatalyst and play an oxidative rather than a reductive role in catalysis when coupled with plasmonic Au particles for light absorption, possibly opening an additional channel for water oxidation in this system.
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Polarized time-resolved X-ray absorption spectroscopy at the Co K-edge is used to probe the excited-state dynamics and photolysis of base-off methylcobalamin and the excited-state structure of base-off adenosylcobalamin. For both molecules, the final excited-state minimum shows evidence for an expansion of the cavity around the Co ion by ca. 0.04 to 0.05 Å. The 5-coordinate base-off cob(II)alamin that is formed following photodissociation has a structure similar to that of the 5-coordinate base-on cob(II)alamin, with a ring expansion of 0.03 to 0.04 Å and a contraction of the lower axial bond length relative to that in the 6-coordinate ground state. These data provide insights into the role of the lower axial ligand in modulating the reactivity of B12 coenzymes.
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Coenzimas , Vitamina B 12 , Espectroscopia por Absorção de Raios X , Vitamina B 12/química , FotóliseRESUMO
We present a dedicated end-station for solution phase high repetition rate (MHz) picosecond hard x-ray spectroscopy at beamline 15-2 of the Stanford Synchrotron Radiation Lightsource. A high-power ultrafast ytterbium-doped fiber laser is used to photoexcite the samples at a repetition rate of 640 kHz, while the data acquisition operates at the 1.28 MHz repetition rate of the storage ring recording data in an alternating on-off mode. The time-resolved x-ray measurements are enabled via gating the x-ray detectors with the 20 mA/70 ps camshaft bunch of SPEAR3, a mode available during the routine operations of the Stanford Synchrotron Radiation Lightsource. As a benchmark study, aiming to demonstrate the advantageous capabilities of this end-station, we have conducted picosecond Fe K-edge x-ray absorption spectroscopy on aqueous [FeII(phen)3]2+, a prototypical spin crossover complex that undergoes light-induced excited spin state trapping forming an electronic excited state with a 0.6-0.7 ns lifetime. In addition, we report transient Fe Kß main line and valence-to-core x-ray emission spectra, showing a unique detection sensitivity and an excellent agreement with model spectra and density functional theory calculations, respectively. Notably, the achieved signal-to-noise ratio, the overall performance, and the routine availability of the developed end-station have enabled a systematic time-resolved science program using the monochromatic beam at the Stanford Synchrotron Radiation Lightsource.
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Reliably identifying short-lived chemical reaction intermediates is crucial to elucidate reaction mechanisms but becomes particularly challenging when multiple transient species occur simultaneously. Here, we report a femtosecond x-ray emission spectroscopy and scattering study of the aqueous ferricyanide photochemistry, utilizing the combined Fe Kß main and valence-to-core emission lines. Following UV-excitation, we observe a ligand-to-metal charge transfer excited state that decays within 0.5 ps. On this timescale, we also detect a hitherto unobserved short-lived species that we assign to a ferric penta-coordinate intermediate of the photo-aquation reaction. We provide evidence that bond photolysis occurs from reactive metal-centered excited states that are populated through relaxation of the charge transfer excited state. Beyond illuminating the elusive ferricyanide photochemistry, these results show how current limitations of Kß main line analysis in assigning ultrafast reaction intermediates can be circumvented by simultaneously using the valence-to-core spectral range.
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Large-scale CO2 electrolysis can be applied to store renewable energy in chemicals. Recent developments in gas diffusion electrodes now enable a commercially relevant current density. However, the low selectivity of the CO2 reduction reaction (CO2RR) still hinders practical applications. The selectivity of the CO2RR highly depends on the electrocatalyst. Sn catalysts are considered promising cathode materials for the production of formic acid. The selectivity of Sn catalysts can be regulated by controlling their morphology or alloying them with secondary metals. Herein, we enhanced the selectivity of CO2 reduction to formic acid by synthesizing Sn-Cu@Sn dendrites that have a core@shell architecture. The Sn-Cu@Sn dendrites were prepared by a scalable electro-deposition method. The electronic structure was modified to suppress a reaction pathway for CO production on the Sn surface. Notably, the Sn shell inhibited the cathodic corrosion of Cu during the CO2RR. On a gas diffusion electrode, the Sn-Cu@Sn dendrites exhibited 84.2% faraday efficiency to formic acid for 120 h with high stability.
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The nature of the S-vacancy is central to controlling the electronic properties of monolayer MoS2. Understanding the geometric and electronic structures of the S-vacancy on the basal plane of monolayer MoS2 remains elusive. Here, operando S K-edge X-ray absorption spectroscopy shows the formation of clustered S-vacancies on the basal plane of monolayer MoS2 under reaction conditions (H2 atmosphere, 100-600 °C). First-principles calculations predict spectral fingerprints consistent with the experimental results. The Mo K-edge extended X-ray absorption fine structure shows the local structure as coordinatively unsaturated Mo with 4.1 ± 0.4 S atoms as nearest neighbors (above 400 °C in an H2 atmosphere). Conversely, the 6-fold Mo-Mo coordination in the crystal remains unchanged. Electrochemistry confirms similar active sites for hydrogen evolution. The identity of the S-vacancy defect on the basal plane of monolayer MoS2 is herein elucidated for applications in optoelectronics and catalysis.
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Monolayer MoS2 is a promising semiconductor to overcome the physical dimension limits of microelectronic devices. Understanding the thermochemical stability of MoS2 is essential since these devices generate heat and are susceptible to oxidative environments. Herein, the promoting effect of molybdenum oxides (MoO x ) particles on the thermal oxidation of MoS2 monolayers is shown by employing operando X-ray absorption spectroscopy, ex situ scanning electron microscopy and X-ray photoelectron spectroscopy. The study demonstrates that chemical vapor deposition-grown MoS2 monolayers contain intrinsic MoO x and are quickly oxidized at 100 °C (3 vol% O2/He), in contrast to previously reported oxidation thresholds (e.g., 250 °C, t ≤ 1 h in the air). Otherwise, removing MoO x increases the thermal oxidation onset temperature of monolayer MoS2 to 300 °C. These results indicate that MoO x promote oxidation. An oxide-free lattice is critical to the long-term stability of monolayer MoS2 in state-of-the-art 2D electronic, optical, and catalytic applications.
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Ru-complexes are widely studied because of their use in biological applications and photoconversion technologies. We reveal novel insights into the chemical bonding of a series of Ru(ii)- and Ru(iii)-complexes by leveraging recent advances in high-energy-resolution tender X-ray spectroscopy and theoretical calculations. We perform Ru 2p4d resonant inelastic X-ray scattering (RIXS) to probe the valence excitations in dilute solvated Ru-complexes. Combining these experiments with a newly developed theoretical approach based on time-dependent density functional theory, we assign the spectral features and quantify the metal-ligand bonding interactions. The valence-to-core RIXS features uniquely identify the metal-centered and charge transfer states and allow extracting the ligand-field splitting for all the complexes. The combined experimental and theoretical approach described here is shown to reliably characterize the ground and excited valence states of Ru complexes, and serve as a basis for future investigations of ruthenium, or other 4d metals active sites, in biological and chemical applications.
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In electrocatalytic water splitting systems pursuing for renewable energy using sunlight, developing robust, stable and easily accessible materials operating under mild chemical conditions is pivotal. We present here a unique nanoparticulate type silver-oxide (AgOx-NP) based robust and highly stable electrocatalyst for efficient water oxidation. The AgOx-NP is generated in situ in a HCO3(-)/CO2 system under benign conditions. Micrographs show that they exhibit a nanoscale box type squared nano-bipyramidal configuration. The oxygen generation is initiated at low overpotential, and a sustained O2 evolution current density of >1.1 mA cm(-2) is achieved during prolonged-period water electrolysis. The AgOx-NP electrocatalyst performs exceptionally well in metal-ion free neutral or near-neutral carbonate, phosphate and borate buffers relative to recently reported Co-oxide and Ni-oxide based heterogeneous electrocatalysts, which are unstable in metal-ion free electrolytes and tend to deactivate with time and lose catalytic performance during long-term experimental tests.
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Microkinetic analyses of aqueous electrochemistry involving gaseous H2 or O2, i.e., hydrogen evolution reaction (HER), hydrogen oxidation reaction (HOR), oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), are revisited. The Tafel slopes used to evaluate the rate determining steps generally assume extreme coverage of the adsorbed species (θ≈0 or ≈1), although, in practice, the slopes are coverage-dependent. We conducted detailed kinetic analyses describing the coverage-dependent Tafel slopes for the aforementioned reactions. Our careful analyses provide a general benchmark for experimentally observed Tafel slopes that can be assigned to specific rate determining steps. The Tafel analysis is a powerful tool for discussing the rate determining steps involved in electrocatalysis, but our study also demonstrated that overly simplified assumptions led to an inaccurate description of the surface electrocatalysis. Additionally, in many studies, Tafel analyses have been performed in conjunction with the Butler-Volmer equation, where its applicability regarding only electron transfer kinetics is often overlooked. Based on the derived kinetic description of the HER/HOR as an example, the limitation of Butler-Volmer expression in electrocatalysis is also discussed in this report.
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A simple and versatile method for the preparation of photocatalyst particulates modified with effective cocatalysts is presented; the method involves the sequential soaking of photocatalyst particulates in solutions containing bifunctional organic linkers and metal ions. The modification of the particulate surfaces is a universal and reproducible method because the molecular linkers utilize strong covalent bonds, which in turn result in modified monolayer with a small but controlled quantity of metals. The photocatalysis results indicated that the CdS with likely photochemically reduced Pd and Ni, which were initially immobilized via ethanedithiol (EDT) as a linker, were highly efficient for photocatalytic hydrogen evolution from Na2S-Na2SO3-containing aqueous solutions. The method developed in this study opens a new synthesis route for the preparation of effective photocatalysts with various combinations of bifunctional linkers, metals, and photocatalyst particulate materials.
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Hidrogênio/química , Níquel/química , Paládio/química , Processos Fotoquímicos , Sulfetos/química , Catálise , Modelos Moleculares , Conformação Molecular , Propriedades de SuperfícieRESUMO
Tungsten carbide exhibits platinum-like behavior, which makes it an interesting potential substitute for noble metals in catalytic applications. Tungsten carbide nanocrystals (≈5 nm) are directly synthesized through the reaction of tungsten precursors with mesoporous graphitic C(3)N(4) (mpg-C(3)N(4)) as the reactive template in a flow of inert gas at high temperatures. Systematic experiments that vary the precursor compositions and temperatures used in the synthesis selectively generate different compositions and structures for the final nanocarbide (W(2)C or WC) products. Electrochemical measurements demonstrate that the WC phase with a high surface area exhibits both high activity and stability in hydrogen evolution over a wide pH range. The WC sample also shows excellent hydrogen oxidation activity, whereas its activity in oxygen reduction is poor. These tungsten carbides are successful cocatalysts for overall water splitting and give H(2) and O(2) in a stoichiometric ratio from H(2)O decomposition when supported on a Na-doped SrTiO(3) photocatalyst. Herein, we present tungsten carbide (on a small scale) as a promising and durable catalyst substitute for platinum and other scarce noble-metal catalysts in catalytic reaction systems used for renewable energy generation.